AN ABSTRACT OF THE THESIS OF
Carin A. Huset for the degree of Doctor of Philosophy in Chemistry presented on May
22, 2007.
Title: Determination of Fluorochemicals in Waste-Dominated Aqueous Systems
Abstract approved: _____________________________________________________
Douglas F. Barofsky,
Jennifer A. Field
While fluorochemicals have been detected all over the world and in wastewater
treatment plants, the effect of wastewater effluent on the receiving waters has not been
evaluated.
In the first study, the mass flow of fluorochemicals emanating from
wastewater treatment plants along the Glatt River in Switzerland was evaluated. The
fluorochemical concentrations in daily composite samples of river water and
wastewater were measured using LC/MS/MS. On average, the seven wastewater
treatment plants proved ineffective in completely removing fluorochemicals from the
influent and in some individual cases, the effluent concentrations of fluorochemicals
were elevated when compared to the influent.
Fluorochemical concentrations in
wastewater were dominated by PFOS followed by PFHxS and PFOA; PFOS was
detected in 100% of the samples. In the Glatt River, PFOS, PFOA and PFHxS were
detected in all samples. Mass flows were determined and showed that the mass
loading from the treatment plants is additive and that the mass flow along the river is
conserved. Per capita discharges for the plants along the Glatt River were calculated
and found to account for the upstream concentrations of fluorochemicals at the
headwaters of the Glatt River.
In the second study, a method for the quantitative analysis of fluorochemicals
in landfill leachates was developed to assess the amount of fluorochemicals emanating
from landfills. The method employed solid phase extraction with EnviCarb cleanup
prior to analysis by large volume injection LC/MS/MS. Perfluorocarboxylates (C4C10) were the dominant species observed in landfill leachates. PFBA concentrations
ranged from 63 – 1800 ng/L and PFOA concentrations ranged from 130 – 1100 ng/L.
The most abundant perfluorosulfonate measured in leachate was perfluorobutane
sulfonate (110 -2300 ng/L), which was measured in all samples. PFOS was also
detected in all samples at concentrations from 38 – 160 ng/L, including in leachates
obtained from sites which received waste only after the 2002 phase out of PFOS.
Fluoroalkyl sulfonamides, which was are precursors to PFOS and PFBS were also
detected in leachate, often in concentrations exceeding that of their degradation
product. Concentrations of MeFOSAA, which is indicative of the chemicals used in
textile and carpet treatments, ranged from ND – 290 ng/L, while concentrations of
EtFOSAA, which is associated with polymeric paper coating applications, ranged
from 7 to 480 ng/L. The analogous C4 sulfonamide, MeFBSAA, was observed at
concentrations ranging from 11 – 540 ng/L including at sites that have been closed
since before the phase out of PFOS and subsequent introduction of PFBS as a
substitute.
The distribution of fluorochemicals in landfills that operated under
leachate recirculation conditions were not different from landfills that did not circulate
leachate.
©Copyright by Carin A. Huset
May 22, 2007
All Rights Reserved
Determination of Fluorochemicals in Waste-Dominated Aqueous Systems
by
Carin A. Huset
A THESIS
submitted to
Oregon State University
in partial fulfillment of
the requirements of the
degree of
Doctor of Philosophy
Presented May 22, 2007
Commencement June 2007
Doctor of Philosophy thesis of Carin A. Huset presented on May 22, 2007.
APPROVED:
Co-Major Professor, representing Chemistry
Co-Major Professor, representing Chemistry
Chair of the Department of Chemistry
Dean of the Graduate School
I understand that my thesis will become a part of the permanent collection of Oregon
State University libraries. My signature below authorizes release of my thesis to any
reader upon request.
Carin A. Huset, Author
ACKNOWLEDGEMENTS
I would like to thank my graduate committee, Drs. William Baird, Douglas Barofsky,
Jennifer Field, Vincent Remcho and Staci Simonich, for the support and guidance over
the years. I would especially like to thank Jennifer Field and Douglas Barofsky for
giving me the opportunity to work with them in the lab an to learn so much from them
about life. Thank you to everyone in Jennifer Field’s laboratory (especially Carl,
Aurea, Rob, Ralph, Melissa and Kim), the Mass Spectrometry Laboratory (especially
Martha, Melissa, Hong, Ben, Jeff, Brian, Ben, Rick, Yury, Valery, Lilo, Max and
Sarah) and Staci Simonich’s laboratory (especially Luke, Sascha and Glenn), past and
present, for talking science, troubleshooting problems and all the other help over the
years.
I want to thank my parents for always believing in me and never giving me any
reasons to doubt my abilities or potential. Thank you to all my family and friends for
support and encouragement. Thanks to Dana, Emily, Richard, Cindy, Nell, Kristina
and Leslee for all the terrific stress reduction through exercise. I want to thank many
friends (Erin, Molly, Michaela, Molly, Eric, Jean, Jen, Sally, and Katy) for all the fun
and getting me to let my hair down. Special thanks to my husband Pete for love,
support, encouragement, and roughly 250,000 miles of commuting.
CONTRIBUTION OF AUTHORS
Drs. Douglas Barofsky and Jennifer Field provided direction and guidance in all
aspects of preparing these manuscripts. Ms Chiaia assisted with data collection and
analysis for the mass flow study. Dr Kohler, Dr Giger, and Dr Jonkers were involved
with sampling strategy and collection of samples for the mass flow study. Dr Barlaz
facilitated sample collection and assisted with data interpretation for landfill sites.
TABLE OF CONTENTS
Introduction……………………………………………………………..
Page
1
Background………………………………………..……………
1
Synthesis…..……………………………………………………..
2
Applications……………………………………………………..
3
Toxicology …………………………….………………………..
4
Environmental fate and distribution.……………………………
6
Sources and exposure routes……………………………………..
9
Introduction to Chapter 2 and 3……...…………………………..
10
References………………………………………………………..
14
Mass flow of fluorochemicals in a Swiss River Valley……………….....
25
Abstract………………………………………..………………..
26
Introduction……………………………………………………..
27
Experimental……………………………………………….……
28
Standards and reagents.…………………………………
River and WWTP sampling…………………………….
Liquid chromatography/tandem mass spectrometry……
Quality control………………………………………….
Instrumental detection and quantitation limits………….
28
29
29
31
32
Results and discussion…………………………………………..
32
Chromatography and quality control…………………...
WWTP removal efficiency……………………………...
WWTP inputs to the Glatt River………………………...
Concentrations of fluorochemicals in Glatt River………
Mass flow of fluorochemicals……………………………
Per capita discharge of fluorochemicals in the Glatt
Valley……………………………………………………
32
34
34
36
36
38
TABLE OF CONTENTS (Continued)
Acknowledgements……………………………………………....
41
References………………………………………………………..
42
Quantitative determination of fluorochemicals in landfill leachates……
51
Abstract…………………………………………………………..
52
Introduction………………………………………………………
54
Experimental……………………………………………………..
56
Standards…………………………………………………
Leachate samples………………………………………...
Solid phase extraction……………………………………
Liquid Chromatography/Tandem Mass Spectrometry
(LC/MS/MS)……………………………………………..
Accuracy and precision…………………………………..
56
57
58
Results and discussion…………………………………………...
63
59
62
Chromatography…………………………………………
Cartridge selection and elimination of background..…….
Breakthrough……………………………………………..
Envicarb and matrix effects……………………………...
Accuracy and precision…………………………………..
Estimated (whole) method detection limit……………….
Demonstration of method in leachate..…………………..
Perfluorocarboxylates…….…………………………..….
Perfluorosulfonates……………………………………….
Fluorotelomer sulfonates…………………………………
Fluoroalkyl sulfonamides………………………….......…
Fluorochemical concentration trends………………..…....
Relationship with sludge………………………………….
63
63
64
64
66
67
67
68
69
71
71
72
73
Acknowledgements……………………………………………….
75
References………………………………………………………..
75
Summary and Conclusions....……………………………………….........
85
References………………………………..………………………
86
TABLE OF CONTENTS (Continued)
Page
Bibliography……………………………………………………………
88
Appendices……..………………………………………………………
Appendix 1: Supporting information for Mass flow of
fluorochemicals in a Swiss River Valley ……………………….
96
Appendix 2: Supporting information for quantitative
determination of fluorochemicals in landfill leachates………….
97
101
LIST OF FIGURES
Page
Figure
2.1
Map of Glatt River area of Switzerland with three river sampling
stations and seven wastewater treatment plants…...........................
48
Measured and calculated mass flows of fluorochemicals
(g/day ± 95% CI) in the Glatt River………………..……………
49
2.3
Per capita mass flows in United States compared to Switzerland..
50
3.1
Chromatogram of fluorochemicals in Site H leachate sample……
84
2.2
LIST OF TABLES
Page
Table
1.1
Fluoroalkyl carboxylates…………………………………………
21
1.2
Fluoroalkyl sulfonates……………………………………………
22
1.3
Fluoroalkyl sulfonamides………………………………………...
23
1.4
Semi-volatile precursors: fluorotelomer alcohols and fluoroalkyl
sulfonamides……………………………………………………...
24
Sampling locations, average, minimum, and maximum flow for
each station and population served by each treatment plant....…..
44
Average weekly (n=7) concentration (ng/L ± 95% CI) of analytes
at each WWTP and river station……………………………...…..
45
Average weekly mass flows (g./day ± 95% CI) of fluorochemicals
in WWTP effluent and at Glatt river stations ………...………….
46
Estimation of WWTP contribution to mass flow of fluorochemicals
originating from Greifensee, which is the headwaters of the Glatt
River……………………………………………………………..
47
Site characteristics and chemical characterizations leachate sampling
sites………………………………………………………………
80
Analytical precision as indicated by RSD of replicate extractions of
a single leachate sample, accuracy as indicated by % recovery
± 95% CI and EMDL……………………………………………
81
Concentration (ng/L ± 95% CI) of fluorochemicals in 12 leachate
samples…..………………………………………………………
82
2.1
2.2
2.3
2.4
3.1
3.2
3.3
LIST OF APPENDIX FIGURES
Page
Figure
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
Linear regression of concentration (ng/L) of PFBA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
106
Linear regression of concentration (ng/L) of PFPA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
107
Linear regression of concentration (ng/L) of PFHxA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
108
Linear regression of concentration (ng/L) of PFHpA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
109
Linear regression of concentration (ng/L) of PFOA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
110
Linear regression of concentration (ng/L) of PFNA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
111
Linear regression of concentration (ng/L) of PFDA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
112
Linear regression of concentration (ng/L) of PFBS in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
113
LIST OF APPENDIX FIGURES (Continued)
Figure
2.9
2.10
2.11
2.12
2.13
2.14
2.15
2.16
2.17
Page
Linear regression of concentration (ng/L) of PFHxS in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
114
Linear regression of concentration (ng/L) of PFOS in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
115
Linear regression of concentration (ng/L) of 6:2 FtS in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
116
Linear regression of concentration (ng/L) of 8:2 FtS in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
117
Linear regression of concentration (ng/L) of MeFBSAA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
118
Linear regression of concentration (ng/L) of MeFOSAA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
119
Linear regression of concentration (ng/L) of EtFOSAA in
leachate determined by standard addition and from a
solvent curve. Error bars represent ± 95% CI. ……………..…....
120
Correlation between concentration 6:2 FtS (ng/L) and age of refuse
as indicated by year opened for 12 sites………………………....
121
Correlation between concentration of PFOS (ng/L) and age of refuse
as indicated by year opened for Site D……………………..…....
122
LIST OF APPENDIX FIGURES (Continued)
Page
Figure
2.18
2.19
2.20
2.21
2.22
2.23
2.24
2.25
2.26
2.27
Correlation between concentration ∑PFOS (ng/L) and age of refuse
as indicated by year opened for Site D…………………………..
123
Correlation between concentration 6:2 FtS (ng/L) and age of refuse
as indicated by year opened for Site D…………………………...
124
Correlation between concentration 8:2 FtS (ng/L) and age of refuse
as indicated by year opened for Site D…………………………...
125
Correlation between concentrations of PFOA and PFDA (ng/L) for
12 leachate samples………………………………………………
126
Correlation between concentrations of PFOA and PFNA (ng/L) for
12 leachate samples……………………………………………….
127
Correlation between concentrations of PFOA and ∑PFOS (ng/L) for
12 leachate samples………………………………………………
128
Correlation between concentrations of PFDA and PFNA (ng/L) for
12 leachate samples………………………………………………
129
Correlation between concentrations of PFHpA and PFHxA (ng/L) for
12 leachate samples………………………………………………
130
Correlation between concentrations of PFPA and PFBA (ng/L) for 12
leachate samples…………………………………………….…..
131
Correlation between concentrations of PFHxS and PFOS (ng/L) for 12
leachate samples……………………………………………….…
132
LIST OF APPENDIX FIGURES (Continued)
Page
Figure
2.28
Correlation between concentrations of EtFOSAA and MeFOSAA (ng/L)
for 12 leachate samples…………………………………………..
133
2.29
Correlation between concentrations of ∑PFCA and ∑PFS (ng/L) for 12
leachate samples…………………………………………………
134
LIST OF APPENDIX TABLES
Page
Table
1.1
Fluorochemical analyte names, acronyms, multiple reaction
monitoring (MRM) transitions, and instrumental limits of detection
and quantitation…………………………………………………...
98
Analyte concentrations (ng/L ± 95% CI) determined from solvent
based calibration curves and by standard addition for WWTP
influent, WWTP effluent, and Glatt River water……..………….
99
Fluorochemical analytes, acronyms, mass transitions monitored, and
internal and instrumental standards used for quantitation .………
102
2.2
Percent recovery of fluorochemical analytes from Envicarb……
103
2.3
Concentration (ng/L ± 95% CI) of fluorochemical analytes in
leachate as indicated by pairs of standard addition and solvent
curve values from 7 leachate samples and linear regression
from paired values………………………………………….……..
104
1.2
2.1
INTRODUCTION
BACKGROUND
Fluorochemicals are a class of compounds with unique physical-chemical properties
that make them commercially useful and at the same time pervasive in the
environment
and
resistant
to
degradation.
Commercial
applications
for
fluorochemicals include uses in both consumer products such as shampoos, carpet
treatments and in floor cleaners, and industrial applications including silicon chip
etching and polymer manufacturing. The most common fluorochemicals found in the
environment are anionic fluorosurfactants including perfluorocarboxylates (PFCAs,
Table 1.1), perfluoroalkyl sulfonates (PFASs) and fluorotelomer sulfonates (Table
1.2), and fluoroalkyl sulfonamides (Table 1.3). Neutral fluorochemicals, including
fluorotelomer alcohols and fluoroalkyl sulfonamides (Table 1.4) are precursors to
PFCAs and PFASs. The compounds in Tables 1.1, 2, 3, and 4 share some structural
characteristics: a perfluorinated chain consisting of 4-14 carbons and a polar head
group. Perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS), which both
contain eight carbons, were the building blocks for most of the commercial
applications for fluorochemicals.
Fluoroalkyl sulfonamides and fluorotelomer
alcohols (Table 1.4) are degraded through atmospheric reactions and in aqueous
wastewater treatment, whereas their degradation products, the PFASs and PFCAs,
respectively, are resistant to degradation. Under pressure from the US EPA, the major
purveyor of the eight carbon chain chemistry (e.g. PFOS & PFOA), namely 3M,
phased out its production of PFOS and PFOA in 2002.
2
Other fluorochemical
manufacturers, also facing regulatory pressure, have reduced PFOA emissions and
have recently agreed to a total PFOA phase out by 2015.1
SYNTHESIS
There are two main synthetic pathways used to produce fluorochemicals,
electrochemical fluorination (ECF) and telomerization.2 The ECF process, developed
and used for over 50 years by the 3M Company, has been used to produce PFASs and
PFOA.3 In this process, a hydrocarbon feedstock is dissolved in hydrogen fluoride in
an electrochemical cell.2,
3
Passing a direct current through the cell, causes the
hydrogens on the feedstock molecules to be replaced with fluorine and hydrogen to be
generated at the cathode. The reaction is harsh, and while the result is perfluorination
of the feedstock, carbon bonds can also be broken resulting in rearrangements of the
fluorocarbon chain and introduction of many impurities. Rearrangements include the
formation of branched fluorocarbon chains and the formation of both even and odd
numbered perfluorinated chains.
The presence of odd numbered or branched
perfluorinated carbon chains has been used to try to distinguish source (or
manufacturer) of fluorochemicals found in environmental samples.4 While PFASs,
such as PFOS, have direct commercial applications as surfactants in industrial
processes and in fire fighting foams, the bulk of the material produced is derivitized
for production of fluorinated polymers used for surface treatments; in 2000, coatings
for paper and textiles accounted for 79% of the perfluorooctane sulfonate based
5
chemistry produced by3M.
3
The chemistry used to synthesize the fluorinated
monomers used in these coatings is described in Kissa2 and Lehmler3.
The second main method used to produce fluorochemicals relies on a
telomerization process utilizing primarily tetrafluoroethylene.2,
3
Fluorochemicals
produced using this method have perfluorinated carbon chains with even numbers of
carbons, are linear (no branching of the fluorocarbon chain can occur by this synthetic
pathway), and may have a hydrogenated ethane spacer.2 Fluorochemicals synthesized
through telomerization include even numbered PFCAs such as PFOA and
fluorotelomer alcohols and sulfonates, for example, 8:2 fluorotelomer alcohol (8:2
FtOH) and 6:2 fluorotelomer sulfonate (6:2 FtS), respectively (Table 1.4 and Table
1.2).6 The nomenclature denotes the number of perfluorinated carbons (8 and 6) and
the hydrogenated spacer (2) which is characteristic of fluorotelomer chemistry. The
subsequent derivitization of fluorotelomer sulfonates and alcohols for the production
of fluorinated monomers is also described by Kissa2 and Lehmler3 and parallels the
synthesis of fluorinated ECF produced monomers.
