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Supplementary information

Bioaccumulation and human exposure of perfluoroalkyl acids

(PFAAs) in vegetables from the largest vegetable production base of

China

Meng Zhang a,b, Pei Wang a,c, Yonglong Lu a,b,c *, Xiaotian Lu d, Anqi Zhang a,b,

Zhaoyang Liu e, Yueqing Zhang f, Kifayatullah Khan g, Suriyanarayanan

Sarvajayakesavalu h

a State Key Laboratory of Urban and Regional Ecology, Research Center for Eco-

Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China

b University of Chinese Academy of Sciences, Beijing 100049, China

c Key Laboratory of the Ministry of Education for Coastal Wetland Ecosystems,

College of the Environment and Ecology, Xiamen University, Fujian 361102, China

d Key Lab of Urban Environment and Health, Institute of Urban Environment, Chinese Academy of Sciences, 1799 Jimei Road, Xiamen 361021, Chinae Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil

Science, Chinese Academy of Sciences, Nanjing 210008, China

f Key Laboratory of Pesticide Environmental Assessment and Pollution Control,

Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environment,

Nanjing 210042, China

g Department of Environmental and Conservation Sciences, University of Swat, Swat

19130, Pakistan

h Vinayaka Mission's Research Foundation, Salem 636308, India

* Corresponding author:

Yonglong Lu

Tel: 86-10-62915537

Fax: 86-10-62918177

E-mail: [email protected]

Sample collection and preparationAt each sampling site, 1L of well water was collected and stored in a 1-L polypropylene bottle, one mixed greenhouse soil and one mixed open field soil were collected in sealed polyethylene bags. For vegetables, 3-5 single items were randomly selected and pooled together per species at each site.

Table S1. Information on topsoil, irrigation water (ground water) and vegetable samples collected at each sampling site.

Site

Greenhouse vegetables Open field vegetables TopsoilIrrigation

waterFruit vegetables Leafy vegetables Root

GreenhouseOpen fieldTomato Cucumber

Sponge gourd

Sweet pepper EggplantBalsam

pearZucchini Cabbage Spinach Rape Radish Carrot

S1 √ √ √ √ √ √ √

S2 √ √ √ √ √ √ √ √ √

S3 √ √ √ √ √ √ √ √

S4 √ √ √ √ √ √ √ √ √

S5 √ √ √ √ √ √ √ √ √

S6 √ √ √ √ √ √ √ √ √ √

S7 √ √ √ √ √ √ √ √ √

S8 √ √ √ √ √ √ √ √

S9 √ √ √ √ √ √ √ √

S10 √ √ √ √ √ √ √ √

S11 √ √ √ √ √ √ √ √ √

S12 √ √ √ √ √ √ √ √

S13 √ √ √ √ √ √ √

S14 √ √ √ √ √ √ √ √ √

S15 √ √ √ √ √ √ √

S16 √ √ √ √ √ √ √ √ √

S17 √ √ √ √ √ √ √ √

S18 √ √ √ √ √ √

Extraction and instrumental methods

Water sample: Sequentially, load 4 mL 0.1% NH4OH in methanol, 4 mL methanol and 4 mL Milli-Q water through the Oasis WAX SPE cartridge. Then load 400 mL unfiltered water sample with 5 ng interior standard of each mass labeled PFAAs in it. Wash the cartridge with 4 mL 25 mM ammonium acetate (pH=4). Elute the air dried cartridge with 4 mL methanol and 4 mL 0.1% NH4OH in methanol. The eluent was collected and reduced to near-dryness under nitrogen gas and then reconstituted to 1 mL with methanol. The solution was filtered with a Acrodisc syringe filter with GHP membrane (13 mm, 0.2 µm, Pall Life Sciences, East Hills, NY, US) and separated into an autosampler vial with polypropylene (PP) snap top and polyethylene (PE) septa and then quantified using HPLC-MS/MS system.

Soil sample: Weigh out 2 g (dry weight) soil into a 50 mL PP centrifuge tube, add 5 ng mass-labelled internal standards. Sample was alkaline digested with 2 mL 100 mM NaOH in acetonitrile (8 : 2 / acetonitrile : Milli-Q water) and ultra-sonicated for 30 min. Then extract the PFAAs from digested soil with 20 mL acetonitrile and shake for 30 min at 250 rpm. Add 0.1 mL 2M HCl and centrifuge the mixture at 3000 rpm for 15 min. Transfer the supernatant into a new tube. Repeat the extraction procedure once with 10 mL acetonitrile. The combined extract was concentrated to 1 mL by nitrogen and further cleaned up with a Supelclean ENVI-Carb SPE tube and an Oasis WAX SPE cartridge. Before loading the concentrated extract, the ENVI-Carb cartridge was preconditioned by loading 1 mL methanol three times. After loading the concentrated extract, the cartridge was washed with another three times of 1 mL methanol and collected together with the extract. Then the collection was diluted to 100 mL with Milli-Q water and further cleaned up with the same procedure as for water sample.

