Journal Name: Food Chemistry

Supplementary material for:

Rapid analysis of tristyrylphenol ethoxylates in cucumber-field system using

supercritical fluid chromatography-tandem mass spectrometry

Zejun Jianga,b, Xiaolin Caoa,b, Hui Lia,b, Chan Zhanga,b, A. M. Abd El-Atyc, Ji Hoon Jeongd,

Yong Shaoa,b, Hua Shaoa,b, Maojun Jina,b, Fen Jina,b,*, Jing Wanga,b,*

a Key Laboratory of Agro-product Quality and Safety, Institute of Quality Standard & Testing

Technology for Agro-Products, Chinese Academy of Agricultural Sciences, Beijing 100081, P. R.

Chinab Key Laboratory of Agri-food Safety and Quality, Ministry of Agriculture of China, Beijing 100081,

P. R. Chinac Department of Pharmacology, Faculty of Veterinary Medicine, Cairo University, 12211 Giza, Egyptd Department of Pharmacology, College of Medicine, Chung-Ang University, Seoul, Republic of

Korea

* Corresponding authors:

Tel.: +86-10-8210-6570; E-mail: jinfen@caas.cn (F. Jin)

Tel.: +86-10-8210-6568; E-mail: wangjing05@caas.cn; w_jing2001@126.com (J. Wang)

Number of pages: 18 (including the cover page)

Number of texts: 1

Number of figures: 7

Number of tables: 4

Number of references: 5

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Table of Contents (18 pages, 1 text, 7 figures, 4 tables)

Text S1. Purification and characterization of TSPxEOs

standard. .............................................................................S3

Fig. S1. Chemical structure of tristylphenol ethoxylates (TSPxEOs)………….........................................................S5

Fig. S2. The full scan mass spectrum of 2 mg mL−1 AE-601 using LC-ESI-Q-TOF-MS..........................................S6

Fig. S3. Chromatographic comparisons of AE-601 before and after purification......................................................S7

Fig. S4. Comparison of percentage distribution of the purified TSPxEOs standard using theoretical calculation and

molar absorption coefficient method..........................................................................................................................S8

Fig. S5. Cleanup performance using different

sorbents...............................................................................................S9

Fig. S6. Matrix effects (MEs) of TSPxEOs oligomers (x = 6–29) in cucumber, leaves, and

soil..............................S10

Fig. S7. Typical chromatograms of (A) blank cucumber sample, (B) cucumber spiked at 0.1 mg kg−1, (C) blank

leaves sample, (D) leaves spiked at 0.1 mg kg−1, (E) blank soil, and (F) soil spiked sample at 0.1 mg

kg−1......................S11

Table S1. Molecular weight, retention time, adduct ion, and MS/MS parameters of the tested analytes................S12

Table S2. Normalized concentrations of individual oligomers of TSPxEOs (x = 6–29) used in calibration

standards...................................................................................................................................................................S14

Table S3. Mean recoveries (%) and precision (intra-day RSDr and inter-day RSDR, %) of individual TSPxEOs

oligomers (x = 6–29) in cucumber, leaves, and soil at three fortification levels.....................................................S15

Table S4. Determination coefficients, (R2), limits of detection (LOD, μg kg−1), and limits of quantification (LOQ,

μg kg−1) of the tested analytes in acetonitrile (ACN), cucumber, leaves, and soil......................................S17

References................................................................................................................................................................S18

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Text S1. Purification and characterization of TSPxEOs standard

Agricultural emulsifier 601# (AE-601, generously gifted by Jiangsu Zhongshan Chemical Co.,

