Suspect and Nontarget Screening of Per- and Polyfluoroalkyl

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Suspect and Nontarget Screening of Per- and Polyfluoroalkyl Substances in Wastewater from a Fluorochemical Manufacturing Park Yi Wang, Nanyang Yu, xiaobin zhu, Huiwei Guo, Jianguo Jiang, Xuebing wang, Wei Shi, Jichun Wu, Hongxia Yu, and Si Wei Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b03030 • Publication Date (Web): 13 Sep 2018 Downloaded from http://pubs.acs.org on September 14, 2018

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Environmental Science & Technology

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Suspect and Nontarget Screening of Per- and Polyfluoroalkyl Substances in

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Wastewater from a Fluorochemical Manufacturing Park

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† Yi Wang#, , Nanyang Yu#,‡, Xiaobin Zhu†,*, Huiwei Guo‡, Jianguo Jiang†, Xuebing

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Wang‡, Wei Shi‡, Jichun Wu†, Hongxia Yu‡, Si Wei‡,*

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†

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School of Earth Sciences and Engineering, Nanjing University, Nanjing, People's

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Republic of China

MOE Key Laboratory of Surficial Geochemistry, Department of Hydrosciences,

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‡

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Environment, Nanjing University, Nanjing, People’s Republic of China

State Key Laboratory of Pollution Control and Resource Reuse, School of the

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#

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authors.

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*

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Phone: +86 25 8968 0356; fax: +86 25 8968 0356; e-mail: [email protected] (S.W.).

These authors contributed equally to this work and should be considered co-first

Phone: +86 25 8968 0356; fax: +86 25 8968 0356; e-mail: [email protected] (X.Z.).

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ACS Paragon Plus Environment


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Abstract:

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Although per- and polyfluoroalkyl substances (PFASs) have always been a key

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issue in the global environmental field, there are still a lot of undiscovered PFASs in

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environment due to new PFAS alternatives developed by manufacturers. Wastewater

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treatment plants (WWTPs), as one of the sources for PFASs, are the important process

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of releasing new PFASs into the environment. In this study, suspect screening and

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PFAS homologue analysis with quadrupole time-of-flight tandem mass spectrometry

30

were used to discover PFASs in wastewater from a WWTP near Yangtze River.

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Fifteen classes with 90 PFASs were identified, including 12 legacy PFASs (2 classes),

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41 previously reported PFASs (7 classes), and 37 new PFASs (6 classes), and 18 of

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these PFASs were also detected in the nearby Yangtze River. Only one PFASs class

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were removed through treatment processes (Fold Change < 1/6). Conversely, four

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PFASs classes increased through treatment processes (Fold Change > 6), which could

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be the transformation products of PFAS precusors. These results implied that most

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discovered PFASs were also not effectively removed in the WWTP. Chlorine

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substituted perfluoroalkyl carboxylates (Cl-PFCAs) as the main component of

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wastewater were detected only in downstream, meaning that Cl-PFCAs in

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downstream possibly originated from the WWTP.

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TOC art

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47

Introduction

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Per- and polyfluoroalkyl substances (PFASs) are relatively new contaminants

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and contain the CnF2n+1 group.1 They are widely used in the industrial fields of

50

papermaking2, leather3, textile4, and fire-fighting foams5-6 owing to their unique

51

hydrophobic and oleophobic properties. However, their extremely high C-F bond

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energy can make them stable and persistent in the environment, and thus, PFASs have

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been extensively detected in water7-8, organisms6, 9, air10, and sludge11. In particular,

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perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) as two

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typical PFASs have strong persistence, bioaccumulation, and potential toxicity, which

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have drawn widespread attention.12 As several long-chain PFASs have been banned

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from production and use,13-14 short-chain and new PFASs are used as alternatives.

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More than 3000 PFASs are, or have been, on the global market, but most research and

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regulations continue to focus on a limited selection.15 In response to the global

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fluorine chemical problem, China has also taken a series of measures such as the

61

project “Reduction and Phase-out of PFOS in Priority Sectors in China” supported by

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the Global Environment Facility (GEF).16 However, current measures on PFASs are

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limited to existing PFASs.

64

High-resolution mass spectrometry (HRMS) such as quadrupole time-of-flight

65

mass spectrometry (QTOF-MS) with high resolution (i.e., RP ≥ 10,000), which

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provides accurate mass, isotopic distribution, and MS/MS spectra, play an important

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role in the identification of unknown or emerging pollutants. HRMS has been applied

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to identified emerging PFASs in aqueous film forming foams (AFFF)5, 17-19 and the


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serum of firefighters6, and a lot of novel non-ionic, cationic, zwitterionic, and anionic

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PFASs were discovered in AFFF. Meanwhile, AFFF was an important source of

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PFASs for wastewater20. Therefore, these research implied many unknown or

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emerging PFASs could enter our environment.

73

Actually, Lin21 have summarized that known PFASs accounted for less than 40%

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in the extractable organic fluorine (EOF) components of environmental matrices,

75

including water, soil, and sediment, indicating the presence of a large number of

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unknown organic fluorides in the environment. Wastewater treatment plants

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(WWTPs), as a link between society and the environment, are considered as an

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important point source for PFASs.22-23 Most treated effluents are discharged directly to

79

nearby rivers or coastal water with exposure to drinking water or seafood.

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In the past, research on PFASs in wastewater mainly focused on the sources and

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distribution of PFOS, PFOA,24-26 and other legacy PFASs.27-30 Recently, several

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papers on the removal efficiency of PFASs in WWTPs have found that most of the

83

PFASs were not effectively removed or even increased through traditional treatment

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processes.31-32 Based on 12 previous studies, Arvaniti and Stasinakis33 concluded that

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PFASs were only removed through activated carbon, nanofiltration, reverse osmosis,

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or advanced oxidation and reduction processes.

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Current study on unknown or emerging PFASs in wastewater were limited.

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Dauchy et al27 measured 51 PFASs in WWTPs but found that the explained

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absorbable organic fluorine (AOF) of the effluent could not be more than 52% and

90

was lower than that of the influent. Thus, the effluent contained a large amount of



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unidentified organic fluorine, which were most likely produced during wastewater

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treatment or sludge treatment. Recently, several studies have used HRMS to identify

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emerging PFASs in wastewater or impacted rivers.7,

94

polyfluorinated alternatives have been detected, and their composition and structure

95

are becoming increasingly more complicated. The emphasis of this study lies in

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identification of emerging PFASs in wastewater and the assessment of the fate and

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removal efficiency of emerging PFASs in wastewater treatment processes using a

98

retrospective PFASs screening with QTOF HRMS. Meanwhile, the detected PFASs

99

from the WWTP were analyzed in the surrounding river with suspect screening to

100

34-36

Many emerging

indicate the impacts from WWTP.

101 102

Material and Methods

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Chemicals and Reagents

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Details regarding the authentic standards and reagents used in this study are

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shown in Table S1. All solvents and reagents used were HPLC grade. Water used for

106

mobile phase and procedural blank was LCMS grade. Additional homologues were

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checked for all standards in powders, and the percentage of other homologues was

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below 0.6%37.

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Sample Collection and Preparation

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Water samples were collected in 2011 from one of the largest fluorochemical

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industrial park in China, which is located in Changshu, Jiangsu Province near the

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Yangtze River. Influent and effluent samples were collected by peristaltic pump for 4


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hours from the WWTP of the fluorochemical industrial park. Three water samples

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each were collected from downstream of the Yangtze River near the WWTP and the

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Yangtze River in the Nanjing section in 2011 and 2013, respectively (Figure S1).