Plant sample: Weigh out 1 g (dry weight) tissue powder into a 50 mL PP centrifuge tube, add 5 ng mass-labelled internal standards and 5 mL 0.4 M NaOH. Vortex and put the tube in the fridge overnight. Add 4 mL 0.5 M tetrabutylammonium hydrogen sulfate and 5 mL 0.25 M Na2CO3-NaHCO3 buffer and then vortex the mixture. Add 10 mL methyl tert-butyl ether to the tube and shake for 5 minutes at 700 rpm and then ultrasonic for 10 min. Centrifuge the mixture at 3000 rpm for 10 min. Transfer the supernatant into a new tube. Repeat the extraction procedure twice with 5 mL methyl tert-butyl ether. The combined extract was concentrated to 1 mL by nitrogen and further cleaned up with a LC-Florisil SPE tube and a Supelclean ENVI-Carb SPE tube. Before loading the concentrated extract, the LC-Florisil cartridge was preconditioned by loading 10 mL methanol and 10 mL methyl tert-butyl ether. After loading the concentrated extract, the cartridges was washed with 10 mL methyl tert-

butyl ether. The filtrate was discarded and PFAAs was adsorbed on the sorbent. Then wash the cartridge with 10 mL MeOH-MTBE (30:70, V:V) and collect. The elution was reduced to 1 mL under nitrogen and further cleaned up with an ENVI-Carb cartridge using a same procedure as for soil sample. After that, the extract was reduced to 1 mL under nitrogen. Then the solution was filtered with a syringe PP filter and separated into an autosampler vial and then quantified using HPLC-MS/MS system.

An Agilent 1290 Infinity HPLC System equipped with an Agilent 6460 Triple Quadrupole LC/MS System (Agilent Technologies, Palo Alto, CA, USA) was used for separation and quantification of target compounds. HPLC system was fitted with an analytical column (Aglient ZORBAX Eclipse Plus C18, 2.1×100 mm, 3.5 μm particle size) and a guard column (Agilent 1290 Infinity In-line filter with 0.3μm SS frit). The column temperature was kept at 40 °C. Mobile phases were 2 mM ammonium acetate (A) and acetonitrile (B). The flow rate is 0.3 mL/min. For each sample, the injection volume is 5 μL. Gradient conditions start with 80% A and 20% B and held for 0.5 min, then changed to 90% B at 12 min and held for 2 min, then returned to 20% B at 16 min followed with 4 min post time. Target compounds were identified by negative ions generated by electrospray ionization (ESI) coupled with multiple reaction monitoring mode (MRM). The source gas temperature was kept at 350 °C with a flow rate of 9 L/min. Nebulizer pressure was 40 psi, capillary was 3500 V negative, delta EMV(-) was 300V. The optimized MS/MS parameters used for identifying and quantifying individual PFAAs were same with what used by Wang et al. (2016) in our group.

Table S2. Conditions for HPLC and ESI- MS.HPLC conditions

Analytical column Aglient ZORBAX Eclipse Plus C18, 2.1×100 mm, 3.5μm

Guard column Agilent 1290 Infinity In-line filter with 0.3μm SS frit

Column temperature 40 ℃Injection volume 5 μL

Mobile phase A= 2 mM ammonium acetateB= 100% Acetonitrile

Run time 14 min + 6 min post time

Flow rate 0.3 mL/min

Gradient Time (min) Mobile phase

0 20% B

0.5 20% B

12 90% B

14 90% B

MS conditions

Acquisition parameters ESI mode, negative ionization, MRM

Source gas temperature 350 ℃Source gas flow rate 9 L/min

Nebulizer pressure 40 psi

Capiliary 3500 V negative

Delta EMV(-) 400 V

Table S3. Total organic matter (TOC), pH, and total nitrogen (TN) in soil samples from Shouguang vegetable base.

SiteCulture condition

TOC (%) pH TN (%)

1 Greenhouse 1.71 6.19 0.21 Open field 0.79 7.30 0.09














15 Open field 0.97 7.53 0.09 16 Greenhouse 1.30 7.52 0.15

Open field 0.86 7.72 0.08 17 Greenhouse 1.96 6.74 0.19

Open field 0.41 7.67 0.05 18 Open field 2.30 7.24 0.22

1-i

1-o

2-i

2-o

3-i

3-o

4-i

4-o

5-i

5-o

6-i

6-o

7-i

7-o

8-i

8-o

9-i

9-o

10-i

10-o

11-i

11-o

12-i

12-o

13-i

13-o

14-i

14-o

15-o

16-i

16-o

17-i

17-o

18-o

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%PFOS

PFHxS

PFBS

PFDoA

PFUdA

PFDA

PFNA

PFOA

PFHpA

PFHxA

PFPeA

PFBA

Rel

ativ

e ab

unda

nce

%

Figure S1. Relative abundance of soil PFAAs in Shouguang vegetable base. i, greenhouse soil. o, open field soil.

Table S4. Internal standards, LOD, LOQ and matrix spike recoveries (MSRs ± SD) of individual PFAAs (n=5) in vegetables.PFAA

(Internal

standard)

Sponge gourd a

Cucumber b Tomato a Balsam pear b

Eggplant aSweet pepper a

Zucchini a Cabbage a Rape a Spinach a Radish a Carrot a Soil a Water b

PFBA LOD 0.14 0.12 0.12 0.17 0.15 0.18 0.08 0.11 0.08 0.07 0.07 0.15 0.05 0.08(13C4 PFBA) LOQ 0.47 0.41 0.39 0.56 0.49 0.58 0.28 0.37 0.28 0.22 0.23 0.49 0.25 0.22

MSR 85.8 ± 3.6 94.8 ± 7.4 90.7 ± 2.9 91.9 ± 4 87.1 ± 3.9 91.5 ± 3.1 96.5 ± 5.1 84.7 ± 8.2 97.3 ± 98.8 ± 4.1 85.6 ± 3.7 94 ± 6.5 73.3 ± 1 109 ± 3.2

