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Junichi Osuga Mass Spectrometry Application Group JEOL Ltd.

Introduction of New JMS-T100GCV “the AccuTOF GCv 　４Ｇ ”. JMS-T100GC “AccuTOF GC ｖ ”. JMS-T100GCV “AccuTOF GCv 　４Ｇ ”. Junichi Osuga Mass Spectrometry Application Group JEOL Ltd. 1. 2. AccuTOF GC ｖ 4G JMS-T100GCV. FD/FI ionization is available EI/FD/FI Ion source

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Junichi Osuga Mass Spectrometry Application Group JEOL Ltd.

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  1. Introduction of New JMS-T100GCV “the AccuTOF GCv　４Ｇ” JMS-T100GC “AccuTOF GCｖ” JMS-T100GCV “AccuTOF GCv　４Ｇ” Junichi Osuga Mass Spectrometry Application GroupJEOL Ltd.

  2. 1 2 AccuTOF GCｖ4GJMS-T100GCV FD/FI ionization is available EI/FD/FIIon source Useful to get molecular ion & Type Analysis Exact mass measurement with easy operation One point calibration & High resolution any time new 3 Stable high sensitivity with even full spectra acquisition 5 4 new Auto-tuning assist function Automatic sensitivity adjusting 7 High speed data acquiring Fast GC/MS & Comprehensive 2DGC-MS 7890A GC New 7890A GC Control software 6 new

  3. the Ultimate GC/MS-TOFMSEI,CI,FI,FD IonSource for high throughput qualitative analyses of trace components… Gas Chromatograph – Time-of-Flight Mass Spectrometer JMS-T100GCV “AccuTOF GCｖ 4G” Concept of T100GCV • Achieving higher throughput by Fast GC • Identify compounds not in library database byAccurate Mass Measurement

  4. Feature of T100GCV Stable and Highly Sensitive in Full Spectrum Mode Stable and efficient ion transfer optics has been developed. Compatible with Fast GC High speed data acquisition compatible with the speed of Fast GC Always operates in high resolution No trade-off between sensitivity and mass resolution Easy Accurate Mass Measurement With single internal mass reference ion.

  5. Ｓｐｅｃｆｉｃａｔｉｏｎ of JMS-T100GCV “AccuTOF GCv

  6. High Sensitivity and Compatible with Fast GC/MS “AccuTOF GCｖ” Almost all ions will reach the detector Ion Source Ion TransferOptics Detector GC TOFMS • High ion transmission; almost all ions will reach the detector. • More than 10,000 ToF spectra can be performed in one second.

  7. Ion source and Ion transfer optics Source magnet Slit Electrostatic lenses Isolation valve Socket chamber Deflector Ion stream • Socket chamber system • Easy to clean up the ion chamber and to replace a filament • Isolation valve • The vacuum condition of flight tube is kept by closing the isolation valve even if the ion source was vented.

  8. Ion source and Ion transfer optics Source magnet Slit Electrostatic lenses Isolation valve Socket chamber Deflector Ion stream If the big amount of helium ions introduce into the analyzer... ⇒Space charge effect from helium ions occurs. ⇒Big amount of ions gives the damage to the detector.

  9. Ion source and Ion transfer optics Source magnet Slit Electrostatic lenses Isolation valve Socket chamber Deflector Ion stream of sample Ion stream of helium 1. Source Magnet : The lighter ions have bigger influence from the magnet. 2. 2nd Lens :The stream of helium ion is deflected dramatically by optimizing the voltage of 2nd lenses. 3. Deflector ： The stream of ions except for helium is corrected by deflector.

  10. Ion source and Ion transfer optics Source magnet Slit Electrostatic lenses Isolation valve Socket chamber Deflector Ion stream of sample Ion stream of helium • This ion optics achieved the elimination of helium ions more than 99.9%. • ⇒Achieve the high ion transmission • ⇒Prevent to reduce the life time of MCP detector.

  11. Picture of ion source Source magnet Socket type ion chamber Introduction line for GC Capillary column Easy to remove ion chamber from main body. Easy to cleaning Easy to replace the filament Source magnet Introduction linefrom reserver filament ionization chamber ionization chamber filament

  12. Analysis of Pesticides Comparison between conventional GC and FastGC Conventional GC Column:ZB-5ms, 30m, 0.25mm I.D. Temp. Program 80°C(1min) - 20°C/min - 140°C 4°C/min - 200°C (0min) 8°C/min - 300°C (5.5min) Acquisition Speed : 0.67sec/spec 35min FastGC Column:DB-5, 10m, 0.18mm I.D. Temp. Program 50°C(1min) - 60°C/min - 300°C Acquisition Speed : 0.04sec/spec High speed temp. program with short and narrow bore column is used in FastGC application. High speed data acquisition need to be available for MS. 6min

  13. 0.54s = 14points Chromatograms with different data acquisition rate Intensity Intensity Retention time[min] Retention time[min] 0.04s 0.4s 25spectra/sec 2.5spectra/sec Retention time［min］

  14. Feature of T100GC Stable and Highly Sensitive in Full Spectrum Mode Stable and efficient ion transfer optics has been developed. Compatible with Fast GC High speed data acquisition compatible with the speed of Fast GC Always operates in high resolution No trade-off between sensitivity and mass resolution Easy Accurate Mass Measurement With single internal mass reference ion.

