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SUPPLEMENTARY INFORMATION to the paper entitled:

Evaluation of gas chromatography - electron ionization - full scan high resolution Orbitrap mass spectrometry for pesticide residue analysis

Hans G.J. Mol*, Marc Tienstra, Paul Zomer

RIKILT – Wageningen UR, Akkermaalsbos 2, 6708 WB, Wageningen, The Netherlands

*Corresponding author. E-mail address: [email protected], tel.: +31 317 480 318

Supplementary information Mol et al, GC-EI-Orbitrap-MS 1

Content Page

Table S1 List of pesticides, retention times, exact m/z of ions 3

Table S2 Linearity of instrument response 5

Table S3 Performance characteristics for individual pesticides 6

Figure S1 Schematic representation of the EI-Q-Orbitrap 8

Figure S2 Examples EI-Orbitrap spectra vs NIST EI-quadrupole spectra 9a) hexachlorobenzeneb) chlorpyrifosc) pirimicarbd) disulfotone) dieldrinf) fenitrothiong) dichlorvos

Figure S3 Resolving power of the orbitrap mass analyzer vs m/z16

Figure S4 TIC chromatograms of tomato, leek, orange17

Figure S5 Effect of AGC target value and TIC on detectability19

Figure S6 Example selection quantifier and qualifier ion21

Figure S7 Example estimation LOD, LOQ, LOI22


Table S1. Pesticides included in the study, with retention times and exact masses of quantifier and qualifier ions.