APPLICATIONS
The applications of fluorochemicals include both industrial uses and incorporation into
consumer products. The perfluorinated alkyl chain has the unique property of being
both oleophobic and hydrophobic; it can repel both oil and water, respectively. As
surfactants, fluorochemicals are more effective at lowering the surface tension of
water than hydrocarbon surfactants.2 Anionic fluorochemical surfactants are used in
4
fire fighting (aqueous film forming foams, AFFF), in adhesives, as antistatic agents,
in polishes and waxes, in cleaners, as emulsifiers or lubricants in cosmetics, in printing
inks, as wetting agents for the production of semiconductors, in insecticides, and as
emulsifers in fluoropolymer manufacture.2
The primary use for non-ionic
fluorochemicals such as fluorotelomer alcohols and fluoroalkyl sulfonamides is the
formation of monomers for polymeric applications for surface treatments.2,
5
The
resulting polymers are coated onto materials to repel oil in food product applications
including fast food containers, pet food bags, candy wrappers and margarine cartons,
and used in textile products including carpet treatments, leather and clothing to
prevent soiling.2
TOXICOLOGY
The fluorochemicals most commonly studied in toxicological studies are PFOS and
PFOA.7-9 PFOA induces liver tumors in rats and mice, but the relevance of the mode
of action to humans is not fully understood.10
Nevertheless, in 2006, the EPA
indicated that it is considering classifying PFOA as a “probable human carcinogen” in
a draft document currently under review.11 Reproductive and developmental
toxicological effects for PFOS and PFOA, which have been reviewed elsewhere,9, 12
include decreased fetal weight,12 increased mortality, decreased growth rate, and other
dose dependent developmental effects in neonatal mice and rats.13,
14
Several
fluorotelomer alcohols demonstrated estrogenic activity in vitro breast cancer cells,
while PFOS and PFOA were not active.15
5
Precursors to perfluoroalkyl carboxylates and perfluoroalkyl sulfonates,
fluorotelomer alcohols and fluoroalkyl sulfonamides, demonstrate in vitro and in vivo
transformations. Fluoroalkyl sulfonamides, were transformed into PFOS in rat liver
microsomes16 and trout liver microsomes,17 respectively.
8:2 FtOH (Table 1.4)
formed PFOA, PFNA, and various fluorotelomer acid intermediates when dosed in
vivo to rats18, 19 and in vitro to rat liver hepatocytes.19 In a study of pregnant rats, 8:2
FtOH was dosed to dams, and suspected biodegradation products, PFOA and PFNA
were found both in newborn pups and in cross fostered pups, suggesting
biotransformation and subsequent placental and lactational transfer.20,
21
These
findings suggest that exposure to fluorochemical precursor compounds is a source of
PFOS, PFOA and other fluorochemicals in humans and biota.
Perfluoroalkyl carboxylates and perfluoroalkyl sulfonates were found to
bioaccumulate and bioconcentrate in trout, and the degree of accumulation or
concentration increased with increasing chain length.22,
23
Accumulation of
fluorochemicals in tissues is species dependent, but usually follows the trend blood >
kidney> liver; fluorochemicals do not accumulate in lipid tissues like many other
organic pollutants (polychlorinated biphenyls etc).23
Biomagnifications of
fluorochemicals were also found in food webs in the Great Lakes,24 the arctic,25 and in
Lake Ontario.26 An association between higher body burden of fluorochemicals and
dietary consumption of fish has been suggested for fishermen in the Baltic Sea
region.27 Recently, consumption guidelines based on fish tissue concentrations of
PFOS have been issued for fish in Minnesota in both Lake Calhoun (an urban lake in
Minneapolis) and in certain areas of the Mississippi River.28
6
ENVIRONMENTAL FATE AND DISTRIBUTION
Many of the same properties that make fluorochemicals commercially useful
molecules mean imbue them great potential to be environmentally persistent. The
fluorocarbon bond is among the strongest found in nature, and since a bonded fluorine
is similar in size to a bonded hydrogen, the result of perfluorination is a molecule
which is highly resistant to chemical degradation.
Fluorochemicals that are not
perfluorinated are more susceptible to degradation processes. Indirect photolysis of
8:2 FtOH in natural water (Lake Ontario) formed PFOA, fluorotelomer acids, and
PFNA with a half-life of 92 ± 10 h.29 PFCAs were degraded photochemically with the
aid of a tungstic heteropolyacid catalyst30 and the persulfate ion (S2O82-).31
Perfluorinated chemicals are also more resistant to biotransformation than are
partially fluorinated chemicals. 6:2 FtS was partially defluorinated by a defluorinating
Pseudonmonas strain while PFOS was resistant to degradation.32 Fluorochemical
degradation by sewage treatment plant cultures has been observed for FtOHs33-36 and
fluoroalkyl sulfonamides.37
Degradation of FtOHs formed PFCAs, fluorotelomer
acids and other fluorotelomer intermediates,33-36 while fluoroalkyl sulfonamide
degradation yielded other sulfonamides, PFOS and a small amount of PFOA.37
However, neither PFOS nor PFOA were degraded in sewage treatment plant sludge
cultures.38
Formation of PFCAs from the atmospheric oxidation of semi-volatile
fluorotelomer alcohols has been studied through the use of a smog chamber.39 The
7
mechanism of unzipping fluorotelomer alcohols, (hydroxyl radical initiated
oxidation, resulting in PFCAs and other intermediate products) is the proposed source
of global PFCA distribution.40 This so called polyfluorinated alcohol atmospheric
reaction and transport (PAART) hypothesis41 has been invoked to explain arctic
distribution of perfluorinated acids42 as well as the presence of PFASs in remote areas
through the atmospheric transport and reaction of fluoroalkyl sulfonamides. 43, 44
Fluorochemicals are globally distributed in air, water, wildlife, and humans.
Concentrations of fluorochemicals in urban surface waters in the US generally range
from ~5-50 ng/L PFOS.45-47 PFOA concentrations are typically lower, ~1-20 ng/L.45,
47
For comparison to Europe, the average concentrations of PFOS and PFOA in the
Rhine River are lower, at 9 and 2 ng/L, respectively.48 In this same study of the Rhine
River and its tributaries, land application of fluorochemical contaminated waste
resulted in high local river concentrations of fluorochemicals (maximum
concentrations 33,900 ng/L PFOA and 5,900 ng/L PFOS) and even drinking water
contamination (maximum concentrations 519 ng/L PFOA and 22 ng/L PFOS).
Fluorochemical concentrations at contaminated sites in the US ranged from 760 ng/L
PFOS (Superfund site)45 to 2,210,000 ng/L PFOS (AFFF spill)49 and 600 ng/L PFOA
downstream from a fluorochemical manufacturing facility46 up to 11,300 ng/L
following an AFFF spill.49 The concentrations of fluorochemicals in remote locations
and in oceans are, in general, orders of magnitude lower than the levels found in urban
areas or near point sources; however, in the open ocean, PFOA concentrations tend to
be higher than PFOS, 0.01-1 ng/L and <0.001-0.1 ng/L respectively.50
8
PFOS and PFOA are the most commonly studied fluorochemicals; however,
other analytes detected somewhat frequently include PFHpA, PFNA, and PFHxS.45, 47,
50
Fluorotelomer sulfonates are not commonly analyzed but have also been found in
AFFF impacted groundwater at high concentrations; maximum concentration of 6:2
FtS was 14,600,000 ng/L.51
The distribution of fluorochemicals in biota is broad and has been reviewed
recently by Houde et al.52 Most biomonitoring studies have focused on fish53, 54 and
aquatic invertebrates,55 fish eating birds,56,
57
and fish eating mammals.57-59
Fluorochemicals are found in tissues from species in remote locations far from
sources, production or applications of fluorochemicals.60-62
Fluorochemicals are
ubiquitous in human serum with PFOS concentrations generally higher than PFOA,
~30 ng/mL and 5 ng/mL, repectively.63 Occupationally exposed workers did not
follow the same trend and had higher concentrations, 880 ng/mL for PFOS and 7320
ng/mL for PFOA.64 Preliminary evidence exists for a decrease in PFOS and PFOA
concentrations in blood by about one half since the phase out in 2002.65
Semi-volatile fluoroalkyl sulfonamides and fluorotelomer alcohols (Table 1.4)
have been detected in air samples from urban and remote locations in North
America,66-68 in Asian air masses,69 in Europe,70 the Arctic,71 and the Southern
Hemisphere.72
Fluorotelomer alcohol and fluoroalkyl sulfonamide concentrations
were highest near urban centers69,
facilities.73
70, 72
or point sources such as manufacturing
A few studies of indoor air samples have found fluorochemical
concentrations to be higher than outdoor air samples.67,
68
Some anionic
fluorochemical species (e.g. PFOS and PFOA) have been measured in the particulate
phase of air samples.
72, 74
9
The recent detection of fluorochemicals in the arctic
atmosphere71 lends support to the PAART theory, which is also supported by arctic ice
cap measurements.42
SOURCES AND EXPOSURE ROUTES
The direct and indirect sources of PFCAs to the environment are due to the PFCA
manufacture and use, and through reaction impurities or environmental degradation to
form PFCAs, respectively.75 The primary application of PFOS (and other PFASs) has
been for producing polymeric surface treatments, which was 80% of the production in
2000,5 so it is assumed that the primary route of PFOS to the environment is indirect
(through residual reaction impurities or subsequent degradation of final products).
Residual fluorochemicals have been measured on treated consumer products76, 77 or in
surface treatments.78, 79 Foods that had been packaged had higher levels of fluoroalkyl
sulfonamides than other grocery items suggesting transfer from paper or packaging
materials that had been treated with fluorochemicals (which is an approved
application).80
Environmental background levels of fluorochemicals contribute to exposure of
fluorochemicals. Fishermen were found to have higher levels of fluorochemicals in
their blood than others in the same geographic area; their dietary fish consumption is
the suspected cause of the elevated levels.27 Maternal transfer to the developing fetus
or baby has been demonstrated for rats and mice,21 and now in humans through both
fetal cord blood,81 and breast milk82. A recent study of matched human serum and
10
breast milk pairs found significant correlations for levels of PFOA and PFOS in
breast milk and maternal serum.83 House dust and indoor air have been identified as
exposure routes for semivolatile fluorochemicals.68
INTRODUCTION TO CHAPTERS 2 AND 3
Wastewater treatment plays the important role of serving as an interface between
human activity and the environment through the promiscuous medium of water. Not
only does wastewater treatment remove human waste from water before discharge, but
it is also supposed to remove chemicals like anthropogenic compounds and hormones
from the water. These tasks are accomplished through engineered systems applying a
combination of biological, physical and chemical treatment processes. In some cases,
the system is highly effective for its purpose (e.g. reducing biological oxygen
demand), but in other cases, water treatment can cause problems. For example, a class
of commonly used surfactants, alkylphenol ethoxylates, undergo biodegradation
during wastewater treatment and produce alkylphenols that are estrogenic in nature
and are more harmful to aquatic biota than the initial alkylphenol ethoyxlates.84
Wastewater treatment plants have been identified as point sources of
fluorochemicals. Wastewater treatment facilities in Iowa,78 New York State,85 the
Pacific Northwest region,86 and at ten sites across the US87 were ineffective at
removing fluorochemicals from their effluents. While the distribution and behavior of
fluorochemicals at each of the plants varied, likely a result of different inputs, the
concentration of some fluorochemicals was actually increased in effluent relative to
11
influent. Mass flow studies have revealed significant increases in PFOS, PFOA,
PFNA and PFDA at one wastewater treatment plant,85 and significant increases due to
biological treatment for PFOS and PFDS.86
Significant decreases in some
fluorochemical species were observed after the trickling filtration, activated sludge
treatment and primary clarification steps, but the concentrations of 6:2 FtS and PFOA
were not significantly affected during wastewater treatment.86
Fluoroalkyl
sulfonamides, which demonstrated high affinity for sludge, had increased mass flows
during treatment.86
Fluorochemicals are discharged in wastewater; however, the
degree to which a wastewater treatment plant contributes to the fluorochemical
pollutant load of its receiving waters has not been studied.
In the Chapter 2, the role of the wastewater treatment plant as a point source is
investigated directly. Daily composite samples were collected for seven wastewater
treatment plants and river sampling stations over the course of one week in the Glatt
River Valley in Switzerland. We measured fluorochemical concentrations (C6-C10
PFCAs; C4, C6, C8 and C10 PFASs; a fluoroalkyl sulfonamide, FOSA, and 6:2 FtS) in
the influents, effluents, and receiving waters and determined the mass loading of
fluorochemicals to the river system. The wastewater treatment plants (n = 7) in this
study were also ineffective at removing fluorochemicals from effluent.
Higher
concentrations of PFOS at one treatment plant are suspected to be the result of local
furniture manufacturing centers and a flavor and fragrance manufacturer. Per capita
discharges of fluorochemicals were calculated based on the population served by each
treatment plant, and these per capita estimates were used to account for upstream
wastewater contributions to the fluorochemical load in the river. The mass loading of
12
fluorochemicals into the river measured directly by the wastewater treatment plant
effluents and calculated indirectly through per capita discharge estimates were found
to be equivalent to the actual fluorochemical mass load in the river and no major
removal mechanisms (sedimentation, or degradation) were observed (indirectly).
In Chapter 3, a method that was developed to quantitatively measure the levels
of fluorochemicals in landfill leachate is described. Landfills represent a somewhat
unknown repository for fluorochemicals. Since many applications of fluorochemicals
are to solids, it is likely that landfills may be a significant source of fluorochemicals,
either through leaching of groundwater, or the treatment of leachate (at wastewater
treatment plants). However, the amount of fluorochemicals present in landfills has yet
to be assessed. Some communities in Minnesota have found their groundwater (and
drinking water) to be contaminated from landfills in the vicinity that had previously
received waste from 3M’s fluorochemical manufacturing facilities.88 Fluorochemicals
were also recently measured in composted waste solids in Switzerland.89
Our method for quantification of fluorochemicals in landfill leachates
employed solid phase extraction and Envicarb sample clean up steps prior to high
performance liquid chromatographic separation and negative ion electrospray
ionization tandem mass spectrometric detection. Due to the presence of matrix effects
during analysis, standard addition experiments were used to ensure the accuracy of the
analysis. The developed method was applied to 12 leachate samples representing
seven distinct sites and concentrations of 24 fluorochemical analytes were determined
(Table 1.1, 1.2 and 1.3). PFCAs, PFASs, fluorotelomer sulfonates and fluoroalkyl
sulfonamides were all detected in leachate samples. PFCAs were the most abundant
13
analytes detected in landfill leachates, with concentrations of many species greater
than 1000 ng/L.
Other notable findings include the detection of C4 analytes
(perfluorobutane sulfonate, methyl perfluorobutane sulfonamidoacetic acid and
perfluorobutanoate) in both recently opened landfills, and landfills that stopped
receiving wastes before 2002.
PFOS and sulfonamide precursors (ethyl
perfluorooctane sulfonamidoacetic acid and methyl perfluorooctane sulfonamidoacetic
acid) were also detected in samples of all ages, indicating release of PFOS and related
compounds post phase out of PFOS production by 3M, which is consistent with
measurements in wastewater.85, 87, 90
Due to their usage patterns and disposal mechanisms, fluorochemicals are
present in both solid and liquid waste streams.
It is important to the overall
understanding of the fate and transport of fluorochemicals that the sources from waste
treatment are characterized. Although indirect release of PFOA was calculated to be
insignificant relative to the direct releases observed during fluoropolymer
manufacturing,75 the presence of fluorochemicals in waste streams, even after
production has been phased out (as in the case of PFOS) suggests that the indirect
sources (release from treated products or degradation) of fluorochemicals will persist
after the direct sources have been eliminated.
14
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21
Table 1.1: Fluoroalkyl carboxylates
Analyte
PFBA
PFPA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
PFDoDA
PFTrDA
PFTDA
FOUEA
Structure
22
Table 1.2: Fluoroalkyl sulfonates
Analyte
PFBS
PFHxS
PFOS
PFDS
6:2 FtS
8:2 FtS
Structure
23
Table 1.3: Fluoroalkyl sulfonamides
Analyte
MeFBSA
MeFBSAA
FOSA
FOSAA
MeFOSAA
EtFOSAA
Structure
24
Table 1.4: Semi-volatile precursors: fluorotelomer alcohols & fluoroalkyl
sulfonamides
Analyte
6:2 FtOH
8:2 FtOH
MeFOSE
EtFOSE
Structure
25
MASS FLOW OF FLUOROCHEMICALS IN A SWISS RIVER VALLEY
Carin A Huset1, Aurea C Chiaia1, Douglas F Barofsky1, Niels Jonkers2, Hans-Peter
Kohler2, Walter Giger2, Jennifer A Field3
1
Department of Chemistry, Oregon State University, Corvallis, OR
2
EAWAG, Duebendorf, Switzerland
3
Department of Environmental and Molecular Toxicology, Oregon State University,
Corvallis, OR
In preparation for submission to Environmental Science and Technology
26
ABSTRACT
Fluorochemicals are persistent contaminants that are globally distributed in air, water,
sediments, and biota. Wastewater treatment plants (WWTP) play an important role in
the mitigation of pollutant releases from municipalities to aquatic and terrestrial
environments. However, because WWTPs are point sources of fluorochemicals, it is
important to understand their contribution to fluorochemicals burdens in the greater
context of watersheds. To this end, over a one week period, the mass flows of 11
fluorochemicals from seven WWTPs that discharge effluent to the Glatt River in
Switzerland were measured and compared to the measured mass flows within the Glatt
River. Overall, the WWTPs did not affect the removal of fluorochemicals except for
perfluorodecane sulfonate (PFDS). Effluents from WWTPs and Glatt River water
were dominated by perfluorooctane sulfonate (PFOS), which was detected in all
samples, followed by perfluorohexane sulfonate (PFHxS) and perfluorooctanoate
(PFOA). The mass flows emanating from WWTPs were found to be conserved within
the Glatt river, which indicates the input from the WWTPs is additive and removal
mechanisms within the Glatt river are not significant.