PFPeA LOD 0.09 0.07 0.08 0.08 0.1 0.05 0.08 0.02 0.06 0.05 0.06 0.08 0.03 0.05(13C4 PFBA) LOQ 0.3 0.22 0.26 0.25 0.33 0.18 0.28 0.05 0.2 0.17 0.2 0.27 0.08 0.15

MSR 88.9 ± 6.1 77.3 ± 2.2 72.8 ± 4.1 78.8 ± 3.6 84.6 ± 6.5 72.1 ± 2.4 80.1 ± 3.3 73.4 ± 5 71.7 ± 7 84.4 ± 2.8 87.8 ± 6.6 87.7 ± 7.4 72.5 ± 88.2 ±

PFHxA LOD 0.08 0.11 0.07 0.09 0.15 0.19 0.07 0.09 0.06 0.04 0.03 0.07 0.01 0.04(13C4 PFHxA) LOQ 0.27 0.37 0.24 0.31 0.51 0.63 0.24 0.32 0.2 0.14 0.11 0.22 0.04 0.15

MSR 97.3 ± 3.9 98.5 ± 2.5 99.2 ± 2.5 98.5 ± 3.9 91.1 ± 7.8 93.1 ± 4.2 97.5 ± 6.2 91.9 ± 4.2 93.4 ± 92.2 ± 3.3 86.6 ± 8 98.7 ± 1.5 79.4 ± 90.1 ±

PFHpA LOD 0.03 0.06 0.06 0.06 0.1 0.02 0.07 0.02 0.03 0.03 0.03 0.01 0.01 0.06(13C4 PFHxA) LOQ 0.09 0.2 0.22 0.19 0.33 0.08 0.24 0.07 0.09 0.09 0.09 0.04 0.03 0.15

MSR 94.2 ± 5.4 95.7 ± 3.1 101.6 ± 99.5 ± 3.5 90.2 ± 5.1 108.2 ± 6.1 99.8 ± 4 91.1 ± 3.3 96.9 ± 97.1 ± 4.4 95.5 ± 98.2 ± 3.2 75.8 ± 79 ± 4.3

PFOA LOD 0.04 0.05 0.01 0.04 0.03 0.05 0.05 0.01 0.02 0.03 0.03 0.02 0.02 0.05(13C4 PFOA) LOQ 0.15 0.16 0.03 0.12 0.1 0.16 0.16 0.05 0.08 0.1 0.11 0.06 0.05 0.19

MSR 88.5 ± 5.9 85.4 ± 1.6 87.8 ± 1.8 88.9 ± 4.7 79.7 ± 1.8 85.2 ± 2.8 83.1 ± 3.1 87.4 ± 5.3 94.4 ± 88.7 ± 2.8 90.6 ± 5 85.7 ± 3.7 72.4 ± 104 ± 1

PFNA LOD 0.04 0.01 0.02 0.06 0.07 0.06 0.01 0.06 0.02 0.02 0.02 0.06 0.01 0.06(13C4 PFNA) LOQ 0.13 0.02 0.05 0.2 0.22 0.19 0.03 0.21 0.08 0.06 0.07 0.18 0.03 0.13

MSR 94.3 ± 5.4 97.2 ± 3.9 94.7 ± 5.9 97.7 ± 3.6 92.9 ± 3.8 97.8 ± 7.9 89.6 ± 2.8 81.3 ± 3.3 81.4 ± 96.3 ± 7 87.1 ± 4.4 89.3 ± 3.2 80 ± 0.6 87.4 ±

PFDA LOD 0.02 0.04 0.01 0.02 0.06 0.05 0.03 0.01 0.03 0.04 0.02 0.01 0.01 0.05(13C4 PFDA) LOQ 0.06 0.12 0.03 0.06 0.19 0.15 0.09 0.05 0.1 0.12 0.08 0.04 0.02 0.15

MSR 93.1 ± 8.1 87.9 ± 1.9 89.7 ± 2.9 90 ± 1.8 86.2 ± 6 93.6 ± 7.6 90.6 ± 6.8 91.4 ± 5.3 92.1 ± 86.1 ± 1.8 77.5 ± 3.3 85.5 ± 4.8 75.2 ± 100 ± 5.4

PFUdA LOD 0.01 0.02 0.02 0.03 0.06 0.02 0.03 0.05 0.06 0.03 0.08 0.05 0.01 0.03(13C4 PFUdA) LOQ 0.02 0.05 0.05 0.11 0.19 0.06 0.09 0.17 0.2 0.11 0.25 0.17 0.03 0.08

MSR 92.5 ± 10.2 88.2 ± 3.1 87.3 ± 3.5 93.6 ± 4.6 88.1 ± 9 95.7 ± 3.5 92.9 ± 5.3 89.2 ± 4.1 94.6 ± 94.6 ± 3.7 88.7 ± 4.6 98.1 ± 5.7 77.4 ± 97.8 ± 3

PFDoA LOD 0.03 0.02 0.01 0.01 0.07 0.01 0.04 0.02 0.02 0.01 0.07 0.04 0.01 0.05(13C2 PFDoA) LOQ 0.09 0.07 0.04 0.03 0.22 0.05 0.13 0.07 0.08 0.03 0.22 0.12 0.04 0.13

MSR 94.1 ± 7.2 89.4 ± 3.4 87.7 ± 1.4 98.3 ± 5 87.3 ± 7.9 92.9 ± 2.5 94.6 ± 2.3 94.5 ± 1.8 95.8 ± 98.8 ± 3.4 89.1 ± 3.8 102.4 ± 83.2 ± 8 88.8 ±