Quan Quan qual qual qual qual qual qual qual qual qual qualCompound Name Mol. Form Exact mass tr (min) m/z-1 m/z-1 m/z-2 m/z-2 m/z-3 m/z-3 m/z-4 m/z-4 m/z-5 m/z-5 m/z-6 m/z-6Dichlorvos C4H7Cl2O4P 219.94590 7.80 C4ClH7O4P 184.97650 C2H8PO4 127.01547 C4H7Cl(37)O4P 186.97355 C2H6O3P 109.00491 C4H7Cl2O4P 219.94535Biphenyl C12H10 154.07825 8.10 C12H10 154.07770 C12H9 153.06988 C12H8 152.062052-phenylphenol C12H10O 170.07317 9.69 C12H10O 170.07262 C11H9 141.06988 C12H9O 169.06479 C9H7 115.05423Hexachlorobenzene C6Cl6 281.81312 11.67 C6Cl5Cl(37) 283.80962 C6Cl4Cl(37)2 285.80667 C6Cl6 281.81257 C6Cl4Cl(37) 248.84076 C6Cl3Cl(37) 213.87191 C6Cl2Cl(37) 178.90306Chlorpropham C10H12ClNO2 213.05566 11.89 C6ClH6N 127.01833 C7H6NO2Cl 171.00816 C10H12ClNO2 213.05511 C8H9NCl 154.04180HCH, alpha C6H6Cl6 287.86007 12.10 C6Cl3H4 180.93731 C6H4Cl2Cl(37) 182.93436 C6H5Cl3[37]Cl 218.91104 C6H5Cl4 216.91399 C3H3Cl2 108.96063 C6H4Cl2 145.96846HCH, gamma (lindane) C6H6Cl6 287.86007 12.81 C6Cl3H4 180.93731 C6H4Cl2Cl(37) 182.93436 C6H5Cl3[37]Cl 218.91104 C6H5Cl4 216.91399 C3H3Cl2 108.96063 C6H4Cl2 145.96846Pyrimethanil C12H13N3 199.11095 12.86 C12H13N3 199.11040 C12H12N3 198.10257 C11H9N3 183.07910 C7H6N2 118.05255 C11H10N3 184.08692Propazine C9H16ClN5 229.10942 13.03 C8H13ClN5 214.08540 C5H7ClN5 172.03845 C9H16ClN5 229.10887 C8H13Cl(37)N5 216.08245 C6H10N5Cl 187.06192 C6H10N5 152.09307HCH, beta C6H6Cl6 287.86007 13.05 C6Cl3H4 180.93731 C6H4Cl2Cl(37) 182.93436 C6H5Cl3[37]Cl 218.91104 C6H5Cl4 216.91399 C3H3Cl2 108.96063 C6H4Cl2 145.96846Diazinon C12H21N2O3PS 304.10105 13.08 C10H15N2O 179.11789 C8H12N2O2P 199.06309 C7H9N2O 137.07094 C12H21N2O3PS 304.10050 C10H16O2N2P 227.09439 C8H12N2O 152.09441Trifluralin C13H16F3N3O4 335.10929 13.16 C8H5F3N3O4 264.02267 C11H11F3N3O4 306.06962 C8H5F3N3O3 248.02775 C7H5O2N2F3 206.02976 C11H11F3N3O3 290.07470Terbuthylazine C9H16ClN5 229.10942 13.23 C8ClH13N5 214.08540 C5H8N5Cl 173.04627 C8H13Cl(37)N5 216.08245 C9H16ClN5 229.10887 C5H8N5 138.07742Disulfoton C8H19O2PS3 274.02848 13.34 C4H8S 88.03412 H2O2PS 96.95076 C2H7OPS2 141.96705 C4H10O2PS 153.01336 C4H11O2PS2 185.99326 C8H19O2PS3 274.02793Spiroxamine I (7) C18H35NO2 297.26678 13.52 C6H14N 100.11208 C8H16N 126.12773 C5C(13)H14N 101.11543 C11H20O2N 198.14886 C8H18ON 144.13829Fenpropidin C19H31N 273.24565 13.61 C6H12N 98.09643 C5C(13)H12N 99.09978 C19H31N 273.24510 C11H13 145.10118 C9H9 117.06988Spiroxamine II (7) C18H35NO2 297.26678 13.91 C6H14N 100.11208 C8H16N 126.12773 C5C(13)H14N 101.11543 C11H20O2N 198.14886 C8H18ON 144.13829Pirimicarb C11H18N4O2 238.14298 14.09 C8H12N3O 166.09749 C11H18N4O2 238.14243 C3H6NO 72.04439Chlorpyrifos-methyl C7H7Cl3NO3PS 320.89499 14.16 C7H7Cl2NO3PS 285.92558 C7H7ClCl(37)NO3PS 287.92263 C2H6O2PS 124.98206Fenpropimorph C20H33NO 303.25622 14.29 C7H14NO 128.10699 C7H12N 110.09643 C6C(13)H14NO 129.11035 C20H33NO 303.25567Chlorothalonil C8Cl4N2 263.88156 14.58 C8Cl3Cl(37)N2 265.87806 C8Cl4N2 263.88101 C8Cl2Cl(37)2N2 267.87511 C8N2 124.0056 C8N2Cl3 228.91216Chlorpyrifos C9H11Cl3NO3PS 348.92629 15.03 C5Cl3H2NO 196.91965 C5H2Cl2Cl(37)NO 198.91670 C5H3Cl2NO3PS 257.89428 C9H11Cl2NO3PS 313.95688 C7H7O3NCl2PS 285.92558 H2O2PS 96.95076Metalaxyl C15H21NO4 279.14706 15.08 C12H16NO2 206.11756 C11H14N 160.11208 C13H18NO2 220.13321 C13H16NO3 234.11247 