Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods
Pengxiang Yang,1 Keith Waddell,1 Brian M. Ruddy,2 Matt Ashby,2 and Leonard Nyadong3 1Thermo Fisher Scientific, San Jose, CA;2 Taxon Biosciences, Tiburon, CA; 3Phillips 66, Houston, Texas Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods Pengxiang Yang1, Keith Waddell1 Brian M. Ruddy2, Matt Ashby2, and Leonard Nyadong3 1Thermo Fisher Scientific, San Jose, California; 2Taxon Biosciences, Tiburon, California; 3Phillips 66, Houston, Texas
FIGURE 7. The mass spectrum of petroleum sample over 549.0 – 552.0 m/z FIGURE 3. Schematic of the Orbitrap Elite Hybrid MS. The 00-offset lens is FIGURE 5. The impact of Orbitrap MS AGC setting on the ion distribution of ionized by ESI, APCI and APPI. Overview Results located between S-Lens and square quadrupole. (Ref. 3) petroleum sample. APCI was used to ionize sample and Orbitrap was the mass analyzer. 00-offset was set at 6. Purpose: A brief comparison of three different ionization methods was carried out on Ionization Methods 551.2731 NL: 6.01E2 the ultra-high resolution mass spectrometer (Thermo Scientific™ Orbitrap Elite™ 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e4 #1-50 RT: 0.01-0.68 AV: 50 NL: 1.80E5 100 Three different ionization techniques, ESI, APCI and APPI, are available in the Ion T: FTMS + c APCI corona Full ms [100.00-1000.00] ESI 13-012162_ESI#334-371 RT: 199.1 5.08-5.64 AV: 38 T: FTMS + p Hybrid Ion Trap-Orbitrap MS) for petroleum analysis. A comparative analysis was made 100 549.2574 ESI Full ms [100.00-1400.00] Max ion source platform. The complementary nature of the application of each 551.3303 278.2 50 on ionization efficiency, ion distributions, and ionization competition. The three 80 264.2 290.2 332.3 550.3103 ionization method is summarized in Figure 1, which shows the APPI has more broader 374.3 ionization method are electrospray (ESI), atmosphere pressure chemical ionization 60 AGC: 5E4 549.1189 549.4412 549.8009 550.5292 551.1538 551.6119 552.1885 application than APCI, typically for the non-polar compounds. The advantage of using 390.3 0 236.2 416.3 550.4507 NL: 4.45E5 (APCI) and atmosphere pressure photo ionization (APPI). 40 444.4 100 185.1 13-012162 _apci#1-500 RT: APPI on non-polar compounds has recently been accepted for petroleum analysis. 486.4 20 526.5 APCI 0.00-6.85 AV: 500 T: FTMS +
Relative Abundance Relative 183.1 Methods: The extracted petroleum samples were directly injected by syringe pump 570.5 622.5 FIGURE 1. The targeted compounds of three different ionization techniques with 664.6 722.7 758.7 801.7 892.2 967.5 p APCI corona Full ms into the mass spectrometer. Three different ionization sources (ESI, APCI, APPI) were 0 50 551.4586 [100.00-1400.00] regard to the polarity and molecular weight of analytes. (Ref.1) 100 200 300 400 500 600 700 800 900 1000 549.4429 m/z 549.5942 used and the data were collected and analyzed by Thermo Scientific™ Xcalibur 548.8722 549.3443 549.8323 550.3567 550.5976 550.9258 551.3259 551.5524 552.1808
Relative Abundance 0 00-offset lens 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e5 #1-50 RT: 0.00-0.71 AV: 50 NL: 1.52E6 551.4594 NL: 1.10E3 software. 100 T: FTMS + c APCI corona Full ms [100.00-1000.00] 550.4515 13-012162_appi#1-269 RT: 199.1 100 APPI 0.01-3.88 AV: 269 T: FTMS + p APCI corona Full ms Results: APPI is the most promising ionization method for petroleum analysis because 549.5950 80 AGC: 5E5 50 [100.00-1400.00] nonpolar compounds can be ionized more efficiently than by APCI and ESI. The 551.3012 FIGURE 4. The impact of 00-offset potential on the ion distribution of petroleum 60 absence of radical ions in the APPI method enables efficient data processing and 548.6190 549.3376 549.7366 550.3263 550.5983 551.1261 551.5531 552.0343 264.2 0 sample. APCI was used to ionize sample and linear ion trap was the mass analyzer. 40 185.1 278.2 236.2 549.0 549.5 550.0 550.5 551.0 551.5 552.0 formula prediction. 332.3 20 105.1 157.1 360.3 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_0 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.06E7 Abundance Relative 402.3 444.4 500.4 540.5 580.5 624.6 664.6 706.6 748.7 802.7 836.6 904.8 934.9 991.2 T: ITMS + p APCI corona Full ms [100.00-1000.00] 0 106.1 100 100 200 300 400 500 600 700 800 900 1000 FIGURE 8. The mass spectrum of petroleum sample over 600 – 650 m/z ionized Introduction m/z 80 by APCI and APPI. The ionized ions from APCI and APPI are identical. 00-offset: 0 V 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e6 #1-50 RT: 0.01-0.90 AV: 50 NL: 2.90E6 The mass spectrometer has proven itself in the petroleum industry as an essential 60 T: FTMS + c APCI corona Full ms [100.00-1000.00] 108.1 153.1 199.1 199.1 100 NL: 3.27E5 analytical and process control instrument. The instrument is touted as a means to 40 105.1 606.5132 100 620.5288 13-012162 _apci#1-500 RT: 80 analyze and separate crude oil and petroleum samples that contain complicated 20 109.1 185.1 106.1 200.1 622.5444 647.4194 0.00-6.85 AV: 500 T: FTMS Relative Abundance Relative 250.2 618.5131 278.2 304.2 80 604.4976 + p APCI corona Full ms 346.3 400.3 442.3 484.3 530.4 570.4 612.5 662.6 704.6 742.6 810.7 856.7 896.8 931.0 966.9 60 AGC: 5E6 hydrocarbons which have very similar masses. Because the organic composition of the 0 128.1 634.5444 [100.00-1400.00] 60 610.5445 630.5131 100 200 300 400 500 600 700 800 900 1000 636.5600 polar components of petroleum is so complex, its characterization was until recently The ionization mechanism of ESI, APCI and APPI was illustrated in Figure 2. APPI ion 40 185.1 624.5601 644.5288 m/z 236.2 40 source uses a Krypton lamp, which emits photons at 10.0 eV and 10.6 eV. Photon 20 264.2 638.5758 APCI limited to bulk properties (such as color, viscosity and density) until the emergence of 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_5 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.17E5 Abundance Relative 290.2 614.4818 628.4974 332.2 20 642.5131 T: ITMS + p APCI corona Full ms [100.00-1000.00] 388.3 430.4 470.4 524.4 564.5 632.5 664.6 703.5 770.2 796.3 868.7 915.4 961.0 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) which energy from Krypton lamp is sufficient to ionize most analytes, and is lower than the 0 Abundance Relative 199.2 100 200 300 400 500 600 700 800 900 1000 100 0 NL: 4.60E3 ionization potentials of common reversed-phase solvents such as water, methanol, m/z 622.5454 offers the highest available, mass resolving power, and mass accuracy. The need to 00-offset: 5 V 100 608.5297 13-012162_appi#1-300 RT: 80 634.5453 and acetonitrile. 264.2 292.3 647.4202 0.01-4.32 AV: 300 T: FTMS volatilize the sample limited the obtainable molecular weight range (especially for 318.3 80 610.5453 618.5139 624.5610 632.5296 + p APCI corona Full ms 60 346.3 Comparison of ESI, APCI and APPI 390.3 [100.00-1400.00] heteroatom containing species). Since electron impact ionization produced extensive FIGURE 2. The ionization mechanism of (a) ESI source (HESI II), (b) APCI, and (c) 236.2 60 604.4983 638.5767 40 185.2 418.3 fragmentation (especially of alkyl chains), electrospray ionization (ESI) is a soft 456.3 616.4984 631.5218 644.5296 APPI. Positive charge (protonation) is added by potential through (a) ESI probe, 183.2 498.4 With the same mass spec settings (00-offset: 6 and AGC: 5E4), three different 40 20 540.4 APPI Relative Abundance Relative 580.5 622.5 ionization technique and more useful to characterize polar compounds. But ESI has the (b) corona discharge needle, (c) Krypton lamp. (Ref. 2) 664.5 718.6 776.7 804.7 856.8 890.9 938.8 978.9 ionization techniques were studied and compared. 