Ltd., Nanjing, Jiangsu, China) was used as the source for TSPxEOs, which are not commercially

available as reference substances. This product is a technical mixture of homologues with different

numbers of styrene and ethoxylate units (Fig. S1). The main components were identified by liquid

chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry (LC-ESI-Q-

TOF-MS). The full scan mass spectrum of AE-601 (Fig. S2) obtained by LC-ESI-TOF-MS displayed

several series of signals with almost Gaussian-shaped distributions characteristic pattern. Same as

other ethoxylated surfactants, the mass differences of 44.02 Da or 22.01 Da were observed in

neighboring oligomers in AE-601, which correspond to single- and double-charged ethylene oxide

group. All ions were dominated by ammonium adduct ions ([M + NH4]+ or [M + 2NH4]2+). As a

result, the three most homologous series of oligomers in AE-601 were named as TSPxEOs,

distyrylphenol ethoxylates (DSPxEOs), and tetrastyrylphenol ethoxylates (TeSPxEOs). Because

DSPxEOs and TeSPxEOs were relatively low in abundance; TSPxEOs was used for further

experimental work throughout the MS

For quantitative analysis, TSPxEOs, the main component in AE-601, was prepared by purifying

AE-601 using preparative liquid chromatography. The purified TSPxEOs was used as reference

standards. Fig. S3 provides a chromatographic comparison of AE-601 before and after purification.

Subsequently, the ethoxymer distribution of the purified TSPxEOs standard was determined using

the molar absorption coefficient technique proposed by Wang & Fingas (1993) and the theoretical

calculation technique proposed by Michel, Brauch, Worch, & Lange (2012). The molar absorption

coefficient technique was obtained based on the assumption that the molar response factors of

individual oligomers of ethoxylated surfactants are independent from the length of the ethoxylate

chain and rather constant (Ciofi et al., 2016; Wang et al., 1993). Whereas, the theoretical calculation

applied for characterization of trisiloxane surfactants (Michel et al., 2012) and alkylphenol

ethoxylates (Jiang et al., 2017)

The percentage composition of individual oligomers of TSPxEOs obtained by both approaches

are presented in Fig. S4. The observed distributions are represented by normalizing the mass fraction

summation of all fractions equivalent to 1. The results obtained by theoretical and experimental

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approaches in Fig. S4 have shown the percentage distribution of TSPxEOs (x = 6–27) were rather

similar in shape and were centered at x = 16, which indicates a good agreement between the two

models.

Data representing the percentage composition of oligomers with x <5 and x >27 cannot be

measured by a molar absorption coefficient technique, owing to the fact that oligomers with x <5

were not well resolved from each other and those with x >27 were quite low in abundance.

Individual concentrations of TSPxEOs oligomers (x = 1–5, and x = 30) obtained by theoretical

calculation might not be close to reality. Consequently, further method development (quantitative

analysis) was limited to 6 ≤ x≤ 29 and the percentage distribution of the purified TSPxEOs standards

(6 ≤ x≤ 29) obtained by theoretical calculation was used for quantitative analysis throughout the

study.

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Fig. S1. Chemical structure of tristylphenol ethoxylates (TSPxEOs).

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Fig. S2. The full scan mass spectrum of 2 mg mL−1 AE-601 using LC-ESI-Q-TOF-MS. Agilent 1290 series LC coupled to 6545 Q-TOF (Agilent Technologies, Waldbronn, Germany) equipped with electrospray Jet Stream Technology operating in positive ion mode under the following operation parameters: injection volume, 5 µL; flow rate, 0.3 mL min−1; column temperature, 40 °C; mobile phase, 10 mM CH3CHOONH4 in MeOH (isocratic); mass scanning range, 400-1600 m/z; acquisition rate, 0.6 spectra s−1; fragmentor voltage, 135 V; skimmer voltage, 65 V; octopole RF, 750 V; gas temperature, 320 °C; drying gas, 8 L min−1; nebulizer pressure, 35 psig; sheath gas flow, 11 L min−1; sheath gas temperature, 350 °C were used for identification.