C9H10N 132.08078 C12H18ON 192.13829Vinclozolin C12H9Cl2NO3 284.99595 15.13 C10Cl2H8N 212.00283 C10H9ClN 178.04180 C9H6NCl2 197.98718 C7H3Cl2NO 186.95862 C6H3NCl 123.99485 C12H9Cl2NO3 284.99540Parathion-methyl C8H10NO5PS 263.00173 15.18 C8H10NO5PS 263.00118 C2H6O2PS 124.98206 C2H8PO4 127.01547 C2H6O3P 109.00491 C7H7O4NP 200.01072Fenitrothion C9H12NO5PS 277.01738 15.59 C9H11NO4PS 260.01409 C2H6O2PS 124.98206 C9H12NO5PS 277.01683 C2H8O4P 127.01547 C2H6O3P 109.00491 C2H8O3PS 142.99263Parathion C10H14NO5PS 291.03303 16.11 C10H14NO5PS 291.03248 C2H6O3P 109.00491 C6H5O2NS 155.00355 C6H5NO3 139.02639 C6H5O4NP 185.99507 C8H10O5NPS 263.00118Pendimethalin C13H19N3O4 281.13756 16.28 C11H14N3O4 252.09788 C9H10ON2 162.07876 C9H9O2N3 191.06893 C9H10O3N3 208.07167 C13H19N3O4 281.13701DDE p.p' C14H8Cl4 315.93801 16.31 C14Cl2H8 245.99976 C14H8ClCl(37) 247.99681 C14H8Cl3Cl(37) 317.93451 C14H8Cl4 315.93746 C14H8 176.06205 C14H7Cl 210.02308Endosulfan alpha C9H6Cl6O3S 403.81688 16.31 C5Cl4Cl(37) 236.84076 C8H4Cl2 169.96846 C7H6Cl2 159.98411 C7H4Cl2Cl(37) 194.93436 C8H3Cl3 203.92948 C7H2Cl4Cl(37) 262.85641Kresoxim-methyl C18H19NO4 313.13141 16.68 C8H6N 116.04948 C11H12NO3 206.08117 C9H9N 131.07295Dieldrin C12H8Cl6O 377.87063 16.75 C7H2Cl4Cl(37) 262.85641 C7H2Cl5 260.85936 C8H4Cl4Cl(37) 276.87207 C12H8Cl6O 377.87008 C6H7 79.05423DDT o.p' C14H9Cl5 351.91469 17.07 C13Cl2H9 235.00758 C13H9ClCl(37) 237.00463 C13H8Cl 199.03090 C14H9Cl 212.03873 C14H8Cl2 245.99976 C13H9 165.06988Procymidone C13H11Cl2NO2 283.01668 17.14 C13Cl2H11NO2 283.01614 C13H11ClCl(37)NO2 285.01319 C12H11ONCl2 255.02122 C6H8O 96.05697DDD p.p' C14H10Cl4 317.95366 17.38 C13Cl2H9 235.00758 C13H9ClCl(37) 237.00463 C13H8Cl 199.03090 C14H9Cl 212.03873 C13H9 165.06988Chlorobenzilate C16H14Cl2O3 324.03200 17.43 C13H9OCl2 251.00250 C7H4ClO 138.99452 C13H9OClCl(37) 252.99955 C7H4Cl(37)O 140.99157 C6H4Cl 110.99960Chloropropylate C17H16Cl2O3 338.04765 17.52 C13H9OCl2 251.00250 C7H4ClO 138.99452 C13H9OClCl(37) 252.99955 C7H4Cl(37)O 140.99157 C6H4Cl 110.99960Endosulfan beta C9H6Cl6O3S 403.81688 17.56 C8H4Cl2 169.96846 C5Cl4Cl(37) 236.84076 C7H4Cl2Cl(37) 194.93436 C7H6Cl2 159.98411 C8H3Cl3 203.92948 C7H2Cl4Cl(37) 262.85641Bupirimate C13H24N4O3S 316.15691 17.63 C10H17N4O3S 273.10159 C10H17N4 193.14477 C11H18N3O 208.14444 C13H24N4O3S 316.15636 C8H12ON3 166.09749DDT p.p' C14H9Cl5 351.91469 17.88 C13Cl2H9 235.00758 C13H9ClCl(37) 237.00463 C13H8Cl 199.03090 C14H9Cl 212.03873 C14H8Cl2 245.99976 C13H9 165.06988Resmethrin I (6) C22H26O3 338.18820 17.92 C12H11O 171.08044 C9H15 123.11683 C11H11 143.08553 C10H8 128.06205Fipronil C12H4Cl2F6N4OS 435.93871 18.08 C11Cl2F3H4N4OS 366.94295 C11H4ClCl(37)F3N4OS 368.94000 C7H2Cl2F3 212.94802 C7H2ClCl(37)F3 214.94507 C8H4N2Cl2F3 254.96981Resmethrin II (6) C22H26O3 338.18820 18.10 C12H11O 171.08044 C9H15 123.11683 C11H11 143.08553 C10H8 128.06205Bifenthrin C23H22ClF3O2 422.12604 18.92 C14H13 181.10118 C13H10 166.07770 C13H9 165.06988 C12H9 153.06988Endosulfan sulfate C9H6Cl6O4S 419.81180 19.08 C5Cl5Cl(37) 271.80962 C5Cl4Cl(37)2 273.80667 C7H3Cl3Cl(37) 228.89539 C5Cl4Cl(37) 236.84076 C9H6O4Cl4Cl(37)S 386.83945 C9H6O4Cl5Cl(37)S 421.80830Oxadixyl C14H18N2O4 278.12666 19.19 C9H10N 132.08078 C10H13NO 163.09917 C12H13O3N2 233.09207 C8H10N 120.08078 C14H18N2O4 278.12611