Per capita discharges of
fluorochemicals were calculated from the populations served by the WWTPs studied
and the values determined also account for the fluorochemicals content of the
headwaters of the Glatt River, which is Greifensee, a lake that also receives
wastewater.
27
INTRODUCTION
Measurements of direct inputs of fluorochemicals to the environment via the discharge
of municipal WWTP effluents indicate that WWTPs are point sources of
fluorochemicals. Municipal wastewaters contain fluorochemicals due to the use of
fluorochemicals in household cleaners1 and products applied to improve stain
resistance2,
highly
3
and, in some cases, municipalities treat landfill leachates which are
contaminated
with
fluorochemicals4.
Unfortunately,
conventional
biological/mechanical wastewater treatment has limited effectiveness in removing
fluorochemicals from aqueous wastestreams, and therefore WWTPS are point sources
for fluorochemicals that enter the environment3, 5, 6. Sinclair and Kannan attributed
increases in perfluorocarboxylates in effluent to degradation of precursor compounds
during secondary treatment, with no significant removals observed6. A study of 10
wastewater treatment plants across the US showed inconsistent removal of
fluorochemicals; even among plants with the same types of treatment processes and in
some cases, wastewater treatment resulted in production of fluorochemicals5.
Relatively few studies have placed the discharge of WWTPs into a broader
context.
Boulanger et al.7 conducted a mass budget of perfluorooctane sulfonyl
fluoride (POSF) based fluorochemicals in Lake Ontario and estimated that the most
significant inputs were inflows to the system from Lake Erie and WWTP effluents,
while removal through sorption, volatilization or degradation were determined not to
be significant.
28
The objective of the present study was to quantify fluorochemicals in the
Glatt River of Switzerland and the contribution of WWTPs to the river’s observed
mass flow.
In addition, the relative efficiency of seven WWTP’s removal of
fluorochemicals also was evaluated. The concentrations of four perfluoroalkyl
sulfonates (C4-C8), five perfluoroalkyl carboxylates (C6-C10) one fluorotelomer
sulfonate (6:2 FtS), and one perfluoroalkyl sulfonamide (FOSA) were measured in 24
hr composite samples over a period of one week in both WWTP and in Glatt River
water.
From WWTP effluent concentrations and WWTP flow data, WWTP
contributions to the Glatt River mass flows were computed and compared to the actual
measured mass flows.
EXPERIMENTAL
Standards and Reagents. Standards of potassium perfluorobutane sulfonate (PFBS),
potassium perfluorohexane sulfonate (PFHxS), potassium perfluorooctane sulfonate
(PFOS), perfluorooctane sulfonamide (FOSA), and dual labeled
18
O-perfluorooctane
sulfonate (18OPFOS) were donated by the 3M Company (St. Paul, MN). Standards of
perfluorodecane sulfonate (PFDS), perfluorodecanoic acid (PFDA), perfluorononanoic
acid (PFNA), perfluorooctanoic acid (PFOA) and perfluoroheptanoic acid (PFHpA)
were purchased from Aldrich Chemical (Milwaukee, WI). Perfluorohexanoic acid
(PFHxA) was purchased from Fluka (Buchs, Switzerland).
1H,1H,2H,2H-
tridecafluorooctane sulfonate (6:2 FtS) was purchased from Apollo Scientific Limited
(Derbyshire, U.K.). Dual labeled [1,2-13C2]-perfluorooctanoic acid (13CPFOA) was
29
purchased from Perkin-Elmer (Wellesley, MA). Optima grade methanol (MeOH)
was purchased from Fischer for use as an HPLC solvent.
Ammonium acetate
(NH4OAC) was purchased from Mallinckrodt (Phillipsburg, NJ).
River and WWTP Sampling. The Glatt River (Figure 2.1) is located in
northern Switzerland, east of Zurich, and in a watershed inhabited by 175,000
residents. The Glatt River flows 35 km from its origin at Greifensee to the Rhine
River and receives effluent from eight WWTPs (Table 2.1).8
9
Flow-proportional, 24
hr composite samples of WWTP influent and effluent were collected daily for seven
consecutive days from seven out of the eight municipal WWTPs that discharge into
the Glatt River (Table 2.1, Figure 2.1); the eighth WWTP is small and was not
included in this study. Flow proportional, 24 hr composite samples of Glatt River
water were collected at three sampling sites including 1) the point at which the Glatt
River flows out of Greifensee, 2) 15 km downriver, and 3) and at a point just before
the Glatt River joins the Rhine River (Figure 2.1).
WWTP and river samples were collected initially in glass bottles at the
sampling stations but were subsequently transferred to high density polyethylene
bottles.
All samples were filtered through Whatman GF/D filters (Whatman,
Maidstone, England), frozen, and shipped to Oregon State University where they
remained frozen until analysis.
Liquid Chromatograph/Tandem Mass Spectrometry. Frozen samples were
thawed to room temperature, shaken, and 2 mL was aliquoted into microcentrifuge
tubes and centrifuged at 10000 rpm for 15 min.
Supernatant was removed and
30
transferred to a 2 mL glass autosampler vial that was then spiked with 30 pg each of
the 18OPFOS and 13CPFOA internal standards and analyzed.
Separations were performed on an Agilent 1100 HPLC system (Agilent, Palo
Alto, CA). A 900 µL volume of sample was injected directly onto a 2.0 mm x 4.0 mm
C18 Security Guard cartridge (Phenomenex, Torrence, CA) followed by a 150 x 2.1
mm Targa C18 column (Higgins Analytical, Mountain View, CA). The mobile phase
system consisted of 2 mM ammonium acetate with 5% methanol (A) and methanol (B)
at a temperature of 25 oC and a flow rate of 200 µL/min. The initial mobile phase
(10% A, 90% B) was held for 4 min and then ramped to 45% B over 6.5 min and held
for two min. The mobile phase was then ramped to 90% B over one min and held
until 18 min.
The HLPC was interfaced to a Quattro Micro tandem mass spectrometer
(Waters, Milford, MA) through an electrospray ionization source operated in negative
mode. Quantification of analytes was performed through multiple reaction monitoring
with one transition monitored for each analyte. Details of the mass spectrometry
conditions and transitions monitored are provided in Table 1.1 under Supporting
Information (SI).
Calibration curves were prepared daily and run before and after each batch
(~20 samples) of samples.
Linear regressions were based on internal standard
calibration, not forced through the origin, were fit to 1/X, with typical r2 values of 0.97
or greater. The internal standard
18
OPFOS was used for quantification of PFBS,
PFHxS, PFOS, PFDS, 6:2 FtS, and FOSA while 13CPFOA was used for quantification
of PFHxA, PFHpA, PFOA, PFNA, and PFDA. Calibration curves were comprised of
31
standards ranging from 1 ng/L to 300 ng/L (or higher as necessary) with internal
standard concentrations of 25 ng/L. Quality control standards at 30 or 75 ng/L were
analyzed within each batch of samples. A deviation of greater than 20% from the
theoretical value required that samples preceding the faulty standard be reanalyzed.
Replicate measurements were performed on 20% of randomly selected samples and
the results were averaged.
Quality Control. To assess the effect of filtering the river water, two samples
of nanopure water were filtered with the same GF/D filters used to filter river water
samples into HDPE bottles and shipped with the rest of the samples. Two samples of
unfiltered nanopure water in HDPE bottles were sent along with the treatment plant
and river water samples to serve as travel blanks.
Method blanks, which were used to ensure clean sample preparation, consisted
of RO/DI water prepared in the same manner as samples (including internal standard
spikes) and analyzed with every batch of samples. Instrumental blanks were used to
monitor for any instrumental background and carryover from samples and standards.
Instrumental blanks consisted of DI water spiked with both internal standards and
were run after every 2-3 samples with at least 3-4 blanks run per every 10 samples.
Standard-addition experiments were performed since peak areas for the
internal standards were ~50% less for wastewater and river water samples relative to
that of standards and method blanks. Standard-addition experiment samples were
prepared using a total of eight aliquots for each of the three study matrices: WWTP
influent, WWTP effluent, and river water. For each type of sample matrix, four
aliquots were spiked at four different analyte levels to increase the analyte’s response
10
32
1.5 to 3 times that of the background signal and additionally spiked with internal
standards (30 pg 18OPFOS and 13CPFOA). The remaining four aliquots received only
internal standard spikes (30 pg 18OPFOS and 13CPFOA). .All eight samples for each
matrix were analyzed and data analysis included assessment of the measured
concentrations and their attendant error from solvent-based calibration curves and
from regression of the standard-addition data. In addition, for WWTP influents,
single-point spike-addition experiments were performed to aid in correctly assigning
peak identity, which was necessary for PFBS, PFHxS, and PFDS.
Instrumental Detection and Quantification Limits The instrumental limits
of detection and quantitation (LOD and LOQ) were determined using a NIOSH
method11. In short, an estimation of the detection limit is made based on a signal to
noise ratio of 3:1, then 12 standard solutions are prepared spanning the range from ten
times less to ten times more than the estimated detection limit. These 12 standards are
analyzed and the responses used to generate a linear regression. The LOD and LOQ
are calculated using both the standard error of the regression and the slope of the
regression. In cases where replicate samples gave analyte concentrations above LOQ
on one replicate and below the LOQ on the other replicate, these samples were
assigned a concentration equal to the LOQ.
RESULTS AND DISCUSSION
Chromatography and Quality Control.
The solvent gradient employed was a
modification of that described by Schultz et al.5 It allowed for more rapid elution of
analytes.
33
By maintaining the column at a 90% MeOH during injections and
between samples, the approach provides the added benefit of reducing any
‘background’ in fluorochemicals leaching from instrument components.
Large
volume injections (900µL) were used to increase sensitivity without additional sample
preparation (eg. solid phase extraction)5.
The filtered and unfiltered nanopure (blank) samples prepared at the same time
as the river water samples contained no fluorochemicals above detection limit. .
Filtration of a composite river water sample containing PFOA, PFOS and PFHxS did
not affect concentrations, which indicates neither positive nor negative artifacts due to
filtration. However, plastic filter holders, which contained PTFE components, were
avoided as we discovered they contained PFOA; therefore, glass filter holders were
used instead. Method blanks prepared with each batch of samples did not contain any
measurable level fluorochemicals. Instrumental blanks were monitored and when
responses were detected in blanks after wastewater or river water samples, they were
flagged and reanalyzed.
Matrix effects did not affect analyte quantification from solvent-based
calibration curves as indicated by a series of standard-addition experiments.
Concentrations determined from solvent-based calibration curves and by standard
addition gave statistically equivalent values at the 95% CI (Appendix 1Table 2). For
WWTP influents, at times it was difficult to make peak assignments so single-point,
spike additions were employed for qualitative identification of PFBS, PFHxS and
PFDS which allowed for more accurate peak identifications. Instrumental LOD and
34
LOQ were determined to be between 1.2 and 9.4 ng/L and 4.1 and 31 ng/L,
respectively (Appendix 1 Table 1).
WWTP Removal Efficiency. Daily concentration profiles for each analyte
indicated variability in influent and effluent concentrations with no consistent trend in
either over the one week sampling period (Table 2.2). To assess the removal of
fluorochemicals
during
wastewater
treatment,
daily
influent
and
effluent
concentrations were compared for each WWTP for each of the seven days of
sampling. PFDS was only observed in influent a few days at five of the plants but in
each of these cases there was nearly 100% removal from the aqueous phase. PFDS
removal is likely the result of sorption to biosolids during treatment, which was
observed by Schultz et al12 and also supported measurements on WWTP sludges by
Higgins et al
13
. PFDA and PFNA were also removed during treatment for 2 and 5
days, respectively, at two separate plants, which may also be the result of sorption to
biosolids13. For the remainder of the fluorochemical analytes, no clear trends were
observed when comparing influent and effluent concentrations. For example, PFOS
was removed at Dubendorf on four days, produced on one day and no significant
change was observed on two days (data not shown). Weekly average influent and
effluent concentrations in Table 2.2 indicate few statistically-significant differences
between effluent and influent concentrations, demonstrating the poor removal
efficiency of fluorochemicals during wastewater treatment.
WWTP Inputs to the Glatt River. The concentration of fluorochemicals in
the effluents of seven WWTPs that discharge to the Glatt River followed a general
trend of PFOS>PFHxS>PFOA>PFBS>6:2 FtS (Table 2.2). PFBS was detected 40%
35
of effluents at an average concentration of 3.5 ng/L which is similar to PFBS
concentrations in US effluents as reported by Schultz et al5 and in Scandinavia14.
PFHxS was detected in 90% of the effluents in this study with an average
concentration of 26 ng/L (Table 2.2), which is five to ten times higher than what has
been reported5614. PFOS was detected in every wastewater effluent (and influent)
collected in this study and was present in the highest concentrations (Table 2.2).
Concentrations of PFOS at Dubendorf are the highest reported in wastewater influent
(maximum concentration 790 ng/L) since the phaseout of POSF chemistry; higher
effluent concentrations were reported prior to 2002 (5000 ng/L)15.
The high
concentrations of PFOS at Dubendorf were not correlated with significantly higher
levels of other fluorochemicals which suggests a different source for the PFOS load to
this WWTP. The Dubendorf area contains furniture manufacturing sites and a flavor
and fragrance company which could potentially be additional sources for PFOS to the
WWTP influent.
POSF compounds have been historically used in coatings
applications which include wood treatments. PFDS was only observed in 6% of
effluent samples as it was removed during treatment, the only analyte consistently
removed in a survey of 10 WWTPs5. 6:2 FtS concentrations in Swiss effluents
(average 2.2 ng/L) were lower than the concentrations observed by Schultz et al, the
only other measurements of fluorotelomer sulfonates in wastewater5. The average
FOSA concentrations in effluent, 2.4 ng/L, were lower than US effluent
concentrations5.
Concentrations of PFHxA and PFHpA, which were detected in 36% and 64%
of effluents respectively, were similar to US WWTPs.5 PFOA, which was detected in
14
36
98% of effluents tested, ranged from 13 to 35 ng/L and are similar to Scandinvian
and US5 effluents from 2004, but are lower than the values reported by Sinclair and
Kannan in a study of NY state WWTPs in 2006, even those plants without an
industrial component to their wastewater.6
Concentrations of Fluorochemicals in Glatt River.
PFOS, PFHxS and
PFOA were each detected in 100% of the Glatt River samples at average
concentrations of 49, 12, and 8 ng/L respectively (Table 2.2). PFBS and PFHpA were
also detected in the Glatt River but at lower frequency (68% and 32 %, respectively)
and at lower average concentrations (4 and 1 ng/L, respectively) (Table 2.2). The
average concentrations of fluorochemicals in the Glatt River are higher than those
reported in surface waters in Scandinavia;14 the sum of seven fluorochemicals in
Norwegian surface water was 10 ng/L while the concentrations for PFOS alone in the
Glatt River ranged from 27 - 93 ng/L (Table 2.2). The most abundant analyte detected
in lake water samples from Scandinavia was PFOA, while in the Glatt, PFOS had the
highest concentrations, which suggests different usage in fluorochemical containing
products between the two regions. Skutlarek et al found Rhine River concentrations
of PFOA and PFOS that were similar to Glatt River concentrations, but PFBS was the
most abundant fluorochemical observed and at higher levels than observed in the Glatt
River.16 The concentrations of PFOS and PFOA in the Glatt River are in the same
range as in other studies without industrial sources (eg AFFF, fluorochemical
manufacture).1718
Mass Flow of Fluorochemicals. To determine the contribution of the WWTP
effluents to the mass flow of the Glatt river, the mass flow at each river sampling point
37
was calculated for PFBS, PFHxS, PFOS, PFHpA, and PFOA based on the average
flow of each WWTP and the average measured fluorochemical concentrations in each
WWTP. Dubendorf concentrations were excluded from these calculations due to the
suspected industrial input. These calculated values individual WWTP mass flows
were compared to the mass flows at each river sampling station computed from the
measured total flow and fluorochemicals concentrations. This calculation was done
for PFBS, PFHxS, PFOS, PFHpA, and PFOA since they were the most frequently
detected in WWTP effluents and also in Glatt river water. The initial mass flow
(Table 2.3) at the headwaters of the Glatt River (Greifensee) was the mass flow at the
first Glatt River sampling station (R1; Figure 2.1). For the mass flow at the second
Glatt river sampling station (R2; Figure 2.1), the mass flows associated with the
WWTPs at Falladen (Fa), Bassersdorf (Ba), and Kloten (Kl) were added to that of R1
(Table 2.3). To calculate the mass flow of fluorochemicals in the Glatt at the third
Glatt River sampling station (R3) where the Glatt River joins the Rhine, the mass
flows associated with the WWTPs of Niederglatt (Ni), Bulach (Bu) and Glattfelden
(Gl) (Figure 2.1) were added to that of R2. These ‘calculated’ mass flows based on
measured flows and fluorochemicals concentrations were compared to the actual
measured mass flow based on samples of river water obtained at R1, R2, and R3
(Figure 2.3). To determine if significant differences at the 95% CI existed between
the calculated and measured mass flows, uncertainly due to variations in measured
concentrations and in flows were computed.
No statistically significant difference was observed between the mass flow
measured and the mass flow calculated for any of the fluorochemicals (Figure 2.3);
38
this implies that the mass flow of fluorochemicals in the river is conserved and that
no unaccounted for sources of fluorochemicals exist along the river.