20 limited reach for petroleum analysis since petroleum crude oils typically contain 90% 0 100 200 300 400 500 600 700 800 900 1000 As shown in Figure 6 and 7, the ion distributions were observed from the three 0 hydrocarbons, nonpolar compounds. m/z 600 605 610 615 620 625 630 635 640 645 650 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6 #1-201 RT: 0.00-0.76 AV: 201 NL: 1.55E5 ionization techniques. Briefly, ESI is much more efficient for polar molecules and An ion trap based hybrid mass spectrometer (Orbitrap Elite MS) , with sufficiently high T: ITMS + c APCI corona Full ms [100.00-1000.00] 292.3 typically ionized many highly polar compound, heteroatom-containing components 100 199.2 278.3 320.3 362.3 – mass resolving power (m/Δm 240,000 @ m/z 400) and a m/z range up to 2000 Da was 390.4 (NnOoSs) of the petroleum sample. APCI shows the capability of ionizing the As shown in Figure 8, APCI and APPI produced identical ions from 600 650 m/z 404.4 80 250.3 00-offset: 6 V which indicated all ions generated by APPI are protonated ions like those from APCI utilized to analyze petroleum samples extracted from crude oil which were injected 430.4 petroleum components, both polar and non-polar compounds, but mainly focusing on 60 456.4 and that radical ions were not generated by APPI. The absence of radical ions directly by syringe. Three ionization methods, electrospray ionization (ESI), 236.3 484.4 nonpolar compounds. APPI gives access to many of the remaining 90% of petroleum 530.5 40 185.3 atmosphere pressure chemical ionization (APCI) and atmosphere pressure photo 554.5 – significantly reduced the workload of predicting the formula of each ions. 582.5 components hydrocarbon compounds including benzo- and dibenzothiophenes, 20 183.3 624.6 ionization (APPI) were used and ion distribution and polarity of compounds were Abundance Relative 664.6 708.7 128.3 752.7 806.8 854.8 892.9 946.9 furans, cycloalkanes, and polycyclic aromatic hydrocarbons (PAHs) not observed by 0 studied. Various MS scan modes and ion transfer optical potentials were investigated 100 200 300 400 500 600 700 800 900 1000 ESI. Conclusion to determine the approaches that provided high quality information with a wide m/z m/z FIGURE 6. The ion distribution of petroleum sample ionized by ESI, APCI and The performance of ultrahigh mass-resolution Orbitrap Elite mass spectrometer and range. (a) (c) As shown in Figure 4, the adjustment of the 00-offset potential from 0 to 6 V led to an APPI separately. Orbitrap was the mass analyzer with the AGC setting of 5E4 three ionization techniques on the petroleum analysis were investigated in this study. intensity decrease for low m/z ions and the accumulation of high m/z ions. The access and the 00-offset of 6. . The adjustment on 00-offset lens and AGC is needed to get the correct ion (b) of the 00-offset is important for petroleum analysis because it can control the low m/z Methods 13-012162_ESI #338-360 RT: 5.14-5.48 AV: 23 NL: 6.50E4 distribution from petroleum samples. ions entering the mass analyzer, thereby allowing the capacity of analyzer (ion trap T: FTMS + p ESI Full ms [100.00-1400.00] 288.17 Sample Preparation 100 . and/or Orbitrap analyzer) to be fully used by the targeted high m/z ions. As shown in 273.16 ESI The compounds ionized by ESI are the polar compounds having a relatively low Figure 4, 00-offset was optimized at 6 and used for data collection in experiments. 80 181.10 molecular mass. Samples: The extracted samples from refinery pipelines supplied by Taxon Bioscience 304.17 60 363.21 . Samples were dissolved into 1 mg/mL by Toluene, then diluted to 250 µg/mL by In order to obtain optimal performance in the trapping device, the ion population needs 40 The nonpolar compounds in petroleum samples can be ionized by APCI and 394.22 to be kept within a certain range. Therefore, a procedure is needed to predict the 20 APPI, and APPI shows an advantage over APCI in ionizing the large nonpolar different solvent based on the ionization method prior to direct injection. 470.28
Relative Abundance Relative 547.34 663.45 748.60 888.92 944.44 1029.91 1190.50 1304.57 appropriate accumulation time. Automatic control of the number of ions in the Orbitrap 0 compounds. Dilution solvent analyzer is achieved by measuring the total ion charge from a pre-scan and by 200 400 600 800 1000 1200 1400 m/z . Only protonated ions are generated from APPI and radical ions were not • calculating the ion injection time. Automatic Gain Control (AGC™) ensures that the ion For APPI and APCI: Toluene 13-012162 _apci #375-400 RT: 5.13-5.48 AV: 26 NL: 1.04E7 observed, which simplified the data processing and formula prediction. trap is always filled with the optimum number of ions for any scan type. T: FTMS + p APCI corona Full ms [100.00-1400.00] • For ESI: 1% Formic Acid and 5% DCM in 50:50 Toluene:Methanol 406.36 APCI 418.36 As shown in Figure 5, the AGC optimization was studied along with ion distribution. 10 Mass Spectrometry 472.40 References Optimization of Orbitrap Elite MS The AGC setting was found to have a significant impact on ion distribution. Although 540.47 662.44 Ionization Source: the higher AGC setting allowed more ions to enter the Orbitrap mass analyzer, 2.9E6 5 391.33 566.48 1. Product specification of APPI/APCI combination ion source, Thermo Scientific Orbitrap Elite MS is a high performance hybrid mass spectrometer 165.07 (AGC: 5E6) vs 1.52E6 (AGC: 5E5) vs 1.8oE5 (AGC: 5E4), the ion distribution of the 269.23 674.58 http://www.thermoscientific.fr/com/cda/product/detail/0,1055,19246,00.html 756.65 Electrospray (HESI II) combining the use of an Orbitrap analyzer with a linear ion trap. The DC potential of the Abundance Relative 838.73 923.01 1021.12 1106.22 1220.36 1306.44 petroleum sample was poor because more low m/z ions entered the Orbitrap mass 0 2. Application note 347: Mechanism of [M+H]+ Formation in Atmospheric Pressure optic lens in the first vacuum stage can be optimized to the ion distribution of petroleum analyzer. To maximize a broad m/z range distribution the low AGC setting of 5E4 is 200 300 400 500 600 700 800 900 1000 1100 1200 1300 Atmosphere Pressure Chemical Ionization (APCI) – m/z Photoionization Mass Spectrometry, Thermo Fisher Scientific Inc. compounds which typically cover the mass range 200 1000 m/z. By optimizing the DC preferred. The package of ions is collected in the ion trap and the number of ions was Atmosphere Pressure Photo ionization (APPI) potential, the kinetic energy of ions was controlled, which means the ions could be 13-012162_appi #208-226 RT: 3.00-3.26 AV: 19 NL: 5.35E4 controlled by AGC. The ion package is send to C-Trap and cooled down, focused and T: FTMS + p APCI corona Full ms [100.00-1400.00] accelerated or slowed down as appropriate. Ion Trap and Orbitrap Elite (Mass Resolution = 240,000) sent to the Orbitrap analyzer for analysis. C-trap, like all RF devices, has an m/z 688.59 APPI 871.95 Acknowledgements 552.47 702.61 In this study, the setting of 00-offset in Figure 3 was observed to have a significant dependent potential well to trap ions. So if a mix of ions is sent into C-trap, the lower 10 Positive scan 622.55 956.05 We would like to thank Jean Jacques Dunyach from Thermo Fisher Scientific for impact on the intensity of ions from petroleum. Ions have the same velocity from the m/z ions are trapped by a deeper well and the high m/z ions are trapped by a 998.10 1068.17 5 206.24 supplying the APPI source information. AGC: 5E4 - 5E6 vacuum drop in the first vacuum stage after the ion beam passes through the transfer shallower well. If a mix of ions fills up C-trap such that space charge starts to be of the 1161.28 1246.38 130.88 335.06 tube. The increasing of the 00-offset potential slows down the ions, allowing the low m/z same order as the well depth, then the high m/z ions will be spilled out firstly. By Abundance Relative 223.68 474.42 1349.49 Mass Spectrum (average of 100-200 scans) 0 All trademarks are the property of Thermo Fisher Scientific and its subsidiaries. ions to be prevented from entering the linear trap mass analyzer and Orbitrap mass reducing the number of ions via setting a low AGC value, more high m/z ions could be 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 obtained on spectrum. m/z This information is not intended to encourage use of these products in any manners that might infringe the Data Collection and Analysis analyzer. intellectual property rights of others. Xcalibur software PO64143-EN 0614S
