Liquid chromatography/mass spectrometry method for determination of perfluorooctane sulfonyl fluoride upon derivatization with benzylamine

Article abstract of DOI:10.1021/ac201117k

Perfluorooctane sulfonyl fluoride (PFOSF) is a main precursor of environmentally ubiquitous perfluorooctanesulfonate (PFOS), and the quantity released to the environment is substantial. Determination of PFOSF, particularly at low concentrations, presents

Full text of DOI:10.1021/ac201117k

LETTER
pubs.acs.org/ac
Liquid Chromatography/Mass Spectrometry Method for
Determination of Perfluorooctane Sulfonyl Fluoride upon
Derivatization with Benzylamine
Cuirong Sun,†,‡ Hezhi Sun,† Yongquan Lai,‡ Jingjing Zhang,† and Zongwei Cai*,‡
†Department of Chemistry, Zhejiang University, Hangzhou, China
‡Department of Chemistry, Hong Kong Baptist University, Hong Kong SAR, China
S Supporting Information
b
ABSTRACT: Perfluorooctane sulfonyl fluoride (PFOSF) is a main precursor of
environmentally ubiquitous perfluorooctanesulfonate (PFOS), and the quantity
released to the environment is substantial. Determination of PFOSF, particularly at
low concentrations, presents significant challenges for high-performance liquid
chromatography and liquid chromatography/mass spectrometry (LC/MS) anal-
yses due to the lack of chromophore and ionizable functional group, respectively. In
this study, a new method was developed by derivatizing PFOSF with benzylamine
to allow rapid quantitative analysis by using LC/MS. The method demonstrated
good linearity in the range from 2 to 80 ng mLÀ1 with r2 > 0.994 for the
derivatization product while the absolute detection limit was 2.5 pg. LiquidÀliquid and liquidÀsolid extraction procedures were
established for analysis of water and soil samples, and recoveries were in the range of 51À128%. In addition, the derivatization was
selective for PFOSF, whereas PFOS did not nearly react. The developed simple analytical method with good reproducibility might
not only be applied for analysis of PFOSF in the environment but also be applicable for supporting investigations on environmental
fate of PFOSF, particularly its environmental and biotransformation to PFOS.
erfluorinated compounds (PFCs), a class of compounds with
excellent surface activity and chemical and thermal stability,
is volatile with an estimated global release of 6 800 to 45 250
tons between 1970 and 2002 to the air and water from various
sources.17 It has been hypothesized that, during the life cycles of
PFOSF, the chemical could potentially degrade to PFOS in the
environment to an undetermined degree.18,19 However, there
have been no published reports on a successful methodology for
the quantitative determination of PFOSF and its pathway of
transforming to PFOS.
PFOSF cannot be easily protonated or deprotonated due to
the lack of ionizable functional group and thus may not be
directly amenable to electrospray ionization mass spectrometry
(ESI-MS). Although a direct probe mass spectrometric analysis
with chemical ionization showed the PFOSF molecular ion peak,
the subsequent relevant analysis by gas chromatography mass
spectrometry (GC/MS) did not produce any chromatographic
peaks under either the positive or negative ion mode.20 Further-
more, the direct analysis of PFOSF by using high-performance
liquid chromatography with visible, UV, or fluorescence detec-
tion may be impossible due to the lack of chromophore in the
molecule. No successful method for the quantitative determina-
tion of PFOSF has been reported, to the best of our knowledge.