Table S1. Pesticides included in the study, with retention times and exact masses of quantifier and qualifier ions (continued).

Quan Quan qual qual qual qual qual qual qual qual qual qualCompound Name Mol. Form Exact mass tr (min) m/z-1 m/z-1 m/z-2 m/z-2 m/z-3 m/z-3 m/z-4 m/z-4 m/z-5 m/z-5 m/z-6 m/z-6Tetramethrin I (8) C19H25NO4 331.17836 19.44 C9H10NO2 164.07061 C8C(13)H10NO2 165.07396 C9H15 123.11683 C7H7O 107.04914 C8H7O2 135.04406PCB198 (ISTD) C12H2Cl8 425.76647 19.47 C12H2Cl6Cl(37)2 429.76002 C12H2Cl7Cl(37) 427.76297 C12H2Cl5Cl(37) 357.82527 C12H2Cl6Cl(37) 392.79412Iprodione C13H13Cl2N3O3 329.03340 19.60 C12H10N3O3Cl2 314.00937 C12H10N3O3ClCl(37) 316.00642 C7H3NOCl2 186.95862 C7H3NOClCl(37) 188.95567 C9H7O2N2Cl2 244.98791Tetramethrin II (8) C19H25NO4 331.17836 19.63 C9H10NO2 164.07061 C8C(13)H10NO2 165.07396 C9H15 123.11683 C7H7O 107.04914 C8H7O2 135.04406Cyhalothrin (1) C23H19ClF3NO3 449.10056 20.64 C8H9ClF3 197.03394 C8H7F2 141.05103 C14H10ON 208.07569 C13H9O 181.06479 C14H11NO 209.08352Cyhalothrin-lambda C23H19ClF3NO3 449.10056 20.91 C8H9ClF3 197.03394 C8H7F2 141.05103 C14H10ON 208.07569 C13H9O 181.06479 C14H11NO 209.08352Bitertanol C20H23N3O2 337.17903 20.94 C12H10O 170.07262 C8H14ON3 168.11314 C4H6ON3 112.05054 C11H9 141.06988 C12H8 152.06205Etofenprox C25H28O3 376.20385 21.20 C11H15O 163.11174 C13H11O 183.08044 C9H11O 135.08044 C7H7O 107.04914Cypermethrin I (2) C22H19Cl2NO3 415.07420 21.89 C7H9Cl2 163.00758 C7H8Cl 127.03090 C14H11NO 209.08352 C13H9O 181.06479 C12H8 152.06205 C7H9ClCl(37) 165.00463Cypermethrin II (2) C22H19Cl2NO3 415.07420 22.04 C7H9Cl2 163.00758 C7H8Cl 127.03090 C14H11NO 209.08352 C13H9O 181.06479 C12H8 152.06205 C7H9ClCl(37) 165.00463Cypermethrin III (2) C22H19Cl2NO3 415.07420 22.08 C7H9Cl2 163.00758 C7H8Cl 127.03090 C14H11NO 209.08352 C13H9O 181.06479 C12H8 152.06205 C7H9ClCl(37) 165.00463Cypermethrin IV (2) C22H19Cl2NO3 415.07420 22.18 C7H9Cl2 163.00758 C7H8Cl 127.03090 C14H11NO 209.08352 C13H9O 181.06479 C12H8 152.06205 C7H9ClCl(37) 165.00463Fenvalerate SR,RS (5) C25H22ClNO3 419.12882 22.57 C7ClH6 125.01525 C14H11O2N 225.07843 C10H12Cl 167.06220 C13H9O 181.06479 C25H22ClNO3 419.12827 C14H11NO 209.08352Fenvalerate SS,RR (5) C25H22ClNO3 419.12882 22.76 C7ClH6 125.01525 C14H11O2N 225.07843 C10H12Cl 167.06220 C13H9O 181.06479 C25H22ClNO3 419.12827 C14H11NO 209.08352Deltamethrin trans (3) C22H19Br2NO3 502.97317 22.93 C7H9BrBr(81) 252.90450 C7H9Br(81) 173.98616 C7H9Br 171.98821 C7H9Br2 250.90655 C7H9Br(81)2 254.90246 C13H9O 181.06479Deltamethrin cis C22H19Br2NO3 502.97317 23.17 C7H9BrBr(81) 252.90450 C7H9Br(81) 173.98616 C7H9Br 171.98821 C7H9Br2 250.90655 C7H9Br(81)2 254.90246 C13H9O 181.06479Azoxystrobin C22H17N3O5 403.11682 23.55 C20H14N3O3 344.10297 C21H14N3O5 388.09280 C19H11O3N3 329.07949 C10H6O2N 172.03931 C20H14O4N3 360.09788 C22H17N3O5 403.11627Dimethomorph I (4) C21H22ClNO4 387.12374 23.71 C17H14ClO3 301.06260 C17H14O3Cl(37) 303.05965 C21H22ClNO4 387.12319 C9H9O3 165.05462Dimethomorph II (4) C21H22ClNO4 387.12374 24.02 C17H14ClO3 301.06260 C17H14O3Cl(37) 303.05965 C21H22ClNO4 387.12319 C9H9O3 165.05462

Bold = molecular ionGrey cells: m/z with background noise

(1) isomer is impurity/conversion product of lambda-cyhalothrin(2) cypermethrin, standard is mixture of isomers(3) isomer is impurity/conversion product of cis-deltamethrin(4) dimethomorph, standard is mixture of isomers(5) RS, SR, RR isomers are impurity/conversion products of esfenvalerate (S,S-isomer)(6) resmethrin, standard is mixture of isomers(7) spiroxamine, standard is mixture of isomers(8) tetramethrin, standard is mixture of isomers