The
perfluoroalkyl carboxylates and perfluoroalkyl sulfonates are known to be resistant to
biotransformation19,
20
and photodegradation.
Due to the low volatility of these
fluorochemicals21, losses to the atmosphere are predicted to be low. Sorption to
suspended solids or sediments in the river could also be a loss mechanism,22 but the
agreement between measured and calculated loads suggests that if sorption occurs, it is
not an important loss mechanism in this system. Other fluorochemical inputs to the
system could include degradation of precursor compounds potentially present in
effluent or from other sources such as precipitation23, 24 and run-off from contaminated
sites.16 In comparison, fluoroquinolones showed a net removal along the stretch of the
river due to sorption9 while clarithromycin was not removed significantly.25 Mass
flows of phenolic endocrine disruptors measured from the same samples as this study
found removal along the course of the river for bisphenol A, phenylphenol and
parabens (methyl, ethyl, propyl, butyl and benzyl) but conservation of mass flow for
nonylphenol, nonylphenol ethoyxlates (1-10 ethoxymers) or nonylphenol ethoxy
acetic acids (ethoxymers 1-4).26 The mass flow of fluorochemicals associated with
Greifensee, the headwaters of the Glatt River (R1, Figure 2.1), is greater than the sum
of the total contributions of the seven WWTPs that discharge to the Glatt River (Table
2.3). This is likely due to the upstream presence of nine WWTPs that discharge to
Greifensee.27
Per Capita Discharge of Fluorochemicals in the Glatt Valley. To determine
upstream WWTP contributions to the Glatt, per capita discharges of fluorochemicals
39
were computed. Assuming that the fluorochemicals were principally originating
from the population as opposed to specific point sources, the known population of
each of the communities served by each of the WWTPs (Table 2.1) and the measured
mass flows of fluorochemicals at each WWTP (Table 2.3) were used to calculate per
capita discharges (Table 2.4) for PFBS, PFHxS, PFOS, PFHpA and PFOA and ranged
from 2 to 47 µg/day/person. Assuming the average per capita discharge for the
WWTPs along the Glatt River is representative of the usage/discharge of other
communities in Switzerland, the mass flows of fluorochemicals measured in
Greifensee outflow at R1 was compared to that calculated using the population of the
Greifensee catchment (107,000 people)27 and the hydraulic flow measured at R1
(Table 2.4). The estimated mass flows for PFBS, PFHxS, PFHpA, and PFOA were not
significantly different from the measured mass flows for these analytes while the mass
flows measured for PFOS were 3 times higher than the estimate (Table 2.4). This
latter anomaly is not resolved by incorporating the mass flow associated with the
Dubendorf WWTP (not initially included due to suspected industrial input) into the
calculations . It could be due to different treatment efficiencies of upstream WWTPs,
or industrial inputs, or contaminated sites as was recently discovered in a German
river water study.16 Given, however, the high variability observed for effluent PFOS
concentrations along the Glatt River, it is not possible to know whether
underestimation of the upstream WWTP contribution is due to effluent variability
without actually measuring upstream WWTP effluents.
Swiss per capita discharges for fluorochemicals were compared to US values.
The per capita discharge for the plants reported in Schultz et al. and Sinclair et al.
40
could be calculated since both the flow of the treatment plants and population
served were reported.5, 6 Sinclair et al. reported average mass flows for 2 plants in
New York State using average concentrations for 5 days6 and Schultz et al. reported
24 hour composite concentrations, flow for each plant sampled (10), and population
served; hence we calculated daily, per capita mass flows for the 10 US plants and an
average per-capita discharge5. The 10-day mass flows from Schultz et al12 were
combined with population to calculate an additional per capita mass flow (Figure 2.4).
The average per capita mass flows in the Glatt Valley for PFOS and PFHxS are higher
than any of the per capita mass flows for these compounds in the US (Figure 2.4).
Another difference between the four per capita estimates is the high per capita mass
flow of PFOA, PFNA and PFDA in New York State relative to the per capita mass
flows of these compounds in the other studies; these high values reflect industrial
sources and may not reflect a ‘true’ per capita.
This study reports the first measurements of fluorochemicals in Swiss WWTPs
and waterways. Fluorochemicals were detected in all samples through direct injection
LC/MS/MS and were not subject to matrix effects (ion suppression or enhancement)
during analysis.
The distribution of fluorochemicals in Swiss effluents suggests
different fluorochemical use patterns when compared to US effluents. Swiss WWTPs,
which were dominated by PFOS, followed by PFHxS>PFOA>PFBS>6:2 FtS, did not
effectively remove fluorochemicals from wastewater, and directly contributed to the
mass loading of fluorochemicals in the Glatt River. Industrial inputs are suspected to
contribute to high fluorochemical concentrations at one WWTP. PFOS, PFHxS and
PFOA were measured in all river water samples at average concentrations of 49, 12
41
and 8 ng/L, respectively. The per capita discharge of fluorochemicals accounted for
most of the upstream mass loading to the Glatt River from Greifensee.
ACKNOWLEDGEMENTS
The authors would like to thank Swiss Water Authority operators for sample
collection, Jeff Morré for mass spectrometric assistance, Carl Isaacson for insight in
the completion of this manuscript, and 3M for the donation of authentic standards.
We are grateful for financial support from from DuPont (unrestricted gift) and the
Mass Spectrometry Facilities and Services Core of the Environmental Health Sciences
Center, Oregon State University, grant number P30 ES00210, National Institute of
Environmental Health Sciences, National Institutes of Health.
42
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44
Table 2.1: Sampling locations, average, minimum, and maximum flow for each station and population served by each
treatment plant.
Minimum flow
Maximum Flow
Average flow
Sampling station
Population served
(L/day)
(L/day)
(L/day)
Greifensee (R1)
359424000
321408000
427680000
NA
Falladen (Fa)
12151714
9472000
17391000
27800
Dubendorf (Du)
17560286
14982000
25505000
35000
Bassersdorf (Ba)
8929286
6325000
16413000
13000
Kloten-Opfikon (Kl)
20837143
17070000
31850000
25900
Oberglatt (R2)
457302857
381888000
641088000
NA
Niederglatt (Ni)
21926000
13751000
39433000
30000
Bulach (Bu)
12364286
8470000
24180000
23200
Glattfelden (Gl)
1076286
613000
2404000
3100
Rhine (R3)
658800000
520128000
1097280000
NA
NA = does not apply since this is a river sampling station
See Figure 2.1 for sampling station locations
45
Table 2.2: Average weekly (n=7) concentration (ng/L) ±95% CI of analytes at each WWTP and river station
Station
Fa
Ba
Type
Influent
Effluent
Influent
Effluent
PFBS
3.8 ± 3.6
3.9 ± 6.8
0.6 ± 1.3
1.8 ± 4.5
PFHxS
0.5 ± 1.2
3 ± 3.2
12 ± 4.7
2.8 ± 2.8
Influent
5.8 ± 5.5
47 ± 31
Effluent
7.2 ± 9.3
53 ± 30
Influent
Effluent
Influent
Effluent
7.3 ± 5.7
8.4 ± 4.5
1.1 ± 1.3
1.1 ± 1.7
54 ± 34
93 ± 95
10 ± 3.3
11 ± 5.8
PFOS
71 ± 36
103 ± 32
19 ± 10
16 ± 3
449
±
200
303
±
120
134 ± 50
119 ± 37
76 ± 30
92 ± 30
Influent
0.6 ± 1.3
5.0 ± 4.6
33 ± 23
Effluent
2.2 ± 1.9
10 ± 3.2
23 ± 6
Influentb
1.5 ± 2.6
16 ± 16
117 ± 38
Effluent
Riverc
Riverc
River
ND
7.8 ± 12
2.8 ± 1.7
1.9 ± 2.2
19 ± 11
9.4 ± 3.6
14 ± 5.6
14 ± 5.6
144 ± 46
44 ± 7.3
60 ± 22
43 ± 16
Du
Kl
Ni
Bu
Gl
R1
R2
R3
a
PFDS
26 ± 46
<LOQ
ND
ND
6:2 FtS
5.6 ± 14
3.8 ± 3.3
6.5 ± 9.1
1.9 ± 3.0
FOSA
ND
3.4 ± 5.3
<LOQ
<LOQ
PFHxA
ND
0.7 ± 1.7
ND
5.5 ± 8.9
PFHpA
16 ± 36
0.6 ± 1.0
6.7 ± 5.0
6.3 ± 3.8
PFOA
6.3 ± 11
28 ± 12
5.1 ± 3.4
17 ± 6.6
PFNA
ND
ND
ND
ND
PFDA
ND
<LOQ
1.9 ± 3.0
2.8 ± 3.3
ND
8.3 ± 4.2
3.4 ± 5.3
1.4 ± 2.2
1.1 ± 1.0
35 ± 11
5.1 ± 8.4
ND
ND
1.9 ± 3.0
1.7 ± 4.1
14 ± 20
4.1 ± 5.9
35 ± 8.8
0.4 ± 0.9
ND
36 ± 41
4.5 ± 7
18 ± 33
ND
130
±
150
ND
160
±
120
2.2 ± 5
ND
ND
ND
3.8 ± 3.3
1.9 ± 3.0
2.8 ± 3.3
1.9 ± 3.0
5.1 ± 5.8
8.4 ± 5.3
<LOQ
3.4 ± 5.3
ND
2.1 ± 3.6
0.7 ± 1.7
0.7 ± 1.7
4.2 ± 6.2
5.1 ± 5.0
2.2 ± 3.0
3.4 ± 4.2
28 ± 20
30 ± 13
8.9 ± 8.3
12 ± 9.7
ND
0.8 ± 2.0
ND
<LOQ
ND
2.4 ± 5.9
1.9 ± 3.0
1.9 ± 3.0
7.3 ± 4.9
3.4 ± 5.3
1.4 ± 3.4
9.9 ± 20
9.0 ± 11
ND
1.9 ± 3.0
0.9 ± 2.3
<LOQ
ND
0.8 ± 1.9
27 ± 16
ND
ND
6.6 ± 0
ND
ND
1.2 ± 1.4
9.0 ± 8.0
ND
ND
2.8 ± 3.3
ND
ND
ND
<LOQ
<LOQ
ND
<LOQ
36 ± 16
ND
ND
ND
0.3 ± 0.7
0.7 ± 1.1
0.9 ± 1.0
2.7 ± 7.0
13 ± 9.4
7.0 ± 3.4
8.0 ± 3.3
7.5 ± 3.7
ND
ND
ND
ND
<LOQ
ND
ND
ND
Some reported values <LOD due to averaging
Glattfelden influent n = 5 (two bottles out of seven broke during sample collection)
c
Greifensee and Rhine n=6
Bold values indicate significant difference between influent and effluent concentrations.
ND = not detected
< LOQ = below the limit of detection
b
46
Table 2.3: Average weekly mass flowsa (g/day ± 95% CIb) of fluorochemicals in WWTP effluent and at Glatt river stations.
R1
Fa
Ba
Du
K1
R2
Ni
Bu
G1
R3
a
PFBS
2.8±4.3
0.05±0.08
0.03±0.08
0.06±0.09
0.18±0.10
1.3±0.82
0.02±0.04
0.03±0.03
NA
1.3±1.5
PFHxS
3.4±1.3
0.04±0.04
0.05±0.05
0.47±0.33
1.9±2.0
6.4±2.8
0.25±0.18
0.12±0.07
0.02±0.02
9.4±4.8
PFOS
PFDS
15.7±3.1
NA
1.3±0.5
NA
0.28±0.08
NA
2.7±1.5
NA
2.5±1.0 0.09±0.15
27.6±11.2
NA
2.0±1.2
NA
0.28±0.15
NA
0.16±0.10
NA
28.6±14.2
NA
6:2 FtS
NA
0.05±0.04
0.03±0.05
0.02±0.03
0.04±0.06
NA
0.04±0.07
0.01±0.03
NA
NA
FOSA
NA
0.04±0.07
NA
0.02±0.03
0.18±0.12
NA
0.07±0.12
NA
NA
NA
PFHxA
NA
0.01±0.02
0.10±0.16
0.12±0.19
0.04±0.08
NA
0.02±0.04
NA
0.04±0.03
NA
PFHpA
0.25±0.4
0.01±0.01
0.11±0.07
0.04±0.05
0.11±0.11
0.40±0.47
0.08±0.10
0.01±0.02
NA
1.8 ± 4.6
PFOA
PFNA
2.5±1.3
NA
0.33±0.17
NA
0.3±0.13
NA
0.31±0.15
NA
0.63±0.32 0.02±0.04
3.7±1.6
NA
0.26±0.25
NA
0.33±0.24
NA
0.01±0.01
NA
5.0±2.9
NA
PFDA
NA
NA
0.05±0.06
NA
0.05±0.12
NA
0.04±0.07
NA
NA
NA
Mass flow values (g/day) calculated using average flows (Table 2.1) and average concentrations (Table 2.2) at each station.
95%CI calculated using pooled standard deviations from average flow and average concentrations.
NA = Not applicable since analyte not detected; therefore, no mass flow computed.
b
47
Table 2.4: Estimation of WWTP contribution to mass flow (± 95% CI?) of
fluorochemicals originating from Greifensee, which is the headwaters for the Glatt
River.
Estimated Mass
Flow at Greifensee
outflow (from
upstream WWTP
contribution)
(µg/day/person)
(g/day)
(g/day)
2.0 ± 2.3
2.8 ± 4.3
0.2 ± 0.2
PFBS
16.4 ± 30
3.4 ± 1.3
1.8 ± 3.2
PFHxS
46.9 ± 26
15.7 ± 3.1
5.0 ± 2.7
PFOS
2.0 ± 2.4
0.2 ± 0.4
0.2 ± 0.2
PFHpA
12.6 ± 7.8
2.5 ±1.3
1.3 ± 0.8
PFOA
a
Average per capita discharge calculated for WWTPs Fa, Ba, Kl, Ni, Bu, Gl.
Average per
capita discharge
in Glatt Valleya
Measured Mass
Flow at
Greifensee
outflow
48
Figure 2.1: Map of Glatt River area of Switzerland with three river sampling
stations and seven wastewater treatment plants.
R3
Gl
Bu
Ni
Kl
Ba
R2
Du
Fa
R1
49
Figure 2.2: Measured and calculated mass flows of fluorochemicals (g/day ±
95% CI) in the Glatt River.
45
40
35
mass flow (g/day)
30
25
20
15
10
5
0
Griefensee
PFOS measured mass flow
PFOA measured mass flow
PFHxS measured mass flow
PFHpA measured mass flow
PFBS measured mass flow
Oberglatt
PFOS calc mass flow
PFOA calc mass flow
PFHxS calc mass flow
PFHpA calc mass flow
PFBS calc mass flow
sampling station
Rhine
Figure 3: Per capita mass flows in United States compared to Switzerland
100
220 µg/day/person
Per capita mass flow (ug/day/person)
80
60
40
20
0
PFBS
PFHxS
PFOS
PFDS
Schultz mass flow 1 WWTP
Schultz average 10 US WWTPs
Huset average 7 Swiss WWTPs
Sinclair average 2 NY State WWTPs
Data from Reference 5, 6 & 12
6:2 FtS
FOSA
Analyte
PFHxA
PFHpA
PFOA
PFNA
PFDA
51
QUANTITATIVE DETERMINATION OF FLUOROCHEMCIALS IN
LANDFILL LEACHATES
Carin A Huset, Morton Barlaz, Douglas F Barofsky, Jennifer A Field
Department of Chemistry, Oregon State University
Department of Civil, Construction and Environmental Engineering, North Carolina
State University
Environmental Health Sciences Center, Oregon State University
Department of Environmental and Molecular Toxicology, Oregon State University
In preparation for submission to Environmental Science and Technology
52
ABSTRACT
The presence of fluorochemicals in the wastewater treatment system has highlighted
aqueous waste as an interface between fluorochemical use and environmental systems.
Although the bulk of fluorochemicals have been produced for incorporation onto or
into solid materials, the fate of fluorochemicals after the disposal of treated solids is
unknown. To begin to assess the quantities of fluorochemicals present in the aqueous
waste of landfills (leachate), a method was developed for the quantitative
determination of fluorochemicals in landfill leachate using solid phase extraction,
dispersive carbon sorbent cleanup and HPLC-ESI MS/MS analysis. Standard addition
experiments were employed to treat matrix effects present in leachate extracts. The
method was demonstrated for the analysis of 12 leachate samples, including leachate
from historical sites which closed in the 1980’s. Perfluorocarboxylates were the most
abundant
analytes
detected
perfluoropentanoate,
in
leachate,
perfluorohexanoate,
including
perfluorobutanoate,
perfluoroheptanoate,
and
perfluorooctanoate, in excess of 1000 ng/L at some sites.
Longer-chained
carboxylates (C11-C14) were infrequently detected in leachates.
Perfluorooctane
sulfonate (PFOS), which was phased out of production in 2002, was detected in all
leachate samples (average concentration 100 ng/L), even in samples obtained from
refuse generated after 2002. Notably, older (pre-2002) leachate samples were found to
contain
perfluorobutane
sulfonate
(PFBS)
and
methyl
perfluorobutane
sulfonamidoacetic acid (MeFBSAA), replacement chemicals to PFOS, while newer
leachate samples contained PFOS and ethyl perfluorooctane sulfonamidoacetic acid
53
(EtFOSAA) and methyl perfluorooctane sulfonamidoacetic acid (MeFOSAA),
which are indicators of older formulations. Fluoroalkyl sulfonamides (EtFOSAA,
MeFOSAA and MeFBSAA), which are precursors to PFOS and PFBS, were detected
in all samples, in some cases exceeding concentrations of PFOS and PFBS.
Fluorotelomer sulfonates were also detected in leachate, at concentrations exceeding
PFOS.