Because of the unavailable analytical methodology, studies on the
environmental fate, degradation, and transport of PFOSF in the
P
are widely used in the production of fluoropolymers, inks, water
repellents, and as coatings on paper and textiles during the past
50 years.1,2 PFCs were found to be persistent, bioaccumulative,
toxic even at trace amount, and ubiquitous in the environ-
ment.3,4 Among PFCs, the eight carbon chained perfluorooc-
tanesulfonate (PFOS) and perfluorooctanoic acid (PFOA)
were found to be environmentally persistent and globally
distributed in soil,5,6 waters,7,8 atmosphere,9,10 and even in
the bloodstream of the general population and wildlife,11À13
typically with PFOS at higher concentrations than PFOA.14,15
PFOS is extremely persistent and has substantial bioaccumulat-
ing and biomagnifying properties, although it does not follow
the classic pattern of other persistent organic pollutants (POPs)
by partitioning into fatty tissues but instead binds to proteins in
the blood and liver. The chemical has a capacity to undergo
long-range transport and also fulfills the toxicity criteria of the
Stockholm Convention. Therefore, PFOS, perfluorooctane
sulfonyl fluoride (PFOSF), and PFOA were added as new
POPs in the Stockholm Convention in 2009.16
Although PFOS is often found at the highest levels in
environmental monitoring compartments, PFOSF was pro-
duced in much greater quantities because it is the main
precursor of PFOS. The commercial production of PFOSF
began over half a century ago, and the total amount produced
from 1970 to 2002 was estimated to be ∼100 000 tons. PFOSF
Received: May 1, 2011
Accepted: June 30, 2011
Published: June 30, 2011
r
2011 American Chemical Society
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environment are extremely limited. It is also currently unknown
how much PFOSF contributes to the burden of environment,
due to lack of a suitable method for the quantitative determina-
tion by HPLC, LC/MS, and GC/MS.
extracted with dichloromethane, and the combined organic layers
were dried over Na2SO4. Filtration and solvent evaporation left a
crude product which was further purified by chromatography on silica
gel (hexane to hexane/ethyl acetate = 10/1) to give the produced
BFOSA product that was mixed amides including line and branch
chain isomers because the reaction agent PFOSF was a technical
mixture.
Line amide (L-BFOSA) was separated and prepared on a
Varian Prostar semipreparative HPLC (Varian Co.). A reversed-
phase Shim-pack PRC-ODS column (20 mm  250 mm, 10 μm)
was used for the separation. A mixture of water and acetonitrile
(35:65, v/v) was used as the mobile phase. The collected frac-
tions were evaporated to dryness for subsequent MS and NMR
analyses. L-BFOSA was obtained as a white solid with a mp of
115.5À116.5 °C. The calculated elemental compositions for
C15H8F17NO2S were C, 30.57; H, 1.37; N, 2.38, while the
detected values were C, 31.06; H, 1.40; N, 2.31.
Derivatization of Trace PFOSF and Sample Extraction. An
amount of 250 μg of benzylamine in 50 μL of triethylamine was
added into 1À100 ng PFOSF in 1 mL of anhydrous dichloro-
methane solution. The reaction mixture was stirred at room
temperature for 12 h. The solvent was evaporated to dryness
using a nitrogen evaporator. The residue was dissolved in 1 mL
of acetonitrile, vortex mixed, and centrifuged at 12 000 rpm for
20 min prior to the LC/MS analysis.
The sample preparation procedure for environmental analysis
included extraction of target compounds from water and soil.
Environmental soil collected from a local land field was used for
the method development with the property of the air-dried soil:
pH 6.4 when adding into distilled water; 1.5% total organic
matter; 0.84% total organic carbon; 56.4% sand, 22.2% silt,
and 21.4% clay. Briefly, 10 mL of distilled water or 10 g of soil
was spiked with PFOSF at a concentration of 100 ng mLÀ1 or
100 ng gÀ1. The sample was extracted with 10 mL of dichlor-
omethane two times. The combined organic layers were dried
over Na2SO4. A volume of 1 mL of the combined supernatant
was then transferred into another tube for the derivatization
described above.