Table S2. Linearity of instrument response

area Response deviation from ion ratio in percentage relative to m/z 283.80984pg on-column m/z 283.80984 factor (RF) average RF m/z 248.84091 m/z 213.87192 m/z 176.90601 m/z 141.93723

0 7360.1 29,533 295,330 -5% 31% 16% 10% 24%

0.25 71,810 287,240 -7% 34% 17% 11% 22%0.5 166,112 332,224 7% 31% 19% 10% 24%

1 299,000 299,000 -4% 31% 18% 12% 25%2.5 742,108 296,843 -4% 31% 18% 11% 24%

5 1,501,931 300,386 -3% 31% 19% 12% 24%10 2,939,115 293,912 -5% 33% 20% 13% 24%25 7,461,103 298,444 -4% 34% 20% 13% 26%50 14,825,810 296,516 -4% 34% 21% 13% 26%

100 32,568,099 325,681 5% 34% 20% 13% 25%250 80,974,729 323,899 4% 35% 20% 13% 25%500 162,741,351 325,483 5% 35% 20% 13% 25%

1,000 337,721,551 337,722 9% 34% 20% 13% 24%2,500 843,789,124 337,516 9% 34% 21% 12% 25%5,000 1,644,160,649 328,832 6% 33% 22% 12% 25%

10,000 2,878,115,212 287,812 -7% 32% 23% 12% 28%25,000* 6,091,632,974 243,665 -22% 30% 22% 12% 28%50,000* 8,955,954,615 179,119 -42% 31% 22% 13% 30%

Determined by injection of 1 µL solvent standard hexachlorobenzene in iso-octane. Resolvingpower 60K, AGC 3e6. MEW = ± 5 ppm.Response factor = area/pg on-column. For calculation of average RF, the two highest amounts were excluded.* broad/fronting chromatographic peak due to overloading of GC column.


Table S3. Performance characteristics for individual pesticides

Tomato Leek OrangeiLOD iLOQ iLOI Rec(%) RSD(%) Rec(%) RSD(%) iLOD iLOQ iLOI Rec(%) RSD(%) Rec(%) RSD(%) iLOD iLOQ iLOI Rec(%) RSD(%) Rec(%) RSD(%)