2 Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods Pengxiang Yang1, Keith Waddell1 Brian M. Ruddy2, Matt Ashby2, and Leonard Nyadong3 1Thermo Fisher Scientific, San Jose, California; 2Taxon Biosciences, Tiburon, California; 3Phillips 66, Houston, Texas
FIGURE 7. The mass spectrum of petroleum sample over 549.0 – 552.0 m/z FIGURE 3. Schematic of the Orbitrap Elite Hybrid MS. The 00-offset lens is FIGURE 5. The impact of Orbitrap MS AGC setting on the ion distribution of ionized by ESI, APCI and APPI. Overview Results located between S-Lens and square quadrupole. (Ref. 3) petroleum sample. APCI was used to ionize sample and Orbitrap was the mass analyzer. 00-offset was set at 6. Purpose: A brief comparison of three different ionization methods was carried out on Ionization Methods 551.2731 NL: 6.01E2 the ultra-high resolution mass spectrometer (Thermo Scientific™ Orbitrap Elite™ 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e4 #1-50 RT: 0.01-0.68 AV: 50 NL: 1.80E5 100 Three different ionization techniques, ESI, APCI and APPI, are available in the Ion T: FTMS + c APCI corona Full ms [100.00-1000.00] ESI 13-012162_ESI#334-371 RT: 199.1 5.08-5.64 AV: 38 T: FTMS + p Hybrid Ion Trap-Orbitrap MS) for petroleum analysis. A comparative analysis was made 100 549.2574 ESI Full ms [100.00-1400.00] Max ion source platform. The complementary nature of the application of each 551.3303 278.2 50 on ionization efficiency, ion distributions, and ionization competition. The three 80 264.2 290.2 332.3 550.3103 ionization method is summarized in Figure 1, which shows the APPI has more broader 374.3 ionization method are electrospray (ESI), atmosphere pressure chemical ionization 60 AGC: 5E4 549.1189 549.4412 549.8009 550.5292 551.1538 551.6119 552.1885 application than APCI, typically for the non-polar compounds. The advantage of using 390.3 0 236.2 416.3 550.4507 NL: 4.45E5 (APCI) and atmosphere pressure photo ionization (APPI). 40 444.4 100 185.1 13-012162 _apci#1-500 RT: APPI on non-polar compounds has recently been accepted for petroleum analysis. 486.4 20 526.5 APCI 0.00-6.85 AV: 500 T: FTMS +
Relative Abundance Relative 183.1 Methods: The extracted petroleum samples were directly injected by syringe pump 570.5 622.5 FIGURE 1. The targeted compounds of three different ionization techniques with 664.6 722.7 758.7 801.7 892.2 967.5 p APCI corona Full ms into the mass spectrometer. Three different ionization sources (ESI, APCI, APPI) were 0 50 551.4586 [100.00-1400.00] regard to the polarity and molecular weight of analytes. (Ref.1) 100 200 300 400 500 600 700 800 900 1000 549.4429 m/z 549.5942 used and the data were collected and analyzed by Thermo Scientific™ Xcalibur 548.8722 549.3443 549.8323 550.3567 550.5976 550.9258 551.3259 551.5524 552.1808
Relative Abundance 0 00-offset lens 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e5 #1-50 RT: 0.00-0.71 AV: 50 NL: 1.52E6 551.4594 NL: 1.10E3 software. 100 T: FTMS + c APCI corona Full ms [100.00-1000.00] 550.4515 13-012162_appi#1-269 RT: 199.1 100 APPI 0.01-3.88 AV: 269 T: FTMS + p APCI corona Full ms Results: APPI is the most promising ionization method for petroleum analysis because 549.5950 80 AGC: 5E5 50 [100.00-1400.00] nonpolar compounds can be ionized more efficiently than by APCI and ESI. The 551.3012 FIGURE 4. The impact of 00-offset potential on the ion distribution of petroleum 60 absence of radical ions in the APPI method enables efficient data processing and 548.6190 549.3376 549.7366 550.3263 550.5983 551.1261 551.5531 552.0343 264.2 0 sample. APCI was used to ionize sample and linear ion trap was the mass analyzer. 40 185.1 278.2 236.2 549.0 549.5 550.0 550.5 551.0 551.5 552.0 formula prediction. 332.3 20 105.1 157.1 360.3 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_0 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.06E7 Abundance Relative 402.3 444.4 500.4 540.5 580.5 624.6 664.6 706.6 748.7 802.7 836.6 904.8 934.9 991.2 T: ITMS + p APCI corona Full ms [100.00-1000.00] 0 106.1 100 100 200 300 400 500 600 700 800 900 1000 FIGURE 8. The mass spectrum of petroleum sample over 600 – 650 m/z ionized Introduction m/z 80 by APCI and APPI. The ionized ions from APCI and APPI are identical. 00-offset: 0 V 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e6 #1-50 RT: 0.01-0.90 AV: 50 NL: 2.90E6 The mass spectrometer has proven itself in the petroleum industry as an essential 60 T: FTMS + c APCI corona Full ms [100.00-1000.00] 108.1 153.1 199.1 199.1 100 NL: 3.27E5 analytical and process control instrument. The instrument is touted as a means to 40 105.1 606.5132 100 620.5288 13-012162 _apci#1-500 RT: 80 analyze and separate crude oil and petroleum samples that contain complicated 20 109.1 185.1 106.1 200.1 622.5444 647.4194 0.00-6.85 AV: 500 T: FTMS Relative Abundance Relative 250.2 618.5131 278.2 304.2 80 604.4976 + p APCI corona Full ms 346.3 400.3 442.3 484.3 530.4 570.4 612.5 662.6 704.6 742.6 810.7 856.7 896.8 931.0 966.9 60 AGC: 5E6 hydrocarbons which have very similar masses. Because the organic composition of the 0 128.1 634.5444 [100.00-1400.00] 60 610.5445 630.5131 100 200 300 400 500 600 700 800 900 1000 636.5600 polar components of petroleum is so complex, its characterization was until recently The ionization mechanism of ESI, APCI and APPI was illustrated in Figure 2. APPI ion 40 185.1 624.5601 644.5288 m/z 236.2 40 source uses a Krypton lamp, which emits photons at 10.0 eV and 10.6 eV. Photon 20 264.2 638.5758 APCI limited to bulk properties (such as color, viscosity and density) until the emergence of 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_5 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.17E5 Abundance Relative 290.2 614.4818 628.4974 332.2 20 642.5131 T: ITMS + p APCI corona Full ms [100.00-1000.00] 388.3 430.4 470.4 524.4 564.5 632.5 664.6 703.5 770.2 796.3 868.7 915.4 961.0 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) which energy from Krypton lamp is sufficient to ionize most analytes, and is lower than the 0 Abundance Relative 199.2 100 200 300 400 500 600 700 800 900 1000 100 0 NL: 4.60E3 ionization potentials of common reversed-phase solvents such as water, methanol, m/z 622.5454 offers the highest available, mass resolving power, and mass accuracy. The need to 00-offset: 5 V 100 608.5297 13-012162_appi#1-300 RT: 80 634.5453 and acetonitrile. 264.2 292.3 647.4202 0.01-4.32 AV: 300 T: FTMS volatilize the sample limited the obtainable molecular weight range (especially for 318.3 80 610.5453 618.5139 624.5610 632.5296 + p APCI corona Full ms 60 346.3 Comparison of ESI, APCI and APPI 390.3 [100.00-1400.00] heteroatom containing species). Since electron impact ionization produced extensive FIGURE 2. The ionization mechanism of (a) ESI source (HESI II), (b) APCI, and (c) 236.2 60 604.4983 638.5767 40 185.2 418.3 fragmentation (especially of alkyl chains), electrospray ionization (ESI) is a soft 456.3 616.4984 631.5218 644.5296 APPI. Positive charge (protonation) is added by potential through (a) ESI probe, 183.2 498.4 With the same mass spec settings (00-offset: 6 and AGC: 5E4), three different 40 20 540.4 APPI Relative Abundance Relative 580.5 622.5 ionization technique and more useful to characterize polar compounds. But ESI has the (b) corona discharge needle, (c) Krypton lamp. (Ref. 2) 664.5 718.6 776.7 804.7 856.8 890.9 938.8 978.9 ionization techniques were studied and compared. 