Although GC/MS analysis combined with chemical deriva-
tization might provide good quantitative ability, the derivatiza-
tion procedure applied for LC/MS quantitative analysis is less
known. Compared with GC, LC can tolerate much higher
sample loading and avoid sample degradation during the
analysis. A general derivatization LC/MS methodology has
been developed for determination of a class of commonly
encountered alkyl esters of sulfonates or sulfates by using
trialkylamines as the derivatization agents with good linearity
and recoveries.21 Fatty alcohol, neurosteroids, and vitamin D
could be detected with amines as a derivatizing agent to
improve the ionization activity in the ESI sourse.22,23
PFOSF can be easily transformed into sulfonamides with good
yield. N-alkylperfluorooctane sulfonamides have been in commer-
cial production for insecticide applications since the 1950s.24,25
PFOSF-based substances such as perfluorooctanyl sulfonamides
including N-ethylperfluorooctane sulfonamide (N-EtFOSA), N-
ethyl perfluorooctane sulfonamidoethanol (N-EtFOSE), N-methyl
perfluorooctane sulfonamidoethanol (N-MeFOSE) can be directly
amenable to GC/MS analysis using electron ionization or chemical
ionization.26 Recently, Arsenault used 19F nuclear magnetic resonance
(19F NMR) spectroscopy to elucidate the structure of PFOSF
isomers by converting the analytes to sulfonamides with good
yield.27 Benzylamine was chosen as the key nucleophile to build
the SÀN bond.28 To contribute this knowledge to the trace
analysis of PFOSF, the objective of this study was to develop a
simple and sensitive LC/MS method upon the derivatization of
PFOSF with benzylamine.
’ EXPERIMENTAL SECTION
Chemicals and Standards. PFOSF (98%) was purchased
from Sigma-Aldrich (St. Louis, MO). PFOS (>98%) was
purchased from TCI Chemical (Shanghai, China). Triethyl-
amine (99%), anhydrous sodium sulfate, and benzylamine
(99%) were purchased from Acros Organics (Geel, Belgium).
Ultragrade dichloromethane was purchased from Duksan Pure
Chemicals (Gyungkido, Korea). HPLC grade acetonitrile was
obtained from Merck Co. (Darmstadt, Germany), and distilled
water was further purified by a Milli-Q purification system
(Millipore, Bedford, MA).
Sample Preparation for Stability Investigations of PFOSF.
PFOSF was diluted with acetonitrile to the concentration of
100 μg mLÀ1 as a stock solution. The solution was diluted with
tap water to achieve a final concentration of 20 ng mLÀ1. The
PFOSF samples were analyzed on days 0, 5, and 10 by LC/MS for
the purpose of stability examination. In order to investigate the
stability of PFOSF in water, PFOS standard working solutions
at eight calibration levels in the range of 0.5À50 ng mLÀ1 were
prepared by suitable dilutions of the PFOS stock solution with
tap water.
LC/MS Analysis and FTICRMS Analysis of BFOSA. An
Agilent 1100 series HPLC system (Agilent Technologies, Palo
Alto, CA) coupled to a Bruker Esquire 4000 ion trap mass
spectrometer (BrukerÀFranzen Analytik GmbH, Bremen,
Germany) with an ESI source was used for LC/MS analysis.
An Agilent extend C-18 column (2.1 mm  150 mm, 5 μm) was
used for the separation. Mobile phase consisted of water and
acetonitrile (25:75, v/v) at a flow rate of 0.2 mL minÀ1 with the
detection wavelength of 254 nm. A volume of 5 μL of sample was
injected for analysis. The ion source temperature was set at
250 °C, and the ESI needle voltage was set at 4.0 kV. Nitrogen
was used as the nebulizing gas at a pressure of 25 psi and the
drying gas at a flow rate of 8 L minÀ1. The effluent in the first 2.5
min was diverted to waste to minimize the contamination of the
ion source.
The accurate mass measurement on the molecular and frag-
ment ions of L-BFOSA was performed on an Apex III (7.0 T)
Fourier transform ion cyclotron resonance (FTICR) mass
spectrometer (Bruker, Billerica, MA) by infusing L-BFOSA in
Synthesis of Benzylperfluorooctane-1-Sulfonamide (BFOSA).
PFOSF (2.50 g, 4.98 mmol) was carefully added dropwise to a
vigorously stirred solution of benzylamine (3.43 g, 32.0 mmol) in
anhydrous dichloromethane (10 mL) and Et3N (2.45 g, 24.2 mmol)
at 0 °C. The reaction mixture was stirred at the temperature for 1 h
before letting it warm up to room temperature within 20 h. Then,
8 mL of aqueous HCl (10%) was added. The aqueous phase was
methanol into the FTICR MS source at a flow rate of 3 μL minÀ1
.