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Detailed information is presented in Table S2.

117

The samples were stored in 1 L polypropylene bottles and shipped to the

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laboratory at 4 °C prior to analysis and were extracted within 4 weeks. The bottle was

119

shaken to mix water sample, and then 250 ml influent and 500 ml effluent were

120

separately used for solid-phase extraction. Oasis MAX cartridge (6 cc, 500 mg,

121

Waters, USA) preconditioned with 2% NH4OH in methanol, methanol, and water.

122

Oasis MCX cartridge (6 cc, 150 mg, Waters, USA) preconditioned with 2% HCOOH

123

in methanol, methanol, and water. Oasis HLB cartridge (6 cc, 500 mg, Waters, USA)

124

preconditioned with n-hexane, dichloromethane, methanol, and water. The three

125

cartridges were connected with polypropylene adapters to enrich unknown PFASs as

126

much as possible. Oasis MAX cartridge, Oasis MCX cartridge, and Oasis HLB

127

cartridge were eluted by 10mL of 2% HCOOH in methanol, 10mL of 2% NH4OH in

128

methanol, and 6mL of methanol, respectively. The eluent was combined and

129

concentrated to 500 µL under nitrogen, and then centrifugated at 6000 rpm for 5 min.

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Finally, 100 µL of the concentrated supernatant was filled in a polypropylene vial and

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stored at -20°C before the QTOF-MS analysis.

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River water were extracted by previous reported method38. Briefly, 1000 mL

133

water samples were extracted by Oasis WAX cartridge (6 cc, 150 mg, Waters, USA)

134

preconditioned with 0.1% NH4OH in methanol, methanol, and water. The cartridge



135

was washed with ammonium acetate buffer (25mM, pH 4) and methanol. PFASs were

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eluted with 4mL of 0.1% NH4OH in methanol. The eluent was concentrated to 500

137

µL under nitrogen. The concentrate transferred into a polypropylene vial and stored at

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-20°C before the QTOF-MS analysis.

139

Instrumental Analysis.

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High performance liquid chromatography (HPLC; Infinity 1260, Agilent

141

Technologies, Waldbronn, Germany) was used to separate samples on the BEH C18

142

column (2.1 mm × 50 mm, 2.5 µm, Waters, USA) with 2 mM ammonium acetate, 5%

143

acetonitrile in water and methanol. Mobile phase gradient elution conditions are

144

shown in Table S3. The high-resolution hybrid QTOF mass spectrometer (Triple TOF

145

5600, AB SCIEX, Foster City, CA, USA) was operated with a negative electrospray

146

ionization (ESI-) source to collect QTOF-MS data under the information dependent

147

analysis mode (resolution ~30000), which included 1 TOF-MS scan and 20 MS/MS

148

high-resolution scans in one cycle. Detailed QTOF parameters are shown in

149

supporting information.

150

Quality Control and Quality Assurance

151

The procedural blank sample was processed with water, which was used to

152

deduct blank contamination during the data analysis. The instrument was

153

automatically calibrated every 5 sample injections using calibration solution delivered

154

via a calibration delivery system to check the mass accuracy of instrument (< 5 ppm).

155

To test the sensitivity of the instrument analysis, four different levels of known PFAS

156

standard solutions (0.1 µg/L, 0.5 µg/L, 1 µg/L, 5 µg/L) were used for verification,


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which contained three perfluoroalkyl sulfonates (PFSAs), nine perfluoroalkyl

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carboxylates (PFCAs), and two polyfluoroalkyl phosphoric acid diesters (diPAPs)

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(Table S4). The procedural recovery sample was spiked 0.5 ng known PFAS

160

standards (1 ng/L each PFAS in water) to check the recovery of method. The variation

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of intensity between measurements was evaluated by the triplicate analysis of the

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influent sample (Figure S2). The matrix effects of influent and effluent were

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evaluated by the intensity of internal standard in samples and standard solution (Table

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S5).

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Suspect screening and nontarget strategy.

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Firstly, all samples were scanned with the PFAS suspect list. The PFAS suspect

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list contains three parts: legacy PFASs, known PFASs, and newly reported PFASs in

168

recent years.5-7,34-36,39 In addition, one PFASs list on the US EPA CompTox Chemistry

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Dashboard (PFASTRIER is a compilation of PFAS kindly provided by Xenia Trier,

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David

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https://comptox.epa.gov/dashboard/chemical_lists/pfastrier)

172

screening.40 The suspect screening methods were adopted from Barzen-Hanson et al.5

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The peaks of suspects were picked by the exact mass within 0.01Da. Positive hits

174

were selected by (a) signal to noise ratio (S/N) greater than 3, (b) intensity greater

175

than 1000, (c) an accurate mass error less than 5 ppm error, and (d) isotope ratio

176

difference less than 10%. The structure of positive hits was confirmed using the mass

177

spectra from literature and database (database from AB Sciex and MassBank

178

(www.massbank.eu)).

Lunderberg,

Graham

Peaslee,

Zhanyun


Wang was

and also

colleagues, used

for


179

For nontarget analysis, all peaks were extracted from raw data using the function

180

“Enhance peak find” in Peakview 1.2 (AB Sciex) and the following parameters were

181

set for initial filtering: 1) S/N greater than 3; 2) intensity greater than 1000; 3)

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approximate LC peak width of 10 s and chemical noise intensity multiplier of 1.5. The

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peak was proceeded further with an intensity higher than ten times the intensity of the

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corresponding peak from the procedural blank. The extracted peak list included the

185

mass, retention time (RT), and intensity for each peak, and this list was used to find

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potential PFAS homologues with a mass difference in CF2 (49.99681 Da) or CH2CF2

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(64.01246 Da) unit by MATLAB scripts. CF2 and CH2CF2 were the repeated unit for

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the industrial synthesis of PFAS homologues. The nontarget screening process is

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presented in Figure S3. Each series of homologues was separately checked with

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extracted ion chromatogram (XIC) and RT, and a good peak shape and an ascending

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trend of mass vs. RT should be observed. Finally, a series of candidate homologues

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were picked up for further identification.

193

The molecular formula was determined by the “Formula Finder” function in

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PeakView® 1.2 based on accurate mass with less than 5 ppm error, isotope ratio

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difference less than 10%, and fragments in MS/MS spectrum with less than 5 mDa

196

error (Details on molecular formula calculation parameters in supporting information).

197

The structure was predicted using MS/MS fragments with less than 5 mDa error5, as

198

well as by referring to literature, mass spectral database (database from AB Sciex and

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MassBank (www.massbank.eu)), and characteristic fragments. If there were several

200

available MS/MS spectra, the referenced MS/MS spectra was selected from literature


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and database based on the similar acquired condition (instrument type, collision

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energy, ion mode). For the database from AB Sciex, the PeakView can comparison

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two MS/MS spectra and calculate the match score. For the other MS/MS spectra, we

204

conducted a visual comparison. An adjusted Kendrick mass defect plot is shown to

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reveal potential homologue PFASs using the equation by Myers et al.41 To make the

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analysis more comparable, we divided PFASs screening results into five different

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confidence levels according to Schymanski et al.42 who validated a method on

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dividing the results of high-resolution screening based on the abundance of evidence.

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For level1, the molecular structure was determined by reference standards. For

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level2a, the molecular structure was determined by matching with literature database.