54
INTRODUCTION
Fluorochemicals are found in environmental samples from all over the world; in air
samples from the arctic1 and the southern hemisphere,2 in biological samples3
including human blood4, 5 and in surface water,6 precipitation,7 8 and wastewater9. The
widespread distribution of fluorochemicals in wildlife,3 humans,10 water,11, 12 and air,13
is a concern because the toxicological effects of fluorochemicals are not yet fully
understood. The US EPA has classified perfluorooctanoate (PFOA) as a probable
carcinogen,14
and
perfluorooctane
sulfonate
(PFOS),
PFOA
and
other
perfluorocarboxylates have been found to bioaccumulate and biomagnify in fish15, 16.
Biodegradation studies have shown perfluoroalkyl carboxylates and sulfonates to be
resistant to biodegradation,17 so while the toxicological effects are not fully
understood, the persistence and widespread distribution is causing concern.
A primary application of fluorochemicals has been to impart water and oil
repellency, in the form of polymeric coatings, to solid materials such as paper and
packaging products (including food wrappers), and textile and carpet products.18 In
2000, the manufacturer of PFOS-based chemcials reported 36% of its US production
was incorporated into textile, leather and carpet coatings, while 41% was used for
coatings of paper and packaging materials19
The production of one type of
fluorochemical used to prepare surface treatments, PFOS, was phased out in 2002
amid bioaccumulation concerns.20
Perfluorobutane sulfonate (PFBS), which is
reportedly not bioaccumulative, was introduced as a substitute to PFOS;5 however,
both PFBS and PFOS are observed in the environment despite the PFOS phase out9
55
which may be an indicator of their persistence and pervasiveness. Production of
PFOA which is used in the manufacturing of fluoropolymers, will be phased out by
2015.21
Solid materials (microwave popcorn bags and frying pans) treated with
fluorochemical coatings have been shown to release PFOA22,
23
and fluorotelomer
alcohols (FtOHs)23 during use, and fast foods (eg. pizza and french fries) have been
found to contain higher levels of fluorochemicals than grocery foods (eg. dairy, meat,
eggs), a circumstance attributed to transfer of fluorochemicals from the coated
packaging materials.24 Liquid surface protection products were also found to contain
unreacted monomers from production of polymeric coatings, fluoroalkyl sulfonamides
and FtOHs,25 as well as PFOS and PFOA26.
While fluorochemicals have been studied for their behavior during the
treatment of aqueous municipal waste, little is known about their occurrence and fate
on treated solids after disposal in landfills. In the US in 2005, 55% of solid waste was
disposed to landfills, and little information currently exists about the occurrence and
behavior of fluorochemicals in landfill leachates. Landfill leachate is the term given
to water that is collected in a lined landfill; often leachate is recirculated through the
landfill to enhance decomposition of waste. Landfill leachate is highly concentrated
with organic contaminants, salts, and dissolved organic matter. The complex nature of
leachate poses analytical challenges for both chromatographic separation and mass
spectrometric detection. To date, fluorochemicals have been reported only in Swiss
solid waste composts,27 in leachates from Scandinavian landfills,28 and in landfills and
industrially-impacted groundwater in Minnesota2930. To begin to understand the scope
of fluorochemicals present in solid waste, an analytical method was developed to
56
quantify fluorochemicals in the challenging matrix of landfill leachates. In the
following, this method is described and its application to leachate samples obtained
from landfills of different ages and operating under various strategies is demonstrated.
EXPERIMENTAL
Standards. Standards of potassium perfluorobutane sulfonate (PFBS), potassium
perfluorohexane sulfonate (PFHxS), potassium perfluorooctane sulfonate (PFOS),
perfluorooctane sulfonamide (FOSA), perfluorooctane sulfonamido acetic acid
(FOSAA), methyl perfluorooctane sulfonamido acetic acid (MeFOSAA), potassium
ethyl perfluorooctane sulfonamido acetic acid (EtFOSAA), methyl perfluorobutane
sulfonamide
(MeFBSA),
methyl
perfluorooctane
sulfonamido
acetic
acid
(MeFBSAA), 1H, 1H, 2H, 2H-perfluorodecane sulfonate (8:2 FtS) and dual labeled
18
O-perfluorooctane sulfonate (18OPFOS) were donated by the 3M Company (St. Paul,
MN).
Standards
of
perfluorodecane
sulfonate
(ammonium
salt
in
water/butoxyethanol; PFDS), perfluorotetradecanoate (PFTDA), perfluorotridecanoate
(PFTrDA), perfluorododecanoate (PFDoDA), perfluoroundecanoate (PFUnDA),
perfluorodecanoate (PFDA), perfluorononanoate (PFNA), perfluorooctanoate (PFOA),
perfluoroheptanoate (PFHpA), perfluoropentanoate (PFPA) and perfluorobutanoate
(PFBA),were
purchased
from
Aldrich
Chemical
(Milwaukee,
WI).
Perfluorohexanoate (PFHxA) was purchased from Fluka. 2H perfluoro-2-octenoic
acid
(FOUEA)
was
purchased
from
Wellington
Laboratories
(Canada).
1H,1H,2H,2H-perfluorooctane sulfonate (6:2 FtS) was purchased from Apollo
Scientific Limited (Derbyshire, U.K.).
57
The instrumental and internal standard,
perfluoro (2-ethoxyethane) sulfonate (PFEES), was purchased from Oakwood
Research Chemicals (West Columbia, SC).
The internal standard, [1,2-13C2]-
perfluorooctanoate (13CPFOA), was purchased from Perkin-Elmer (Wellesley, MA).
The
internal
standards,
[1,2-13C2]-perfluorodecanoate
deuterioethylperfluoro-1-octane
sulfonamidoacetic
acid
(13CPFDA),
and
(d5EtFOSAA),
purchased from Wellington Laboratories. The internal standard, dual-labeled
perfluorooctane sulfonate (18OPFOS), was donated by 3M.
Nwere
18
O-
The name, acronym,
fragmentation reaction (transition) monitored by tandem mass spectrometry (MS/MS)
and internal standard used for each analyte are listed in Table 3.1 of the supporting
information (SI) accompanying this paper (Appendix 2 Table 1).
Leachate Samples.
Eleven leachate samples were collected by landfill
managers in 125 ml polypropylene bottles and shipped overnight on ice to Oregon
State University. The site characteristics of each landfill are listed in Table 3.1. Sites
receiving primarily municipal solid waste (as opposed to construction or demolition)
were selected for sampling. One site (Site D) allowed the opportunity to obtain
samples from different areas (cells) of the landfill that had been closed for several
years. The methods of sampling varied from site to site and included bailer, peristaltic
pump, and from a tap. The remainder of each leachate sample remained frozen until
analysis.
For use during methods development, a five L sample of leachate was obtained
from the laboratory of Dr. Barlaz and consists of leachate derived from well-
58
decomposed municipal waste collected in 2006 directly from a garbage truck, and
incubated in a laboratory bioreactor at 37°C with recirculation of leachate
Each leachate was also analyzed for total organic carbon (TOC), chloride, and
conductivity analysis which was conducted by an outside lab (CH2MHill, Corvallis,
OR) using standard EPA methods 415.1; 300.0A; and 120.1, respectively.
Solid Phase Extraction. Leachate samples were thawed to room temperature
and 5 ml aliquots were removed and spiked with internal standards (2 ng each of
13
CPFOA,
13
CPFDA, and
18
OPFOS, and 10 ng d5EtFOSAA) prior to extraction.
Leachate extractions were performed on a Supelco (Bellefonte, PA) vacuum manifold
fitted with Delrin valves, which were donated by Supelco, to replace the PTFE values.
Oasis HLB cartridges (200 mg, 6cc, Waters, Milford, MA) were rinsed 2 times with 6
mL of 10% formic acid in isopropanol (v/v) to remove residual fluorochemicals,
including PFOS and PFOA. The cartridges were then rinsed 2 times with 6 mL of
50:50 MeOH:H2O, and then conditioned with 12 mL of MeOH followed by 12 mL of
H2O without allowing the cartridges to go dry at any point. Note: no 20% MeOH
wash step31 was used after sample loading since this caused breakthrough.
Samples were then extracted at a flow rate of 1 drop per sec. Eluate was
collected and stored for breakthrough analyses. The cartridges were removed from the
manifold and centrifuged at 2500 rpm for 5 min to remove residual water. Cartridges
were then returned to the manifold and eluted using a total of 2.5 mL MeOH; 1 mL
followed by two separate 0.75 mL fractions. Solvent was allowed to soak completely
into the cartridge bed before proceeding to dropwise elution and the three fractions
were combined.
59
Extracts were cleaned up using a dispersive carbon sorbent (EnviCarb) as
described in Powley et al.32 Briefly, a small amount (~20 mg) of 120/400 mesh
EnviCarb (Supelco, Bellefonte, PA) was added to a micro centrifuge tube along with
50 µL glacial acetic acid and a 1 mL aliquot of leachate extract. The centrifuge tube
was capped, vortexed for 30 sec and then centrifuged at 14000 rpm for 30 min. A 0.3
mL aliquot of this extract was removed, spiked with 60 pg PFEES as the instrumental
standard, and diluted with water to a total volume of 1.2 mL before LC/MS/MS
analysis.
Procedural blanks consisting of HLB cartridges prepared and extracted in the
same manner as the leachate samples were set up with each batch of samples analyzed.
The procedural blanks were made up of tap water spiked with each of the four internal
standards.
Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS).
Separations were performed on an Agilent 1100 HPLC system (Palo Alto, CA) fitted
with large volume injection kit. Samples and standards (900 µL) were injected onto a
150 mm x 2.1 mm, 5 µm Targa C18 column (Higgins Analytical, Mountain View, CA)
with a 2.0 mm x 4.0 mm C18 Security Guard guard cartridge (Phenomenex, Torrence,
CA) that was heated to 30 oC.
The LC system employed 2 mM ammonium acetate
with 5% methanol (solvent A) and methanol (solvent B) pumped at a flow rate of 0.2
mL/min. The initial solvent conditions were 90% solvent B for the first 4 min at
which point the gradient changed to 45% solvent B over the next 6.5 min, where it
was maintained for 2 min. At 12.5 min, the gradient was returned to 90% solvent B
over 1 min, where it remained until the end of the analysis at 18 min. The LC was
60
interfaced to a Waters Quattro Micro tandem mass spectrometry system (Waters,
Beverly, MA) through an electrospray ionization interface operated in a negative-ion
mode. The MS/MS system was operated in multiple reaction monitoring mode with
one precursor to product transition tracked for each analyte (Appendix 2 Table 1).
Instrumental blanks (deionized water without internal standard) were prepared
and analyzed after every 3-4 samples to monitor instrumental background and
potential carryover from high level samples. Peaks in instrumental blanks, which
includes carryover, had S/N less than 3.
Internal standard calibration was performed with four stable-isotope-labeled
internal standards including
13
CPFOA,
13
CPFDA,
18
OPFOS, and d5EtFOSAA
(Appendix 2 Table 1). PFEES was used as an instrumental standard to monitor
instrument performance and as an internal standard for select analytes. Calibration
curves spanning a range from 1.2 to 2400 pg were prepared in 1:3 MeOH:H2O with
1% acetic acid. Curves were linear, weighted 1/x, and not forced through zero. The
solvent-based calibration curves were used for quantitative analysis for all leachate
extracts. The calibration curves were prepared daily and run at the beginning and at
the end of each set of samples with calibration check standards (30 pg) run after every
6-10 samples.
Standard addition also was used to quantify fluorochemicals in landfill
leachate extracts as described in Harris.33 For quantification by standard addition,
eight total aliquots were prepared. Four aliquots received only internal standards and
the other four aliquots were spiked to increase each analyte’s signal ~ 0.5, 1, 1.5 and 3
times that of the endogenous signal. Endogenous fluorochemical concentrations were
61
determined from linear regression of the eight data points with the intercept on the
X-intercept interpreted as the ‘true’ concentration of analyte. The uncertainty, which
is expressed in this work as the limit of the 95% confidence interval (CI) was used (in
what amounts to a two sided t test at p=0.05) to evaluate the statistical significance of
differences between measurements. The uncertainty of the extrapolated concentration
was calculated as the error of the regression at this point as a 95%CI.
The two methods of quantitation, internal standard quantitation based on a
solvent curve and standard addition, were compared through analysis of a subset of
seven leachates using both methods.
The agreement between both quantitation
methods was analyte and sample dependent, but significant correlations (p = 0.01)
were found for the analytes detected. In some cases, solvent curves under-predicted
the concentration (e.g. PFBA, PFBS) while in other cases, solvent curves resulted in
an over-prediction of the concentration (e.g. 6:2 FtS and MeFOSAA). To conserve
resources, the correction factors determined from these regressions were applied to the
quantitation of the rest of the sample set to correct for matrix effects.
Fluorochemical
concentrations,
whether
determined
by
solvent-based
calibration curves or by standard addition were not assigned a value unless the
analyte’s signal met a signal to noise value of 10 or greater (criteria used as a
functional limit of detection) and the assigned concentration was within the linear
calibration range for that specific analyte. The estimated method detection limit
(EMDL) was determined using the method outlined in EPA method 820A, which
utilizes the signal to noise for analytes and internal standards measured in both low
level calibration curve points and in leachate extracts to calculate detection limits.
62
Accuracy and Precision. The accuracy of the entire analytical method was
evaluated through spike and recovery experiments. Because no landfill leachate was
blank, the first step was to generate an ‘operationally-defined’ blank. A large volume
(30 mL) of a single leachate was extracted in 5 mL portions as described in the
preceding text without the addition of internal standards. The resulting eluates (not
extracts) from these extractions were used for spike and recovery experiments. First,
the fluorochemical concentrations in the ‘blank’ were determined by spiking four 5
mL portions with 2 ng each of 13CPFOA, 13CPFDA, 18OPFOS, and 10 ng d5EtFOSAA
and extracting as described above. The concentrations were determined from solventbased calibration curves only. In addition, 5 mL aliquots of the blank were spiked
with 3 ng of each analyte to give a nominal concentration of 200 ng/L for all analytes
and 2 ng each of
13
CPFOA,
13
CPFDA,
18
OPFOS, and 10 ng d5EtFOSAA and then
extracted as described above. All extracts were combined and from this pooled extract,
four aliquots were analyzed directly and four were spiked with standards for
quantification by standard addition.
Extracts were quantified through standard
addition as described above and recovery was determined after subtracting the
background (determined from solvent curve as concentrations in background were
low). Since background correction was employed, the error was calculated from the
pooled standard deviations of both standard-addition experiments (n=8 measurements)
and the measurements of the residual fluorochemicals in the blank (n=4) for a total of
12 samples analyzed. To evaluate the precision of whole method, three aliquots of
leachate (Site H) were extracted as described above and the extracts were analyzed
separately.
63
RESULTS AND DISCUSSION
Chromatography.
Modifications
in
the
gradient
allowed
both
chromatographic separation of analytes and a reduction in background contamination
or carryover typically observed from the internal plumbing of the LC and highly
concentrated samples respectively. Maintaining the solvent at 90% MeOH during and
between sample loadings apparently prevents contamination due to fluorochemicals
accumulating at the head of the LC column. Matching the solvent composition of the
extracted samples by adding acetic acid and methanol to the calibration standards
proved necessary to ensure reproducible retention times; as an added benefit, it also
sharpened chromatographic peak shapes. Selected-transition chromatograms for each
of the fluorochemicals assayed in this study are displayed in Figure 3.1; the peak
shapes and chromatographic interferences are typical of those observed in the
chromatograms of leachate extracts
Cartridge Selection and Elimination of Background. Oasis HLB cartridges
successfully retained a wide range of perfluorocarboxylates, fluoroalkyl sulfonates &
sulfonamides, including perfluorobutane analytes from leachate.
Although Oasis
WAX (weak anion exchange) cartridges were reported to give the best recovery for
the widest range of fluorochemical analytes including the shorter-chained analytes,31
our preliminary leachate extractions using WAX cartridges in our laboratory resulted
in the elution of fluorochemicals in both the anion exchange and the neutral fractions.
Poor performance of WAX is likely due to nature of leachate (high TOC, chloride, and
64
conductivity, Table 3.1), which likely exceeds the anion exchange capacity of the
WAX cartridges.
Background contamination from SPE was eliminated by replacing parts on the
vacuum manifold and applying a 10% formic acid in IPA rinse. The vacuum manifold
was an initial source of contamination to SPE extracts (determined by rinses of
methanol and water through the manifold). Replacement of the PTFE values in the
manifold with Delrin values eliminated the background from the manifold.
Fluorochemicals were detected in subsequent HLB blank extractions, even when
prepared by gravity elution (ie without the use of the manifold). PFOA and PFOS
contamination of 60 mg HLB cartridges was 50 and 60 pg, respectively. Cartridges
were rinsed with 10% formic acid in IPA as the first extraction step which eliminated
the contamination.
Breakthrough. Preliminary extraction experiments with the combination of
10 mL of leachate and a 60 mg HLB cartridge resulted in breakthrough. During
attempts to reduce breakthrough, we discovered that breakthrough was proportional to
the volume of leachate loaded; concentrations in breakthrough were 1-10% of the
initial leachate concentration (data not shown). Breakthrough was observed even after
loading 1 mL of leachate onto a 200mg cartridge. A final volume of 5 mL of leachate
with a 200 mg HLB cartridge was the best compromise between minimal loss due to
breakthrough and maximum analyte loading.
EnviCarb Clean up and Matrix effects.
Preliminary standard-addition
experiments performed on leachate extracts without EnviCarb cleanup indicated
substantial matrix effects as indicated by statistically-different concentrations
65
determined from solvent-based calibration curves and from standard-addition
treatment of the data. Therefore, EnviCarb was selected for the cleanup of HLB
extracts. Prior to implementing the EnviCarb clean up,32 fluorochemical recovery
from the EnviCarb was determined. Over 60% of analytes investigated for this study
had EnviCarb recoveries (Appendix 2 Table 2) between 80-110% and ranged from
69% (PFDS) to 210% (PFTDA).