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Fig. S3. Chromatographic comparisons of AE-601 before (upper panel) and after purification (lower panel). Chromatographic conditions were: Column, XBridge C18 column (2.1 mm i.d. × 150 mm, 3.5 µm, Waters, Ireland); column temperature, 25 °C; mobile phase( A), acetonitrile and mobile phase (B), water; flow rate, 0.2 mL min−1; injection volume, 10 μL; the gradient, 0–2 min, 20% A; 2–15 min, 20–95% A; 15–20 min, 95% A; 20–21 min, 95–20% A; 21–30 min, 20% A; detector, diode array detector (DAD); and detection wavelength, 224 nm.

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111112113114115116117118

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Perc

enta

ge c

ompo

sitio

n (%

)

Number of ethoxylate units

Theoretical calculation Molar absorption coefficient method

Fig. S4. Comparison of percentage distribution of the purified TSPxEOs standard using theoretical

calculation and molar absorption coefficient method.

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Fig. S5. Cleanup performance using different sorbents. The scheme number for the given vials is the

same as reported in Table 2.

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40M

atri

x ef

fect

(%)

Number of ethoxylate units

Soil Cucumber Leaves

Fig. S6. Matrix effects (MEs) of TSPxEOs oligomers (x = 6–29) in cucumber, leaves, and soil.

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Fig. S7. Typical chromatograms of (A) blank cucumber sample, (B) cucumber spiked at 0.1 mg kg−1, (C) blank leaves sample, (D) leaves spiked at 0.1 mg kg−1, (E) blank soil, and (F) soil spiked sample at 0.1 mg kg−1. Peaks order are the same as shown in Fig. 2.

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Table S1. Molecular weight, retention time, adduct ion, and MS/MS parameters of the tested analytes.

No.Compound

(Abbr. Name)

Molecular

weight (g/mol)

Retention

time (min)Adduct ion

MRM

transitions*

Q1 pre

bias (V)

CE

(V)

Q3 pre

bias (V)