  15. Easy Accurate Mass Measurement • Magnetic sector (double focusing) MS • Trade-off between Sensitivity and Mass Resolution • Many internal mass reference ions are required. • AccuTOF GC・・・ • No trade-off between Sensitivity and Mass Resolution • Single internal mass reference ion is sufficient • -> Accurate mass can be obtained using any single internal mass reference ion with known exact mass; e.g. GC column background.

  16. Exact mass measurement by TOFMS system • Only one peak as the internal calibrant is enough for accurate mass measurement. • Easier than magnetic sector • Available for EI, CI and even FD/FI Unknown peak Sector MS • Internal calibrant • PFK, PFTBA, etc. • Column bleed peaks • Peak of 207, 281 ... • Any known peaks m/z Calibrant peak AccuTOF m/z

  17. Comparison between conventional GC/MS and“AccuTOF GCｖ”

  18. Basic configuration and optional attachments Basic configuration • “AccuTOF GC” Basic Unit • GC（Agilent7890A GC） • PC 、DVD+RW • Printer Optional attachments • Direct Exposure Probe(DEP) • Direct Insertion Probe(DIP) • CI (Chemical Ionization) ion source • FD/FI (Field Desorption/Field Ionization) ion source • EI/FD/FI ion source

  19. FD（Field Desorption） and FI（Field Ionization） FD and FI are the ionization technique based on tunneling effect that is induced in high electric potential field. FD or FI ionization occurs by electron transfer from sample molecule to emitter by tunneling effect. As FD/FI ionization is very soft, molecular ion hardly decompose. It means that the molecular ion can be created by FD/FI easily. emitter

  20. Comparison between EI and FI- Mass spectra of C14H30 measured by EI or FI - EI(+) m/z 57 　（C4H9+） Many fragment peak m/z 71（C5H11+） Very small peak from molecular ion M+（m/z 198） m/z 85（C6H13+） Clear peak from molecular ion M+ m/z 198 FI(+) No fragment peak Mass spectrum by FD/FI is very simple, because of the softness of those ionization techniques.

  21. Analysis of Liquid Crystal-Exact mass measurement by FastGC/EI, CI- EI(+) FD(+) M+ m/z 830 No M+ ion CI(+) iso-butane PEG600 as internal calibrant No [M＋H]+ ion

  22. Performance and Application Data • Performance data • Sensitivity • Mass accuracy • Application data • Analysis of Liquid crystal by Accurate mass measurement • Analysis of PCB by FastGC • DEI/DCI measurement • Analysis of light oil by 2DGC

  23. Performance data – Sensitivity Sample: Octafluoronaphthalene(OFN) S/N:154.8 Retention time［min］ Mass Chromatogram of 1pg OFN Mass spectrum of 1pg OFN and result of library search by NIST database

  24. Hexachlorobenzene: Theoretical value 281.81312 Performance data – Mass accuracy HCB m/z282 PFK m/z219

  25. Performance data- Resolution and sensitivity Test sample ： 1pgOctafluoronaphthalene (OFN) 0 10 20 30 40 50 After 45 hours S/N：134 1st Injection S/N：127

  26. Analysis of Liquid crystal (1) Sample: Liquid crystal from commercial electric calculator EI ◎ ◎ CI

  27. Analysis of Liquid crystal (2) Result of library search for ◎ Result of accurate mass measurement for ◎

  28. Analysis of Liquid crystal (3) Sample: Liquid crystal from commercial electric calculator 111.11872 69.07151 195.06891 EI ★ CI ★ 334.18021 Estimated structural formula of ★

  29. Analysis of PCBs in transformer oil Sample: Mixture of KC300/400/500/600(125pg each) in 1% transformer oil TIC TrCB Total PCBs TeCB PeCB Ionization volt.: 18eV Ionization current: 300μA Ion source temp.: 250℃

  30. CH２-O-CO-C17H35 C17H35-CO-O-CH CH２-O-CO-C17H35 DEI/DCI measurement EI mode [M-OCOC17H35]+ 607 C57H110O6 M.W.890 267 341 [ M ] + 890 CI mode ( NH3 ) [ M + NH4] + 908 607 Direct Exposure Probe (DEP) 341 Mass spectra of tristearin