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For level2b, the structure was determined by diagnostic experience evidence. For

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level3, the location of substituents was not clear and isomers existed. Only PFASs

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with level 3 and above were summarized and reported.

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For water samples from Yangtze River, the suspect screening was conducted with

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all identified PFASs with level 3 and above from wastewater samples. The positive

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hits in water samples were confirmed by (a) signal to noise ratio (S/N) greater than 3,

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(b) intensity greater than 1000, (c) an accurate mass error less than 5 ppm error, (d)

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isotope ratio difference less than 10%, and (e) the retention time error less than 1 min.

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If the MS/MS spectra was acquired, a qualitative fragment confirmation was also

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compared with the fragments from the MS/MS spectra acquired in wastewater

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samples.

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Data analysis.



223

In order to explore the fate and removal efficiency of PFASs through treatment

224

processes of the WWPT, the fold changes (FCs) of PFASs between the influent and

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the effluent were calculated with the intensity of peak in Microsoft Office Excel 2010.

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The value of FCs indicated that PFASs were removed (FCs < 1) or increased (FCs > 1)

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through treatment processes. The undetected PFASs were assigned half of the

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intensity condition for PFAS screening (peak intensity = 500) to avoid missing values

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in the statistical analysis.

230 231

RESULTS AND DISCUSSION

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Quality Control and Quality Assurance

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The results show that all the added PFASs could be identified at a concentration

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of 5 ppb, and several PFASs were detected at 0.1 ppb using the screening methods

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(Table S4). The procedural recovery of PFAS standards was ranged from 78% to

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110% (Table S4). For the triplicate analysis of the influent sample, we found 89.6%

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of peaks with a relative deviation of intensity lower than 20% and 95.9% of peaks

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with a relative deviation of intensity lower than 30% (Figure S2). The matrix effect

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of influent and effluent ranged from 0.83 to 1.68 and from 0.44 to 4.51, respectively

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(Table S5). Therefore, the matrix effect was an important factor to affect the intensity

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of PFASs in samples.

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Discovery of legacy and emerging PFASs

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According to the suspect and nontarget methods described above, 15 classes (90

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homologs) of PFASs with level 3 and above were identified from the wastewater. All


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results are provided in Figure 1, Table 1, Table S6 and Table S7. The detected

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compounds included legacy PFASs, reported PFASs, and newly discovered PFASs.

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The fragments and neutral loss of newly identified PFASs were summarized in Table

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S8. Except for class 5 using CF2CH2 strategy, the other 14 classes using CF2 strategy

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showed 14 horizontal lines in the CF2 adjusted mass defect plot (Figure 1B), which

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implied these peaks in the same line were homologues with CF2 units. The ESI

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positive mode was also analyzed, while only PFASs with level 4 or level 5 were

252

identified (Table S9).

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Legacy PFASs

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Class 1 and 2 were PFSAs and PFCAs. Only PFOS and eleven PFCAs were

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identified. The molecular formula error ranged from -0.1 to 3.4 ppm except for m/z

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162.9833 (C3F5O2-) with 5.6 ppm. We compared MS/MS spectra and retention times

257

between the samples and standards under the same instrument conditions. Except for

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C3-C4 and C15 PFCAs, other eight perfluoroalkyl carboxylates and PFOS were

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confirmed with level 1 by standards (ΔRT < 1min). The list is provided in Table S10.

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Discovery of per- or poly-fluorinated monocarboxylate (PFmonoCAs)

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Class 3. A total of 14 homologues were identified as hydro-substituted PFCAs

262

(H-PFCAs) with a mass error of -4.0 to 1.8 ppm, except for m/z 194.9897 (C4F6HO2-)

263

with 5.5 ppm. In the MS/MS spectrum, [M-64]- fragment with errors of -1.1 to 1.8

264

mDa corresponding to neutral losses of HF (20 Da) and CO2 (44 Da) was found for all

265

masses in this class. Compared with the reported MS/MS spectra of H-PFCAs34, three

266

reported fragments (-1.4-0.24 mDa) were confirmed, and m/z 218.9840 (C3F7-, -2.2



267

mDa), m/z 230.9846 (C5F9-, -1.6 mDa), and m/z 280.9818 (C6F11-, -1.2 mDa) were

268

additionally detected in the observed MS/MS spectra in this study (Figure S4). After

269

the loss of HF, CnF2n-1- fragments were formed and the attached C atoms form a

270

double bond. Furthermore, CnF2n+1- fragments, which formed by the breaking of the

271

fluorocarbon chain, indicates that the H atom is not at the end of the fluorocarbon

272

chain. Washington et al predicted that 2H-PFOA is a possible degradation product of

273

PFOA and speculated that the H atom was in α position according to a soil

274

experiment.43 However, we still attributed class 3 to level 3 because of the uncertainty

275

in the substituted position of the hydrogen atom. Although H-PFCAs were also

276

detected in the procedural blank, resulting from the LCMS water and/or HPLC system,

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the intensity of H-PFCAs in samples was 10 times higher than that in the procedural

278

blank. H-PFCAs have been detected in a Chinese WWTP34 and downstream of a

279

manufacturing plant in Alabama, US,7.

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Class 4. The molecular formula of this class is CnF2n-3O3- (-2.4-1.4 ppm).

281

[M-44]- and [M-110]- fragments, which formed by the neutral loss of CO2 (-4.6-0.89

282

mDa) and C2F2O3 (-1.57--0.78 mDa), were found in the MS/MS spectrum. These two

283

fragments indicated that the structure of this class contained a carboxyl group and a

284

C−O bond. Furthermore, CnF2n-1- fragments indicate the presence of C=C bonds.

285

Therefore, this class was identified as unsaturated polyfluoroalkyl ether carboxylates.

286

The MS/MS spectrum of m/z 390.9638 (C8F13O3-) was almost the same with that of

287

Barzen-Hanson et al who conducted research on groundwater research contaminated

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by aqueous film-forming foam5 (Figure S5). Considering the position of the double


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bond was uncertainty, three homologues were identified as level 3 in this class.

290

Class 5. Using the CF2CH2 strategy, we found a class of polyfluorocarboxylic

291

acids C2nH2nF2nO2 (-3.9-2.9 ppm), and observed a mass loss of 64 Da (CO2HF,

292

-1.1-0.86 mDa) and a series loss of 20 Da (HF, -0.17-0.93 mDa) in the MS/MS

293

spectrum. The MS/MS fragment spectra of the class were similar to those described

294

by GebbinK et al39 and Newton et al7 (Figure S6). Therefore, five homologues were

295

identified as level 2a by the reported MS/MS spectrum in this class. This class was

296

detected in a river near a manufacturing plant in Decatur, Alabama for the first time

297

by Newton et al, who presumed this class to be products or byproducts of a

298

manufacturing process that uses 1,1-difluoroethene.7 We also found a historical

299

production record of 1,1-difluoroethene44 and polyvinylidene difluoride45 in the

300

fluorochemical plant, supporting the hypothesis of Newton et al.