The precursor ion was generated in the negative ion mode by
using an ESI source. XMASS software, version 6.1.1, was used for
instrument control, data acquisition, and processing. The spray
voltage was 4.5 kV. The temperature of the capillary was 250 °C.
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Scheme 1. Synthesis of Benzylperfluorooctane-1-
sulfonamide
Nitrogen was used as the nebulizing and drying gases, and argon
was used as the collision gas.
Nuclear Magnetic Resonance Analysis of BFOSA. 1H NMR
and 13C NMR spectra of the produced BFOSA and L-BFOSA
were recorded on a Bruker Advance 500 NMR spectrometer
instrument with a QNP probe head at ambient temperature using
CDCl3 as the solvent. 19F NMR spectra of both L-BFOSA and
the produced BFOSA were recorded on a Bruker Avance DPX
400 (375.50 MHz) NMR spectrometer equipped with a Bruker
SEF 19F/1H dual probehead. The data were acquired on Silicon
Graphics O2 workstations using XWINNMR, version 2.1
(Bruker Analytik, GmbH, Germany).
Figure 1. SIM chromatogram of sulfonamide: (a) the produced BFO-
SA and (b) L-BFOSA.
environment including the aqueous environment for a certain
time period and thus result in environment pollution.
Benzylperfluorooctane-1-sulfonamide (BFOSA). Although
PFOSF is stable in water, the chemical is found to be reactive
with benzylamine to produce benzyl perfluorooctane sulfonam-
ide (Scheme 1). Triethylamine was used as a base to the catalytic
benzylamine reaction with PFOSF. It should be noted that the
commercial standard of PFOSF was actually a mixture of about
30% branch and 70% line PFOSF.34,35 Therefore, the produced
BFOSA was mixed amides including line and branch chain
isomers. The pure line amide (L-BFOSA) was separated from
the reaction product mixture for its structure identification.
’ RESULTS AND DISCUSSION
Stability of PFOSF in Water. It has been hypothesized that
PFOSF could potentially degrade to PFOS in the aqueous
environment.18,19 PFOS was proposed as the terminal transfor-
mation product for the stability study because it was extremely
stable. Thus, there have been significant concerns on the
transformation of PFOSF to PFOS under various environmental
conditions. In order to investigate the stability of PFOSF in
water, determination of PFOS in water samples with a certain
time period of PFOSF exposure was performed. Because PFOS
has been widely considered as the major degradation product of
PFOSF, the stability experiment on PFOSF was performed by
determining and comparing the PFOS levels in the control and
PFOSF-exposed water samples. A series of calibration standard
solutions of PFOS were prepared and analyzed by using LC/MS
for the investigation on the possibility of transformation of
PFOSF to PFOS. The analysis of PFOS was performed based
on the reported LC/MS method.29,30 PFOS showed good
linearity at the range from 0 to 50 ng mLÀ1 with r2 of 0.998.