20 limited reach for petroleum analysis since petroleum crude oils typically contain 90% 0 100 200 300 400 500 600 700 800 900 1000 As shown in Figure 6 and 7, the ion distributions were observed from the three 0 hydrocarbons, nonpolar compounds. m/z 600 605 610 615 620 625 630 635 640 645 650 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6 #1-201 RT: 0.00-0.76 AV: 201 NL: 1.55E5 ionization techniques. Briefly, ESI is much more efficient for polar molecules and An ion trap based hybrid mass spectrometer (Orbitrap Elite MS) , with sufficiently high T: ITMS + c APCI corona Full ms [100.00-1000.00] 292.3 typically ionized many highly polar compound, heteroatom-containing components 100 199.2 278.3 320.3 362.3 – mass resolving power (m/Δm 240,000 @ m/z 400) and a m/z range up to 2000 Da was 390.4 (NnOoSs) of the petroleum sample. APCI shows the capability of ionizing the As shown in Figure 8, APCI and APPI produced identical ions from 600 650 m/z 404.4 80 250.3 00-offset: 6 V which indicated all ions generated by APPI are protonated ions like those from APCI utilized to analyze petroleum samples extracted from crude oil which were injected 430.4 petroleum components, both polar and non-polar compounds, but mainly focusing on 60 456.4 and that radical ions were not generated by APPI. The absence of radical ions directly by syringe. Three ionization methods, electrospray ionization (ESI), 236.3 484.4 nonpolar compounds. APPI gives access to many of the remaining 90% of petroleum 530.5 40 185.3 atmosphere pressure chemical ionization (APCI) and atmosphere pressure photo 554.5 – significantly reduced the workload of predicting the formula of each ions. 582.5 components hydrocarbon compounds including benzo- and dibenzothiophenes, 20 183.3 624.6 ionization (APPI) were used and ion distribution and polarity of compounds were Abundance Relative 664.6 708.7 128.3 752.7 806.8 854.8 892.9 946.9 furans, cycloalkanes, and polycyclic aromatic hydrocarbons (PAHs) not observed by 0 studied. Various MS scan modes and ion transfer optical potentials were investigated 100 200 300 400 500 600 700 800 900 1000 ESI. Conclusion to determine the approaches that provided high quality information with a wide m/z m/z FIGURE 6. The ion distribution of petroleum sample ionized by ESI, APCI and The performance of ultrahigh mass-resolution Orbitrap Elite mass spectrometer and range. (a) (c) As shown in Figure 4, the adjustment of the 00-offset potential from 0 to 6 V led to an APPI separately. Orbitrap was the mass analyzer with the AGC setting of 5E4 three ionization techniques on the petroleum analysis were investigated in this study. intensity decrease for low m/z ions and the accumulation of high m/z ions. The access and the 00-offset of 6. . The adjustment on 00-offset lens and AGC is needed to get the correct ion (b) of the 00-offset is important for petroleum analysis because it can control the low m/z Methods 13-012162_ESI #338-360 RT: 5.14-5.48 AV: 23 NL: 6.50E4 distribution from petroleum samples. ions entering the mass analyzer, thereby allowing the capacity of analyzer (ion trap T: FTMS + p ESI Full ms [100.00-1400.00] 288.17 Sample Preparation 100 . and/or Orbitrap analyzer) to be fully used by the targeted high m/z ions. As shown in 273.16 ESI The compounds ionized by ESI are the polar compounds having a relatively low Figure 4, 00-offset was optimized at 6 and used for data collection in experiments. 80 181.10 molecular mass. Samples: The extracted samples from refinery pipelines supplied by Taxon Bioscience 304.17 60 363.21 . Samples were dissolved into 1 mg/mL by Toluene, then diluted to 250 µg/mL by In order to obtain optimal performance in the trapping device, the ion population needs 40 The nonpolar compounds in petroleum samples can be ionized by APCI and 394.22 to be kept within a certain range. Therefore, a procedure is needed to predict the 20 APPI, and APPI shows an advantage over APCI in ionizing the large nonpolar different solvent based on the ionization method prior to direct injection. 470.28
Relative Abundance Relative 547.34 663.45 748.60 888.92 944.44 1029.91 1190.50 1304.57 appropriate accumulation time. Automatic control of the number of ions in the Orbitrap 0 compounds. Dilution solvent analyzer is achieved by measuring the total ion charge from a pre-scan and by 200 400 600 800 1000 1200 1400 m/z . Only protonated ions are generated from APPI and radical ions were not • calculating the ion injection time. Automatic Gain Control (AGC™) ensures that the ion For APPI and APCI: Toluene 13-012162 _apci #375-400 RT: 5.13-5.48 AV: 26 NL: 1.04E7 observed, which simplified the data processing and formula prediction. trap is always filled with the optimum number of ions for any scan type. T: FTMS + p APCI corona Full ms [100.00-1400.00] • For ESI: 1% Formic Acid and 5% DCM in 50:50 Toluene:Methanol 406.36 APCI 418.36 As shown in Figure 5, the AGC optimization was studied along with ion distribution. 10 Mass Spectrometry 472.40 References Optimization of Orbitrap Elite MS The AGC setting was found to have a significant impact on ion distribution. Although 540.47 662.44 Ionization Source: the higher AGC setting allowed more ions to enter the Orbitrap mass analyzer, 2.9E6 5 391.33 566.48 1. Product specification of APPI/APCI combination ion source, Thermo Scientific Orbitrap Elite MS is a high performance hybrid mass spectrometer 165.07 (AGC: 5E6) vs 1.52E6 (AGC: 5E5) vs 1.8oE5 (AGC: 5E4), the ion distribution of the 269.23 674.58 http://www.thermoscientific.fr/com/cda/product/detail/0,1055,19246,00.html 756.65 Electrospray (HESI II) combining the use of an Orbitrap analyzer with a linear ion trap. The DC potential of the Abundance Relative 838.73 923.01 1021.12 1106.22 1220.36 1306.44 petroleum sample was poor because more low m/z ions entered the Orbitrap mass 0 2. Application note 347: Mechanism of [M+H]+ Formation in Atmospheric Pressure optic lens in the first vacuum stage can be optimized to the ion distribution of petroleum analyzer. To maximize a broad m/z range distribution the low AGC setting of 5E4 is 200 300 400 500 600 700 800 900 1000 1100 1200 1300 Atmosphere Pressure Chemical Ionization (APCI) – m/z Photoionization Mass Spectrometry, Thermo Fisher Scientific Inc. compounds which typically cover the mass range 200 1000 m/z. By optimizing the DC preferred. The package of ions is collected in the ion trap and the number of ions was Atmosphere Pressure Photo ionization (APPI) potential, the kinetic energy of ions was controlled, which means the ions could be 13-012162_appi #208-226 RT: 3.00-3.26 AV: 19 NL: 5.35E4 controlled by AGC. The ion package is send to C-Trap and cooled down, focused and T: FTMS + p APCI corona Full ms [100.00-1400.00] accelerated or slowed down as appropriate. Ion Trap and Orbitrap Elite (Mass Resolution = 240,000) sent to the Orbitrap analyzer for analysis. C-trap, like all RF devices, has an m/z 688.59 APPI 871.95 Acknowledgements 552.47 702.61 In this study, the setting of 00-offset in Figure 3 was observed to have a significant dependent potential well to trap ions. So if a mix of ions is sent into C-trap, the lower 10 Positive scan 622.55 956.05 We would like to thank Jean Jacques Dunyach from Thermo Fisher Scientific for impact on the intensity of ions from petroleum. Ions have the same velocity from the m/z ions are trapped by a deeper well and the high m/z ions are trapped by a 998.10 1068.17 5 206.24 supplying the APPI source information. AGC: 5E4 - 5E6 vacuum drop in the first vacuum stage after the ion beam passes through the transfer shallower well. If a mix of ions fills up C-trap such that space charge starts to be of the 1161.28 1246.38 130.88 335.06 tube. The increasing of the 00-offset potential slows down the ions, allowing the low m/z same order as the well depth, then the high m/z ions will be spilled out firstly. By Abundance Relative 223.68 474.42 1349.49 Mass Spectrum (average of 100-200 scans) 0 All trademarks are the property of Thermo Fisher Scientific and its subsidiaries. ions to be prevented from entering the linear trap mass analyzer and Orbitrap mass reducing the number of ions via setting a low AGC value, more high m/z ions could be 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 obtained on spectrum. m/z This information is not intended to encourage use of these products in any manners that might infringe the Data Collection and Analysis analyzer. intellectual property rights of others. Xcalibur software PO64143-EN 0614S
Thermo Scientific Poster Note• PN-64143-ASMS-EN-0614S 3 Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods Pengxiang Yang1, Keith Waddell1 Brian M. Ruddy2, Matt Ashby2, and Leonard Nyadong3 1Thermo Fisher Scientific, San Jose, California; 2Taxon Biosciences, Tiburon, California; 3Phillips 66, Houston, Texas