301

Class 6. CnF2n-1- and [M-44]- fragment ions (-2.6-4.1 mDa) were detected in the

302

MS/MS spectra of class 6, by which unsaturated perfluorocarboxylates (UPFCAs,

303

CnF2n-3O2- -1.1--0.42 ppm) were speculated for this class. The parent ions of m/z

304

524.9598 (C11F19O2- , -0.42 ppm) and 574.9565 (C12F21O2-, -0.59 ppm) were

305

congeners with the highest intensity. In their MS/MS spectrum, two series of CnF2n+1-

306

(-0.58--1.4 mDa) and CnF2n-1- (-2.6-4.1 mDa) fragments were detected, and the

307

maximum CnF2n+1- fragment (C3F7- for C11F19O2-, -1.4 mDa; C4F9- for C12F21O2-, -0.58

308

mDa) and the minimum CnF2n-1- fragment (C5F9- for C11F19O2-, 4.1 mDa; C6F11- for

309

C12F21O2-, -0.98 mDa) could identify the position of the double bond. Thus, the

310

position of the double bond between 7C and 8C was inferred for C11F19O2- and



311

C12F21O2-, which were identified as level 2b based on the MS/MS spectrum (Figure

312

S7). For the remaining homologues, the position of the double bond could not be

313

determined. Therefore, they were tentatively considered as level 3.

314

Class 7. [M-44]-, [M-78]-, and [M-94]- fragments were detected in the MS/MS

315

spectrum of this class, which implied the neutral loss of CO2 (-1.6-3.6 mDa),

316

C2H3FO2 (-3.0-2.6 mDa), and C2H3FO3 (-3.2--0.62 mDa) occurred in the collision

317

cell (Figure 2). Based on the [M-44]- fragment, a carboxyl group was a substructure

318

for this class. While, an ether bond was also in the structure for this class, and [M-78]-

319

and [M-94]- fragments formed by the breaking of two C-O single bonds. A series of

320

CnF2n-3- fragments indicated the existence of a fluorinated carbon chain for these

321

homologues. Thus, combined with the fragments in MS/MS spectrum, the formula for

322

this class was identified as CnH3F2n-6O3- (-2.6-0.46 ppm), which implied two double

323

bonds in the structure. One double bond was located in the carboxyl group, and the

324

other one double bond was located in the carbon chain. The [M-94]- fragment was the

325

maximum CnF2n-3- fragments and contained two double bonds, thus a neutral loss of

326

HF and the formation of a C=C double bond occurred in the process of

327

collision-induced dissociation. Therefore, [M-78]-, and [M-94]- fragments were

328

formed by two steps: one is the neutral loss of HF, and the other one is the cleavage of

329

the C-O ether bond. Finally, the structure of this class was identified as

330

Cn-2HF2n-6OCH2COO-. Due to the uncertainty of the position of C=C double bond and

331

the hydro-substituted position, the confidence level was assign to level 3.

332

Class 8. [M-78]-, [M-98]-, and [M-114]- fragments were detected in the MS/MS


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spectrum of this class, which implied the neutral loss of C2H3FO2 (-0.71-1.9 mDa),

334

C2H4F2O2 (1.2-2.9 mDa), and C2H4F2O3 (-3.4--0.25 mDa) occurred in the collision

335

cell (Figure S8). A series of CnF2n-3- fragments (-2.3--0.22 mDa) were also detected

336

in the MS/MS spectrum of this class, which indicated the existence of a fluorinated

337

carbon chain for these homologues. Combined with the fragments in MS/MS

338

spectrum, the formula for this class was identified as CnH4F2n-4O3- (-4.0-2.3 ppm),

339

which implied one double bond in the structure. Although [M-44]- fragment was not

340

detected in the MS/MS spectrum of this class, this fragment was formed by in-source

341

collision induced dissociation and detected in the TOF-MS scan with the same

342

retention time and peak shape (Figure S7). Addition, we did not find other ions with

343

the same retention time (< 0.1 min) and peak shape (multi peak). Thus, a carboxyl

344

group was a substructure for this class and the double bond was located in the

345

carboxyl group. Based on [M-98]- and [M-114]- fragments, an ether bond was also in

346

the structure for this class. The [M-114]- fragment was the maximum CnF2n-3-

347

fragments and contained two double bonds, which implied neutral loss of two

348

molecular of HF and the formation of two C=C double bonds occurred in the process

349

of collision-induced dissociation. Therefore, similar to class 7, [M-78]-, [M-98]-, and

350

[M-114]- fragments were formed by two processes (the neutral loss of HF and the

351

cleavage of the C-O ether bond). Finally, the structure of this class was identified as

352

Cn-2H2F2n-5OCH2COO-. Due to the uncertainty of the hydro-substituted position, the

353

confidence level was assign to level 3.

354

Class 9. [M-44]- fragment was detected in the MS/MS spectrum of this class,



355

which implied a neutral loss of CO2 (0.07-1.1 mDa). Based on the [M-44]- fragment,

356

a carboxyl group was a substructure for this class. A series of CnF2n-3- fragments

357

(-0.77-1.0 mDa) indicated the existence of a fluorinated carbon chain for these

358

homologues. Thus, combined with the fragments in MS/MS spectrum, the formula for

359

this class was identified as CnF2n-5O2- (-1.81-7.2 ppm). Therefore, this class was

360

identified as unsaturated perfluorocarboxylates with two C=C double bonds. However,

361

the position of the C=C double bond was not confirmed. Thus, this class was

362

identified as level 3. The MS/MS spectrum of C6F7O2- is shown in Figure S9.

363

Discovery of perfluorinated dicarboxylate

364

Class 10. [M-108]- fragment was detected in the MS/MS spectrum of this class,

365

which implied that a neutral loss of C2HFO4 (two molecules of CO2 and one molecule

366

of HF, -0.49-3.3 mDa) occurred in the collision cell and the structure of this class

367

contained two carboxyl groups (Figure S10A and S10C). Fragments CnF2n+1

368

(-1.2-0.8 mDa) and CnF2n−1 (-3.0-0.9 mDa) were also detected in the spectrum, which

369

implied a fluorinated carbon chain substructure. Combined with fragments in MS/MS

370

spectrum, this class was identified as perfluoroalkyl dicarboxylates (PFdiCAs)

371

(CnHF2n-4O4-, 0.4-3.5ppm) with level 2b. These fragment ions and neutral loss

372

reaction were also observed in the MS/MS spectrum of standards (Figure S10B and

373

S10D). Perfluorodecane dicarboxylate and perfluorododecane dicarboxylate were

374

further confirmed as level 1 by standards (ΔRT = 0.04–0.08 min, match score of

375

MS/MS spectra = 94.6-96.3).

376

Discovery of perfluorinated ethers/alcohols (PFE/As)


Page 18 of 44

Page 19 of 44


377

Class 11. Molecular formulas C3F7O- and C4F9O- were easily identified based on

378

their mass and isotopic distribution with 3.4 and 4.5 ppm. The fragment 118.9925

379

(C2F5-, 0.50 ppm) in the MS/MS spectrum of C3F7O- indicates oxygen atom on the

380

end group (Figure S11). The MS/MS spectrum of C4F9O- containing CF3- (1.54 mDa),

381

CF3O- (-0.07 mDa), C2F5O- (-1.28 mDa), and C3F7O- (-1.09 mDa) fragments (Figure

382

S11) showed a straight chain structure, and therefore, the position of oxygen atom

383

should be at the terminal. Thus, this class was identified as perfluoroalkyl alcohols

384

(PFAs) with level 2b. Yan46 found that the m/z 234.9811 C4F9O- was a possible

385

intermediate compound of degradation of PFOA under photolysis with isopropanol

386

condition.