  31. Comprehensive 2DGC combined with AccuTOF GCv Comprehensive 2D GC (GCxGC) system works as the continuous heart-cut system by using two kinds of capillary column combined with modulator system. After every eluting compound from the 1st column is trapped by modulator, those are separated again by the 2nd column. As the 1st and 2nd column have different polarity generally, GCxGC has high separation ability. It means that GCxGC system could be powerful tool for the analysis of complex samples such as petrochemicals. In the case of GCxGC system combined with MS as detector, the GCxGC system requires the high-speed spectra acquiring capability for MS system, because the chromatographic peak eluted from GCxGC system would always be very sharp. From the point of view concerning the sensitivity and the spectra acquiring speed, Time-of-flight mass spectrometer (TOFMS) is the best detector for GCxGC. FastGC column; DB-WAX(2m, 0.10mm, 0.10mm) Analysis time : 3~7sec Injection Port Modulator: Working as continuous trap system at 3~7sec interval by liquid nitrogen cryo. Modulator MS detector 2nd column 1st column • AccuTOF GC : • High resolution • High speed data acquisition GC Oven Conventional column: DB-5(30m, 0.25mm, 0.25µm） Analysis time : 30~60min

  32. Analysis of Light Oil- Comprehensive 2DGC/EI with high resolution - > Sample Diesel oil, Kerosene > MS condition Mass range : m/z 35 ~ 500 Data acquisition speed : 40ms Ionization mode : EI Ionization voltage 70V Ionization current 300µA > GCxGC condition GCxGC : Agilent7890A GC with KT2004 (Zoex Corporation) 1st column : HP-1ms, 30m, 0.25mm I.D., 0.25µm 2nd column : DB-17, 2m, 0.1mm I.D., 0.1µm Injection mode : Split(200:1) Oven temp. program : 50°C(1min) - 5°C/min - 280°C (6min) Carrier gas : Helium(Constant pressure : 680kPa) Modulation period : 6 sec

  33. 3D image Analysis of Light Oil- Comprehensive 2DGC/EI with high resolution - AccuTOF GCV Kerosene 2nd Dimension(DB-17) Diesel oil 1st Dimension(HP-1ms) All 2DGC chromatogram were created by GC Image software (Zoex Corporation).

  34. Analysis of Light Oil- Comprehensive 2DGC/EI with high resolution - AccuTOF GCV EIC image GCxGC GCxGC TIC Mass chromatogram with GCxGC A B C Overlapped chromatogram image of three mass chromatograms (m/z 184, 198, 212) with GCxGC Dibenzothiophene C12H10S

  35. Analysis of Light Oil- Comprehensive 2DGC/EI with high resolution - 184 212 A C 198 B AccuTOF GCV EIC image GCxGC GCxGC TIC Mass chromatogram with GCxGC A B C Mass spectra of A, B and C Observed value Error (mmu) Estimated composition [M]+ m/z 212 [M]+ m/z 184 A C A 184.0343 -0.4 C12H8S 152.0619 -0.7 C12H8 B 198.0495 -0.8 C13H10S [M]+ m/z 198 B 152.0620 -0.6 C12H8 C 212.0654 -0.6 C14H12S 152.0622 -0.4 C12H8

  36. Summary for T100GCV Stable and Highly Sensitive in Full Spectral Mode Unlike conventional mass spectrometers, no trade-off between mass resolution and sensitivity. Various ionization methods are available EI, CI, DEI, DCI, FD/FI,EI/FD/FI Easy Accurate Mass Measurement Single Internal Reference Mass Any ion with know exact mass can be used. Fast GC/MS・２DGC-HRTOFMS High speed data acquisition: 0.04 s spectrum recording interval

  37. High mass resolving power⇒ High selectivity, High accuracy Mass resolving power Instrumental capability for separation of two peaks A example of the difference of mass resolving power at m/z 28（Image） Low High 1,000 3,000 分解能 分解能 Nominal Mass CO 28 N2 28 C2H4 28 N N Exact Mass CO 27.9949 N2 28.0061 C2H4 28.0313 2 2 C C H H 2 2 4 4 CO CO High selectivity High resolution GC-MS may be possible to separate object ion and matrix ion. High accuracy （accurate mass measurement） Confirmation of accurate mass of each monoisotopic ion

  38. 高い質量精度 内部標準イオン1つで精密質量が得られるため • 磁場型MSに比べて簡便な操作 • 多彩なイオン化法に対応（EI，CI，FI，FD，DEI，DCI） 磁場型MS Intensity 未知イオン 内部標準イオン m/z GC-TOFMS Intensity m/z

  39. It is possible to use a known ion as a internal standard 1. The case of using internal standard 2. The case of using column bleed 3. The case of using molecular ion of interest compound