1 TSP1EO 450.26 0.93 [M+NH4]+468.4>105.2 -23 -29 -17

468.4>269.1 -23 -14 -41

2 TSP2EO 494.28 1.08 [M+NH4]+512.4>105.1 -28 -39 -29

512.4>183.2 -24 -21 -32

3 TSP3EO 538.31 1.30 [M+NH4]+556.4>105.1 -20 -41 -17

556.4>227.3 -26 -21 -23

4 TSP4EO 582.33 1.47 [M+NH4]+600.4>105.1 -29 -46 -17

600.4>271.3 -27 -26 -44

5 TSP5EO 626.36 1.64 [M+NH4]+644.5>105.1 -32 -50 -38

644.2>419.3 -27 -23 -47

6 TSP6EO 670.39 1.80 [M+NH4]+688.5>105.2 -35 -63 -44

688.5>567.4 -35 -20 -41

7 TSP7EO 714.41 1.95 [M+NH4]+732.5>105.1 -35 -55 -27

732.5>611.3 -35 -17 -33

8 TSP8EO 758.44 2.11 [M+NH4]+776.6>105.1 -29 -33 -47

776.6>551.4 -29 -25 -38

9 TSP9EO 802.47 2.27 [M+NH4]+820.6>105.1 -32 -60 -41

820.6>329.2 -41 -30 -14

10 TSP10EO 846.49 2.42 [M+NH4]+864.7>105.1 -44 -65 -41

864.7>89.1 -26 -38 -14

11 TSP11EO 890.52 2.58 [M+NH4]+908.7>105.2 -31 -59 -17

908.7>177.0 -35 -31 -10

12 TSP12EO 934.54 2.73 [M+NH4]+952.7>105.1 -38 -65 -23

952.7>89.0 -40 -46 -14

13 TSP13EO 978.57 2.89 [M+NH4]+996.7>105.1 -38 -65 -17

996.7>329.3 -29 -36 -20

14 TSP14EO 1022.60 3.04 [M+NH4]+1040.8>105.1 -41 -61 -17

1040.8>89.3 -32 -51 -38

15 TSP15EO 1066.62 3.19 [M+NH4]+1084.8>105.1 -32 -64 -17

1084.8>89.1 -32 -45 -35

16 TSP16EO 1110.65 3.34 [M+NH4]+1128.8>105.1 -44 -65 -17

1128.8>133.1 -44 -38 -47

17 TSP17EO 1154.68 3.48 [M+2NH4]2+595.6>105.2 -30 -22 -42

595.6>89.2 -30 -29 -34

18 TSP18EO 1198.70 3.63 [M+2NH4]2+617.6>105.2 -24 -23 -16

617.6>89.2 -24 -31 -36

19 TSP19EO 1242.73 3.77 [M+2NH4]2+639.6>105.2 -42 -26 -32

639.6>89.2 -38 -31 -14

20 TSP20EO 1286.75 3.91 [M+2NH4]2+661.7>105.2 -26 -40 -40

661.7>89.2 -34 -33 -34

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21 TSP21EO 1330.78 4.05 [M+2NH4]2+683.7>105.2 -26 -38 -14

683.7>89.2 -26 -33 -34

22 TSP22EO 1374.81 4.19 [M+2NH4]2+705.7>105.2 -32 -37 -40

705.7>89.2 -36 -34 -32

23 TSP23EO 1418.83 4.32 [M+2NH4]2+727.7>105.1 -28 -44 -16

727.7>89.2 -28 -35 -34

24 TSP24EO 1462.86 4.44 [M+2NH4]2+749.8>105.1 -38 -55 -16

749.8>89.1 -28 -35 -14

25 TSP25EO 1506.89 4.56 [M+2NH4]2+771.8>105.1 -38 -48 -16

771.8>89.2 -38 -36 -36

26 TSP26EO 1550.91 4.68 [M+2NH4]2+793.8>105.1 -30 -52 -16

793.8>89.2 -30 -36 -34

27 TSP27EO 1594.94 4.78 [M+2NH4]2+815.9>105.1 -42 -54 -16

815.9>89.2 -32 -37 -14

28 TSP28EO 1638.96 4.90 [M+2NH4]2+837.9>105.2 -32 -49 -31

837.9>89.2 -32 -38 -20

29 TSP29EO 1682.99 5.00 [M+2NH4]2+859.9>105.1 -32 -50 -41

859.9>89.2 -32 -42 -35

30 TSP30EO 1727.02 5.11 [M+2NH4]2+881.9>105.1 -44 -51 -41

881.9>89.2 -44 -40 -35

Note: * Quantifier transition in bold.

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Table S2. Normalized concentrations of individual oligomers of TSPxEOs (x = 6–29) used in calibration standards.

No. Oligomer Concentration (μg L–1)

