Supporting Information

Transcription

1 Supporting Information Authors Erich D. Strozier 1, Douglas D. Mooney 2, David A. Friedenberg 1, Theodore P. Klupinski 1, and Cheryl A. Triplett 1 Affiliations 1. Battelle Memorial Institute, 505 King Avenue, Columbus, Ohio Early Moon, LLC, 1391 West 5th Avenue Suite 423, Columbus OH Title Use of Two-Dimensional Gas Chromatography with Time-of-Flight Mass Spectrometric Detection and Random Forest Pattern Recognition Techniques for Classifying Chemical Threat Agents and Detecting Chemical Attribution Signatures Table of Contents Table S-1. GC GC-TOFMS Operating Parameters. Figure S-2. Representative three-dimensional chromatogram showing dicrotophos from source MYN. Figure S-3. Side-by-side three-dimensional chromatograms for dichlorvos sources RN and MXN. Figure S-4. Side-by-side three-dimensional chromatograms for dichlorvos sources R5 and MX5. Figure S-5. Side-by-side three-dimensional chromatograms for dicrotophos sources MYN and PsN. Figure S-6. Side-by-side three-dimensional chromatograms for chlorpyrifos sources SgN and DwUKN. Figure S-7. Example heat map plot depicting the oval area variables concept for dichlorvos RN. Figure S-8. Example overlay of selected ion chromatograms and associated spectra for the peak tentatively identified as chlorpyrifos-methyl in chlorpyrifos sample DwUSN (black trace) but not present in sample DwUKN (blue trace). Table S-9. Confusion Matrix for BRF using Oval Area variables on dichlorvos data. S-1

2 Table S-10. The distribution of the top 1% of Simple Importance values from Oval Area variables across all pairs of sources for dichlorvos. Table S-11. Verification status of dichlorvos for all CASs based on In/Out variables in neat sources only. Table S-12. Confusion Matrix for BRF using In/Out variables on dicrotophos data. Table S-13. Confusion Matrix for BRF using Oval Area variables on dicrotophos data. Table S-14. The number of compounds that perfectly separate pairs of sources for dicrotophos according to In/Out variables. Table S-15. The distribution of the top 1% of Simple Importance values from Oval Area variables across all pairs of sources for dicrotophos. Table S-16. Verification status of dicrotophos CASs based on In/Out variables in neat sources only. Table S-17. Confusion matrix for BRF using Oval Area variables on chlorpyrifos data. Table S-18. The number of compounds that perfectly separate pairs of source materials for chlorpyrifos. Table S-19. The distribution of the top 1% of Simple Importance values from Oval Area variables across all pairs of sources for chlorpyrifos. Table S-20. Verification status of chlorpyrifos CASs based on In/Out variables in neat sources only. S-2

3 Table S-1. GC GC-TOFMS Operating Parameters. GC GC-TOFMS System Leco Pegasus 4D GC Primary Column 100% dimethylpolysiloxane, 30 m, 0.25 mm i.d., 1 µm d f GC Secondary Column 50% phenyl polysilphenylene-siloxane 1 m, 0.1 mm i.d., 0.1 µm d f GC Carrier Gas Helium GC Carrier Gas Flow Rate Constant flow, 1.2 ml/min GC Inlet Temperature 250 C GC Injection Volume 1 µl splitless GC Primary Column Oven Program 45 C (1.5 min hold) C/min C/min; hold 1 min C/min, hold 16 min GC Secondary Column Oven Program 80 C (1.5 min hold) C/min C/min, hold 11 min 20 C GC Modulator temperature offset from first oven GC Modulation Time 3 seconds Transfer Line Temperature 290 C MS Source Temperature 200 C MS Detector Voltage 1800 v MS Acquisition Masses amu MS Data Acquisition Rate 100 spectra per second S-3

4 Figure S-2. Representative three-dimensional chromatogram showing dicrotophos from source MYN. Dicrotophos is the large peak eluting just after 2315 seconds in the first dimension. Note that the chromatograms were purposely overloaded for the primary material (dicrotophos in this case) in order to enable detection of low abundance impurities. S-4

5 Figure S-3. Side-by-side three-dimensional chromatograms for dichlorvos sources RN (left) and MXN (right). The large peak just after 1300 seconds in the first dimension of each panel is dichlorvos. The chromatograms are scaled to show impurities thus the dichlorvos peaks have been cut off at the top. S-5

6 Figure S-4. Side-by-side three-dimensional chromatograms for dichlorvos sources R5 (left) and MX4 (right). The large peak just after 1300 seconds in the first dimension of each panel is dichlorvos. The chromatograms are scaled to show impurities thus the dichlorvos peaks have been cut off at the top. S-6

7 Figure S-5. Side-by-side three-dimensional chromatograms for dicrotophos sources MYN (left) and PSN (right). The large peak just after 2300 seconds in the first dimension of each panel is dicrotophos. The chromatograms are scaled to show impurities thus the dichrotophos peaks have been cut off at the top. S-7