FIGURE 7. The mass spectrum of petroleum sample over 549.0 – 552.0 m/z FIGURE 3. Schematic of the Orbitrap Elite Hybrid MS. The 00-offset lens is FIGURE 5. The impact of Orbitrap MS AGC setting on the ion distribution of ionized by ESI, APCI and APPI. Overview Results located between S-Lens and square quadrupole. (Ref. 3) petroleum sample. APCI was used to ionize sample and Orbitrap was the mass analyzer. 00-offset was set at 6. Purpose: A brief comparison of three different ionization methods was carried out on Ionization Methods 551.2731 NL: 6.01E2 the ultra-high resolution mass spectrometer (Thermo Scientific™ Orbitrap Elite™ 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e4 #1-50 RT: 0.01-0.68 AV: 50 NL: 1.80E5 100 Three different ionization techniques, ESI, APCI and APPI, are available in the Ion T: FTMS + c APCI corona Full ms [100.00-1000.00] ESI 13-012162_ESI#334-371 RT: 199.1 5.08-5.64 AV: 38 T: FTMS + p Hybrid Ion Trap-Orbitrap MS) for petroleum analysis. A comparative analysis was made 100 549.2574 ESI Full ms [100.00-1400.00] Max ion source platform. The complementary nature of the application of each 551.3303 278.2 50 on ionization efficiency, ion distributions, and ionization competition. The three 80 264.2 290.2 332.3 550.3103 ionization method is summarized in Figure 1, which shows the APPI has more broader 374.3 ionization method are electrospray (ESI), atmosphere pressure chemical ionization 60 AGC: 5E4 549.1189 549.4412 549.8009 550.5292 551.1538 551.6119 552.1885 application than APCI, typically for the non-polar compounds. The advantage of using 390.3 0 236.2 416.3 550.4507 NL: 4.45E5 (APCI) and atmosphere pressure photo ionization (APPI). 40 444.4 100 185.1 13-012162 _apci#1-500 RT: APPI on non-polar compounds has recently been accepted for petroleum analysis. 486.4 20 526.5 APCI 0.00-6.85 AV: 500 T: FTMS +
Relative Abundance Relative 183.1 Methods: The extracted petroleum samples were directly injected by syringe pump 570.5 622.5 FIGURE 1. The targeted compounds of three different ionization techniques with 664.6 722.7 758.7 801.7 892.2 967.5 p APCI corona Full ms into the mass spectrometer. Three different ionization sources (ESI, APCI, APPI) were 0 50 551.4586 [100.00-1400.00] regard to the polarity and molecular weight of analytes. (Ref.1) 100 200 300 400 500 600 700 800 900 1000 549.4429 m/z 549.5942 used and the data were collected and analyzed by Thermo Scientific™ Xcalibur 548.8722 549.3443 549.8323 550.3567 550.5976 550.9258 551.3259 551.5524 552.1808
Relative Abundance 0 00-offset lens 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e5 #1-50 RT: 0.00-0.71 AV: 50 NL: 1.52E6 551.4594 NL: 1.10E3 software. 100 T: FTMS + c APCI corona Full ms [100.00-1000.00] 550.4515 13-012162_appi#1-269 RT: 199.1 100 APPI 0.01-3.88 AV: 269 T: FTMS + p APCI corona Full ms Results: APPI is the most promising ionization method for petroleum analysis because 549.5950 80 AGC: 5E5 50 [100.00-1400.00] nonpolar compounds can be ionized more efficiently than by APCI and ESI. The 551.3012 FIGURE 4. The impact of 00-offset potential on the ion distribution of petroleum 60 absence of radical ions in the APPI method enables efficient data processing and 548.6190 549.3376 549.7366 550.3263 550.5983 551.1261 551.5531 552.0343 264.2 0 sample. APCI was used to ionize sample and linear ion trap was the mass analyzer. 40 185.1 278.2 236.2 549.0 549.5 550.0 550.5 551.0 551.5 552.0 formula prediction. 332.3 20 105.1 157.1 360.3 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_0 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.06E7 Abundance Relative 402.3 444.4 500.4 540.5 580.5 624.6 664.6 706.6 748.7 802.7 836.6 904.8 934.9 991.2 T: ITMS + p APCI corona Full ms [100.00-1000.00] 0 106.1 100 100 200 300 400 500 600 700 800 900 1000 FIGURE 8. The mass spectrum of petroleum sample over 600 – 650 m/z ionized Introduction m/z 80 by APCI and APPI. The ionized ions from APCI and APPI are identical. 00-offset: 0 V 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e6 #1-50 RT: 0.01-0.90 AV: 50 NL: 2.90E6 The mass spectrometer has proven itself in the petroleum industry as an essential 60 T: FTMS + c APCI corona Full ms [100.00-1000.00] 108.1 153.1 199.1 199.1 100 NL: 3.27E5 analytical and process control instrument. The instrument is touted as a means to 40 105.1 606.5132 100 620.5288 13-012162 _apci#1-500 RT: 80 analyze and separate crude oil and petroleum samples that contain complicated 20 109.1 185.1 106.1 200.1 622.5444 647.4194 0.00-6.85 AV: 500 T: FTMS Relative Abundance Relative 250.2 618.5131 278.2 304.2 80 604.4976 + p APCI corona Full ms 346.3 400.3 442.3 484.3 530.4 570.4 612.5 662.6 704.6 742.6 810.7 856.7 896.8 931.0 966.9 60 AGC: 5E6 hydrocarbons which have very similar masses. Because the organic composition of the 0 128.1 634.5444 [100.00-1400.00] 60 610.5445 630.5131 100 200 300 400 500 600 700 800 900 1000 636.5600 polar components of petroleum is so complex, its characterization was until recently The ionization mechanism of ESI, APCI and APPI was illustrated in Figure 2. APPI ion 40 185.1 624.5601 644.5288 m/z 236.2 40 source uses a Krypton lamp, which emits photons at 10.0 eV and 10.6 eV. Photon 20 264.2 638.5758 APCI limited to bulk properties (such as color, viscosity and density) until the emergence of 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_5 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.17E5 Abundance Relative 290.2 614.4818 628.4974 332.2 20 642.5131 T: ITMS + p APCI corona Full ms [100.00-1000.00] 388.3 430.4 470.4 524.4 564.5 632.5 664.6 703.5 770.2 796.3 868.7 915.4 961.0 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) which energy from Krypton lamp is sufficient to ionize most analytes, and is lower than the 0 Abundance Relative 199.2 100 200 300 400 500 600 700 800 900 1000 100 0 NL: 4.60E3 ionization potentials of common reversed-phase solvents such as water, methanol, m/z 622.5454 offers the highest available, mass resolving power, and mass accuracy. The need to 00-offset: 5 V 100 608.5297 13-012162_appi#1-300 RT: 80 634.5453 and acetonitrile. 264.2 292.3 647.4202 0.01-4.32 AV: 300 T: FTMS volatilize the sample limited the obtainable molecular weight range (especially for 318.3 80 610.5453 618.5139 624.5610 632.5296 + p APCI corona Full ms 60 346.3 Comparison of ESI, APCI and APPI 390.3 [100.00-1400.00] heteroatom containing species). Since electron impact ionization produced extensive FIGURE 2. The ionization mechanism of (a) ESI source (HESI II), (b) APCI, and (c) 236.2 60 604.4983 638.5767 40 185.2 418.3 fragmentation (especially of alkyl chains), electrospray ionization (ESI) is a soft 456.3 616.4984 631.5218 644.5296 APPI. Positive charge (protonation) is added by potential through (a) ESI probe, 183.2 498.4 With the same mass spec settings (00-offset: 6 and AGC: 5E4), three different 40 20 540.4 APPI Relative Abundance Relative 580.5 622.5 ionization technique and more useful to characterize polar compounds. But ESI has the (b) corona discharge needle, (c) Krypton lamp. (Ref. 2) 664.5 718.6 776.7 804.7 856.8 890.9 938.8 978.9 ionization techniques were studied and compared. 