387

Class 12. We observed that the [M-66]- fragment (-1.58-4.72 mDa),

388

corresponding to mass losses CF2O, in the MS/MS spectrum of each peak, and thus,

389

the alcohol or ether bond is located on the terminal (Figure S12). A series of CnF2n+1

390

(0.13-0.34 mDa) and CnF2n-1 (-0.78--0.58 mDa) fragments were also detected in the

391

MS/MS spectrum, indicated a fluorinated carbon chain structure. Based on the exact

392

mass, isotope distribution, and the fragments, the molecular formula of this class was

393

calculated as CnF2n-1O- (-1.4-2.6 ppm) except for m/z 146.9886 (C3F5O-) with a

394

slightly high mass error (7.9 ppm). The molecular formula indicated a double bond in

395

the carbon chain. However, the position of the C=C double bond was uncertainty. The

396

maximum CnF2n+1- fragment and the minimum CnF2n-1- fragment were not matched

397

(Figure S11), which could indicate a mixture of isomers with different position of the

398

C=C double bond in the same peak. Addition, the predicted pKa of unsaturated



Page 20 of 44

399

perfluoroalkyl alcohols (UPFAs) ranged from 1.2 to 5.3 with the online tool in

400

ChemAxon (https://chemaxon.com/), which supported the negative ionization mode

401

for UPFAs. Therefore, this class was identified as UPFAs with level 3.

402

Discovery

403

ethers/alcohols

of chlorine substituted

perfluoroalkyl

carboxylates/sulfonates/

404

Class13. This is a series of chlorine substituted perfluoroalkyl carboxylates

405

(Cl-PFCAs); The presence of the [M-44]- fragment (-2.5-4.4 mDa) indicates a class of

406

carboxylic acid. The isotope distribution ([M]−: [M + 2]−≈3:1) and Cl- fragment (3.4 to

407

5.9 mDa) indicate the presence of one Cl atom, then the molecular formulae of 11

408

homologues was obtained as CnF2n-2ClO2- (-3.2-2.8 ppm) were found. Despite the

409

lack of abundant meaningful product ions, the MS/MS spectrum of the product ion

410

484.9416 (C9F18Cl-, 0.94 mDa) in C10F18O2Cl- were confirmed by the reported

411

MS/MS spectrum by Liu et al.34 (Figure S13). In addition, the observed CnF2n+1-

412

indicated the location of Cl substitution was not the ω position of the fluorinated

413

carbon chain. While the location of Cl substitution was still uncertain. Therefore, this

414

class was identified as level 3.

415

Class 14. This class contains chlorine substituted perfluoroalkyl sulfonates

416

(Cl-PFSAs), including Cl-PFOS and Cl-PFHpS. Firstly, the isotope distribution ([M]−:

417

[M+2]−≈3:1) indicates the presence of chlorine atom for this class. In addition,

418

fragments SO3- (-0.76 and 1.4 mDa) and SO3F- (-1.6 and -1.1 mDa) indicate the

419

existence of the sulfonic acid group. According to isotopic distribution and MS/MS

420

spectrum, CnF2nClSO3- is the most suitable formula with few errors of -0.34 and -0.25


Page 21 of 44


421

ppm. Rotander et al6 confirmed the position of the chlorine by comparing it to a

422

standard supplied by Wellington Laboratories. The m/z 114.9262 (SO3Cl−) and

423

129.9541 (SO3CF2-) confirmed that the Cl atom was in α position or 8C in the sample

424

and standard, respectively. In this study, we found SO3CF2- or SO3C2F4- in the

425

MS/MS spectra of Class 14 (Figure S14). Therefore, we identified the Cl atom was in

426

ω position of Cl-PFSAs with level 2b, and then 8-Cl-PFOS was confirmed by

427

reference standard with level 1 (ΔRT = 0.03min, match score of MS/MS spectra =

428

85.6).

429

Class 15. This class comprises unsaturated chlorine substituted perfluorinated

430

ethers/alcohols (Cl-PFE/As) with -2.5 to -0.99 ppm. The isotopic pattern ([M]-: [M

431

+2]- ≈3:1) indicates the presence of chlorine atom for this series. The major ion

432

product [M-66]- revealed that neutral loss of CF2O (0.78-3.0 mDa) was indicative of

433

an ether or alcohol group. Fragments CnF2n-2Cl- (-4.0-1.2 mDa) also indicated the

434

existence of a double bond, but the double bond and Cl position are not certain.

435

Therefore, this class were identified as level 3. Liu et al.34 also reported Cl-PFE/As,

436

and the main product ions m/z 168.9861 (C3F7-, -3.3 mDa), m/z 180.9874 (C4F7-, -2.0

437

mDa), m/z 196.9550 (C4F6Cl-, -4.8 mDa), and m/z 346.9486 (C7F12Cl-, -1.6 mDa)

438

could be matched with our results (Figure S15).

439

For 13 classes of 78 emerging PFASs, 7 classes of 41 PFASs were reported in

440

previous studies, and 6 classes of 37 novel PFASs were discovered in our study

441

(Table 1). A large number of unknown PFASs have been detected from Chinese

442

WWTPs, indicating that unique PFASs have been designed and synthesized, which



443

could substitute existing PFASs. In addition, the emerging PFASs detected in our

444

study may be unintended ingredients, byproducts, or degradation products.

445

Changes of PFAS intensity in wastewater treatment

446

The intensity of the 90 PFASs identified by PFASs screening were calculated

447

(deduction the blank sample) in PeakView1.2 Software. Because the matrix effect can

448

result in the variation of intensity of PFASs, we use the relative matrix effect between

449

effluent and influent of internal standards to reflect the FCs resulted from the

450

difference of matrix (Table S5). For all used internal standards, the estimated upper

451

limits of relative matrix effect were smaller than 6, and the estimated lower limit of

452

relative matrix effect was larger than 1/6 (Table S5). Therefore, we used 6 and 1/6 as

453

the standard for the increasing trend and the decreasing trend, respectively.

454

We found that the FC of class 7 was lower than 1/6 (Figure 1C), which implied

455

that this class could be removed through the treatment processes of WWTPs. The FCs

456

of eight homologs in class 7 ranged from 0.0013 to 0.40, and the FCs of five

457

homologs were lower than 1/6. For class 7, they were identified as polyfluorinated

458

ether telomer acids and contained C-H bonds, which may be metabolized by

459

microorganisms and be oxidizable under ozone or advanced oxidation processes

460

(AOPs)47, and could further transform to other PFASs.

461

We also found that the FCs of four classes (including class 1, 9, 10, 14) were

462

larger than 6 (Figure 1C), and that the FCs of all homologs in these four class were

463

also larger than 6, which indicated that they increased significantly through the

464

treatment processes of WWTPs, implying that several emerging PFASs could be


Page 22 of 44

Page 23 of 44


465

degradation products from wastewater treatment. All sulfonic acids (classes 1 and 14)

466

were detected in the effluent and were below detection limit in the influent,

467

which revealed that wastewater treatment processes could increase these PFASs

468

through the transformation of precursors or the release of sludge. Cui48 found PFOS in

469

the effluent but no PFOS in nearby river samples, and Jin49 detected PFOS only in the

470

effluent at Chang Shu fluorochemical manufacturing park. The detection of PFOS

471

only in the effluent but not influent supports the biodegradation of PFASs precursors

472

in previous reports.31,49 For class 9, they were identified as unsaturated

473

perfluorocarboxylates and contained the C=C double bonds. Class 4 and class 6 also

474

contained the C=C double bonds, and the FCs of these two classes ranged from 1.3 to

475

23. The three classes could increase through the formation of C=C double bonds from

476

precursors or the release of sludge. For class 10, the FCs of seven homologs ranged

477

from 138 to 1988, and they were identified as perfluorinated dicarboxylate.