PFBS LOD 0.09 0.04 0.14 0.16 0.08 0.23 0.12 0.08 0.08 0.07 0.05 0.05 0.01 0.03(18O2 PFHxS) LOQ 0.3 0.13 0.48 0.52 0.27 0.76 0.4 0.28 0.26 0.23 0.18 0.15 0.03 0.09

MSR 125.6 ± 4.9 108.2 ± 5.4 97.4 ± 9 116 ± 6.7 116.5 ± 110.8 ± 4 116.3 ± 106.6 ± 97.9 ± 101.6 ± 6 103.3 ± 119.9 ± 93 ± 4.3 83.5 ±

PFHxS LOD 0.11 0.12 0.04 0.16 0.09 0.15 0.03 0.05 0.05 0.06 0.1 0.08 0.02 0.01(18O2 PFHxS) LOQ 0.35 0.38 0.12 0.55 0.29 0.49 0.09 0.17 0.17 0.2 0.33 0.28 0.05 0.06

MSR 110.7 ± 7.2 102.3 ± 4.5 98.2 ± 8.4 106.1 ± 7 99.7 ± 8.9 112 ± 4.4 93.5 ± 5.1 90.1 ± 6.8 91 ± 7.2 84.6 ± 7.7 87.1 ± 2 95.5 ± 6 79.7 ± 83.5 ±

PFOS LOD 0.07 0.03 0.05 0.09 0.17 0.07 0.08 0.11 0.14 0.08 0.07 0.16 0.01 0.03(13C4 PFOS) LOQ 0.23 0.08 0.18 0.3 0.57 0.24 0.27 0.38 0.47 0.27 0.23 0.53 0.03 0.1

MSR 76.1 ± 7.4 67.4 ± 2.5 71.8 ± 4.7 73.5 ± 4.5 82.3 ± 4.6 76.3 ± 4.3 94.8 ± 6 99.9 ± 4.8 85 ± 6.9 83.7 ± 4.2 74.3 ± 2.1 88.3 ± 5.4 85.3 ± 92.2 ±

Note: a, units for LOD, LOQ and MSR are ng/g dw, ng/g dw and % respectively. b, units for LOD, LOQ and MSR are ng/L, ng/L and % respectively.

Table S5. Average daily vegetable consumption (g/d) and body weight (BW, kg) of different age groups in China.

Preschool children(2~5)

School-age childrenand adolescents

(6~17)

Adults(18~45)

Elderly(>45)

Urban Rural Urban Rural Urban Rural Urban RuralTotal

148.4 124.7 256.1 239.6 330.8 341.4 353.2 339.3Sponge gourd 3 4.2 3.9 6.9 3.7 7.8 4.4 10.1Cucumber 2.5 4.2 6.2 7.9 9.3 12.8 9.2 11Tomato 14.5 7.2 18.3 12.6 22.5 14.7 21.8 13.7Balsam pear 0.1 0.5 1.3 2.7 2 3.1 1.8 2.6Eggplant 3.4 5 8.8 13.6 12.8 20.8 13.2 23.1Sweet pepper 0.5 1.2 1.6 2.7 2.4 3.7 2 2.7Zucchini 2.2 0.5 1.3 0.4 1.2 1.6 1.6 0.9Cabbage 26.8 21.4 56.1 43 70.4 64.8 80.7 69.4Rape 4.2 1.8 9.2 3.4 8.6 6.2 8.4 6.1Spinach 5.5 2.9 4.9 5.5 7.9 6.2 8.6 7.8Radish 6.5 3.2 9.3 7.1 11.6 11.8 16.5 15.8Carrot 3.1 2.3 3.1 2.3 3.3 2.9 4.8 2.6Other vegetables 76.2 70.6 132 131.4 175.1 184.8 180.1 173.4

BW18 17

41.5 36.1 63.6 62.7 63.7 61Note: Data were calculated based on China Health and Nutrition Survey (CHNS) dataset (CHNS).

Table S6. Pearson correlations of PFAAs concentrations in greenhouse soil and PCA rotated component matrix.

Componenta

Pearson

Correlation PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUdA PFDoA PFBS PFOS 1 2 3

4

PFBA 1 .227 .291

.708 -.234

PFPeA .362 1 .200 .934

.089 -.074

PFHxA .291 .848** 1 .168 .938

.066 .086

PFHpA .496 .579* .540* 1 .822 .414

.294 -.119

PFOA .567* .381 .300 .876** 1 .736 .190

.497 -.078

PFNA .242 .314 .314 .903** .767**

1 .932 .129

.120 -.098

PFDA .085 .368 .313 .717** .635**

.774** 1 .891 .187

-.107 .290

PFUdA .343 .293 .319 .671** .477 .769** .720**

1 .815 .153

.062 .005

PFDoA .267 .204 .161 .796** .685* .877** .849* .768** 1 .971 .01 -.065 -.111

* * 7

PFBS -.187 .009 -.042 -.080 -.201 -.048 .028 -.028 .210 1 .083 .080

-.776 -.350

PFOS -.009 -.082 .063 -.086 -.009 -.134 .210 -.030 -.092 -.198 1 -.012 .014

.064 .933

Note: **, Correlation is significant at the 0.01 level (2-tailed). *, Correlation is significant at the 0.05 level (2-tailed). a, Total variance explained was 85.58%.