Inclusion of the EnviCarb clean-up step improved the agreement between
concentrations determined from solvent-based calibration and standard-addition but
did not eliminate the differences. For example, in the laboratory bioreactor leachate
(Site E) the concentrations for 11 out of 24 analytes determined from solvent-based
calibration curves and standard addition were statistically equivalent but five other
analytes were not and the remaining eight analytes were not detected without standard
addition extrapolation (Appendix 2 Table 3). PFEES was selected as an internal
standard for PFBA, PFPA, PFHxA and PFBS after significant matrix effects limited
the agreement between concentrations determined from solvent-based curves and by
standard addition (data not shown). The lack of agreement is likely due to the fact that
the
18
OPFOS and
13
CPFOA internal standards had retention times substantially
different from PFBS and from PFHxA, PFPA and PFBA, respectively. However,
PFEES was spiked into extracts for use as an instrumental standard and, therefore,
does not correct for recovery of these analytes. PFBS, PFHxA, PFPA and PFBA were
all quantitated with PFEES in the method. Matrix effects were observed by others
during the analysis of fluorochemicals in extracts, including in wastewater,34 lake
35
trout,
36
66
and in sediments and sludges . The degree of matrix effects in these
studies was not determined to significantly affect the overall interpretation of the
results.
Accuracy and Precision. Whole method recoveries for 15 out of 24 analytes
were in the range from 65% to 136% (Table 3.2). Recoveries for long-chained
perfluorocarboxylates decreased with increasing chain length, which is consistent with
literature.31 The recoveries of PFOA, PFDA, PFOS and EtFOSAA, for which there
are stable-isotope labeled internal standards, were 72%, 73%, 69% and 65%
respectively. The precision of the method as indicated by relative standard deviation
(RSD) was determined by replicate extractions (n=3) of a single leachate sample.
RSDs ranged from 1% to 31%; 13 of the 20 analytes detected had RSDs less than 10%
(Table 2.2).
LC/MS/MS accuracy was evaluated through the pairs of standard addition and
solvent curve measurements. These seven pairs of measurements were plotted (see
Appendix 2 Figure 1-15) and the relationships for the analytes which were detected
were determined to be statistically significant (p = 0.01) (Appendix 2 Table 3). The
slope (Appendix 2 Table 3) for the linear regressions was close to 1 for PFPA,
PFHpA, PFOA, PFNA, PFDA, PFOS, and MeFBSAA indicating either that the degree
of ion suppression in the matrix was small for these analytes (as in the case of PFHpA,
where six of the seven pairs were statistically equivalent), or that it was very sample
specific and averaged out over large differences between measurements (as in the case
of PFOA, where six of the seven measurements were not statistically equivalent).
Curves with slopes greater than 1.2, as observed for 6:2 FtS, 8:2 FtS, MeFOSAA and
67
EtFOSAA, indicate a bias for over-prediction from solvent curve calibration,
whereas curves with slopes less than 0.8, as observed for PFBA, PFHxA, PFBS, and
PFHxS, indicate a bias for under-prediction from solvent curve calibration. PFUnDA,
PFDoDA, PFTrDA, PFTDA, FOUEA, PFDS, MeFBSA, FOSA, and FOSAA were
detected in so few samples (Appendix 2 Table 3) that regression curves for these
compounds were not computed. All these regression relationships from the first seven
leachate samples made it possible to conserve time and resources in the analyses of the
remaining five leachate samples; specifically, the curves were used to matrix-correct
the concentration estimates for these five samples obtained from solvent calibration
curves. Our approach of determining the degree of matrix effects present in a range of
leachate extracts and then applying a correction factor is a compromise between
standard addition quantitation for all samples and not treating the matrix effects at all.
Ideally, the most accurate values would be determined though standard addition
experiments on all samples, which would not be realistic in a large scale survey.
Estimated (Whole) Method Detection Limit. The EMDL was determined
for each analyte as described in EPA Method 820A and range from 0.5 to 5.4
ng/L(Table 3.2). These values represent the lowest reportable value based on the
signal to noise of samples processed using through the method and the signal to noise
ratio of standards prepared in solvent.
Demonstration of Method in Leachate.
As described above, linear
regressions were used to correct for matrix effects in leachate extracts using the slope
and intercept generated from the linear regressions (Appendix 2 Figures 1-15) with the
95%CI calculated from the pooled error of the solvent curve measurement and the
68
error of the prediction of the linear regression. The matrix-corrected fluorochemical
concentrations are found in Table 3.3. In some cases, the measured solvent curve
value was out of the calibration range for the matrix correction (e.g. PFOA in Site F
samples); in such instances, the concentrations listed in Table 3.3 are not matrixcorrected. In other cases, application of the matrix-correction yielded negative values;
where this has occurred, the concentrations listed in Table 3.3 are not matrixcorrected. Matrix effects (which produce inaccurate solvent curve values due to ion
suppression or enhancement as the case may be) were not consistently observed in any
one leachate sample; the degree of agreement between standard addition and solvent
curve pairs differs from analyte to analyte in all seven leachate samples (Appendix 2
Table 3).
Perfluoroalkyl carboxylates.
Perfluorocarboxylates were detected in all
leachate samples (Table 3.3). The short chained carboxylates, PFBA and PFPA, were
discovered to be the most concentrated of the analytes assayed in eight of the twelve
leachates (maximum concentrations of 1700 ng/L and 1500 ng/L respectively). The
low tendencies for these short chained analytes to sorb on solid materials make it
unlikely that they would be retained in the landfill, and conversely, make it very likely
that they would become enriched in the aqueous phase. There does not appear to be
any indication from the data in Table 3.3 that the practice of leachate recirculation
increases the aqueous concentrations of PFBA and PFPA relative to longer chained
analytes.
In a study of landfills which received fluorochemical industry waste,
groundwater near an unlined landfill which received fluorochemical waste PFBA was
found to be the most abundant fluorochemical at 1200 mg/L29.
69
PFHxA was the second or third most abundant perfluorocarboxylates in 11
of 12 leachates and with the highest concentration observed in the laboratory
bioreactor sample (or Site E) at 2200 ng/L (Table 3.3). PFHpA was the most abundant
analyte in the leachate generated from the laboratory bioreactor (Site E), and at 2800
ng/L, was the highest concentration for any fluorochemical assayed in this study
(Table 3.3). This leachate sample was obtained from refuse in a bioreactor, and
consequently, was highly degraded; therefore, the high concentration of PFHpA in this
sample could be indicative of biodegraded of precursor compounds such as FtOHs37.
FtOHs were detected as unreacted, residual monomers in polymeric products used to
treat carpets25 and degradation of FtOHs to PFCAs has been observed in activated
sludge37-40.
Concentrations of PFOA in leachate ranged from 130 ng/L at Site G, to 1100
ng/L in leachate from Site E, laboratory bioreactor (Table 3.3). The concentrations of
PFNA and PFDA in the laboratory bioreactor sample (Site E), 140 ng/L and 64 ng/L,
respectively, are significantly higher than in the rest of the leachates.
The highest
concentration measured for the longer chained perfluorocarboxylates, PFUnDA,
PFDoDA, PFTrDA, and PFTDA, were 14 (Site D3), 7 (Site B), 18 (Site D3), and 23
ng/L (Site D6) respectively (Table 3.3). FOUEA, which is a metabolite of 8:2 FtOH
degradation,37,
39
was only detected in samples that utilized standard addition as it
present at low endogenous levels and was subject to high chromatographic noise.
Perfluoroalkyl sulfonates.
Perfluoroalkyl sulfonates were detected in all
leachate samples (Table 3.3). PFBS was the most abundant perfluoroalkyl sulfonate
detected in ten of the twelve leachates and in the sample derived from the laboratory
70
bioreactor (which contained only 2006 refuse); its concentration (2300 ng/L) was
significantly higher than that of any other fluorochemical in the samples (Table 3.3).
The lowest concentration of PFBS in leachate (110 ng/L at Site F) is greater than the
highest concentration of for PFBS observed in wastewater effluent (20 ng/L).9 PFBS
chemistry was introduced as a replacement for the PFOS chemistry that was phased
out in 2002;5 nevertheless, PFBS was detected in landfills that stopped accepting
waste before this time (Site D2-5) (Table 3.3). This finding points to the presence of
C4 chemistry in consumer products prior to the 3M phase out. Concentrations of
PFHxS in leachate, which was also phased out of production in 2002, ranged from 110
ng/L (Site F) to 700 ng/L (Site A). PFHxS has been measured in surface water,11
wastewater,34 and house dust,41 the latter possibly originating from treated carpets.
PFOS was measured in all leachate samples, including those from sites that
received waste only after the phase out of PFOS in 2002 (Table 3.1, Sites C, E, G),
indicating that PFOS is still being released from consumer products post phase out. 20
The maximum concentration of PFOS (160 ng/L) was measured at Site A, which
opened before the phase out; however the concentration of PFOS in the laboratory
bioreactor leachate, which was taken from refuse collected in 2006, was comparable to
that measured at Site A (the oldest site, which opened in 1982). The electrochemical
fluorination process generates approximately 70% linear and 30% branched isomers;42
the isomers of PFOS resulting from this manufacturing process can be partially
resolved chromatographically. The PFOS standard used in this study produces a
chromatographic signal for the branched form that is 26% of the total PFOS signal
(data not shown). Interestingly, the chromatographic signals for the branched forms of
71
PFOS contained in the leachate samples assayed in this study shift to 46% of the
total PFOS signal (data not shown), suggesting either that linear PFOS molecules
might be preferentially sorbing on landfill solids or that branched precursors of PFOS
might be preferentially breaking down to PFOS in landfill leachates. PFDS was only
detected in two samples above the EMDL; its concentration at these two sites (15 ng/L
at Site H 13 ng/L at site E) were nearly equivalent (Table 3.3).
Fluorotelomer sulfonates: Fluorotelomer sulfonates were measured in all
landfill leachate samples (Table 3.3). The highest concentration of 6:2 FtS was 370
ng/L at Site B, while the highest concentration of 8:2 FtS was 210 ng/L in leachate
obtained from the laboratory bioreactor (Site E). While fluorotelomer sulfonates are
analogous in structure and function to PFOS, their occurrence in environmental
samples has not been thoroughly investigated. Fluorotelomer sulfonates were first
observed in groundwater43 and have been frequently detected in wastewaters in the
US9 and Switzerland44 and now in leachate which suggests a need for more research
into the sources, fate and transport of these compounds.
Fluoroalkyl sulfonamides: MeFBSAA, MeFOSAA, and EtFOSAA which
are precursors to PFBS and PFOS, respectively,45 are present in leachate samples
(Table 3.3). MeFOSAA and EtFOSAA are biodegradation products respectively of
MeFOSE and EtFOSE monomers and themselves precursors to PFOS.45 Similarly,
MeFBSAA is the analogous precursor to PFBS. While EtFOSAA is an indicator of
paper surface treatments and MeFOSAA was used in carpet treatments,46 MeFBSAA
is used in both applications. MeFBSAA, the most abundant sulfonamide detected,
was present in all samples, and had a maximum concentration of 540 ng/L in the
72
laboratory bioreactor sample (Site E). The concentration of MeFOSAA was highest
at Site C (290 ng/L), which opened after the phase out of PFOS in 2002.20 Since
carpets typically last for much more than five years, the disposal of carpets purchased
and treated prior to 2002 offers one possible explanation for high concentrations of
MeFOSAA at a site that opened after 2002. A study of residual monomers present in
polymeric products used to treat carpets found MeFOSE, a precursor to MeFOSAA, in
these products.25 In addition, both MeFOSE and EtFOSE were measured in indoor air
and dust samples collected in 2002 and 2003.47
Hence, a possible source for
MeFOSAA in leachate samples could be the degradation of residual monomers
(MeFOSE),45 or the decomposition of polymeric carpet-treatment products.
The
highest levels of EtFOSAA (480 ng/L) were detected in leachate from Site B, which
opened in 1996 and is still active. High concentrations of di-ethyl perfluorooctane
sulfonamide, and ethyl perfluorooctane sulfonamide, which are related to EtFOSAA
and indicators of fluorochemical paper coatings, have been detected in fast foods
(which were packaged in presumably treated paper or boxes)24.
Fluorochemical concentration trends: To look for relationships between
fluorochemical concentrations and time (which may be indicative of either
biodegradation, a change in input, or both), the concentration of each analyte was
plotted against the year each landfill opened (Table 3.1), this date being the best
indicator for the age of the refuse. Only 6:2 FtS was found to correlate significantly (p
= 0.05) with the age of landfill (Appendix 2 Figure 16). Since many factors that may
affect fluorochemical concentration are present in a landfill leachate (e.g. including
origin of refuse, acceptance of wastewater treatment plant sludge, recirculation of
73
leachate) it was decided to explore the data gathered in this study for correlations
between concentration and age of refuse at Site D. Significant positive correlations
were observed between PFOS (Appendix 2 Figure 17, p = 0.05), ∑PFOS (the sum of
PFOS and its precursors, EtFOSAA, and MeFOSAA) (Appendix 2 Figure 18, p =
0.05), and 6:2 FtS (Appendix 2 Figure 19, p = 0.02) and the age of samples at Site D.
How to interpret the increase in PFOS and ∑PFOS with time is not obvious because
the active cell at this landfill opened in 1999 (pre-phase out of PFOS) while other sites
that opened after the phase out of PFOS show the same levels for ∑PFOS as before
the phase out. Given the structural similarities between 6:2 FtS and 8:2 FtS, one
might expect them to behave similarly; however the concentration of 6:2 FtS
correlates with age at Site D (Appendix 2 Figure 19), whereas the concentration of 8:2
FtS does not (Appendix 2 Figure 20).
Significant correlations were observed between the leachate concentrations of
PFOA and those of PFDA (Appendix 2 Figure 21, r = 0.71, p = 0.01), PFNA
(Appendix 2 Figure 22, r = 0.620, p = 0.05) and ∑PFOS (Appendix 2 Figure 23, r =
0.71, p = 0.01). PFDA and PFNA concentrations were also significantly correlated
(Appendix 2 Figure 24, r = 0.823, p = 0.001), as were the concentrations of PFHpA
and PFHxA (Appendix 2 Figure 25, r = 0.823, p = 0.001), PFPA and PFBA (Appendix
2 Figure 26, r = 0.658, p = 0.02), PFHxS and PFOS (Appendix 2 Figure 27, r = 0.576,
p = 0.05), EtFOSAA and MeFOSAA (Appendix 2 Figure 28, r = 0.708, p = 0.01) and
∑PFCA and ∑PFS (Appendix 2 Figure 29, r = 0.823, p = 0.001). The preponderance
of correlations of fluorochemical analytes in leachate points to the possibilities of
common origins and or sinks in landfill leachates.
74
Leachate recirculation to enhance biodegradation was employed at all but
four sites (Table 3.1), but the concentrations of fluorochemicals observed at sites that
recirculated leachate were not significantly different that did not do so.
Relationship with receipt of WWTP sludge:
Municipal wastewater
treatment sludge has been shown to remove fluorochemicals from wastewater during
treatment,48 and sludge can be disposed of through land application as biosolids,
incineration, or disposal to landfills. It is suspected that sludges from wastewater
treatment plant contribute significant quantities of fluorochemicals to landfills, either
indirectly through biodegradation of precursors (such as fluorotelomer alcohols and
fluoroalkyl sulfonamides) sorbed to sludge, or directly through desorption from
sludge. In this study, nine of the 12 sites have accepted sludge/biosolids as waste, but
we are unable to determine the true effect of sludge on the concentrations of
fluorochemicals in leachates since so many other factors are also variable (including
recirculation of leachate and age of landfill).
Concentrations of fluorochemical
analytes measured in this study are in the same range as what was found in landfills in
MN which did not receive 3M sludge, but the distribution of fluorochemicals observed
is different. In non-industrially impacted leachates, PFOA and PFHxS were the most
abundant analytes at average concentrations of 1100 ng/L each. PFOS and PFBS were
also detected at 350 and 230 ng/L respectively30. In contrast to our own work, PFBA,
which was one of the most abundant analytes in our survey (63 – 1800 ng/L), was only
found at an average concentration of 28 ng/L in landfills in Minnesota. It is unclear if
the low concentrations of short chained analytes are a reflection of the analytical
challenges associated with these analytes or if this reflects the true distribution of
75
fluorochemicals in these leachates. No information is available for recirculation of
leachate or the age of the refuse at these sites, which makes interpretation difficult,
and the distribution in MN may be affected by inhibition of biodegradation due to cold
winters.
Wastewater treatment and landfills are linked in an interesting cycle as
wastewater treatment sludge can be sent to the landfill for treatment and landfill
leachate can be treated by wastewater treatment plants. The relationship between
aqueous and solid waste treatment and numerous other questions concerning the fate
and occurrence of fluorochemicals in landfill leachates remain. Existing techniques
for extraction of fluorochemicals from solids36,4927 could be applied to examine
concentrations bound to landfill solids and fluorochemicals in landfill gas and
condensate could be measured.2, 5013 The relationship between landfill and wastewater
treatment plant has yet to be determined.
ACKNOWLEDGEMENTS
The authors would like to thank the landfill site managers for sample collection, Carl
Isaacson for insight in the completion of this manuscript, and 3M for the donation of
authentic standards. We are grateful for financial support from DuPont (unrestricted
gift) and the Mass Spectrometry Facilities and Services Core of the Environmental
Health Sciences Center, Oregon State University, grant number P30 ES00210,
National Institute of Environmental Health Sciences, National Institutes of Health.