Pesticide μg/kg μg/kg μg/kg μg/kg μg/kg μg/kg μg/kg μg/kg μg/kg2-phenylphenol 0.5 0.5 10 82 3 70 5 0.5 0.5 0.5 93 3 88 3 pos pos 0.5 85 1 85 2Azoxystrobin 0.5 5 5 63 38 64 7 0.5 5 10 61 1 77 15 0.5 2.5 5 65 6 69 2Bifenthrin 0.5 0.5 0.5 82 5 78 4 0.5 0.5 0.5 91 4 101 3 0.5 0.5 0.5 84 3 89 3Biphenyl pos pos pos 88 4 76 4 pos pos pos 98 4 98 4 pos pos pos 93 1 90 2Bitertanol 0.5 0.5 1 81 4 77 8 0.5 1 2.5 90 2 99 7 0.5 1 2.5 84 3 96 2Bupirimate 0.5 0.5 0.5 66 6 58 6 0.5 0.5 0.5 67 3 77 6 0.5 0.5 0.5 60 3 64 4Chlorobenzilate 0.5 0.5 1 90 5 76 8 0.5 0.5 0.5 92 3 107 6 0.5 0.5 0.5 92 2 98 1Chloropropylate 0.5 0.5 1 88 6 77 4 0.5 0.5 0.5 92 5 109 3 0.5 0.5 0.5 92 2 91 5Chlorothalonil 0.5 1 0.5 25 14 26 8 0.5 0.5 0.5 <10 <10 0.5 0.5 0.5 67 9 91 6Chlorpropham 0.5 0.5 0.5 87 7 76 6 0.5 0.5 0.5 98 5 103 4 0.5 0.5 1 91 3 94 2Chlorpyrifos 0.5 0.5 0.5 89 6 83 6 0.5 0.5 0.5 93 6 102 7 pos pos pos 89 4 97 4Chlorpyrifos-methyl 0.5 0.5 0.5 87 3 76 5 0.5 0.5 0.5 95 3 103 11 0.5 0.5 0.5 94 4 102 3Cyhalothrin-lambda 0.5 0.5 0.5 96 8 78 6 0.5 0.5 0.5 89 4 109 5 0.5 0.5 0.5 94 4 113 2Cypermethrin 1 2.5 1 86 4 76 10 1 2.5 1 93 3 101 11 1 2.5 1 93 4 98 3DDD p,p' 0.5 0.5 0.5 86 3 77 3 0.5 0.5 0.5 91 4 105 7 0.5 0.5 0.5 93 1 99 2DDE p,p' 0.5 0.5 0.5 84 10 69 9 0.5 0.5 0.5 74 2 99 6 0.5 0.5 0.5 78 5 83 3DDT o,p 0.5 0.5 0.5 84 6 73 5 0.5 0.5 0.5 82 6 96 4 0.5 0.5 0.5 87 4 96 4DDT p,p' 0.5 0.5 0.5 84 9 74 9 0.5 1 0.5 84 7 107 7 0.5 1 0.5 84 4 92 4Deltamethrin cis 2.5 10 5 94 10 86 6 1 2.5 2.5 96 5 108 13 2.5 5 5 95 5 95 4Diazinon 0.5 0.5 0.5 90 3 79 5 0.5 0.5 0.5 91 5 109 4 0.5 0.5 0.5 92 3 98 4Dichlorvos 0.5 2.5 0.5 49 4 44 3 0.5 0.5 1 47 5 53 4 0.5 2.5 5(a) 46 5 49 2Dieldrin 0.5 1 0.5 83 4 79 7 0.5 0.5 0.5 87 6 94 4 0.5 0.5 0.5 87 3 96 4Dimethomorph 2.5 5 10 42 36 39 9 2.5 5 10 40 7 52 16 2.5 5 25 40 7 45 4Disulfoton 0.5 0.5 1 92 3 81 4 0.5 1 1 72 8 77 8 0.5 1 1 88 5 98 4Endosulfan alpha 0.5 2.5 1 86 8 75 9 0.5 2.5 0.5 80 3 108 5 1 1 1 87 3 88 3Endosulfan beta 0.5 0.5 0.5 90 2 83 6 0.5 0.5 0.5 83 10 110 4 0.5 1 0.5 91 3 93 4Endosulfan sulfate 0.5 1 0.5 93 6 85 3 0.5 0.5 0.5 104 3 108 5 0.5 0.5 0.5 96 4 98 7Etofenprox 0.5 0.5 1 86 4 73 4 0.5 0.5 1 90 4 101 12 0.5 0.5 1 88 3 84 4Fenitrothion 0.5 0.5 0.5 97 6 83 4 0.5 0.5 0.5 100 6 110 11 0.5 0.5 0.5 94 2 108 1

10 μg/kg 50 μg/kg 10 μg/kg 50 μg/kg 10 μg/kg 50 μg/kg


Table S3. Performance characteristics for individual pesticides (continued)

Tomato Leek OrangeiLOD iLOQ iLOI Rec(%) RSD(%) Rec(%) RSD(%) iLOD iLOQ iLOI Rec(%) RSD(%) Rec(%) RSD(%) iLOD iLOQ iLOI Rec(%) RSD(%) Rec(%) RSD(%)