The method demonstrated high sensitivity with the limit of
detection (LOD) of 0.05 ng mLÀ1 for the PFOS analysis. The
obtained results from LC/MS analysis of the stability experi-
ments indicated that the PFOS level did not increase after
PFOSF existed in tap water for 5 and 10 days at temperature
below 30 °C. PFOSF was also found to be stable in organic
solvents of dichloromethane and acetonitrile at room tempera-
ture. The obtained result of PFOSF stability agreed with the
data reported from previous studies demonstrating that
PFOSF was only slowly hydrolyzed in water. For example,
PFOSF is minimally hydrolyzed in water at 180 °C, even after
several days.31 It was reported that only partial hydrolysis of
short-chain sulfonyl fluoride such as difluoromethanesulfonyl
fluoride was observed after being in water for 4À5 h at 25 °C,
although the short-chain sulfonyl fluoride should theoretically
be more readily hydrolyzed than the long-chain sulfonyl
fluoride like PFOSF.32 Degradation of the short-chain sulfonyl
fluoride was found after its exposure in water for several days at
room temperature.33 Therefore, PFOSF might stay in the
1
Proton signal at δ4.48 in the H NMR spectrum (Supporting
Information, Figure S1) was obtained along with carbon signal at
δ48.9 in 13C NMR spectrum (Supporting Information, Figure
S2) showing a methylene group. Five protons at δ7.30À7.50 and
one at δ5.28 corresponded to benzyl and amine protons,
respectively. No obvious difference was observed between
1
L-BFOSA and the produced BFOSA product in H NMR and
13C NMR spectra. Only three signals in the range from À60 to
À80 in the 19F NMR spectrum of L-BFOSA (Supporting
Information, Figure S3) suggested the presence of just one
CF3 unit. No signal observed at about δÀ190 indicated that
there was no CF unit in the molecule. While the structure of
L-BFOSA was readily identified, many isomer signals could be
observed in the 19F NMR spectrum of the produced BFOSA
(Supporting Information, Figure S4). BFOSA is very stable for
the SÀN bond possessing double-bond character, which is
increased by the high electron-withdrawing effect of the per-
fluoride group.36,37
Most of sulfonamides are prepared from sulfonic acids by
initially converting them into sulfonyl chloride or fluoride and
then reacting with primary or secondary amines because sulfonic
acid is inactive for the direct amide production.38 Reaction of
PFOS with benzylamine was also investigated by comparing its
reaction with that of PFOSF under similar conditions. In the case
of PFOS, no amide was produced even after the 48 h reaction.
Therefore, the sulfonamide reaction was selective for PFOSF
analysis that was not interfered with by PFOS.
LC/MS Analysis of BFOSA. Full-scan ESI-MS analysis in the
negative ion mode was performed for the determination of the
produced BFOSA product. A total of 65% L-BFOSA was
detected in the amide product based on quantification with
L-BFOSA. To increase the sensitivity, selected ion monitoring
mode (SIM) was used for quantitative analysis of the produced
BFOSA by monitoring the [M À H]À ion at m/z 588. A typical
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Figure 2. MS/MS spectrum of deprotonated L-BFOSA.
SIM chromatogram of the produced BFOSA and L-BFOSA is
shown in Figure 1. Three peaks of the produced BFOSA
including L-BFOSA were detected in the corresponding chro-
matograms, indicating that all PFOSF isomers mixture could be
derivatized with benzylamine and detected by LC/MS.
instrument was found when the derivatization reaction was
stopped.
Validation of the Method and Application. A series of
calibration standard solutions of the produced BFOSA were
prepared and analyzed to evaluate the dynamic linear response
for the analysis with the SIM mode. BFOSA showed good
linearity in the range from 2 to 80 ng mLÀ1 (sum (Σ) amide)
with r2 > 0.994. The detection limit of the derivatization product
as defined at S/N = 3 was 2.5 pg with the injection of 5 μL. It
should be pointed out that the method of combining derivatiza-
tion and LC/MS analysis provided a good detection signal when
the PFOSF concentration was 1 ng mLÀ1 in dichloromethane.
To assess the quantitative reproducibility, replicate analysis (n =
6) of 10 ng mLÀ1 PFOSF was carried out. The obtained relative
standard deviation (RSD) was 10.8%.
In addition to the analysis of PFOSF by using LC/MS after its
derivatization, the existing aromatic group in the derivatization
product of PFOSF also allowed detection with UV due to the
introduction of a chromophore. The HPLCÀUV determination
at the wavelength of 254 nm showed good linearity with r2 of
0.990 for the concentration range from 20 to 100 μg mLÀ1 (sum
(Σ) amide), with the detection limit of 25 ng when the injection
volume was 5 μL.