  40. GC/TOFMS GC/QMS GC/(sector)MS About qualitative analysis in GC/MS Measurement with EI, then identify by using library search TOFMS can get the information of accurate mass for many target simultaneously TOFMSでは多成分の精密質量を同時に得ることが出来る。 Reduction with accurate mass Impossible to interpret out of DB library It is difficult in sectorMS measurement to get accurate mass for many target simultaneously It is easy to measure CI or FI with accurate mass

  41. A example of pesticide analysis in food① - Qualitative analysis of Atrazine in ginger matrix - GC condition ：Instrument ： 7890A（Agilent） ： LVI-S200（AiSTI SCIENCE） ：Injection mode： Solvent vent、25uL Injection ：Injector： 60℃(0.5min)→120℃/min→240℃ 　→50℃/min→290℃(39min) ：Column： BPX5、30m×0.25mm、I.D. 0.25um ：Oven temp. ： 60℃(4min)→20℃/min→160℃→5℃/min→220℃ →3℃/min→235℃→7℃/min→340℃（4min） ：Career Gas：He、1.2mL/min（Constant Flow） MS condition ：Instrumant ：JMS-T100GCV（JEOL） ：mass range ：m/z 50-450 ：spectra acquisition speed ：0.4sec（2.5 spectra/sec） ：ionization method ：EI+（70eV、300uA）

  42. Confirmation by mass spectrum-NIST database search- STD 50pg/uL STD 2pg/uL Library search Sample 2pg/uL spiked First candidate is atrazine In this case, it is possible to identify by mass spectrum in food matrix.

  43. Confirmation by mass spectrum-Accurate mass analysis- STD 50pg/uL STD 2pg/uL Sample 2pg/uL spiked Accurate mass for 3 ions,m/z 173、200、215

  44. Accurate mass analysis We can detect with high mass accuracy in food sample（less than 0.9 ×10-3u）GC-TOFMS ① Mass Spectra (with DB search) ② accurate mass analysis

  45. Low Low - - resolutionMS resolutionMS , , 158 158 0.5 0.5 m/z m/z ± ± High - resolution TOFMS 158.02335 0.05 m/z ± In the low resolution mode, mass chromatogram of m/z 158±0.5 (1unit),we can see the artifact peak, caused by co-eluted compound In the high resolution mode, mass chromatogram of m/z 158.02335±0.05 (0.1 unit) , we can distinct co-elution and pesticide completely. ND High selectivity Pesticide Pesticide Atrazine Atrazine Matrix Matrix C C H H ClN ClN 8 8 14 14 5 5 m/z Mw: 215 Mw: 215 CAS#: 1912 CAS#: 1912 - - 24 24 - - 9 9

  46. “Pesticides database with accurate mass table for 375 compounds” • 375 compounds×5 ions= 1875 ionswith accurate mass! • It is possible to edit or add pesticides information! • It is easy to transfer the table for quantitative analysis soft “Escrime” ! • It is easy to make a high selectivity chromatogramby using “Escrime”! • It is possible a rapid quantitative analysis by “Escrime” ! Accurate mass database for pesticides Right drag Quantitative compounds table “Escrime” Accurate mass information of Fosthiazate

  47. A example of pesticide analysis in food② - Analysis of organic phosphorus pesticides in squash- GC condition ：Injection mode ： Pulsed Splitless, 1 mLinjection ：Injection temp. ： 250℃ ：Column ： ZB-5ms, 20 m×0.18 mm, I.D. 0.18 mm ：Oven ： 50 ℃(0.5 min)→45 ℃/min→125 ℃ 　　→20 ℃/min→300 ℃(5 min) ：Career Gas ： He、0.7 mL/min（Constant Flow） MS condition ：Mass Range：m/z 40-450 ： spectra acquisition speed ：0.1 sec （10 spectra/sec） ：Ionization method：EI+（70 V, 300 mA）

  48. Confirmation of mass spectra and calibration Methamidophos (earliest elution component) Fenthion Profenofos Coumaphos (latest elusion component) Mass Spectra in Squash sample （spike STD pesticides to 0.01ppm(final)) • Conc. ： 5, 10, 50, 100 ppb • IS： 9-bromoanthracene(20 ppb) • Relative calibration method

  49. Mass Accuracy, relative peak area (repeatability)

  50. Summary • GC/TOFMS has a small statistical error, is able to get high mass accuracy with one point drift compensation. • Even if in the food sample, GC/TOFMS can determine the composition for each ions with high mass accuracy. • GC/TOFMS get a full spectra in all measurement, so it is easy to identify by using DB search. • GC/TOFMS has a high selectivity. We can use a high resolution mass chromatogram ( narrow m/z width) .

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