76
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Table 3.1: Site characteristics for leachate sampling sites.
Site
Location
A
Gulf Coast
B
Pacific
Northwest
C
West Coast
D-2
D-3
D-4
D-5
Mid-Atlantic
States
Mid-Atlantic
States
Mid-Atlantic
States
Mid-Atlantic
States
Collection
Point
Tank –
Enclosed
AST
Sump (in
cell goes to
riser)
Module DPhase IWest Cell
Area B,
LDPE bailer
Area C,
LDPE bailer
Area D,
LDPE bailer
Area D,
LDPE bailer
Area E, in
line sample
valves
Laboratory
bioreactor
Leachate
riser
Tons
waste
per
day
Years of
operation
Accepts
sludge
Recirculation
of leachate
Average
Annual
Rainfall
(in)
2600
1998-active
Yes
Yes
63
5200
12
22000
2000
1996-active
Yes
No
37
80
1.2
1030
500
2003-active
Yes
Yes
18
1330
4.8
950
260
1982-1988
Yes
No longer
42
730
3.9
93
330
1988-1993
Yes
No longer
42
290
3.1
63
340
1993-1999
Yes
Yes
42
1000
5.1
560
340
1993-1999
Yes
Yes
42
130
1.5
53
373
1999-active
Yes
Yes
42
320
3.5
470
N/A
2006
NA
Yes
NA
1400
18
830
1000
1999-active
No
No
9
5600
12
44
Chloride Conductivity
(mg/L)
(mS/cm)
Total
Organic
Carbon
(mg/L)
D-6
Mid-Atlantic
States
E
Southeast
F
West Coast
G
Mid-Atlantic
States
Sump
1100
2004-active
Yes
No
42
100
1.7
54
H
Mid-Atlantic
States
Leachate
Tank Faucet
(no air
exposure)
2000
1990-active
Yes
Yes
44
1200
4.7
550
81
Table 3.2. Analytical precision as indicated by RSD of replicate extractions of
a single leachate sample, accuracy as indicated by % recovery ± 95% CI, and
EMDL.
Analyte
Precision
Accuracy
EMDL
RSD
% recovery ± 95%CI (SD)
ng/L
PFBA
7
25 ± 5 (7)
4
PFPA
15
39 ± 8 (11)
2.4
PFHxA
4
64 ± 9 (12)
2.2
PFHpA
5
110 ± 12 (26)
1.4
PFOA
1
72 ± 16 (10)
0.8
PFNA
8
120 ± 18 (26)
1.2
PFDA
5
73 ± 7 (10)
0.8
PFUnDA
21
44 ± 3 (4)
1.3
PFDoDA
31
34 ± 6 (9)
1.3
PFTrDA
ND
28 ± 7(10)
2.5
PFTDA
ND
8 ± 3 (5)
4.2
FOUEA
8
68 ± 3 (4)
1
PFBS
4
54 ± 2(2)
0.7
PFHxS
9
80 ± 3 (5)
1.2
PFOS
7
69 ± 1 (4)
1.8
PFDS
21
30 ± 2 (3)
2.1
6:2 FtS
17
74 ± 2 (3)
3.9
8:2 FtS
16
94 ± 7 (10)
2.9
MeFBSA
ND
110 ± 12 (17)
2.2
MeFBSAA
10
140 ± 12 (18)
1
FOSA
5
110 ± 8 (12)
0.5
FOSAA
ND
110 ± 8 (12)
1.5
MeFOSAA
9
71 ± 4 (6)
5
EtFOSAA
6
65 ± 3 (4)
5.4
82
Table 3.3: Concentration (ng/L ± 95% CI) of fluorochemicals in 12 leachate samples
Site
B
170
± 10
120
± 20
270
± 20
100
± 15
1000
± 85
22 ±
6
14 ±
5
<1.3
23 ± 4
Site
D2
430 ±
78
730 ±
52
360 ±
22
160 ±
23
380 ±
33
20 ±
9
ND
PFUnDA
Site
A
1700
± 150
1100
± 260
790 ±
230
330 ±
15
490 ±
15
23 ±
7
15 ±
4
<1.3
<1.3
<1.3
PFDoDA
PFTrDA
<1.3
ND
7±6
<2.5
<1.3
<5
<1.3
<2.5
PFTDA
<4.2
<4.2
ND
<4.2
FOUEA
<5
<1
<1
PFBS
750 ±
100
700 ±
46
160 ±
17
<9
20 ±
6b
280
± 48
160
± 12
100
±8
<2
810 ±
210
430 ±
39
97 ±
13
<2
280 ±
72
30 ±
13
370
± 51
120
± 11
280 ±
45
70 ±
21
PFBA
PFPA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFHxS
PFOS
PFDS
6:2 FtS
8:2 FtS
Site
C
1400 ±
91
1500 ±
180
620 ±
54
340 ±
39
910 ±
40
28 ± 5
Site
D3
250 ±
140
500 ±
120
350 ±
91
150 ±
11
480 ±
27
19 ±
10
11 ±
3
14 ±
6b
<1.3
18 ±
10b
<4.2
Site
D4
1000
± 85
690 ±
130
690 ±
57
220 ±
5
400 ±
39
23 ±
9
5 ± 6a
Site
D5
490 ±
390
330 ±
170
330 ±
100
200 ±
10
430 ±
5
14 ±
7
3±2
Site
E
63 ±
41
460 ±
59
2200
± 310
2800
± 164
1100
± 53
140 ±
23
64 ±
12
<1.3
Site
F
700 ±
90
760 ±
20
1200
± 110
200 ±
11
140 ±
12a
20 ±
10c
4 ± 1a
<1.3
Site
D6
540 ±
210
470 ±
120
430 ±
25
170 ±
7
720 ±
28
26 ±
9
18 ±
3
<1.3
<1.3
Site
G
280 ±
33
270 ±
23
200 ±
25a
98 ±
8
130 ±
1a
11 ±
3a
2±
0.3a
<1.3
1.3 ±
3b
<9
ND
<1.3
ND
<1.3
<2.5
<9
<5
<1.3
ND
<1.3
ND
<4.2
<4.2
ND
<4.2
ND
ND
23 ±
5b
<1
<1
ND
8.7 ±
19b
ND
280 ±
72
170 ±
42
56 ±
17
<2
44 ±
13b
390 ±
34
200 ±
18
91
±6
ND
1000
± 250
380 ±
110
120 ±
11
ND
260 ±
73a
330 ±
49
88 ±
4
<9
890 ±
100
360 ±
99
140 ±
9
<2
110 ±
100
110 ±
40
110 ±
14
ND
140 ±
18a
120 ±
120c
38 ±
13c
ND
120 ±
22
40 ±
16
150 ±
11
74 ±
35
270 ±
13
25 ±
9
2300
± 300
120 ±
8
100 ±
10
13 ±
2b
260 ±
8
210 ±
34
29 ±
11
11 ±
7
56 ±
6
26 ±
9
82 ±
18
11 ±
3
230 ±
62
8 ± 6c
Site
H
1800
± 81
560 ±
21
870 ±
41
190 ±
4
760 ±
7
63 ±
4
44 ±
1
5.8 ±
1b
<9
<5
<4.2
<5
1200
± 47
150 ±
13
120 ±
2
15 ±
3b
220 ±
9
100 ±
5
83
MeFBSA
<2.2
MeFBSAA
FOSA
440 ±
25
<1
FOSAA
MeFOSAA
EtFOSAA
<2.2
ND
<2.2
ND
ND
470 ±
33
<1
120 ±
12
ND
<1.5
ND
100 ±
12
1.4 ±
0
<1.5
130 ±
25
2
<1.5
2.5 ±
0
210
± 11
9±
0.5b
<1.5
ND
110 ±
40
2±
0.3
ND
110 ±
49
47 ±
31
280
± 67
480
± 74
290 ±
57
170 ±
36
12 ±
5
38 ±
27
23 ±
27
21 ±
6
140 ±
43
110 ±
18
58 ±
19
57 ±
9
2.4 ±
0
120 ±
14
<0.5
ND
170 ±
36
140 ±
11
4±0
ND
ND
ND
540 ±
88
2.6 ±
0
12 ±
6b
43 ±
21
230 ±
19
11 ±
15c
ND
ND
36 ±
14c
1±
0.1
ND
140 ±
8
2±
0.6b
ND
ND
ND
8±0
7±
0.1
250 ±
17
270 ±
4
Description of leachate sites in Table 3.1
a
solvent curve value used since matrix correction extrapolated a negative value
b
solvent curve value used since not enough data to matrix correct
c
solvent curve value used since matrix correction ‘cal curve’ out of range
84
Figure 3.1: Chromatogram of fluorochemicals in Site H leachate sample
SUMMARY AND CONCLUSIONS
Wastewater treatment effluents are point sources of fluorochemicals to aquatic
environments.1-3 Wastewater treatment has been shown to be ineffective for complete
removal of fluorochemicals from the aqueous waste stream and, in some cases,
biodegradation during the treatment process results in increases of fluorochemicals in
effluents.2-4 In the Glatt River, the discharge from seven wastewater treatment plants
(WWTP) was determined to be the source of fluorochemical loading along the course
of the river.
Potential future work in this system includes the investigation of
fluorochemical behavior and loading in the summer, when the flow of the Glatt is
lower, so WWTP effluents constitute a larger portion of the total flow. Upstream
contributions of fluorochemicals (presumably in WWTP discharges into Greifensee)
accounted for a significant portion of the mass flow of fluorochemicals in the Glatt.
High levels of fluorochemicals resulting from land application of contaminated waste
were discovered in a recent study of tributaries to the Rhine River,5 and
fluorochemicals were measured in Swiss solid composts intended for land
application.6 It is possible that agricultural activities in the Greifensee catchment
could contribute to the fluorochemicals observed at the Glatt headwaters through
runoff from contaminated soil amendments.
Fluorochemicals have been measured in landfill leachates in active and closed
sites.7 Compounds such as PFOS, which were phased out of production 4 years ago,
are present in landfill sites at the same concentration as before the phase out. Future
studies on fluorochemical concentrations in landfills need to assess the fractions
6
86
associated with the solids in landfills and with the gases emitted from landfills.
The relationship between wastewater treatment plants and landfills should be
investigated because landfills accept sludges and leachates are treated by municipal
WWTP facilities. For example, the removal efficiency of a WWTP could be impacted
after a large volume of leachate is input to the WWTP, resulting in high levels of
fluorochemicals discharged into receiving waters.
If leachate is determined to
contribute significantly to fluorochemical WWTP loads, then the levels of
fluorochemicals released from individual households might not be as high as
previously estimated.1 The sources of the fluorochemicals in landfill leachates have
yet to be determined. Are they present in leachate, for example, because residual
monomers leach out of consumer products that have been treated with
fluoropolymers?8,
9
Or do the fluorochemicals detected in leachate the result from
degradation of fluorinated polymeric materials as suggested by Houde et al?10 One
consequence of the latter scenario is the continued input of fluorochemicals to aquatic
systems even after production of these chemicals is phased out. As the production of
fluorochemicals in current use is phased out, the environmental monitoring of
alternative chemicals needs to take place. To date, most studies analyze for PFOA and
PFOS; there is little baseline information for the fate, distribution, or effects of shorter
chained fluorochemicals or even precursor compounds.
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APPENDICES
97
APPENDIX 1: SUPPORTING INFORMATION FOR MASS FLOW OF
FLUOROCHEMICALS IN A SWISS RIVER VALLEY
Carin A Huset1, Aurea C Chiaia1, Douglas F Barofsky1, Niels Jonkers2, Hans-Peter
Kohler2, Walter Giger2, Jennifer A Field3
1
Department of Chemistry, Oregon State University, Corvallis, OR
2
EAWAG, Duebendorf, Switzerland
3
Department of Environmental and Molecular Toxicology, Oregon State University,
Corvallis, OR
98
Appendix 1 Table 1: Fluorochemical analytes names, acronyms, multiple
reaction monitoring (MRM) transitions, and instrumental limits of detection and
quantification.
Analyte
Acronym
MRM
transition
(m/z)
Perfluorobutane
PFBS
299 Æ 80
sulfonate
Perfluorohexane
PFHxS
399 Æ 80
sulfonate
Perfluorooctane
PFOS
499 Æ 80
sulfonate
Perfluorodecane
PFDS
599 Æ 80
sulfonate
6:2 fluorotelomer
6:2 FtS
426 Æ 81
sulfonate
Perfluorooctane
FOSA
498 Æ 78
sulfonamide
Perfluorohexanoate
PFHxA
313 Æ 269
Perfluoroheptanoate
PFHpA
363 Æ 319
Perfluorooctanoate
PFOA
413 Æ 369
Perfluorononanoate
PFNA
463 Æ 419
Perfluorodecanoate
PFDA
513 Æ 469
a
Determined using method described Kennedy et al. 1
Instrumental
LODa
(ng/L)
Instrumental
LOQa
(ng/L)
2.3
7.7
2.2
7.4
2.3
7.8
9.4
31.1
4.0
13.2
7.1
23.6
2.9
1.2
1.8
1.6
4.0
9.7
4.1
6.1
5.2
13.2
99
Appendix 1 Table 2: Analyte concentrations (ng/L ± 95% CI) determined
from solvent-based calibration curves and by standard addition for WWTP
influent, WWTP effluent, and Glatt River water.
WWTP Influent
WWTP Effluent
Glatt River
Solvent- Standard
SolventStandard
Solvent- Standard
based
addition
based
addition
based
addition
ND
5±7
12 ± 5
11 ± 2
ND
2±3
PFBS
12 ± 5
88 ± 21
80 ± 3
23 ± 5
18 ± 3
PFHxS 20 ± 4
54 ± 15 56 ± 5
140 ± 30
170 ± 9
30 ± 8
28 ± 4
PFOS
ND
0
ND
0.3 ± 4
ND
2±7
PFDS
ND
0.1 ± 0
ND
4±2
6:2 FtS 21 ± 20 16 ± 3
ND
5±9
ND
0
ND
1±1
FOSA
0±4
25 ± 10
30 ± 3
ND
6±7
PFHxA ND
0±2
10 ± 5
12 ± 2
ND
3±2
PFHpA ND
9±2
8±2
39 ± 24
35 ± 4
7±4
10 ± 2
PFOA
ND
0.1 ± 0.5
2±2
2±1
2±5
2±3
PFNA
14 ± 4
10 ± 7
ND
1±1
ND
1.3 ± 3
PFDA
a
Standard addition performed on n=4 aliquots spiked to increase analyte response by
1.5-3 times the background response and n=4 unspiked aliquots. 2
100
References
(1)
(2)
Kennedy, E. R.; Fischbach, T. J.; Song, R. G.; Eller, P. M.; Shulman, S. A.
Analyst 1996, 121, 1163-1169.
Harris, D. C. Quantitative Chemical Analysis; W. Freeman and Co.: New
York, 1991.
101
APPENDIX 2: SUPPORTING INFORMATION FOR QUANTITATIVE
DETERMINATION OF FLUOROHCEMICALS IN LANDFILL LEACHATES
Carin A. Huset, Morton Barlaz, Douglas F. Barofsky, Jennifer A. Field
Department of Chemistry, Oregon State University
Department of Civil, Construction and Environmental Engineering, North Carolina
State University
Environmental Health Sciences Center, Oregon State University
Department of Environmental and Molecular Toxicology, Oregon State University
102
Appendix 2 Table 1: Fluorochemical analytes, acronyms, mass transitions
monitored, and internal and instrumental standards used for quantitation.
Analyte
Acronym
Perfluorobutanoate
Perfluoropentanoate
Perfluorohexanoate
Perfluoroheptanoate
Perfluorooctanoate
Perfluorononanoate
Perfluorodecanoate
Perfluoroundecanoate
Perfluorododecanoate
Perfluorotridecanoate
Perfluorotetradecanoate
2H perfluoro-2-octenoic acid
Perfluorobutane sulfonate
Perfluorohexane sulfonate
Perfluorooctane sulfonate
Perfluorodecane sulfonate
1H-1H-2H-2H-perfluorooctane
sulfonate
1H-1H-2H-2H-perfluorodecane
sulfonate
N-methyl perfluorobutane
sulfonamide
N-methyl perfluorobutane
sulfonamido acetic acid
Perfluorooctane sulfonamide
Perfluorooctane sulfonamido
acetic acid
N-methyl perfluorooctane
sulfonamido acetic acid
N-ethyl perfluorooctane
sulfonamido acetic acid
[1,2-13C2]-perfluorooctanoatea
[1,2-13C2]-perfluorodecanoatea
[18O2]-perfluorooctane sulfonatea
N-deuterioethylperfluoro-1octane sulfonamidoacetic acida
Perfluoro (2-ethoxyethane)
sulfonatea
a
Internal standard
PFBA
PFPA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
PFDoDA
PFTrDA
PFTDA
FOUEA
PFBS
PFHxS
PFOS
PFDS
MRM
transition
213>169
263>219
313>269
363>169
413>369
463>419
513>469
563>519
613>569
663>619
713>669
457>393
299>80
399>80
499>80
599>80
6:2 FtS
427>81
18
OPFOS
8:2 FtS
527>81
18
OPFOS
MeFBSA
312>219
d5EtFOSAA
MeFBSAA
370>219
d5EtFOSAA
FOSA
498>78
d5EtFOSAA
FOSAA
556>498
d5EtFOSAA
MeFOSAA
570>419
d5EtFOSAA
EtFOSAA
584>419
d5EtFOSAA
13
CPFOA
CPFDA
18
OPFOS
415>370
515>470
503>84
PFEES
PFEES
PFEES
d5EtFOSAA
589>419
PFEES
PFEES
315>135
None
13
Internal
standard
PFEES
PFEES
PFEES
13
CPFOA
13
CPFOA
13
CPFOA
13
CPFDA
13
CPFDA
13
CPFDA
13
CPFDA
13
CPFDA
13
CPFOA
PFEES
18
OPFOS
18
OPFOS
18
OPFOS
103
Appendix 2 Table 2: Percent recovery of fluorochemical analytes from
EnviCarb
Analyte
%Recovery ± 95% CI (SD) of
Envicarb cleanup step
PFBA
74 ± 19 (21)b
PFPA
92 ± 24 (27)b
PFHxA
73 ± 22 (24)b
PFHpA
100 ± 17 (19)b
PFOA
77 ± 25 (28)b
PFNA
80 ± 22 (25)b
PFDA
74 ± 9 (10)b
PFUnDA
110 ± 31(17)a
PFDoDA
130 ± 13(7)a
PFTrDA
120 ± 17 (9)a
PFTDA
210 ± 4 (2)a
FOUEA
91 ± 6(7)b
PFBS
93 ± 51(57)b
PFHxS
130 ± 45 (53)b
PFOS
80 ± 11(12)b
PFDS
69 ± 5 (5)b
6:2 FtS
110 ± 42 (55)b
8:2 FtS
110 ± 15 (17)b
MeFBSA
96 ± 2(1)a
MeFBSAA
93 ± 59 (66)b
FOSA
110 ± 10 (11)a
FOSAA
82 ± 18 (51)a
MeFOSAA
85 ± 25 (27)b
EtFOSAA
71 ± 45 (51)b
a
n=2 replicates of SPE extracts each spiked with the amount of each individual analyte needed
to double the initial concentration, cleaned up by EnviCarb. Recovery determined after
background subtraction
b
n=4 replicates of SPE extracts each spiked with the amount of each individual analyte needed
to double the initial concentration, cleaned up by EnviCarb. Recovery determined after
background subtraction.