Table S7. Pearson correlations of PFAAs concentrations in open field soil and PCA rotated component matrix.

Componenta

Pearson

Correlation PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUdA PFDoA PFOS 1 2 3

PFBA 1 -.374 .696 -.189

PFPeA .282 1 .328 .800 -.099

PFHxA .409 .587* 1 .224 .794 .400

PFHpA -.107 .378 .388 1 .846 .160 .023

PFOA .010 .016 -.201 .429 1 .447 -.171

-.687

PFNA -.024 .389 .143 .559* .595** 1 .779 .185 -.440

PFDA -.275 .507* .252 .734**

.365 .845**

1 .928 .185 -.132

PFUdA -.262 .078 .312 .654**

.023 .342 .551* 1 .747 -.054

.510

PFDoA .096 .663**

.599** .441 -.062 .496* .671** .416 1 .558 .650 .103

PFOS -.099 -.085 .346 .073 -.358 -.234 -.057 .438 -.004 1 .083 -.040

.855


Table S8. PFAAs levels (ng/g dw) in the edible parts of vegetables.Sample Site Vegetable PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUdA PFDoA PFBS PFHxS PFOS ∑PFAAs Type

S1 Balsam pear 3.54 0.25 nd nd 0.16 nd nd nd 0.10 nd nd nd 4.27 Fruit vegetables

S1 Cabbage 17.85 1.79 0.56 0.76 1.94 0.06 0.03 nd nd nd 0.06 0.43 23.6 Leafy vegetables

S1 Spinach 3.05 0.50 0.24 0.17 3.17 0.05 nd 0.05 0.03 1.71 0.07 nd 9.07 Leafy vegetables

S1 Radish 1.84 0.07 0.24 0.21 0.22 0.07 0.03 nd 0.09 nd nd nd 2.85 Root vegetables

S2 Eggplant 4.54 0.61 0.22 nd 0.82 0.34 0.28 0.12 0.26 nd nd nd 7.26 Fruit vegetables

S2 Zucchini 1.54 0.21 0.11 nd 0.64 0.04 nd 0.04 0.12 nd nd nd 2.87 Fruit vegetables

S2 Cabbage 11.58 1.11 0.72 1.53 1.33 0.06 0.03 0.10 nd 0.12 nd 0.16 16.8 Leafy vegetables

S2 Rape 4.24 0.07 0.50 0.29 4.08 0.02 0.10 nd 0.03 0.62 0.05 0.07 10.1 Leafy vegetables

S2 Spinach 2.40 0.32 0.30 0.20 2.46 0.06 nd 0.05 0.03 0.17 nd nd 6.05 Leafy vegetables

S2 Radish 2.92 0.92 1.56 0.38 0.32 0.03 nd nd 0.11 nd nd 0.07 6.38 Root vegetables

S3 Sponge gourd 5.98 13.81 2.85 nd 0.31 0.07 nd nd 0.14 nd nd 0.16 23.4 Fruit vegetables

S3 Eggplant 1.89 0.35 0.35 nd 0.26 0.11 0.07 nd 0.13 nd nd nd 3.29 Fruit vegetables

S3 Cabbage 9.34 0.82 1.00 0.87 2.20 nd 0.12 0.05 0.03 nd nd 0.76 15.3 Leafy vegetables

S3 Spinach 2.92 nd 0.30 0.15 2.00 0.03 nd 0.05 0.03 1.75 0.09 nd 7.42 Leafy vegetables

S3 Radish 1.40 0.68 0.77 0.05 0.13 0.08 nd nd 0.09 nd nd nd 3.29 Root vegetables

S4 Sponge gourd 16.66 10.33 5.37 0.26 0.60 nd nd nd 0.11 nd nd 0.08 33.5 Fruit vegetables

S4 Eggplant 2.51 0.60 0.35 nd 0.21 0.19 nd nd 0.17 nd nd nd 4.20 Fruit vegetables

S4 Cabbage 6.56 2.52 1.05 0.85 3.57 0.09 0.07 0.05 0.03 nd nd nd 14.9 Leafy vegetables

S4 Rape 2.23 0.27 0.31 0.05 2.02 0.07 0.03 nd 0.03 0.32 nd nd 5.43 Leafy vegetables

S4 Spinach 1.93 0.52 0.70 0.34 6.66 0.02 0.08 0.10 0.10 nd nd nd 10.6 Leafy vegetables


S5 Tomato 2.46 1.02 0.41 nd 0.17 0.07 nd nd 0.09 nd nd nd 4.34 Fruit vegetables

S5 Sweet pepper 1.44 0.90 0.71 nd 0.17 0.08 nd nd 0.10 nd nd nd 3.50 Fruit vegetables

S5 Cabbage 5.31 1.21 1.06 0.95 2.58 nd 0.03 0.12 nd nd 0.07 nd 11.4 Leafy vegetables

S5 Rape 2.69 0.86 0.92 0.12 1.23 0.02 0.03 0.05 0.03 0.33 0.02 nd 6.32 Leafy vegetables

S5 Radish 2.12 1.30 2.47 0.33 0.31 0.07 0.03 nd 0.12 0.07 nd nd 6.90 Root vegetables

S6 Sponge gourd 2.72 1.41 0.50 0.05 nd 0.06 nd nd 0.12 nd nd nd 4.98 Fruit vegetables

S6 Cucumber 3.95 0.40 0.84 0.94 1.25 0.02 0.15 nd nd nd nd nd 7.63 Fruit vegetables