6 TSP6EO 0.006 0.012 0.023 0.058 0.12 0.23 0.58 1.17 2.34 2.92 5.85

7 TSP7EO 0.016 0.031 0.062 0.16 0.31 0.62 1.56 3.12 6.23 7.79 15.6

8 TSP8EO 0.035 0.071 0.14 0.35 0.71 1.42 3.54 7.09 14.17 17.72 35.4

9 TSP9EO 0.070 0.14 0.28 0.70 1.41 2.81 7.03 14.06 28.12 35.15 70.29

10 TSP10EO 0.12 0.25 0.49 1.24 2.47 4.94 12.36 24.72 49.43 61.79 123.58

11 TSP11EO 0.20 0.39 0.78 1.95 3.90 7.80 19.50 39.00 78.01 97.51 195.01

12 TSP12EO 0.28 0.56 1.12 2.79 5.58 11.16 27.91 55.81 111.63 139.54 279.07

13 TSP13EO 0.37 0.73 1.46 3.65 7.31 14.61 36.53 73.06 146.11 182.64 365.28

14 TSP14EO 0.44 0.88 1.76 4.40 8.81 17.62 44.04 88.09 176.17 220.22 440.44

15 TSP15EO 0.49 0.98 1.97 4.92 9.84 19.69 49.22 98.44 196.88 246.11 492.21

16 TSP16EO 0.51 1.03 2.05 5.13 10.25 20.50 51.25 102.51 205.01 256.26 512.53

17 TSP17EO 0.50 1.00 2.00 5.00 9.99 19.98 49.95 99.91 199.82 249.77 499.54

18 TSP18EO 0.46 0.92 1.83 4.58 9.15 18.30 45.76 91.52 183.03 228.79 457.58

19 TSP19EO 0.40 0.79 1.58 3.95 7.91 15.81 39.53 79.06 158.13 197.66 395.32

20 TSP20EO 0.32 0.65 1.29 3.23 6.46 12.93 32.32 64.63 129.26 161.58 323.15

21 TSP21EO 0.25 0.50 1.00 2.51 5.01 10.03 25.07 50.13 100.26 125.33 250.66

22 TSP22EO 0.18 0.37 0.74 1.85 3.70 7.40 18.50 36.99 73.99 92.48 184.96

23 TSP23EO 0.13 0.26 0.52 1.30 2.60 5.21 13.02 26.03 52.06 65.08 130.15

24 TSP24EO 0.088 0.18 0.35 0.88 1.75 3.50 8.75 17.50 35.01 43.76 87.51

25 TSP25EO 0.056 0.11 0.23 0.56 1.13 2.25 5.63 11.27 22.54 28.17 56.34

26 TSP26EO 0.035 0.070 0.14 0.35 0.70 1.39 3.48 6.96 13.92 17.40 34.79

27 TSP27EO NI 0.041 0.083 0.21 0.41 0.83 2.06 4.13 8.26 10.32 20.64

28 TSP28EO NI NI 0.047 0.12 0.24 0.47 1.18 2.36 4.71 5.89 11.78

29 TSP29EO NI NI NI 0.065 0.13 0.26 0.65 1.30 2.59 3.24 6.48

∑TSPxEOs 5 10 20 50 100 200 500 1000 2000 2500 5000

Note: NI, not include in calibration curves, due to low abundances and sensitivity related issues.

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Table S3. Mean recoveries (%) and precision (intra-day RSDr and inter-day RSDR, %) of individual TSPxEOs oligomers (x = 6–29) in cucumber, leaves, and soil at

three fortification levels.

No. OligomerFortification level

(μg kg−1)

Cucumber Leaves Soil

Mean recoveries RSDr* RSDR

# Mean recoveries RSDr RSDR Mean recoveries RSDr RSDR

6 TSP6EO 0.02, 0.12, 0.58 99.3, 84.3, 83.3 16.1, 10.6, 5.6 15.9, 10.9, 9.7 81.5, 95.6, 84.3 5.8, 2.6, 6.8 6.6, 4.6, 7.8 96.3, 84.6, 100.5 4.8, 11.1, 7.1 7.5, 8.2, 9.7

7 TSP7EO 0.06, 0.31, 1.56 83.9, 84.6, 77.9 8.7, 5.3, 7.2 10.7, 11.6, 9.3 92.3, 88.0, 83.5 13.9, 13.8, 3.8 11.4, 9.5, 5.7 95.5, 95.7, 90.4 11.7, 14.2, 4.9 10.8, 10.6, 7.5

8 TSP8EO 0.14, 0.71, 3.54 89.7, 76.9, 77.6 17.2, 5.6, 5.2 14.8, 9.6, 10.0 92.0, 91.6, 82.2 13.3, 10.1, 4.5 10.0, 9.3, 6.1 79.3, 83.5, 83.5 6.1, 7.6, 3.4 8.4, 7.2, 6.1

9 TSP9EO 0.28, 1.40, 7.02 79.6, 76.9, 73.0 12.6, 5.6, 9.2 11.5, 9.3, 8.1 91.5, 80.3, 73.0 14.1, 3.7, 5.3 8.9, 8.0, 10.5 87.6, 112.9, 69.6 13.3, 3.7, 7.3 11.2, 14.3, 8.1