Pesticide μg/kg μg/kg μg/kg μg/kg μg/kg μg/kg μg/kg μg/kg μg/kgFenpropidin 0.5 0.5 0.5 <10 <10 0.5 0.5 0.5 <10 <10 0.5 0.5 0.5 <10 <10Fenpropimorph 0.5 0.5 0.5 35 3 31 4 0.5 0.5 0.5 37 2 37 5 0.5 0.5 0.5 30 3 29 4Fenvalerate (SS,RR) 0.5 0.5 1 96 16 78 5 0.5 0.5 2.5 88 1 100 10 0.5 0.5 1 92 3 90 3Fipronil 0.5 1 1 85 6 76 13 0.5 1 1 80 6 92 13 0.5 1 1 91 5 90 4HCH, Alpha 0.5 0.5 0.5 90 8 81 3 0.5 0.5 0.5 96 4 102 4 0.5 0.5 0.5 96 6 97 4HCH, beta 0.5 0.5 0.5 89 3 78 3 0.5 0.5 0.5 91 3 106 4 0.5 5 0.5 86 7 97 1HCH, gamma 0.5 0.5 0.5 91 3 77 2 0.5 0.5 0.5 92 6 103 3 0.5 0.5 0.5 93 5 94 3Hexachlorobenzene 0.5 0.5 0.5 78 5 67 4 0.5 0.5 0.5 82 5 94 5 0.5 0.5 0.5 71 3 76 3Iprodione 1 2.5 2.5 90 4 79 7 1 2.5 2.5 96 4 97 10 0.5 1 2.5 93 6 91 5Kresoxim-methyl 0.5 0.5 0.5 91 4 78 5 0.5 0.5 0.5 91 1 103 3 0.5 0.5 0.5 93 2 98 1Metalaxyl 0.5 0.5 0.5 40 6 31 4 0.5 0.5 0.5 45 6 41 6 0.5 0.5 0.5 37 4 38 4Oxadixyl 0.5 0.5 1 (b) <10 <10 0.5 0.5 0.5 <10 <10 0.5 0.5 0.5 <10 <10Parathion 0.5 2.5 1 (c) 94 5 82 8 0.5 2.5 1 91 3 104 5 1 2.5 2.5 92 8 99 2Parathion-methyl 0.5 0.5 2.5 (d) 88 6 78 5 0.5 0.5 0.5 93 5 103 10 0.5 0.5 0.5 92 2 100 3Pendimethalin 0.5 1 0.5 83 5 81 5 0.5 0.5 0.5 94 6 110 7 0.5 0.5 0.5 90 4 100 3Pirimicarb 0.5 0.5 0.5 <10 <10 0.5 0.5 0.5 <10 <10 0.5 0.5 0.5 <10 <10Procymidone 0.5 0.5 2.5 93 5 82 5 0.5 0.5 1 86 5 99 7 0.5 1 1 89 6 96 4Propazine 0.5 0.5 1 88 2 73 5 0.5 0.5 1 82 6 102 3 0.5 5 1 84 8 94 1Pyrimethanil 0.5 0.5 0.5 53 3 45 5 0.5 0.5 0.5 46 10 53 4 0.5 0.5 0.5 43 3 45 5Resmethrin 1 1 2.5 86 8 78 12 1 1 10 <10 <10 1 1 2.5 87 4 81 5Spiroxamine 0.5 0.5 1 <10 <10 0.5 0.5 1 <10 <10 0.5 0.5 2.5 <10 <10Terbuthylazine 0.5 0.5 0.5 93 2 74 5 0.5 0.5 0.5 80 3 111 5 0.5 0.5 0.5 89 3 86 6Tetramethrin 0.5 0.5 0.5 88 3 79 7 0.5 0.5 2.5 96 6 102 6 0.5 0.5 0.5 94 2 94 2Trifluralin 0.5 0.5 0.5 94 5 74 3 0.5 0.5 0.5 88 7 110 6 0.5 0.5 0.5 98 2 96 3Vinclozolin 0.5 0.5 0.5 94 4 80 4 0.5 0.5 0.5 94 5 100 10 0.5 0.5 0.5 90 6 104 2

10 μg/kg 50 μg/kg 10 μg/kg 50 μg/kg 10 μg/kg 50 μg/kg

iLOD, iLOQ, iLOI = instrument limit of detection, quantification, identification as derived from extracts spiked at 0, 0.5, 1, 2.5, 5, 10, 25 ng mL-1 (= μg kg-1 = pg on-column)pos = pesticide found in blank extract between 0.5-2 μg kg-1

(a) using m/z 186.97355 as qualifier ion(b) using m/z 233.09207 as qualifier ion(c) using m/z 155.00355 as qualifier ion


(d) using m/z 245.99844 as qualifier ion


Figure S1.

Figure S1. Schematic representation of the EI-Q-Orbitrap used in the evaluation HCD cell = higher energy collision-induced dissociation cell. Courtesy Thermo Scientific.


Figure S2a. Example output automatic search GC-EI-Orbitrap mass spectrum in NIST library:

HEXACHLOROBENZENE

Note: for searching against nominal mass libraries, the HRMS spectrum (upper spectrum) was converted by the software into a nominal mass spectrum.


Figure S2b. Example output automatic search GC-EI-Orbitrap mass spectrum in NIST library:

CHLORPYRIFOS



Figure S2c. Example output automatic search GC-EI-Orbitrap mass spectrum in NIST library:

PIRIMICARB



Figure S2d. Example output automatic search GC-EI-Orbitrap mass spectrum in NIST library:

DISULFOTON



Figure S2e. Example output automatic search GC-EI-Orbitrap mass spectrum in NIST library:

DIELDRIN



Figure S2f. Example output automatic search GC-EI-Orbitrap mass spectrum in NIST library:

FENITROTHION



GC-EI-Orbitrap accurate mass spectrum for fenitrothion. Presence of m/z 127 and 143 are attributed to reaction of m/z 109 and 125 with water in the C-trap.