20 limited reach for petroleum analysis since petroleum crude oils typically contain 90% 0 100 200 300 400 500 600 700 800 900 1000 As shown in Figure 6 and 7, the ion distributions were observed from the three 0 hydrocarbons, nonpolar compounds. m/z 600 605 610 615 620 625 630 635 640 645 650 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6 #1-201 RT: 0.00-0.76 AV: 201 NL: 1.55E5 ionization techniques. Briefly, ESI is much more efficient for polar molecules and An ion trap based hybrid mass spectrometer (Orbitrap Elite MS) , with sufficiently high T: ITMS + c APCI corona Full ms [100.00-1000.00] 292.3 typically ionized many highly polar compound, heteroatom-containing components 100 199.2 278.3 320.3 362.3 – mass resolving power (m/Δm 240,000 @ m/z 400) and a m/z range up to 2000 Da was 390.4 (NnOoSs) of the petroleum sample. APCI shows the capability of ionizing the As shown in Figure 8, APCI and APPI produced identical ions from 600 650 m/z 404.4 80 250.3 00-offset: 6 V which indicated all ions generated by APPI are protonated ions like those from APCI utilized to analyze petroleum samples extracted from crude oil which were injected 430.4 petroleum components, both polar and non-polar compounds, but mainly focusing on 60 456.4 and that radical ions were not generated by APPI. The absence of radical ions directly by syringe. Three ionization methods, electrospray ionization (ESI), 236.3 484.4 nonpolar compounds. APPI gives access to many of the remaining 90% of petroleum 530.5 40 185.3 atmosphere pressure chemical ionization (APCI) and atmosphere pressure photo 554.5 – significantly reduced the workload of predicting the formula of each ions. 582.5 components hydrocarbon compounds including benzo- and dibenzothiophenes, 20 183.3 624.6 ionization (APPI) were used and ion distribution and polarity of compounds were Abundance Relative 664.6 708.7 128.3 752.7 806.8 854.8 892.9 946.9 furans, cycloalkanes, and polycyclic aromatic hydrocarbons (PAHs) not observed by 0 studied. Various MS scan modes and ion transfer optical potentials were investigated 100 200 300 400 500 600 700 800 900 1000 ESI. Conclusion to determine the approaches that provided high quality information with a wide m/z m/z FIGURE 6. The ion distribution of petroleum sample ionized by ESI, APCI and The performance of ultrahigh mass-resolution Orbitrap Elite mass spectrometer and range. (a) (c) As shown in Figure 4, the adjustment of the 00-offset potential from 0 to 6 V led to an APPI separately. Orbitrap was the mass analyzer with the AGC setting of 5E4 three ionization techniques on the petroleum analysis were investigated in this study. intensity decrease for low m/z ions and the accumulation of high m/z ions. The access and the 00-offset of 6. . The adjustment on 00-offset lens and AGC is needed to get the correct ion (b) of the 00-offset is important for petroleum analysis because it can control the low m/z Methods 13-012162_ESI #338-360 RT: 5.14-5.48 AV: 23 NL: 6.50E4 distribution from petroleum samples. ions entering the mass analyzer, thereby allowing the capacity of analyzer (ion trap T: FTMS + p ESI Full ms [100.00-1400.00] 288.17 Sample Preparation 100 . and/or Orbitrap analyzer) to be fully used by the targeted high m/z ions. As shown in 273.16 ESI The compounds ionized by ESI are the polar compounds having a relatively low Figure 4, 00-offset was optimized at 6 and used for data collection in experiments. 80 181.10 molecular mass. Samples: The extracted samples from refinery pipelines supplied by Taxon Bioscience 304.17 60 363.21 . Samples were dissolved into 1 mg/mL by Toluene, then diluted to 250 µg/mL by In order to obtain optimal performance in the trapping device, the ion population needs 40 The nonpolar compounds in petroleum samples can be ionized by APCI and 394.22 to be kept within a certain range. Therefore, a procedure is needed to predict the 20 APPI, and APPI shows an advantage over APCI in ionizing the large nonpolar different solvent based on the ionization method prior to direct injection. 470.28
Relative Abundance Relative 547.34 663.45 748.60 888.92 944.44 1029.91 1190.50 1304.57 appropriate accumulation time. Automatic control of the number of ions in the Orbitrap 0 compounds. Dilution solvent analyzer is achieved by measuring the total ion charge from a pre-scan and by 200 400 600 800 1000 1200 1400 m/z . Only protonated ions are generated from APPI and radical ions were not • calculating the ion injection time. Automatic Gain Control (AGC™) ensures that the ion For APPI and APCI: Toluene 13-012162 _apci #375-400 RT: 5.13-5.48 AV: 26 NL: 1.04E7 observed, which simplified the data processing and formula prediction. trap is always filled with the optimum number of ions for any scan type. T: FTMS + p APCI corona Full ms [100.00-1400.00] • For ESI: 1% Formic Acid and 5% DCM in 50:50 Toluene:Methanol 406.36 APCI 418.36 As shown in Figure 5, the AGC optimization was studied along with ion distribution. 10 Mass Spectrometry 472.40 References Optimization of Orbitrap Elite MS The AGC setting was found to have a significant impact on ion distribution. Although 540.47 662.44 Ionization Source: the higher AGC setting allowed more ions to enter the Orbitrap mass analyzer, 2.9E6 5 391.33 566.48 1. Product specification of APPI/APCI combination ion source, Thermo Scientific Orbitrap Elite MS is a high performance hybrid mass spectrometer 165.07 (AGC: 5E6) vs 1.52E6 (AGC: 5E5) vs 1.8oE5 (AGC: 5E4), the ion distribution of the 269.23 674.58 http://www.thermoscientific.fr/com/cda/product/detail/0,1055,19246,00.html 756.65 Electrospray (HESI II) combining the use of an Orbitrap analyzer with a linear ion trap. The DC potential of the Abundance Relative 838.73 923.01 1021.12 1106.22 1220.36 1306.44 petroleum sample was poor because more low m/z ions entered the Orbitrap mass 0 2. Application note 347: Mechanism of [M+H]+ Formation in Atmospheric Pressure optic lens in the first vacuum stage can be optimized to the ion distribution of petroleum analyzer. To maximize a broad m/z range distribution the low AGC setting of 5E4 is 200 300 400 500 600 700 800 900 1000 1100 1200 1300 Atmosphere Pressure Chemical Ionization (APCI) – m/z Photoionization Mass Spectrometry, Thermo Fisher Scientific Inc. compounds which typically cover the mass range 200 1000 m/z. By optimizing the DC preferred. The package of ions is collected in the ion trap and the number of ions was Atmosphere Pressure Photo ionization (APPI) potential, the kinetic energy of ions was controlled, which means the ions could be 13-012162_appi #208-226 RT: 3.00-3.26 AV: 19 NL: 5.35E4 controlled by AGC. The ion package is send to C-Trap and cooled down, focused and T: FTMS + p APCI corona Full ms [100.00-1400.00] accelerated or slowed down as appropriate. Ion Trap and Orbitrap Elite (Mass Resolution = 240,000) sent to the Orbitrap analyzer for analysis. C-trap, like all RF devices, has an m/z 688.59 APPI 871.95 Acknowledgements 552.47 702.61 In this study, the setting of 00-offset in Figure 3 was observed to have a significant dependent potential well to trap ions. So if a mix of ions is sent into C-trap, the lower 10 Positive scan 622.55 956.05 We would like to thank Jean Jacques Dunyach from Thermo Fisher Scientific for impact on the intensity of ions from petroleum. Ions have the same velocity from the m/z ions are trapped by a deeper well and the high m/z ions are trapped by a 998.10 1068.17 5 206.24 supplying the APPI source information. AGC: 5E4 - 5E6 vacuum drop in the first vacuum stage after the ion beam passes through the transfer shallower well. If a mix of ions fills up C-trap such that space charge starts to be of the 1161.28 1246.38 130.88 335.06 tube. The increasing of the 00-offset potential slows down the ions, allowing the low m/z same order as the well depth, then the high m/z ions will be spilled out firstly. By Abundance Relative 223.68 474.42 1349.49 Mass Spectrum (average of 100-200 scans) 0 All trademarks are the property of Thermo Fisher Scientific and its subsidiaries. ions to be prevented from entering the linear trap mass analyzer and Orbitrap mass reducing the number of ions via setting a low AGC value, more high m/z ions could be 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 obtained on spectrum. m/z This information is not intended to encourage use of these products in any manners that might infringe the Data Collection and Analysis analyzer. intellectual property rights of others. Xcalibur software PO64143-EN 0614S
4 Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods Pengxiang Yang1, Keith Waddell1 Brian M. Ruddy2, Matt Ashby2, and Leonard Nyadong3 1Thermo Fisher Scientific, San Jose, California; 2Taxon Biosciences, Tiburon, California; 3Phillips 66, Houston, Texas