10 TSP10EO 0.49, 2.47, 12.35 79.6, 78.7, 80.4 8.7, 4.2, 5.5 10.4, 10.3, 10.2 73.8, 77.2, 77.0 15.0, 9.1, 11.3 10.1, 7.2, 10.1 91.2, 99.0, 75.0 3.9, 2.5, 7.2 8.5, 12.5, 7.3

11 TSP11EO 0.78, 3.90, 19.49 77.9, 85.8, 74.0 9.6, 10.0, 5.0 9.2, 10.7, 6.5 82.8, 83.2, 76.1 8.8, 8.4, 20.0 7.3, 7.9, 13.6 86.7, 88.6, 82.5 13.3, 5.7, 12.9 10.0, 8.2, 9.7

12 TSP12EO 1.12, 5.58, 27.89 77.3, 76.6, 74.6 8.1, 7.3, 6.0 10.0, 9.5, 9.2 83.1, 72.7, 86.7 12.8, 11.6, 9.6 9.2, 8.9, 7.2 86.5, 82.9, 85.5 12.8, 8.7, 10.7 9.8, 8.0, 9.4

13 TSP13EO 1.46, 7.30, 36.51 81.9, 79.6, 85.5 10.1, 8.2, 4.4 11.9, 9.7, 8.8 78.7, 90.5, 101.5 13.7, 6.4, 4.3 10.7, 9.7, 5.1 98.4, 79.8, 84.9 3.2, 11.8, 4.1 7.7, 8.4, 7.2

14 TSP14EO 1.76, 8.80, 44.02 76.4, 79.8, 83.6 7.5, 5.7, 9.0 9.1, 7.9, 7.9 86.8, 81.6, 84.7 11.2, 16.6, 7.4 10.3, 12.6, 7.4 90.6, 85.1, 78.0 12.3, 9.0, 8.6 8.6, 8.8, 7.7

15 TSP15EO 1.97, 9.84, 49.19 87.9, 90.6, 82.7 7.6, 4.2, 6.9 10.9, 6.8, 8.7 92.0, 83.1, 95.8 15.5, 9.6, 8.4 12.0, 10.2, 11.1 95.2, 81.3, 79.3 14.4, 7.8, 16.4 12.2, 7.9, 10.3

16 TSP16EO 2.05, 10.24, 51.22 81.1, 80.0, 87.1 7.0, 10.9, 7.1 8.5, 10.6, 6.8 83.4, 88.6, 84.1 10.2, 3.8, 9.3 10.1, 7.9, 7.5 92.7, 88.9, 82.9 17.3, 7.0, 10.9 12.7, 8.8, 8.1

17 TSP17EO 2.00, 9.98, 49.92 79.1, 78.7, 82.7 7.8, 3.1, 12.5 8.2, 6.7, 9.9 90.1, 85.0, 89.5 14.1, 5.9, 6.4 10.9, 9.8, 10.7 93.1, 96.2, 88.8 10.0, 6.6, 8.4 8.6, 8.0, 7.9

18 TSP18EO 1.83, 9.15, 45.73 87.4, 81.2, 86.5 11.9, 6.6, 7.0 12.1, 7.1, 8.9 95.2, 99.3, 98.5 14.0, 4.4, 6.6 15.9, 11.4, 12.4 96.3, 92.3, 89.1 12.4, 5.6, 9.0 12.3, 9.4, 6.9

19 TSP19EO 1.58, 7.90, 39.51 90.0, 80.7, 90.1 7.8, 12.1, 9.5 10.8, 8.9, 10.3 91.2, 92.4, 95.1 18.8, 10.7, 12.9 15.1, 10.6, 11.6 90.3, 82.4, 83.4 6.5, 3.6, 6.9 8.2, 8.3, 8.0