S6 Eggplant 1.56 0.46 0.39 nd 0.27 nd nd nd 0.09 nd nd nd 2.91 Fruit vegetables

S6 Cabbage 3.78 0.50 0.52 0.72 2.63 0.25 0.10 nd nd nd 0.07 nd 8.70 Leafy vegetables

S6 Rape 3.61 0.79 0.59 0.20 1.75 0.08 nd nd nd 0.18 nd nd 7.28 Leafy vegetables


S7 Cucumber 3.52 0.28 0.47 0.12 0.19 0.02 nd nd nd nd nd nd 4.72 Fruit vegetables

S7 Tomato 3.27 2.11 0.88 0.10 0.17 0.05 nd nd 0.10 nd nd nd 6.77 Fruit vegetables

S7 Cabbage 3.98 1.65 1.40 1.06 3.41 0.12 0.03 nd nd nd nd nd 11.8 Leafy vegetables

S7 Rape 7.70 2.99 3.44 0.18 1.82 0.02 nd nd nd 0.19 0.02 nd 16.4 Leafy vegetables

S7 Spinach 2.07 0.49 0.28 0.12 3.67 0.02 nd nd 0.03 1.72 nd 0.11 8.58 Leafy vegetables



S8 Sweet pepper 1.05 0.53 0.22 nd 0.08 nd nd nd 0.10 0.19 nd nd 2.31 Fruit vegetables


S8 Spinach 2.31 0.25 0.27 0.05 1.44 nd nd 0.05 nd 0.14 nd 0.08 4.67 Leafy vegetables

S8 Radish 1.38 0.17 0.17 nd 0.08 0.02 nd nd 0.14 nd nd nd 2.12 Root vegetables

S9 Sponge gourd 2.72 0.57 0.11 0.05 0.18 0.07 nd nd 0.10 nd nd nd 3.88 Fruit vegetables

S9 Cucumber 1.54 0.16 0.46 0.29 0.49 0.08 nd nd nd nd nd 0.05 3.16 Fruit vegetables

S9 Cabbage 2.88 0.21 0.54 0.22 1.58 nd 0.02 nd nd nd nd nd 5.57 Leafy vegetables

S9 Spinach 1.89 nd 0.15 nd 1.60 0.02 nd nd nd 0.08 nd nd 3.88 Leafy vegetables


S10 Sponge gourd 3.76 1.11 0.54 nd 0.21 nd nd nd 0.11 nd nd 0.08 5.92 Fruit vegetables

S10 Cucumber 2.22 0.33 1.31 0.40 0.61 0.19 0.09 0.20 nd nd nd nd 5.43 Fruit vegetables

S10 Cabbage 2.51 0.33 0.24 0.33 2.15 0.06 0.03 nd nd nd nd nd 5.86 Leafy vegetables

S10 Spinach 2.02 nd 0.25 0.21 1.86 0.02 nd nd nd 0.74 nd nd 5.22 Leafy vegetables


S11 Sponge gourd 3.00 0.43 0.09 nd 0.39 0.07 nd nd 0.09 nd nd nd 4.19 Fruit vegetables

S11 Cucumber 1.59 nd 0.45 0.15 0.11 0.02 nd 0.05 nd nd nd nd 2.51 Fruit vegetables

S11 Cabbage 2.92 0.32 0.54 0.52 1.74 nd 0.03 0.05 nd nd nd nd 6.24 Leafy vegetables

S11 Rape 2.07 0.43 0.13 0.05 1.02 0.07 nd nd nd 0.67 0.02 nd 4.52 Leafy vegetables


S11 Radish 1.16 0.29 0.09 0.05 0.16 0.19 nd 0.18 0.09 nd nd nd 2.26 Root vegetables

S12 Sponge gourd 1.48 0.37 0.15 nd 0.15 nd nd nd 0.12 nd nd nd 2.41 Fruit vegetables

S12 Tomato 2.16 1.26 0.48 nd 0.20 0.02 nd nd 0.12 nd nd nd 4.37 Fruit vegetables

S12 Cabbage 6.45 0.75 0.51 1.36 2.02 0.19 0.12 0.05 0.03 nd nd nd 11.6 Leafy vegetables

S12 Spinach 6.70 1.79 3.90 0.47 2.49 0.02 0.10 0.05 0.22 0.17 nd nd 16.0 Leafy vegetables


S13 Eggplant 1.89 0.41 0.31 nd 0.29 0.19 nd nd 0.20 nd nd nd 3.46 Fruit vegetables

S13 Cabbage 4.83 1.72 1.04 1.32 1.57 0.16 0.03 0.05 nd nd nd nd 10.9 Leafy vegetables

S13 Spinach 4.51 0.07 1.23 0.13 3.84 0.02 nd nd nd nd nd nd 9.92 Leafy vegetables


S14 Cucumber 1.39 0.23 1.16 0.58 0.72 0.14 nd 0.05 nd nd nd 0.06 4.41 Fruit vegetables

S14 Sweet pepper 2.24 0.60 0.27 nd 0.12 nd nd nd 0.03 nd nd nd 3.45 Fruit vegetables


S14 Spinach 1.82 0.30 0.29 0.16 1.94 0.02 nd nd 0.03 0.19 nd nd 4.86 Leafy vegetables