FIGURE 7. The mass spectrum of petroleum sample over 549.0 – 552.0 m/z FIGURE 3. Schematic of the Orbitrap Elite Hybrid MS. The 00-offset lens is FIGURE 5. The impact of Orbitrap MS AGC setting on the ion distribution of ionized by ESI, APCI and APPI. Overview Results located between S-Lens and square quadrupole. (Ref. 3) petroleum sample. APCI was used to ionize sample and Orbitrap was the mass analyzer. 00-offset was set at 6. Purpose: A brief comparison of three different ionization methods was carried out on Ionization Methods 551.2731 NL: 6.01E2 the ultra-high resolution mass spectrometer (Thermo Scientific™ Orbitrap Elite™ 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e4 #1-50 RT: 0.01-0.68 AV: 50 NL: 1.80E5 100 Three different ionization techniques, ESI, APCI and APPI, are available in the Ion T: FTMS + c APCI corona Full ms [100.00-1000.00] ESI 13-012162_ESI#334-371 RT: 199.1 5.08-5.64 AV: 38 T: FTMS + p Hybrid Ion Trap-Orbitrap MS) for petroleum analysis. A comparative analysis was made 100 549.2574 ESI Full ms [100.00-1400.00] Max ion source platform. The complementary nature of the application of each 551.3303 278.2 50 on ionization efficiency, ion distributions, and ionization competition. The three 80 264.2 290.2 332.3 550.3103 ionization method is summarized in Figure 1, which shows the APPI has more broader 374.3 ionization method are electrospray (ESI), atmosphere pressure chemical ionization 60 AGC: 5E4 549.1189 549.4412 549.8009 550.5292 551.1538 551.6119 552.1885 application than APCI, typically for the non-polar compounds. The advantage of using 390.3 0 236.2 416.3 550.4507 NL: 4.45E5 (APCI) and atmosphere pressure photo ionization (APPI). 40 444.4 100 185.1 13-012162 _apci#1-500 RT: APPI on non-polar compounds has recently been accepted for petroleum analysis. 486.4 20 526.5 APCI 0.00-6.85 AV: 500 T: FTMS +
Relative Abundance Relative 183.1 Methods: The extracted petroleum samples were directly injected by syringe pump 570.5 622.5 FIGURE 1. The targeted compounds of three different ionization techniques with 664.6 722.7 758.7 801.7 892.2 967.5 p APCI corona Full ms into the mass spectrometer. Three different ionization sources (ESI, APCI, APPI) were 0 50 551.4586 [100.00-1400.00] regard to the polarity and molecular weight of analytes. (Ref.1) 100 200 300 400 500 600 700 800 900 1000 549.4429 m/z 549.5942 used and the data were collected and analyzed by Thermo Scientific™ Xcalibur 548.8722 549.3443 549.8323 550.3567 550.5976 550.9258 551.3259 551.5524 552.1808
Relative Abundance 0 00-offset lens 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e5 #1-50 RT: 0.00-0.71 AV: 50 NL: 1.52E6 551.4594 NL: 1.10E3 software. 100 T: FTMS + c APCI corona Full ms [100.00-1000.00] 550.4515 13-012162_appi#1-269 RT: 199.1 100 APPI 0.01-3.88 AV: 269 T: FTMS + p APCI corona Full ms Results: APPI is the most promising ionization method for petroleum analysis because 549.5950 80 AGC: 5E5 50 [100.00-1400.00] nonpolar compounds can be ionized more efficiently than by APCI and ESI. The 551.3012 FIGURE 4. The impact of 00-offset potential on the ion distribution of petroleum 60 absence of radical ions in the APPI method enables efficient data processing and 548.6190 549.3376 549.7366 550.3263 550.5983 551.1261 551.5531 552.0343 264.2 0 sample. APCI was used to ionize sample and linear ion trap was the mass analyzer. 40 185.1 278.2 236.2 549.0 549.5 550.0 550.5 551.0 551.5 552.0 formula prediction. 332.3 20 105.1 157.1 360.3 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_0 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.06E7 Abundance Relative 402.3 444.4 500.4 540.5 580.5 624.6 664.6 706.6 748.7 802.7 836.6 904.8 934.9 991.2 T: ITMS + p APCI corona Full ms [100.00-1000.00] 0 106.1 100 100 200 300 400 500 600 700 800 900 1000 FIGURE 8. The mass spectrum of petroleum sample over 600 – 650 m/z ionized Introduction m/z 80 by APCI and APPI. The ionized ions from APCI and APPI are identical. 00-offset: 0 V 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e6 #1-50 RT: 0.01-0.90 AV: 50 NL: 2.90E6 The mass spectrometer has proven itself in the petroleum industry as an essential 60 T: FTMS + c APCI corona Full ms [100.00-1000.00] 108.1 153.1 199.1 199.1 100 NL: 3.27E5 analytical and process control instrument. The instrument is touted as a means to 40 105.1 606.5132 100 620.5288 13-012162 _apci#1-500 RT: 80 analyze and separate crude oil and petroleum samples that contain complicated 20 109.1 185.1 106.1 200.1 622.5444 647.4194 0.00-6.85 AV: 500 T: FTMS Relative Abundance Relative 250.2 618.5131 278.2 304.2 80 604.4976 + p APCI corona Full ms 346.3 400.3 442.3 484.3 530.4 570.4 612.5 662.6 704.6 742.6 810.7 856.7 896.8 931.0 966.9 60 AGC: 5E6 hydrocarbons which have very similar masses. Because the organic composition of the 0 128.1 634.5444 [100.00-1400.00] 60 610.5445 630.5131 100 200 300 400 500 600 700 800 900 1000 636.5600 polar components of petroleum is so complex, its characterization was until recently The ionization mechanism of ESI, APCI and APPI was illustrated in Figure 2. APPI ion 40 185.1 624.5601 644.5288 m/z 236.2 40 source uses a Krypton lamp, which emits photons at 10.0 eV and 10.6 eV. Photon 20 264.2 638.5758 APCI limited to bulk properties (such as color, viscosity and density) until the emergence of 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_5 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.17E5 Abundance Relative 290.2 614.4818 628.4974 332.2 20 642.5131 T: ITMS + p APCI corona Full ms [100.00-1000.00] 388.3 430.4 470.4 524.4 564.5 632.5 664.6 703.5 770.2 796.3 868.7 915.4 961.0 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) which energy from Krypton lamp is sufficient to ionize most analytes, and is lower than the 0 Abundance Relative 199.2 100 200 300 400 500 600 700 800 900 1000 100 0 NL: 4.60E3 ionization potentials of common reversed-phase solvents such as water, methanol, m/z 622.5454 offers the highest available, mass resolving power, and mass accuracy. The need to 00-offset: 5 V 100 608.5297 13-012162_appi#1-300 RT: 80 634.5453 and acetonitrile. 264.2 292.3 647.4202 0.01-4.32 AV: 300 T: FTMS volatilize the sample limited the obtainable molecular weight range (especially for 318.3 80 610.5453 618.5139 624.5610 632.5296 + p APCI corona Full ms 60 346.3 Comparison of ESI, APCI and APPI 390.3 [100.00-1400.00] heteroatom containing species). Since electron impact ionization produced extensive FIGURE 2. The ionization mechanism of (a) ESI source (HESI II), (b) APCI, and (c) 236.2 60 604.4983 638.5767 40 185.2 418.3 fragmentation (especially of alkyl chains), electrospray ionization (ESI) is a soft 456.3 616.4984 631.5218 644.5296 APPI. Positive charge (protonation) is added by potential through (a) ESI probe, 183.2 498.4 With the same mass spec settings (00-offset: 6 and AGC: 5E4), three different 40 20 540.4 APPI Relative Abundance Relative 580.5 622.5 ionization technique and more useful to characterize polar compounds. But ESI has the (b) corona discharge needle, (c) Krypton lamp. (Ref. 2) 664.5 718.6 776.7 804.7 856.8 890.9 938.8 978.9 ionization techniques were studied and compared. 20 limited reach for petroleum analysis since petroleum crude oils typically contain 90% 0 100 200 300 400 500 600 700 800 900 1000 As shown in Figure 6 and 7, the ion distributions were observed from the three 0 hydrocarbons, nonpolar compounds. m/z 600 605 610 615 620 625 630 635 640 645 650 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6 #1-201 RT: 0.00-0.76 AV: 201 NL: 1.55E5 ionization techniques. Briefly, ESI is much more efficient for polar molecules and An ion trap based hybrid mass spectrometer (Orbitrap Elite MS) , with sufficiently high T: ITMS + c APCI corona Full ms [100.00-1000.00] 292.3 typically ionized many highly polar compound, heteroatom-containing components 100 199.2 278.3 320.3 362.3 – mass resolving power (m/Δm 240,000 @ m/z 400) and a m/z range up to 2000 Da was 390.4 (NnOoSs) of the petroleum sample. APCI shows the capability of ionizing the As shown in Figure 8, APCI and APPI produced identical ions from 600 650 m/z 404.4 80 250.3 00-offset: 6 V which indicated all ions generated by APPI are protonated ions like those from APCI utilized to analyze petroleum samples extracted from crude oil which were injected 430.4 petroleum components, both polar and non-polar compounds, but mainly focusing on 60 456.4 and that radical ions were not generated by APPI. The absence of radical ions directly by syringe. Three ionization methods, electrospray ionization (ESI), 236.3 484.4 nonpolar compounds. APPI gives access to many of the remaining 90% of petroleum 530.5 40 