104
Appendix 2 Table 3: Concentration (ng/L ± 95%CI) of fluorochemical analytes in leachate as indicated by pairs
of standard addition and solvent curve values from 7 leachate samples and linear regression from paired values.
Analyte
PFBA
PFPA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
PFDoDA
PFTrDA
PFTDA
FOUEA
PFBS
PFHxS
PFOS
PFDS
6:2 FtS
8:2 FtS
MeFBSA
MeFBSAA
FOSA
FOSAA
MeFOSAA
EtFOSAA
Site E
Std addn
Solvent curve
63 ± 22
44 ± 41
460 ± 23
250 ± 60
2200 ± 140
1100 ± 310
2800 ± 89
3200 ± 170
1100 ± 35
1100 ± 53
140 ± 13
160 ± 23
64 ± 3.7
66 ± 12
0
ND
8.7 ± 4.4
7.6 ± 1.9
5 ± 10
ND
10 ± 20
ND
0
ND
2300 ± 130
1200 ± 300
120 ± 14
86 ± 8.4
104 ± 5
110 ± 9.5
16 ± 1.6
13 ± 2.3
260 ± 21
390 ± 8.2
210 ± 25
430 ± 34
4.2 ± 4.7
ND
810 ± 88
540 ± 280
2.6 ± 1.9
ND
12 ± 1.6
12 ± 5.7
43 ± 11
44 ± 21
230 ± 11
230 ± 19
Site C
Std addn
Solvent curve
1400 ± 25
1400 ± 91
1500 ± 36
1500 ± 180
620 ± 14
590 ± 54
340 ± 15
310 ± 39
900 ± 10
1000 ± 40
28 ± 9.6
40 ± 4.8
23 ± 11
16 ± 3.8
0.1 ± 0.3
ND
0.8 ± 0.4
ND
3 ± 1.7
ND
9±6
ND
0
ND
810 ± 36
950 ± 210
430 ± 13
470 ± 39
97 ± 9.2
160 ± 13
0
ND
280 ± 6.8
680 ± 45
70 ± 7.9
170 ± 21
3.2 ± 3.5
ND
440 ± 33
470 ± 110
0.2 ± 1.4
ND
0.2 ± 1.5
ND
290 ± 19
430 ± 57
170 ± 24
260 ± 36
Site A
Std addn
Solvent curve
1700 ± 63
1000 ± 150
1100 ± 170
1000 ± 260
790 ± 50
780 ± 230
328 ± 21
316 ± 15
490 ± 8
640 ± 15
23 ± 1.1
39 ± 6.8
15 ± 0.8
24 ± 3.7
0.4 ± 0.6
ND
0.2 ± 0.7
ND
0
ND
0
ND
1.5 ± 0.6
4±6
750 ± 50
650 ± 100
700 ± 19
470 ± 46
160 ± 8.6
210 ± 17
5.3 ± 1.5
5.2 ± 2.2
280 ± 11
390 ± 72
30 ± 4
61 ± 13
1.9 ± 2.8
ND
440 ± 25
440 ± 150
1.3 ± 1.0
ND
0.7 ± 1.1
ND
110 ± 5
180 ± 49
47 ± 5
83 ± 31
Site B
Std addn
Solvent curve
170 ± 6
150 ± 10
120 ± 13
120 ± 20
270 ± 17
260 ± 20
100 ± 14
100 ± 15
1000 ± 19
1400 ± 85
22 ± 4.1
59 ± 5.6
14 ± 1.9
36 ± 4.9
0
ND
6 ± 1.2
ND
0.4 ± 0.8
ND
1.2 ± 0.9
ND
10 ± 1.2
ND
280 ± 13
330 ± 48
160 ± 8.2
250 ± 12
110 ± 7.5
150 ± 8.1
1.1 ± 0.7
ND
370 ± 20
860 ± 51
120 ± 12
220 ± 11
2.5 ± 1.7
ND
79 ± 11
210 ± 13
6.6 ± 0.2
9.6 ± 0.5
1.1 ±1.2
ND
280 ± 14
530 ± 67
480 ± 19
770 ± 74
105
Appendix 2 Table 3 continued:
Analyte
PFBA
PFPA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
PFDoDA
PFTrDA
PFTDA
FOUEA
PFBS
PFHxS
PFOS
PFDS
6:2 FtS
8:2 FtS
MeFBSA
MeFBSAA
FOSA
FOSAA
MeFOSAA
EtFOSAA
Site D-2
Std addn
Solvent curve
430 ± 34
730 ± 36
360 ± 12
170 ± 4.3
380 ± 5.1
20 ± 2.1
0.3 ± 0.8
0
0
0.2 ± 1.2
2±3
1.1 ± 1.2
280 ± 12
170 ± 7
56 ± 2.5
0.8 ± 0.9
29 ± 2.6
11 ± 1.6
0
110 ± 12
0
0
16 ± 0.4
38 ± 3.5
470 ± 78
620 ± 52
320 ± 22
170 ± 23
570 ± 33
31 ± 8.6
ND
ND
ND
ND
ND
ND
340 ± 72
210 ± 42
97 ± 17
ND
56 ± 11
20 ± 7.2
ND
120 ± 85
ND
ND
39 ± 5.3
70 ± 27
Site D-3
Solvent
Std addn
curve
250 ± 29
190 ± 140
500 ± 29
460 ± 120
350 ± 21
390 ± 91
150 ± 10
180 ± 11
490 ± 31
810 ± 27
19 ± 1.2
36 ± 10
11 ± 0.5
13 ± 2.6
9.5 ± 1.4
14 ± 6.3
0.7 ± 1.4
ND
18 ± 2
18 ± 10
0.7 ± 1.7
ND
21 ± 2.2
44 ± 13
390 ± 6.3
500 ± 34
200 ± 24
250 ± 18
91 ± 9.9
130 ± 6.4
0
ND
56 ± 13
91 ± 5.8
26 ± 4.3
35 ± 9.2
0.5 ± 1.6
ND
58 ± 12
100 ± 25
1.4 ± 1.5
ND
0.9 ± 1.9
ND
23 ± 4.7
27 ± 27
21 ± 0.7
34 ± 6
Site D-6
Std addn
Solvent curve
540 ± 48
470 ± 34
430 ± 19
170 ± 3.6
720 ± 60
26 ± 3.1
18 ± 1.4
0.9 ± 2.5
0.2 ± 0.7
0.7 ± 2.8
13 ± 2.7
3.2 ± 3
890 ± 100
360 ± 110
140 ± 8.9
1.3 ± 1.2
270 ± 67
25 ± 1.8
2.4 ± 2.5
200 ± 14
0.5 ± 0.8
0
173 ± 7.1
140 ± 2.4
750 ± 210
390 ± 120
600 ± 25
170 ± 6.7
490 ± 28
29 ± 8.5
25 ± 3.2
ND
ND
ND
23 ± 4.7
11 ± 2
470 ± 100
480 ± 100
200 ± 8.6
ND
300 ± 13
58 ± 8.6
ND
120 ± 23
ND
ND
210 ± 35
200 ± 11
Slope
R
0.702
1.066
0.406
1.142
0.873
1.102
0.929
N/A
N/A
N/A
N/A
N/A
0.435
0.624
1.153
N/A
2.020
1.985
N/A
1.000
N/A
N/A
1.670
1.515
0.903
0.986
0.915
1.0
0.777
0.975
0.874
N/A
N/A
N/A
N/A
N/A
0.886
0.833
0.910
N/A
0.878
0.993
N/A
0.913
N/A
N/A
0.977
0.979
106
Appendix 2 Figure 1: Linear regression of concentration (ng/L) of PFBA in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
2000
Solvent Curve (ng/L)
1500
y = 0.7024x + 113.57
2
R = 0.815
1000
500
0
0
500
1000
Standard Addition (ng/L)
1500
2000
107
Appendix 2 Figure 2: Linear regression of concentration (ng/L) of PFPA in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
1800
1500
y = 1.0649x - 113.44
Solvent Curve (ng/L)
2
R = 0.9722
1200
900
600
300
0
0
300
600
900
1200
Standard Addition (ng/L)
1500
1800
108
Appendix 2 Figure 3: Linear regression of concentration (ng/L) of PFHxA in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
2500
Solvent Curve (ng/L)
2000
y = 0.4055x + 290.11
2
R = 0.8377
1500
1000
500
0
0
500
1000
1500
Standard Addition (ng/L)
2000
2500
109
Appendix 2 Figure 4: Linear regression of concentration (ng/L) of PFHpA in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
3000
Solvent Curve (ng/L)
y = 1.1416x - 30.308
2
R = 0.9994
2000
1000
0
0
1000
2000
Standard Addition (ng/L)
3000
110
Appendix 2 Figure 5: Linear regression of concentration (ng/L) of PFOA in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
1500
y = 0.8725x + 221.08
2
R = 0.6032
Solvent Curve (ng/L)
1200
900
600
300
0
0
300
600
900
Standard Addition (ng/L)
1200
1500
111
Appendix 2 Figure 6: Linear regression of concentration (ng/L) of PFNA in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
180
150
y = 1.0177x + 15.564
Solvent Curve (ng/L)
2
R = 0.9504
120
90
60
30
0
0
30
60
90
120
Standard Addition (ng/L)
150
180
112
Appendix 2 Figure 7: Linear regression of concentration (ng/L) of PFDA in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
80
y = 0.8484x + 9.5398
2
R = 0.7637
Solvent Curve (ng/L)
60
40
20
0
0
20
40
Standard Addition (ng/L)
60
80
113
Appendix 2 Figure 8: Linear regression of concentration (ng/L) of PFBS in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
3000
Solvent Curve (ng/L)
2500
2000
y = 0.4355x + 288.07
2
R = 0.7852
1500
1000
500
0
0
500
1000
1500
2000
Standard Addition (ng/L)
2500
3000
114
Appendix 2 Figure 9: Linear regression of concentration (ng/L) of PFHxS in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
800
y = 0.6238x + 123.41
2
R = 0.6945
Solvent Curve (ng/L
600
400
200
0
0
200
400
Standard Addition (ng/L)
600
800
115
Appendix 2 Figure 10: Linear regression of concentration (ng/L) of PFOS in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
y = 1.1529x + 30.118
2
R = 0.8284
Solvent Curve (ng/L)
200
100
0
0
100
Standard Addition (ng/L)
200
116
Appendix 2 Figure 11: Linear regression of concentration (ng/L) of 6:2 FtS in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
1000
y = 2.0201x - 52.202
2
R = 0.771
Solvent Curve (ng/L)
800
600
400
200
0
0
200
400
600
Standard Addition (ng/L)
800
1000
117
Appendix 2 Figure 12: Linear regression of concentration (ng/L) of 8:2 FtS in
leachate determined by standard addition and from a solvent curve. Error bars
represent ± 95% CI.
500
y = 1.9854x + 1.7132
2
R = 0.9851
Solvent Curve (ng/L)
400
300
200
100
0
0
100
200
300
Standard Addition (ng/L)
400
500
118
Appendix 2 Figure 13: Linear regression of concentration (ng/L) of
MeFBSAA in leachate determined by standard addition and from a solvent
curve. Error bars represent ± 95% CI.
1000
750
Solvent Curve (ng/L)
y = 1.3219x - 72.456
2
R = 0.8336
500
250
0
0
250
500
Standard Addition (ng/L)
750
1000
119
Appendix 2 Figure 14: Linear regression of concentration (ng/L) of
MeFOSAA in leachate determined by standard addition and from a solvent
curve. Error bars represent ± 95% CI.
600
y = 1.6697x - 14.147
2
Solvent Curve (ng/L)
R = 0.9549
400
200
0
0
200
400
Standard Addition (ng/L)
600
120
Appendix 2 Figure 15: Linear regression of concentration (ng/L) of
EtFOSAA in leachate determined by standard addition and from a solvent curve.
Error bars represent ± 95% CI.
900
y = 1.5153x - 8.8409
2
Solvent Curve (ng/L)
R = 0.9594
600
300
0
0
300
600
Standard Addition (ng/L)
900
121
Appendix 2 Figure 16: Correlation between concentration 6:2 FtS (ng/L) and
age of refuse as indicated by year opened 12 sites.
2010
2005
2
year opened
R = 0.4122
2000
1995
1990
1985
1980
0
50
100
150
200
250
6:2 FtS (ng/L)
300
350
400
122
Appendix 2 Figure 17: Correlation between concentration PFOS (ng/L) and
age of refuse as indicated by year opened for Site D.
2000
2
R = 0.8699
year opened
1995
1990
1985
1980
0
20
40
60
80
100
Concentration PFOS (ng/L)
120
140
160
123
Appendix 2 Figure 18: Correlation between concentration ∑PFOS (ng/L) and
age of refuse as indicated by year opened for Site D.
2000
2
R = 0.7807
year opened
1995
1990
1985
1980
0
100
200
300
Concentration Sum PFOS (ng/L)
400
500
124
Appendix 2 Figure 19: Correlation between concentration 6:2 FtS (ng/L) and
age of refuse as indicated by year opened for Site D.
2000
2
R = 0.8956
year opened
1995
1990
1985
1980
0
50
100
150
200
Concentration 6:2 FtS (ng/L)
250
300
125
Appendix 2 Figure 20: Correlation between concentration 8:2 FtS (ng/L) and age
of refuse as indicated by year opened for Site D.
2000
2
R = 0.1669
year opened
1995
1990
1985
1980
0
10
20
30
40
50
Concentration 8:2 FtS (ng/L)
60
70
80
126
Appendix 2 Figure 21: Correlation between concentrations of PFOA and
PFDA (ng/L) for 12 leachate samples.
75
2
P F D A (ng/L )
R = 0.556
50
25
0
0
200
400
600
PFOA (ng/L)
800
1000
1200
127
Appendix 2 Figure 22: Correlation between concentrations of PFOA and
PFNA (ng/L) for 12 leachate samples.
150
2
PFNA (ng/L)
R = 0.3843
100
50
0
0
200
400
600
PFOA (ng/L)
800
1000
1200
128
Appendix 2 Figure 23: Correlation between concentrations of PFOA and
∑PFOS (ng/L) for 12 leachate samples.
Sum PFOS (ng/L)
1000
2
R = 0.6638
750
500
250
0
0
200
400
600
PFOA (ng/L)
800
1000
1200
129
Appendix 2 Figure 24: Correlation between concentrations of PFDA and
PFNA (ng/L) for 12 leachate samples.
150
125
2
PFNA (ng/L)
R = 0.8699
100
75
50
25
0
0
10
20
30
40
PFDA (ng/L)
50
60
70
130
Appendix 2 Figure 25: Correlation between concentrations of PFHpA and
PFHxA (ng/L) for 12 leachate samples.
PFHxA (ng/L)
2500
2000
2
R = 0.7468
1500
1000
500
0
0
500
1000
1500
PFHpA (ng/L)
2000
2500
3000
131
Appendix 2 Figure 26: Correlation between concentrations of PFPA and
PFBA (ng/L) for 12 leachate samples.
PFBA (ng/L)
2000
1500
2
R = 0.4532
1000
500
0
0
200
400
600
800
1000
PFPA (ng/L)
1200
1400
1600
132
Appendix 2 Figure 27: Correlation between concentrations of PFHxS and
PFOS (ng/L) for 12 leachate samples.
200
2
R = 0.3402
PFOS (ng/L)
150
100
50
0
0
100
200
300
400
500
PFHxS (ng/L)
600
700
800
133
Appendix 2 Figure 28: Correlation between concentrations of EtFOSAA and
MeFOSAA (ng/L) for 12 leachate samples.
300
MeFOSAA (ng/L)
250
2
R = 0.5749
200
150
100
50
0
0
100
200
300
400
EtFOSAA (ng/L)
500
600
134
Appendix 2 Figure 29: Correlation between concentrations of ∑PFCA and ∑PFS
(ng/L) for 12 leachate samples.
4000
S u m P F S (n g /L )
2
R = 0.6907
3000
2000
1000
0
0
2000
4000
Sum PFCA (ng/L)
6000
8000
135