S14 Carrot 1.25 nd nd nd 0.22 nd nd nd 0.09 nd nd nd 1.80 Root vegetables

S15 Cabbage 2.45 0.07 0.35 0.43 2.46 nd nd nd nd nd nd nd 6.03 Leafy vegetables

S15 Rape 4.15 0.85 0.49 0.05 1.51 0.02 0.03 0.05 0.03 0.05 0.02 nd 7.26 Leafy vegetables



S15 Carrot 1.15 0.09 0.07 nd 0.13 nd nd nd 0.09 nd nd nd 1.67 Root vegetables


S16 Tomato 3.15 2.74 1.41 nd 0.18 0.02 nd nd 0.12 0.25 nd 0.19 8.13 Fruit vegetables

S16 Cabbage 4.07 0.38 0.66 0.82 2.94 0.20 0.08 nd 0.04 nd nd nd 9.31 Leafy vegetables

S16 Rape 2.61 0.07 0.20 0.05 0.83 0.07 nd nd nd nd 0.02 0.11 4.03 Leafy vegetables

S16 Spinach 1.57 0.07 0.25 0.12 1.57 0.02 nd nd 0.03 0.08 nd nd 3.78 Leafy vegetables


S17 Cucumber 13.55 4.68 1.36 0.18 0.42 0.06 nd nd nd 0.06 nd nd 20.4 Fruit vegetables

S17 Tomato 2.71 1.21 1.27 nd 0.21 0.02 nd 0.05 0.09 nd nd nd 5.65 Fruit vegetables

S17 Cabbage 7.68 1.24 1.06 1.84 4.02 0.31 0.12 0.05 nd nd nd nd 16.4 Leafy vegetables

S17 Spinach 1.68 0.38 0.25 0.15 1.61 nd nd nd 0.03 0.14 nd nd 4.39 Leafy vegetables

S17 Radish 1.48 0.30 0.33 0.05 0.57 0.14 0.03 nd 0.09 nd nd nd 3.08 Root vegetables

S18 Cabbage 2.95 0.38 0.21 1.16 1.61 0.07 0.03 0.05 nd nd nd 0.35 6.87 Leafy vegetables

S18 Rape 2.46 nd 0.11 0.05 0.97 0.04 nd nd 0.02 0.22 nd nd 4.00 Leafy vegetables

S18 Spinach 1.77 nd 0.19 0.10 2.42 0.02 nd 0.05 nd 0.41 nd 0.09 5.14 Leafy vegetables


Table S9. Pearson correlations of PFAAs concentrations in groundwater collected in the study area and PCA rotated component matrix.PCA Rotated Componenta

Pearson

Correlation PFBA

PFPe

A PFHxA PFHpA PFOA PFNA PFDA PFUdA PFDoA PFBS PFHxS PFOS 1 2 3

PFBA 1 .869 .391 .159

PFPeA .871** 1 .784 .484 -.103

PFHxA .862** .913** 1 .629 .741 .075

PFHpA .836** .716** .611** 1 .962 .011 .183

PFOA .882** .667** .671** .937** 1 .871 .190 .358

PFNA .635** .557* .445 .876** .822** 1 .806 -.007 .056

PFDA .284 .196 .533* .047 .293 -.023 1 -.076 .801 .500

PFUdA .169 -.005 .163 .136 .300 -.013 .571* 1 -.020 .135 .933

PFDoA .303 .330 .632** -.065 .139 -.062 .817** .135 1 -.079 .968 .003

PFBS .610** .447 .262 .685** .570* .466 -.330 -.279 -.248 1 .808 -.260 -.243

PFHxS .524* .578* .368 .652** .450 .417 -.267 -.156 -.216 .799** 1 .776 -.177 -.235

PFOS .296 .038 .217 .226 .386 .009 .469* .824** .040 -.116 -.114 1 .097 .056 .933


Figure S2. The relationship between PFBA found in vegetable edible parts and corresponding irrigation water.

Figure S3. Wind rose in the area around the mega fluorochemical industrial park (FIP) based on the local wind frequency data in the recent 20 years.

Table S10. The Reference Dose of PFAAs recommended by different organizations. Criteria value

Type Setting body ReferencePFBA PFOA PFOS

20 20 RfD a USEPA (USEPA, 2016a; b)

3 2 MRLs a ATSDR (ATSDR, 2018)

2900 18 3.1 RfD a MDH (MDH, 2018b; c; 2019)

6 13 TWIb EFSA (EFSA, 2018)

2 1.8 RfD a NJDWQI

(NJDWQI, 2017;

MDH, 2018a;

NJDWQI, 2018)

Note: RfD, Reference Dose. MRLs, Minimal Risk Levels. TWI, Tolerable Weekly Intake. a, ng/kg bw/d. b, ng/kg bw/week.

Table S11. Sensitivity ratios (SRs, %) of the relative change of estimated daily PFOA intakes to the relative change (∆ CS) of daily consumption of individual vegetables.

Changed parameter2~5 years old 6~17 years old 18~45 years old >45 years old

Urban Rural Urban Rural Urban Rural Urban Rural

Sponge gourd 1.1 2.2 0.9 1.8 0.6 1.4 0.7 1.7

Cucumber 1.3 3.3 2 3.1 2.3 3.5 2.1 2.7

Tomato 1.5 1.1 1.1 0.9 1.1 0.8 0.9 0.7

Balsam pear 0 0.1 0.1 0.2 0.1 0.2 0.1 0.1

Eggplant 1.9 4 2.9 5.5 3.3 5.8 3 5.9

Sweet pepper 0.1 0.3 0.1 0.3 0.2 0.3 0.1 0.2

Zucchini 0.7 0.3 0.3 0.1 0.2 0.3 0.2 0.1

Cabbage 48.5 56 61.1 56.3 59.4 59.4 60.8 57.8

Rape 7.6 4.7 10.2 4.5 7.4 5.8 6.4 5.1

Spinach 33.1 24.9 17.8 24.1 22.2 18.9 21.5 21.5

Radish 3.5 2.5 3.1 2.8 2.9 3.3 3.7 3.9

Carrot 0.7 0.7 0.4 0.4 0.3 0.3 0.4 0.3

Table S12. Estimated daily intakes (EDIs, ng/kg bw/day) of PFOA when the relative change of daily consumption of individual vegetables was 5% and 50%.