8 Figure S-6. Side-by-side three-dimensional chromatograms for chlorpyrifos sources SgN (left) and DwUKN (right). The large peak just before 3342 seconds in the first dimension of each panel is chlorpyrifos. The chromatograms are scaled to show impurities thus the chlorpyrifos peaks have been cut off at the top. S-8

9 Figure S-7. Example heat map plot depicting the oval area variables concept for dichlorvos RN. S-9

10 Figure S-8. Example overlay of selected ion chromatograms and associated spectra for the peak tentatively identified as chlorpyrifos-methyl in chlorpyrifos sample DwUSN (black trace) but not present in sample DwUKN (blue trace). S-10

11 Table S-9. Confusion matrix for BRF using Oval Area variables on dichlorvos data. Row labels indicate true identities, and column labels indicate predicted classifications. Green shading indicates correct classifications. MX4 MXN Bk PsN R5 RN SgN MX MXN Bk PsN R RN SgN Table S-10. The distribution of the top 1% of Simple Importance values from Oval Area variables across all pairs of sources for dichlorvos. MX4 MXN Bk PsN R5 RN SgN MX MXN Bk PsN R RN SgN -- S-11

12 Tentatively Identified Chemically Relevant Table S-11. Verification status of dichlorvos for all CASs based on In/Out variables in neat sources only. Shaded cells indicate components that are either distinctively present or distinctively absent in one source. Detection Status Mass Spectral Library Best Match Compound CAS# MXN RN SgN PsN Ethane, 1,1,1,2-tetrachloro y y y n n n Tetrachloroethylene y y n y n n 2-Butanol, 1-chloro y y y t y y Acetic acid, trichloro-, ethyl ester y y y y n y Acetic acid, dichloro-, ethyl ester y y y y y n Acetic acid, trichloro-, methyl ester y y y y n n Ethane, 1,1,2-trichloro y y y n y n Benzene, 1,2,3-trimethyl y u t y t t Phenol, 2,4,6-trichloro y u t n y n Ethane, pentachloro y y n y n n Acetic acid, chloro y y n t y y Dihydro-4,5-dichloro-2(3H)furanone n u n n y n Pyridazine, 3,6-dichloro n u n n y n 2-Propanol, 1,1,1,3-tetrachloro-2-methyl n u n n y n 5-Chloro-2-methyl-3(2H)-isothiazolone n u n n y n 2-Propanol, 1,1,1-trichloro-2-methyl n u n n y n 2-Hydroxy-3,5,6-trichloropyridine n u n n y n 2,3-Dichloropropionyl chloride n u n n y n 1-Propene, 1,1,2,3-tetrachloro n u y y y n Acetic acid, dichloro-, methyl ester n u y y y n 2-Propanone, 1,1,1,3,3-pentachloro n u y y y n 1-Propene, 1,1,2-trichloro n u y y y n Carbonochloridothioic acid, S -ethyl ester n u y n y t Boronic acid, ethyl-, diethyl ester n u y n y y 2,3-Butanedione, mono(o -methyloxime) n u y t y y Cyclopropane, pentachloro n u y y n n Fumaryl chloride n u y n y y 3-Pentanol, 2-chloro-4-methyl-, (R *,S *)-(.+-.) n u y t y y Acetic acid, chloro-, methyl ester n u y y y n 1,5-Hexadiene, 1,1,2,5,6,6-hexachloro n u y y y n 2-(Dichloromethyl)-3-chloro-2-propenal n/a n u y y y t 4-(Dichloromethyl)-5-chloro-2(3H,5H)-furanone n/a n u y n y n 4-Amino-3-chlorobenzonitrile n u t n y n Oxirane, (trichloromethyl) n u t y n n Benzene, 1-methyl-2-nitroso n u t n y y Propane, 1,1-dichloro n u t y y y 2,5-Dimethyl-3-hexanol acetate n u t n y y Ether, chloromethyl dichloromethyl n u n y y n y - yes; n - no; t - peak observed below software detection threshold; n/a - not available; u - unknown S-12

13 Table S-12. Confusion Matrix for BRF using In/Out variables on dicrotophos data. Row labels indicate true identities, and column labels indicate predicted classifications. Green shading MY8 MYN Bk PsN SgN MY MYN Bk PsN SgN indicates correct classifications. Table S-13. Confusion Matrix for BRF using Oval Area variables on dicrotophos data. Row labels indicate true identities, and column labels indicate predicted classifications. Green shading indicates correct classifications. MY8 MYN Bk PsN SgN MY MYN Bk PsN SgN S-13

14 Table S-14. The number of compounds that perfectly separate pairs of sources for dicrotophos MY8 MYN Bk PsN SgN MY MYN Bk PsN SgN -- according to In/Out variables. Table S-15. The distribution of the top 1% of Simple Importance values from Oval Area MY8 MYN Bk PsN SgN MY MYN Bk PsN SgN -- variables across all pairs of sources for dicrotophos. S-14