20 TSP20EO 1.29, 6.46, 32.30 85.0, 82.5, 87.6 5.1, 5.7, 12.3 8.9, 8.3, 10.6 94.1, 92.7, 93.1 7.2, 12.3, 9.8 10.5, 11.7, 10.3 77.4, 94.0, 93.1 9.0, 7.4, 4.4 8.9, 9.9, 7.2

21 TSP21EO 1.00, 5.01, 25.05 84.2, 78.6, 83.5 4.2, 10.1, 4.3 8.2, 10.2, 7.1 91.0, 96.9, 97.6 15.6, 15.8, 14.8 12.0, 14.2, 11.9 95.7, 81.5, 92.5 6.3, 12.2, 16.0 11.4, 12.2, 12.7

22 TSP22EO 0.74, 3.70, 18.49 78.8, 81.2, 77.8 6.6, 10.2, 3.6 8.3, 10.2, 5.6 72.7, 87.7, 77.5 11.0, 7.3, 13.8 10.1, 8.3, 9.0 82.7, 88.2, 83.2 7.1, 12.7, 14.2 7.3, 9.7, 9.1

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23 TSP23EO 0.52, 2.60, 13.01 73.9, 75.4, 80.1 7.8, 5.2, 6.7 5.9, 5.9, 6.5 80.5, 80.2, 76.6 15.5, 7.2, 10.9 10.3, 6.1, 10.6 76.4, 66.1, 93.2 14.0, 8.4, 8.5 8.9, 11.9, 7.7

24 TSP24EO 0.35, 1.75, 8.75 79.7, 77.6, 82.0 11.9, 9.0, 5.2 9.2, 7.4, 6.4 79.0, 73.0, 72.9 8.0, 6.9, 7.1 7.1, 6.4, 5.4 86.3, 79.4, 78.1 10.9, 4.7, 8.8 9.0, 7.5, 7.4

25 TSP25EO 0.23, 1.13, 5.63 76.6, 80.0, 75.3 6.3, 3.0, 4.8 7.0, 7.4, 6.1 76.0, 88.8, 74.4 9.6, 14.3, 7.8 8.0, 11.9, 9.0 77.8, 79.8, 82.2 9.0, 9.8, 13.0 7.4, 8.8, 9.5

26 TSP26EO 0.14, 0.70, 3.48 87.6, 79.9, 78.8 8.0, 4.7, 9.9 10.4, 6.9, 8.7 64.4, 78.5, 76.5 9.2, 17.3, 19.6 8.5, 11.4, 12.3 73.9, 89.5, 77.4 9.9, 7.5, 3.8 7.6, 10.3, 6.3

27 TSP27EO 0.083, 0.41, 2.06 72.5, 70.1, 78.3 13.7, 10.6, 9.4 9.8, 7.2, 7.1 73.5, 75.9, 73.3 11.7, 9.6, 16.0 7.6, 8.1, 10.0 73.5, 77.2, 64.2 8.4, 7.5, 10.5 7.1, 8.7, 9.3

28 TSP28EO 0.047, 0.24, 1.18 79.9, 75.9, 70.8 11.8, 12.4, 4.8 9.1, 9.1, 5.6 72.2, 74.1, 67.7 15.5, 6.4, 8.7 12.3, 5.3, 6.7 77.1, 83.4, 89.6 8.8, 10.3, 6.4 8.6, 11.7, 13.5

29 TSP29EO ND, 0.13, 0.65 NA, 71.7, 75.3 NA, 8.0, 14.3 NA, 7.2, 11.1 NA, 62.5, 63.5 NA, 13.2, 10.8 NA, 12.4, 9.1 NA, 74.5, 67.3 NA, 1.3, 11.0 NA, 3.7, 9.8

Note: *, n = 6; #, n = 18; ND, not present at detectable levels; NA, data are not available.