Figure S2g. Example output automatic search GC-EI-Orbitrap mass spectrum in NIST library:

DICHLORVOS


160212_059 #654-656 RT: 8.10-8.11 AV: 3 SB: 10 8.05-8.07 , 8.19-8.20T: FTMS + p EI Full lock ms [50.00-500.00]

50 100 150 200 250m/z

0

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127.01554

184.97648

78.99440144.98161

109.00500

219.94537

160212_057 #1378-1383 RT: 8.10-8.11 AV: 6 SB: 17 8.06-8.07 , 8.17-8.19T: FTMS + p EI Full lock ms [50.00-500.00]

50 100 150 200 250m/z

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184.97654127.01558

109.00503

78.99441144.98161

219.94544

GC-EI-Orbitrap accurate mass spectra for dichlorvos (60K). Left: ion injection time = 114 ms (AGC 3e6), right ion injection time = 9.7 ms (AGC 2e5). Changing abundance for m/z/ 109 and m/z 127 are attributed to reaction with water in the C-trap which increases with residence time in the C-trap.


Figure S3. Resolving power of the orbitrap mass analyzer as function of m/z. Bar graph: frequency plot of most abundant ions (N=2078) for 584 pesticides in GC-EI-MS.


Figure S4aRT: 5.00 - 30.00

6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)

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21.40

22.56

14.339.276.32 15.86 23.61

15.89 24.0419.39 24.84

NL:2.64E9TIC F: FTMS + p EI Full ms [50.00-500.00] MS 160111_017

RT: 5.00 - 30.00

6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)

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21.40

15.89

9.2914.33 19.41

6.34

22.4612.02 15.9322.97 23.52

20.84 24.1515.977.77 26.0518.80 26.7313.5811.29


RT: 5.00 - 30.00

6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)

0

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25.97

12.458.99

24.46

24.3621.37

13.0024.02

14.306.56 9.05 22.43 26.115.907.90 19.369.25 15.84

20.1415.90


Figure S4a: TIC chromatograms for tomato (top), leek (middle) and orange (bottom)


Y-axis normalised to most abundant peak.


Figure S4bRT: 5.00 - 30.00

6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)

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15.89 24.04

24.45

19.39

24.84

26.75

20.83 26.796.91 7.69 27.7116.08 19.3614.269.9416.1412.028.07


RT: 5.00 - 30.00

6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)

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14.3319.41

6.34

22.4612.02 15.93

22.97 23.52

20.84 24.05

24.8415.977.77 26.0518.80 26.7313.5811.29 17.36


RT: 5.00 - 30.00

6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)

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18.7611.849.32 26.70

11.26 26.7110.23

16.2526.7318.03

27.8717.2828.92


Figure S4b: TIC chromatograms for tomato (top), leek (middle) and orange (bottom)Y-axis at fixed scale (5.0e8)


Figure S5a. Effect of AGC target value and TIC on detectability

Figure S4b. TIC and extracted ion chromatograms (unsmoothed) for 2.5 pg hexachlorobenzene in leek extract measured with AGC = 3e6. Resolving power 60K. Chromatograms from top to bottom: TIC, m/z 283.80962, m/z 248.84076, m/z 213.87191 and m/z 178.90306. MEW = ± 5 ppm. Percentages in red indicate ion ratios relative to m/z 283.80962. Stick plots show the response for individual scans.


Figure S5b. Effect of AGC target value and TIC on detectability

Figure S4a. TIC and extracted ion chromatograms (unsmoothed) for 2.5 pg hexachlorobenzene in leek extract measured at three different AGC settings. Resolving power 60K. Chromatograms from top to bottom: TIC, m/z 283.80962, m/z 248.84076, m/z 213.87191 and m/z 178.90306. MEW = ± 5 ppm. Percentages in red indicate ion ratios relative to m/z 283.80962.


Figure S6

Figure S6. Selection of quantifier and qualifier for cypermethrin from XICs (MEW ±5 ppm). Sample: leek extracts spiked at concentration corresponding to 5 μg kg-1. Ions: 1 = 181.06479 (C13H9O); 2 = 163.00758 (C7H9Cl2); 3 = 127.03090 (C7H8Cl); 4 = 165.00463 (C7H9Cl37Cl); 5 = 91.05422 (C7H7); 6 = 152.06205 (C12H8); 7 = 209.08352 (C14H11NO). Ions 2 and 3 were selected as quantifier and qualifier (no background noise, high specificity, highest signals).


Figure S7. Estimation of instrument LOD, LOQ, and LOI for iprodion in leek extracts (1 g mL-1). Shown are the XICs (MEW ±5 ppm) for the quantifier (Q) and qualifier (q) ion. Upper rows: stick plots (no smoothing applied) showing the response for individual scans used for estimation of LOD. Lower rows: peaks (smoothed) used for estimation of LOQ and LOI. Percentage values for Q: deviation of response factor from average response factor. Percentage values for q/Q: relative deviation of ion ratio from reference ion ratio. LOD = 1 pg (1 µg kg-1), LOQ and LOI are both 2.5 pg (2.5 µg kg-1).


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