478

To understand the hydrophobicity of these new PFASs, we compared the

479

retention time for 15 PFASs classes (Figure 1D). Seven PFmonoCAs classes have a

480

retention time lower than that of PFCAs with the same number of carbon atoms, while

481

the Cl-PFCAs class have a retention time larger than that of PFCAs with the same

482

number of carbon atoms. Therefore, we inferred that the C=C double bonds, the C-H

483

single bonds, and the ether bonds could result in a stronger hydrophilicity than PFCAs,

484

and that the C-Cl single bonds could result in a stronger hydrophobicity than PFCAs.

485

The effects of the C-Cl single bonds were also found in PFSAs vs Cl-PFSAs and class

486

12 vs class 15. For the functional groups, the order of retention time was as follow:



487

alchols/ethers > sulfonic acids > carboxylic acids > dicarboxylic acids. For PFASs

488

with the same number of fluorinated carbon atoms, the difference of retention time

489

between functional groups was consistent with the difference of retention time for the

490

same number of carbon atoms (Figure S16).

491

PFASs in the surrounding Yangtze River

492

We also analyzed samples from the Yangtze River for assessing the influence of

493

the fluorochemical industry park on the surrounding environment. Water samples of

494

the Yangtze River were analyzed in the same method and the Nanjing Yangtze River

495

section as control. Several emerging PFASs found in the WWTP were also detected in

496

the surrounding Yangtze River, and the samples were correlated. Seven of 15 PFASs

497

classes were found in Yangtze River samples including 4 legacy PFASs and 14

498

emerging PFASs, after deducting the blank response by the suspect screening and

499

nontarget method. Clear differences were found between the PFASs profiles of

500

samples collected upstream and downstream (Figure 3). More PFASs were detected

501

in the downstream samples than in the upstream samples. PFOA, as the predominant

502

component accounted for nearly 50% in the downstream samples, similar to the

503

wastewater. H-PFCAs was the dominant class in the upstream samples, implying that

504

H-PFCAs existed upstream inputs in Yangtze River. Cl-PFCAs as the main

505

component of wastewater was detected only in downstream samples, indicating that

506

Cl-PFCAs in the downstream samples possibly originated from the effluent of

507

WWTPs.

508

IMPLICATIONS AND LIMITATIONS


Page 24 of 44

Page 25 of 44


509

We conducted a retrospective PFASs screening and found 15 PFAS classes (level

510

3 or above) in the wastewater from one of the largest fluorochemical industrial park in

511

China. Due to the low intensity and/or the limit fragments in MS/MS spectra, there

512

was no identified PFASs with a level 3 or above in ESI positive mode (Table S9).

513

Addition, the extract of samples has been kept in -20 °C for 6 years, and the identified

514

PFASs could be the potential transformation products. Most of identified PFAS classes

515

did not removed, even four identified PFAS classes increased through the wastewater

516

treatment processes. Although the result of single samples did not exactly characterize

517

the behavior of emerging PFASs in wastewater treatment processes, the suspect and

518

non-target screening was a discovery tool to find the unremoved PFASs or

519

transformation products from thousands of peaks, and then these will be helpful to

520

design the target analysis and experiments in the next step. Several identified PFASs

521

were also detected in the Yangtze River, additional attention is thus required for these

522

emerging PFASs detected, such as H-PFCAs and Cl-PFCAs. These two classes of

523

PFASs have been detected in the raw wastewater34 and have been widely used as new

524

substitutes of PFASs.34-35,

525

bioaccumulation, potential toxicity, and long-distance migration characteristics, which

526

will provide guidance for correctly assessing their environmental behavior and

527

potential biological effects.

528

Acknowledgements

50-52

Future research should focus on the persistence,

529

This work was supported by Major Science and Technology Program for Water

530

Pollution Control and Treatment (2017ZX07204004), National Natural Science



531

Foundation of China (21677067, 41571386, U1503282, and 41372235), National Key

532

Research and Development Program of China (2016YFC0402800), Taihu Water

533

Pollution Control Fund (TH2016306), Natural Science Foundation of Jiangsu

534

Province (Grant No. BK20160652), Reduction of POPs and PTS Release by

535

Environmentally Sound Management throughout the Life Cycle of Electrical and

536

Electronic Equipment and Associated Wastes in China (5044), Jiangsu provincial

537

Environmental Monitoring Research Fund (1317 and 1605).

538 539

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540

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Perfluoroalkyl Substances in Water by In-Line SPE-HPLC-Orbitrap with In-Source

653

Fragmentation Flagging. Anal. Chem. 2015, 87 (8), 4260-4268.

654

35. Ruan, T.; Lin, Y.; Wang, T.; Liu, R.; Jiang, G., Identification of Novel

655

Polyfluorinated Ether Sulfonates as PFOS Alternatives in Municipal Sewage Sludge

656

in China. Environ. Sci. Technol. 2015, 49 (11), 6519-6527.

657

36. Strynar, M.; Dagnino, S.; McMahen, R.; Liang, S.; Lindstrom, A.; Andersen, E.;

658

McMillan, L.; Thurman, M.; Ferrer, I.; Ball, C. Identification of Novel Perfluoroalkyl

659

Ether Carboxylic Acids (PFECAs) and Sulfonic Acids (PFESAs) in Natural Waters

660

Using Accurate Mass Time-of-Flight Mass Spectrometry (TOFMS). Environ. Sci.

661

Technol. 2015, 49 (19), 11622−11630.

662

37. Yu, N.; Guo, H.; Yang, J.; Jin, L.; Wang, X.; Shi, W.; Zhang, X.; Yu, H.; Wei, S.

663

Non-Target and Suspect Screening of Per- and Polyfluoroalkyl Substances in Airborne



664

Particulate Matter in China. Environ. Sci. Technol. 2018, 52 (15), 8205–8214.

665

38. Yu, N.; Shi, W.; Zhang, B.; Su, G.; Feng, J.; Zhang, X.; Wei, S.; Yu, H.

666

Occurrence of Perfluoroalkyl Acids Including Perfluorooctane Sulfonate Isomers in

667

Huai River Basin and Taihu Lake in Jiangsu Province, China. Environ. Sci. Technol.

668

2013, 47 (2), 710-717.

669

39. Gebbink, W. A.; van Asseldonk, L.; van Leeuwen, S. P. J., Presence of Emerging

670

Per- and Polyfluoroalkyl Substances (PFASs) in River and Drinking Water near a

671

Fluorochemical Production Plant in the Netherlands. Environ. Sci. Technol. 2017, 51

672

(19), 11057-11065.

673

40. Trier, X.; Lunderberg, D.; Peaslee, G.; Wang, Z.Y., PFAS list provided by

674

X.Trier et al. https://comptox.epa.gov/dashboard/ch-emical_lists/pfastrier (accessed

675

October 10, 2017).

676

41. Myers, A. L.; Jobst, K. J.; Mabury, S. A.; Reiner, E. J., Using mass defect plots

677

as a discovery tool to identify novel fluoropolymer thermal decomposition products. J.

678

Mass Spectrom. 2014, 49 (4), 291-296.

679

42. Schymanski, E. L.; Jeon, J.; Gulde, R.; Fenner, K.; Ruff, M.; Singer, H. P.;

680

Hollender, J., Identifying Small Molecules via High Resolution Mass Spectrometry:

681

Communicating Confidence. Environ. Sci. Technol. 2014, 48 (4), 2097-2098.