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Table S4. Determination coefficients (R2), limits of detection (LOD, μg kg−1), and limits of quantification (LOQ, μg

kg−1) for the tested analytes in acetonitrile (ACN), cucumber, leaves, and soil.

OligomerACN Cucumber Leaves Soil

R2 LOD LOQ R2 LOD LOQ R2 LOD LOQ R2 LOD LOQ

TSP6EO 0.9987 0.0002 0.001 0.9992 0.0003 0.001 0.9981 0.0002 0.001 0.9988 0.0002 0.001

TSP7EO 0.9990 0.0009 0.003 0.9993 0.0007 0.002 0.9985 0.0005 0.002 0.9927 0.0005 0.002

TSP8EO 0.9997 0.002 0.005 0.9992 0.001 0.005 0.9980 0.002 0.006 0.9990 0.002 0.005

TSP9EO 0.9991 0.002 0.006 0.9980 0.002 0.008 0.9983 0.002 0.008 0.9983 0.002 0.006

TSP10EO 0.9993 0.002 0.008 0.9995 0.003 0.011 0.9991 0.003 0.011 0.9984 0.003 0.010

TSP11EO 0.9986 0.004 0.012 0.9990 0.004 0.015 0.9974 0.005 0.016 0.9997 0.004 0.013

TSP12EO 0.9959 0.006 0.021 0.9974 0.009 0.028 0.9985 0.009 0.028 0.9992 0.007 0.024

TSP13EO 0.9922 0.009 0.030 0.9968 0.010 0.034 0.9928 0.011 0.035 0.9992 0.009 0.031

TSP14EO 0.9997 0.008 0.026 0.9986 0.010 0.035 0.9982 0.011 0.038 0.9980 0.011 0.036

TSP15EO 0.9991 0.010 0.034 0.9973 0.012 0.039 0.9971 0.012 0.038 0.9988 0.012 0.040

TSP16EO 0.9923 0.010 0.035 0.9960 0.013 0.043 0.9939 0.012 0.040 0.9968 0.012 0.038

TSP17EO 0.9996 0.010 0.034 0.9986 0.013 0.042 0.9966 0.012 0.039 0.9991 0.010 0.034

TSP18EO 0.9991 0.010 0.033 0.9933 0.011 0.035 0.9943 0.010 0.035 0.9976 0.011 0.038

TSP19EO 0.9991 0.008 0.027 0.9980 0.008 0.027 0.9996 0.007 0.023 0.9977 0.011 0.038

TSP20EO 0.9992 0.010 0.033 0.9959 0.009 0.030 0.9979 0.010 0.033 0.9917 0.011 0.036

TSP21EO 0.9996 0.008 0.026 0.9970 0.009 0.031 0.9984 0.008 0.026 0.9984 0.009 0.029

TSP22EO 0.9996 0.007 0.023 0.9986 0.007 0.022 0.9990 0.007 0.023 0.9985 0.007 0.025

TSP23EO 0.9987 0.005 0.017 0.9956 0.005 0.017 0.9975 0.005 0.016 0.9943 0.007 0.024

TSP24EO 0.9984 0.004 0.012 0.9965 0.005 0.016 0.9979 0.004 0.012 0.9964 0.003 0.011

TSP25EO 0.9995 0.008 0.027 0.9983 0.009 0.029 0.9997 0.009 0.032 0.9972 0.008 0.027

TSP26EO 0.9980 0.008 0.028 0.9971 0.009 0.030 0.9988 0.010 0.032 0.9983 0.009 0.029

TSP27EO 0.9960 0.009 0.029 0.9996 0.009 0.031 0.9978 0.010 0.032 0.9960 0.009 0.029

TSP28EO 0.9931 0.010 0.035 0.9986 0.010 0.032 0.9988 0.010 0.033 0.9992 0.009 0.029

TSP29EO 0.9910 0.012 0.039 0.9966 0.011 0.038 0.9976 0.010 0.034 0.9911 0.014 0.048

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