In order to assess recovery of sample preparation, the distilled
water and soil were spiked with a known amount of PFOSF,
respectively. The sample was extracted with dichloromethane
that was also the reaction solvent. The extract was then analyzed
by using the developed derivatization LC/MS method. The
obtained recovery ranged from 55.4% to 128% for water and
51% to 109% for soil analysis. The sample extraction required
only the one-step liquidÀliquid extraction (LLE) or liquidÀsolid
extraction (LSE) by omitting the filtration and removal of solvent
by vacuum, the probable losses of the analyte from adsorption on
the sample vessels and possible vaporization were minimized as
much as possible, particularly considering the volatility of
PFOSF. In addition, background interference from the solvent
and glassware might be eliminated after the derivatization.
Analysis of the product ion spectrum of L-BFOSA indicated
that the precursor ion was fragmented with two fragmentation
routes (Figure 2). One route involved cleavage of the SÀC bond
and yielded the product ion at m/z 419 or cleavage of the CÀC
bond to yield a series of product ions at m/z 269, 219, 169. The
second route involved loss of a molecule of SO2 first and then lost
two molecules of HF, yielding the product ion at m/z 484. The
production of ions at m/z 464, 444, 424, 404, and 384 suggested
the consequent neutral losses of HF. Therefore seven molecules
of HF extruded from the precursor ion could be observed.
Because no proton existed in perfluorooctane unit, the loss of
HF might be a result of the proton transfer or rearrangement
from the benzyl or methylene unit. The accurate masses of both
the molecular ion and fragment ions were measured by using
FTICR/MS/MS. The most probable elemental compositions of
the ions were obtained with a high degree of confidence. The
relative errors between experimental masses andtheoreticalmasses
were within (1.08 ppm (Supporting Information, Table S1).
Optimization of PFOSF Trace Derivatization. Application of
different amines for the derivatization reaction, including ben-
zylamine, 4-methylaniline, 4-nitroaniline, 4-hydroxyaniline, and
2-hydroxyaniline as derivatization reagents, was investigated and
compared. As a result, the anilines were found not effective due to
the decreased electronegative character at the nitrogen. Benzyl-
amine was selected as the derivatization regent for its proper
polarity and good reaction yield. It was found that the excess
concentration of benzylamine was critical for the derivatization
process. Particularly for the reaction with a trace level of PFOSF,
a higher concentration of benzylamine benefited the reaction and
thus provided a better reaction yield.
Although the derivatization method has been used for quanti-
tative determination of some other compounds with the combi-
nation of GC/MS analysis, the reaction yield was often not
evaluated. This is because many derivatization products were not
suitable for being separated and purified. In this study, the
produced BFOSA was used to generate the calibration curve
for the quantitative analysis of the PFOSF derivatization prod-
ucts. The derivatization of PFOSF at concentrations of 2.0, 5.0,
10.0, and 20.0 ng mLÀ1 were investigated. Good reaction yield
was achieved at the range from 72% to 85%. As a control, the
derivatization of a blank sample was investigated. No background
interference such as inherent contamination from the solvent and
’ CONCLUSIONS
Derivatization of PFOSF with benzylamine allowed the quan-
titative analysis of PFOSF by using LC/MS because the pro-
duced benzyl perfluorooctane sulfonamide could be ionized by
ESI-MS and detected with good sensitivity. The developed
derivatization LC/MS method is novel, rapid, simple, and
reproducible for the indirect analysis of PFOSF through the
determination of the derivatization product. Furthermore, the
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LETTER
derivatization procedure combined with LLE and LSE en-
abled the analysis of PFOSF in water and soil samples.
Because of the specific derivatization of PFOSF with benzyl-
amine, the developed method might overcome the universal
interference problem of PFOS that might coexist in the
sample and sample preparation system. The obtained results
from the stability tests demonstrated that PFOSF was stable
in water, and thus it is possible to exist in the global
environment. The developed method may be applied for
the urgently needed investigations on environmental fate,
degradation, and transformation of PFOSF.
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’ AUTHOR INFORMATION
Corresponding Author
*Phone: (852) 3411-7070. Fax: (852) 3411-7348. E-mail: zwcai@
hkbu.edu.hk.
’ ACKNOWLEDGMENT
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The authors gratefully acknowledge financial support from the
Research Grants Council of Hong Kong (Grant HKBU200209)
and the National Natural Science Foundation of China (Grant
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