682

43. Washington, J. W.; Ellington, J.; Jenkins, T. M.; Evans, J. J.; Yoo, H.; Hafner, S.

683

C., Degradability of an acrylate-linked, fluorotelomer polymer in soil. Environ. Sci.

684

Technol. 2010, 44 (2), 849.

685

44. The production record of 1,1-difluoroethene in the Fluorochemical Industrial


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686

Park.

http://www.amip.org.cn/content.aspx?id=25993 (accessed January 9, 2018).

687

45. The production record of polyvinylidene difluoride in the Fluorochemical

688

Industrial Park. http://www.amip.org.cn/content.aspx?id=25621 (accessed January 9,

689

2018).

690

46. Yan, W. Z., Photoreduction of Perfluorooctanoic Acid (PFOA) in Isopropanol

691

Aqueous Solution. MA.Eng. Dissertation, National Taiwan University, Taiwan, China,

692

2010.

693

47. Rahman, M. F.; Peldszus, S.; Anderson, W. B., Behaviour and fate of

694

perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water treatment: a

695

review. Water Res. 2014, 50 (1), 318.

696

48. Cui, R., Levels and composition distribution of perfluoroalkyl substances in water

697

and biological samples from Jiangsu Hi-tech Fluorochemical Industry Park in

698

Changshu,China. Environ Chem 2013, 32 (7), 1318-1327.

699

49. Jin, H.; Zhang, Y.; Zhu, L.; Martin, J. W., Isomer profiles of perfluoroalkyl

700

substances in water and soil surrounding a chinese fluorochemical manufacturing park.

701


702

50. Wang, S.; Huang, J.; Yang, Y.; Hui, Y.; Ge, Y.; Larssen, T.; Yu, G.; Deng, S.;

703

Wang, B.; Harman, C., First Report of a Chinese PFOS Alternative Overlooked for 30

704

Years: Its Toxicity, Persistence, and Presence in the Environment. Environ. Sci.

705

Technol. 2013, 47 (18), 10163.

706

51. Crimmins, B. S.; Xia, X.; Hopke, P. K.; Holsen, T. M., A targeted/non-targeted

707

screening method for perfluoroalkyl carboxylic acids and sulfonates in whole fish



708

using quadrupole time-of-flight mass spectrometry and MS e. Analytical &

709

Bioanalytical Chemistry 2014, 406 (5), 1471-1480.

710

52. Baygi, S. F.; Crimmins, B. S.; Hopke, P. K.; Holsen, T. M., Comprehensive

711

Emerging Chemical Discovery:

712

Michigan Trout. Environ. Sci. Technol. 2016, 50 (17), 9460.

Novel Polyfluorinated Compounds in Lake

713 714 715 716 717 718 719 720 721 722 723 724 725 726 727 728 729 730


Page 34 of 44

Page 35 of 44


731 732

Figure 1. Structure, fold change and retention time of PFASs detected in the

733

influent and effluent through the treatment processes of WWTPs. A: Structure

734

of 15 detected PFASs classes. B: CF2 Adjusted mass defect plot for 15 detected

735

PFASs classes. C: The distribution of fold change (log2 scaled) between the



736

influent and effluent for 15 detected PFASs classes (point: each homolog; line: all

737

homologs in one class). D: The plot of retention time with the number of carbon

738

atoms for each detected PFASs class.

739

740 741

Figure 2. The MS/MS spectrum of C11H3O3F16- in class 7.

742 743 744 745


Page 36 of 44

Page 37 of 44


746 747

Figure 3: Composition of detected PFASs in wastewater and the Yangtze River.

748

The prefix number represents the class of the compound.

749 750 751 752 753 754

Table 1. Structure and detection of emerging PFASs with level 3 or above. The

755

newly identified PFASs class with a bold number in “Class” column, the number

756

in the “Proposed Structure” column refer to the value of n in generic structure in

757

Figure 1A, the bold numbers in the “log2FC” column indicate this value larger

758

than log26 or less than log21/6, and “inf”, “eff”, “YR” in the “Detection in

759

samples” column indicate influent, effluent, and Yangtze River, respectively.