15 Tentatively Identified Chemically Relevant Table S-16. Verification status of dicrotophos CASs based on In/Out variables in neat sources only. Shaded cells indicate components that are either distinctively present or distinctively absent in one source. Detection Status Mass Spectral Library Best Match Compound CAS# MYN SgN PsN 2,3-Dichloro-N,N -dimethyl-propionamide y y n y n 2-Butene, 1,4-dichloro-, (E) y u n y n 2-Butoxyethyl acetate y u n y n 2-Chlorocyclohexanol y u n y n Butanoic acid, 3-oxo-, 1-methylethyl ester y u n y n 2H-Pyran-2-one, 4,6-dimethyl y u n n y Benzene, 1-(dichloromethyl)-4-ethyl y u y n n Hexanedioic acid, bis(2-ethylhexyl) ester y u t y n Diisopropyl methanephosphonate y u y y n O,O,O -Trimethyl thiophosphate y y y t n Phthalic acid, bis(7-methyloctyl) ester y u n y t Phosphoric acid, 2-bromo-1-methylethenyl dimethyl ester y y y y n 1,2-Benzenedicarboxylic acid, diheptyl ester y u y y n Trimethyl phosphonoacetate y y t y y Isopropyl methyl methylphosphonate y u n y t Benzyl butyl phthalate y u n y t Butyrolactone y u t y y 5-[2-(Dimethoxy-phosphoryl)-acetoxy]-hex-2-enoic acid, methyl n/a y u n y y 2-(2-Amino-3,5-dibromophenyl)propene n u n y n Oxirane, 2,2'-[1,4-butanediylbis(oxymethylene)]bis n u n y n Phosphorothioic acid, O -(4-cyanophenyl) O,O -dimethyl ester n u n n y Butane, 1,2,3,4-tetrachloro n u n y n 1-(3-Methyl-2-butenyl)-3,6-diazahomoadamantan-9-one n u y n n 1-(4-Aminophenyl)-3,6-diazahomoadamantan-9-one hydrazone n u y n n Dodec-5-yn-6-one n u n n y 5-Chloro-1-methylimidazole n u y n n Phosphonofluoridic acid, ethyl-, isopropyl ester n u t y n Hex-4-yn-3-one n u y n y Karbutilate n u n y y 1-Dimethylcarbamidoyl-3,3-dimethyldiaziridine n u y y n Phenanthrene, tetradecahydro-4,5-dimethyl n u y y n Phosphorochloridic acid, dimethyl ester n u y y t Pyridine-3-carbonitrile, 1-(2-hydroxypropyl)-4,6-dimethyl-2-oxo- n/a n u y n y y - yes; n - no; t - peak observed below software detection threshold; n/a - not available; u - unknown S-15

16 Table S-17 Confusion matrix for BRF using Oval Area variables on chlorpyrifos data. Row labels indicate true identities, and column labels indicate predicted classifications. Green shading indicates correct classifications, and pink shading indicates incorrect classifications. Bk DwUK4 DwUKN DwUS4 DwUSN PsN SgN Bk DwUK DwUKN DwUS DwUSN PsN SgN Table S-18. The number of compounds that perfectly separate pairs of source materials for chlorpyrifos. Bk DwUK4 DwUKN DwUS4 DwUSN PsN SgN Bk DwUK DwUKN DwUS DwUSN PsN -- 2 SgN -- Table S-19. The distribution of the top 1% of Simple Importance values from Oval Area variables across all pairs of sources for chlorpyrifos. Bk DwUK4 DwUKN DwUS4 DwUSN PsN SgN Bk DwUK DwUKN DwUS DwUSN PsN SgN -- S-16

17 Tentatively Identified Chemically Relevant Table S-20. Verification status of chlorpyrifos CASs based on In/Out variables in neat sources only. Shaded cells indicate components that are either distinctively present or distinctively absent in one source. Detection Status Mass Spectral Library Best Match Compound CAS# DwUKN DwUSN SgN PsN Phosphoramidothioic acid, O,O -diethyl ester y y y n n n Trisulfide, diethyl y u y n n n Triethyl phosphate y y y t t t Tetraethyl dithiopyrophosphate y y y n n t Chlorpyrifos methyl y y n y n y 2-Pyridinecarboxylic acid, 4-amino-3,5,6-trichloro n u y n n n 2-Pyridinecarboxylic acid, 3,4,5,6-tetrachloro n u y y t t 4-Fluoro-3-(trifluoromethyl)benzyl alcohol n u y t n t Phosphorodithioic acid, O,O -diethyl ester n u y n n t Disulfide, 1-methylethyl propyl n u y t y n 4,5,6,7-Tetrachloro-3-hydroxy-3H-isobenzofuran-1-one n u y n y n à-tetraloxime, 8-fluoro-5,6-dimethoxy- n/a n u y n y n Aspidofractinine-1-carboxaldehyde, 17-methoxy-3-methylene-, n u n y n y y - yes; n - no; t - peak observed below software detection threshold; n/a - not available; u - unknown S-17