∆ CS Changed parameter

2~5 years old 6~17 years old 18~45 years old >45 years old

Urban Rural Urban Rural Urban Rural

Urba

n Rural

0% 0.543

0.39

8 0.392 0.374 0.329 0.308 0.369 0.348

5%

Sponge gourd 0.543

0.39

8 0.392 0.374 0.329 0.308 0.369 0.348

Cucumber 0.543

0.39

8 0.392 0.374 0.33 0.308 0.369 0.349

Tomato 0.543

0.39

8 0.392 0.374 0.329 0.308 0.369 0.348

Balsam pear 0.543

0.39

8 0.392 0.374 0.329 0.308 0.369 0.348

Eggplant 0.543

0.39

8 0.392 0.375 0.33 0.308 0.37 0.349

Sweet pepper 0.543

0.39

8 0.392 0.374 0.329 0.308 0.369 0.348

Zucchini 0.543

0.39

8 0.392 0.374 0.329 0.308 0.369 0.348

Cabbage 0.556

0.40

9 0.403 0.384 0.339 0.317 0.38 0.358

Rape 0.545

0.39

8 0.394 0.375 0.33 0.308 0.37 0.349

Spinach 0.552

0.40

3 0.395 0.378 0.333 0.31 0.373 0.352

Radish 0.544

0.39

8 0.392 0.374 0.33 0.308 0.37 0.349

Carrot 0.543

0.39

8 0.392 0.374 0.329 0.308 0.369 0.348

50

% Sponge gourd 0.546

0.40

2 0.393 0.377 0.33 0.31 0.37 0.351

Cucumber 0.547

0.40

4 0.395 0.379 0.333 0.313 0.373 0.353

Tomato 0.547 0.4 0.394 0.375 0.331 0.309 0.371 0.349

Balsam pear 0.543

0.39

8 0.392 0.374 0.329 0.308 0.369 0.348

Eggplant 0.548

0.40

5 0.397 0.384 0.335 0.316 0.375 0.358

Sweet pepper 0.543 0.39 0.392 0.374 0.329 0.308 0.369 0.349

8

Zucchini 0.545

0.39

8 0.392 0.374 0.33 0.308 0.369 0.348

Cabbage 0.674

0.50

9 0.511 0.479 0.427 0.399 0.481 0.449

Rape 0.564

0.40

7 0.411 0.382 0.341 0.316 0.381 0.357

Spinach 0.633

0.44

7 0.426 0.419 0.366 0.337 0.409 0.386

Radish 0.552

0.40

3 0.397 0.379 0.334 0.312 0.376 0.355

Carrot 0.545

0.39

9 0.392 0.374 0.33 0.308 0.37 0.349

References

ATSDR, 2018. Minimal Risk Levels (MRLs) for Hazardous Substances. https://www.atsdr.cdc.gov/mrls/mrllist.asp#237tag. (January 15, 2019)

CHNS, China Health and Nutrition Survey, Survey Data. http://www.cpc.unc.edu/projects/china/data.

EFSA. 2018. Risk to human health related to the presence of perfluorooctane sulfonic acid and perfluorooctanoic acid in food. EFSA Journal.

MDH. 2018a. Final Responses to Comments, Health Risk Limits Proposed Rules, Minnesota Department of Health April 9, 2018.

MDH, 2018b. Toxicological Summary for: Perfluorobutanoate http://www.health.state.mn.us/divs/eh/risk/guidance/gw/pfba2summ.pdf. (January 15, 2019)

MDH, 2018c. Toxicological Summary for: Perfluorooctanoate. http://www.health.state.mn.us/divs/eh/risk/guidance/gw/pfoa.pdf. (January 15, 2019)

MDH. Toxicological Summary for: Perfluorooctane sulfonate. 2019.

NJDWQI. Maximum Contaminant Level Recommendation for Perfluorooctanoic Acid in Drinking Water. 2017.

NJDWQI. Maximum Contaminant Level Recommendation for Perfluorooctane Sulfonate in Drinking Water. 2018.

USEPA. Health Effects Support Document for PFOA 2016a.

USEPA. Health Effects Support Document for PFOS 2016b.

Wang, P., Lu, Y., Wang, T., Meng, J., Li, Q., Zhu, Z., Sun, Y., Wang, R., Giesy, J. P. 2016. Shifts in production of perfluoroalkyl acids affect emissions and concentrations in the environment of the Xiaoqing River Basin, China. Journal of hazardous materials. 307: 55-63.

http://www.health.state.mn.us/divs/eh/risk/guidance/gw/pfoa.pdf

http://www.health.state.mn.us/divs/eh/risk/guidance/gw/pfba2summ.pdf

http://www.cpc.unc.edu/projects/china/data

https://www.atsdr.cdc.gov/mrls/mrllist.asp#237tag

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