Proposed Class

Formula

Level

Detection log2FC

Structure 3

4

5

6

7

8

Page 38 of 44

Proposed Class

Formula

Level

in samples

C4F6H2O2

3

2

0.28

inf; eff

C5F8H2O2

3

3

0.23

inf; eff

C6F10H2O2

3

4

-0.24

inf; eff

C7F12H2O2

3

5

-1.4

inf; eff

C8F14H2O2

3

6

-0.63

inf; eff

Detection log2FC

Structure 8

9

in samples

C12H5O3F19

3

9

-1.0

inf; eff

C13H5O3F21

3

10

0.12

inf; eff

C14H5O3F23

3

11

-0.59

inf; eff

C5F5O2H

3

0

10

eff

C6F7O2H

3

1

12

eff

C9F16H2O2

3

7

-1.7

inf; eff; YR

C7F9O2H

3

2

8.3

eff

C10F18H2O2

3

8

-0.41

inf; eff; YR

C8F11O2H

3

3

5.8

eff

C11F20H2O2

3

9

-0.65

inf; eff; YR

C9F14O4H2

2b

7

8.4

eff

C12F22H2O2

3

10

-1.1

inf; eff; YR

C10F16O4H2

1

8

10

eff

C13F24H2O2

3

11

-0.77

inf; eff; YR

C11F18O4H2

2b

9

9.5

eff; YR

C14F26H2O2

3

12

-3.4

inf; eff

C12F20O4H2

1

10

11

eff; YR

10

C15F28H2O2

3

13

3.1

eff

C13F22O4H2

2b

11

10

eff; YR

C16F30H2O2

3

14

2.6

eff

C14F24O4H2

2b

12

7.9

eff

C17F32H2O2

3

15

-6.7

inf

C15F26O4H2

2b

13

7.1

eff

C6F9O3H

3

2

2.9

inf; eff

C7F11O3H

3

3

3.6

eff

C8F13O3H

3

4

1.3

inf; eff

C6H6F6O2

2b

2

-1.5

C8H8F8O2

2b

3

-8.9

C10H10F10O2

2b

4

C12H12F12O2

2b

C14H14F14O2

2b

C9F15O2H

3

11

C3F7OH

2b

3

-1.3

inf; eff

C4F9OH

2b

4

-0.08

inf; eff; YR

C3F5OH

3

0

-1.4

inf; eff

inf; eff

C4F7OH

3

1

-0.02

inf; eff

inf

C5F9OH

3

2

-2.7

inf; eff

-1.3

inf; eff

C6F11OH

3

3

-0.13

inf; eff

5

-0.50

inf; eff

C7F13OH

3

4

-0.23

inf; eff; YR

6

-0.86

inf; eff

C8F15OH

3

5

-0.55

inf; eff

5

2.4

eff

C4F6O2ClH

3

3

-0.08

inf; eff

12

13

C10F17O2H

3

6

1.4

eff

C5F8O2ClH

3

4

-0.77

inf; eff

C11F19O2H

2b

7-7C,8C*

4.5

eff

C6F10O2ClH

3

5

-1.1

inf; eff

C12F21O2H

2b

8-7C,8C*

4.0

eff

C7F12O2ClH

3

6

-1.1

inf; eff; YR

C13F23O2H

3

9

2.3

eff

C8F14O2ClH

3

7

-1.1

inf; eff; YR

C14F25O2H

3

10

0.42

eff

C9F16O2ClH

3

8

-0.59

inf; eff; YR

C6H4O3F6

3

2

-5.8

inf

C10F18O2ClH

3

9

-0.22

inf; eff; YR

C8H4O3F10

3

4

-7.5

inf

C11F20O2ClH

3

10

-0.94

inf; eff

C9H4O3F12

3

5

-9.4

inf

C12F22O2ClH

3

11

-2.6

inf; eff

C10H4O3F14

3

6

-9.6

inf

C13F24O2ClH

3

12

-4.1

inf; eff

C11H4O3F16

3

7

-3.5

inf; eff

C12H4O3F18

3

8

-2.1

inf; eff

C13H4O3F20

3

9

-1.3

inf; eff

C14H4O3F22

3

10

-1.6

inf; eff

C9H5O3F13

3

6

-3.9

inf; eff

C10H5O3F15

3

7

-4.5

C11H5O3F17

3

8

-2.4

C14F26O2ClH

3

13

-6.2

inf; eff

C7F14ClSO3H

2b

7

3.9

eff

C8F16ClSO3H

1

8

4.1

eff

C7F12OClH

3

4

-1.7

inf; eff

C8F14OClH

3

5

-0.27

inf; eff

inf

C9F16OClH

3

6

0.03

inf; eff

inf; eff

C10F18OClH

3

7

-1.3

inf; eff

14

15

*: 7C,8C indicate the position of the C=C double bond

760


Page 39 of 44


761



Figure 1. Structure, fold change and retention time of PFASs detected in the influent and effluent through the treatment processes of WWTPs. A: Structure of 15 detected PFASs classes. B: CF2 Adjusted mass defect plot for 15 detected PFASs classes. C: The distribution of fold change (log2 scaled) between the influent and effluent for 15 detected PFASs classes (point: each homolog; line: all homologs in one class). D: The plot of retention time with the number of carbon atoms for each detected PFASs class. 205x275mm (300 x 300 DPI)


Page 40 of 44

Page 41 of 44


Figure 2. The MS/MS spectrum of C11H3O3F16- in class 7. 199x94mm (300 x 300 DPI)



Figure 3: Composition of detected PFASs in wastewater and the Yangtze River. The prefix number represents the class of the compound. 106x101mm (300 x 300 DPI)


Page 42 of 44

Page 43 of 44


Table 1. Structure and detection of emerging PFASs with level 3 or above. The newly identified PFASs class with a bold number in “Class” column, the number in the “Proposed Structure” column refer to the value of n in generic structure in Figure 1A, the bold numbers in the “log2FC” column indicate this value larger than log26 or less than log21/6, and “inf”, “eff”, “YR” in the “Detection in samples” column indicate influent, effluent, and Yangtze River, respectively.



Proposed Class

Formula

Level

Detection log2FC

Structure 3

4

5

6

7

8

Page 44 of 44

Proposed Class

Formula

Level

in samples

C4F6H2O2

3

2

0.28

inf; eff

C5F8H2O2

3

3

0.23

C6F10H2O2

3

4

C7F12H2O2

3

C8F14H2O2

Detection log2FC

Structure

in samples

C12H5O3F19

3

9

-1.0

inf; eff

inf; eff

C13H5O3F21

3

10

0.12

inf; eff

-0.24

inf; eff

C14H5O3F23

3

11

-0.59

inf; eff

5

-1.4

inf; eff

C5F5O2H

3

0

10

eff

3

6

-0.63

inf; eff

C6F7O2H

3

1

12

eff

8

9

C9F16H2O2

3

7

-1.7

inf; eff; YR

C7F9O2H

3

2

8.3

eff

C10F18H2O2

3

8

-0.41

inf; eff; YR

C8F11O2H

3

3

5.8

eff

C11F20H2O2

3

9

-0.65

inf; eff; YR

C9F14O4H2

2b

7

8.4

eff

C12F22H2O2

3

10

-1.1

inf; eff; YR

C10F16O4H2

1

8

10

eff

C13F24H2O2

3

11

-0.77

inf; eff; YR

C11F18O4H2

2b

9

9.5

eff; YR

C14F26H2O2

3

12

-3.4

inf; eff

C12F20O4H2

1

10

11

eff; YR

C15F28H2O2

3

13

3.1

eff

C13F22O4H2

2b

11

10

eff; YR

C16F30H2O2

3

14

2.6

eff

C14F24O4H2

2b

12

7.9

eff

C17F32H2O2

3

15

-6.7

inf

C15F26O4H2

2b

13

7.1

eff

C6F9O3H

3

2

2.9

inf; eff

C3F7OH

2b

3

-1.3

inf; eff

C7F11O3H

3

3

3.6

eff

C4F9OH

2b

4

-0.08

inf; eff; YR

C8F13O3H

3

4

1.3

inf; eff

C3F5OH

3

0

-1.4

inf; eff

C6H6F6O2

2b

2

-1.5

inf; eff

C4F7OH

3

1

-0.02

inf; eff

C8H8F8O2

2b

3

-8.9

inf

C5F9OH

3

2

-2.7

inf; eff

C10H10F10O2

2b

4

-1.3

inf; eff

C6F11OH

3

3

-0.13

inf; eff

C12H12F12O2

2b

5

-0.50

inf; eff

C7F13OH

3

4

-0.23

inf; eff; YR

C14H14F14O2

2b

6

-0.86

inf; eff

C8F15OH

3

5

-0.55

inf; eff

C9F15O2H

3

5

2.4

eff

C4F6O2ClH

3

3

-0.08

inf; eff

C10F17O2H

3

6

1.4

eff

C5F8O2ClH

3

4

-0.77

inf; eff

C11F19O2H

2b

7-7C,8C*

4.5

eff

C6F10O2ClH

3

5

-1.1

inf; eff

C12F21O2H

2b

8-7C,8C*

4.0

eff

C7F12O2ClH

3

6

-1.1

inf; eff; YR

C13F23O2H

3

9

2.3

eff

C8F14O2ClH

3

7

-1.1

inf; eff; YR

C14F25O2H

3

10

0.42

eff

C9F16O2ClH

3

8

-0.59

inf; eff; YR

C6H4O3F6

3

2

-5.8

inf

C10F18O2ClH

3

9

-0.22

inf; eff; YR

C8H4O3F10

3

4

-7.5

inf

C11F20O2ClH

3

10

-0.94

inf; eff

C9H4O3F12

3

5

-9.4

inf

C12F22O2ClH

3

11

-2.6

inf; eff

C10H4O3F14

3

6

-9.6

inf

C13F24O2ClH

3

12

-4.1

inf; eff

C11H4O3F16

3

7

-3.5

inf; eff

C14F26O2ClH

3

13

-6.2

inf; eff

C12H4O3F18

3

8

-2.1

inf; eff

C7F14ClSO3H

2b

7

3.9

eff

C13H4O3F20

3

9

-1.3

inf; eff

C8F16ClSO3H

1

8

4.1

eff

C14H4O3F22

3

10

-1.6

inf; eff

C7F12OClH

3

4

-1.7

inf; eff

C9H5O3F13

3

6

-3.9

inf; eff

C8F14OClH

3

5

-0.27

inf; eff

C10H5O3F15

3

7

-4.5

inf

C9F16OClH

3

6

0.03

inf; eff

C11H5O3F17

3

8

-2.4

inf; eff

C10F18OClH

3

7

-1.3

inf; eff

10

11

12

13

14

15

*: 7C,8C indicate the position of the C=C double bond


Suspect and Nontarget Screening of Per- and Polyfluoroalkyl

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