185.3 atmosphere pressure chemical ionization (APCI) and atmosphere pressure photo 554.5 – significantly reduced the workload of predicting the formula of each ions. 582.5 components hydrocarbon compounds including benzo- and dibenzothiophenes, 20 183.3 624.6 ionization (APPI) were used and ion distribution and polarity of compounds were Abundance Relative 664.6 708.7 128.3 752.7 806.8 854.8 892.9 946.9 furans, cycloalkanes, and polycyclic aromatic hydrocarbons (PAHs) not observed by 0 studied. Various MS scan modes and ion transfer optical potentials were investigated 100 200 300 400 500 600 700 800 900 1000 ESI. Conclusion to determine the approaches that provided high quality information with a wide m/z m/z FIGURE 6. The ion distribution of petroleum sample ionized by ESI, APCI and The performance of ultrahigh mass-resolution Orbitrap Elite mass spectrometer and range. (a) (c) As shown in Figure 4, the adjustment of the 00-offset potential from 0 to 6 V led to an APPI separately. Orbitrap was the mass analyzer with the AGC setting of 5E4 three ionization techniques on the petroleum analysis were investigated in this study. intensity decrease for low m/z ions and the accumulation of high m/z ions. The access and the 00-offset of 6. . The adjustment on 00-offset lens and AGC is needed to get the correct ion (b) of the 00-offset is important for petroleum analysis because it can control the low m/z Methods 13-012162_ESI #338-360 RT: 5.14-5.48 AV: 23 NL: 6.50E4 distribution from petroleum samples. ions entering the mass analyzer, thereby allowing the capacity of analyzer (ion trap T: FTMS + p ESI Full ms [100.00-1400.00] 288.17 Sample Preparation 100 . and/or Orbitrap analyzer) to be fully used by the targeted high m/z ions. As shown in 273.16 ESI The compounds ionized by ESI are the polar compounds having a relatively low Figure 4, 00-offset was optimized at 6 and used for data collection in experiments. 80 181.10 molecular mass. Samples: The extracted samples from refinery pipelines supplied by Taxon Bioscience 304.17 60 363.21 . Samples were dissolved into 1 mg/mL by Toluene, then diluted to 250 µg/mL by In order to obtain optimal performance in the trapping device, the ion population needs 40 The nonpolar compounds in petroleum samples can be ionized by APCI and 394.22 to be kept within a certain range. Therefore, a procedure is needed to predict the 20 APPI, and APPI shows an advantage over APCI in ionizing the large nonpolar different solvent based on the ionization method prior to direct injection. 470.28
Relative Abundance Relative 547.34 663.45 748.60 888.92 944.44 1029.91 1190.50 1304.57 appropriate accumulation time. Automatic control of the number of ions in the Orbitrap 0 compounds. Dilution solvent analyzer is achieved by measuring the total ion charge from a pre-scan and by 200 400 600 800 1000 1200 1400 m/z . Only protonated ions are generated from APPI and radical ions were not • calculating the ion injection time. Automatic Gain Control (AGC™) ensures that the ion For APPI and APCI: Toluene 13-012162 _apci #375-400 RT: 5.13-5.48 AV: 26 NL: 1.04E7 observed, which simplified the data processing and formula prediction. trap is always filled with the optimum number of ions for any scan type. T: FTMS + p APCI corona Full ms [100.00-1400.00] • For ESI: 1% Formic Acid and 5% DCM in 50:50 Toluene:Methanol 406.36 APCI 418.36 As shown in Figure 5, the AGC optimization was studied along with ion distribution. 10 Mass Spectrometry 472.40 References Optimization of Orbitrap Elite MS The AGC setting was found to have a significant impact on ion distribution. Although 540.47 662.44 Ionization Source: the higher AGC setting allowed more ions to enter the Orbitrap mass analyzer, 2.9E6 5 391.33 566.48 1. Product specification of APPI/APCI combination ion source, Thermo Scientific Orbitrap Elite MS is a high performance hybrid mass spectrometer 165.07 (AGC: 5E6) vs 1.52E6 (AGC: 5E5) vs 1.8oE5 (AGC: 5E4), the ion distribution of the 269.23 674.58 http://www.thermoscientific.fr/com/cda/product/detail/0,1055,19246,00.html 756.65 Electrospray (HESI II) combining the use of an Orbitrap analyzer with a linear ion trap. The DC potential of the Abundance Relative 838.73 923.01 1021.12 1106.22 1220.36 1306.44 petroleum sample was poor because more low m/z ions entered the Orbitrap mass 0 2. Application note 347: Mechanism of [M+H]+ Formation in Atmospheric Pressure optic lens in the first vacuum stage can be optimized to the ion distribution of petroleum analyzer. To maximize a broad m/z range distribution the low AGC setting of 5E4 is 200 300 400 500 600 700 800 900 1000 1100 1200 1300 Atmosphere Pressure Chemical Ionization (APCI) – m/z Photoionization Mass Spectrometry, Thermo Fisher Scientific Inc. compounds which typically cover the mass range 200 1000 m/z. By optimizing the DC preferred. The package of ions is collected in the ion trap and the number of ions was Atmosphere Pressure Photo ionization (APPI) potential, the kinetic energy of ions was controlled, which means the ions could be 13-012162_appi #208-226 RT: 3.00-3.26 AV: 19 NL: 5.35E4 controlled by AGC. The ion package is send to C-Trap and cooled down, focused and T: FTMS + p APCI corona Full ms [100.00-1400.00] accelerated or slowed down as appropriate. Ion Trap and Orbitrap Elite (Mass Resolution = 240,000) sent to the Orbitrap analyzer for analysis. C-trap, like all RF devices, has an m/z 688.59 APPI 871.95 Acknowledgements 552.47 702.61 In this study, the setting of 00-offset in Figure 3 was observed to have a significant dependent potential well to trap ions. So if a mix of ions is sent into C-trap, the lower 10 Positive scan 622.55 956.05 We would like to thank Jean Jacques Dunyach from Thermo Fisher Scientific for impact on the intensity of ions from petroleum. Ions have the same velocity from the m/z ions are trapped by a deeper well and the high m/z ions are trapped by a 998.10 1068.17 5 206.24 supplying the APPI source information. AGC: 5E4 - 5E6 vacuum drop in the first vacuum stage after the ion beam passes through the transfer shallower well. If a mix of ions fills up C-trap such that space charge starts to be of the 1161.28 1246.38 130.88 335.06 tube. The increasing of the 00-offset potential slows down the ions, allowing the low m/z same order as the well depth, then the high m/z ions will be spilled out firstly. By Abundance Relative 223.68 474.42 1349.49 Mass Spectrum (average of 100-200 scans) 0 All trademarks are the property of Thermo Fisher Scientific and its subsidiaries. ions to be prevented from entering the linear trap mass analyzer and Orbitrap mass reducing the number of ions via setting a low AGC value, more high m/z ions could be 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 obtained on spectrum. m/z This information is not intended to encourage use of these products in any manners that might infringe the Data Collection and Analysis analyzer. intellectual property rights of others. Xcalibur software PO64143-EN 0614S
Thermo Scientific Poster Note• PN-64143-ASMS-EN-0614S 5 Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods Pengxiang Yang1, Keith Waddell1 Brian M. Ruddy2, Matt Ashby2, and Leonard Nyadong3 1Thermo Fisher Scientific, San Jose, California; 2Taxon Biosciences, Tiburon, California; 3Phillips 66, Houston, Texas
FIGURE 7. The mass spectrum of petroleum sample over 549.0 – 552.0 m/z FIGURE 3. Schematic of the Orbitrap Elite Hybrid MS. The 00-offset lens is FIGURE 5. The impact of Orbitrap MS AGC setting on the ion distribution of ionized by ESI, APCI and APPI. Overview Results located between S-Lens and square quadrupole. (Ref. 3) petroleum sample. APCI was used to ionize sample and Orbitrap was the mass analyzer. 00-offset was set at 6. Purpose: A brief comparison of three different ionization methods was carried out on Ionization Methods 551.2731 NL: 6.01E2 the ultra-high resolution mass spectrometer (Thermo Scientific™ Orbitrap Elite™ 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e4 #1-50 RT: 0.01-0.68 AV: 50 NL: 1.80E5 100 Three different ionization techniques, ESI, APCI and APPI, are available in the Ion T: FTMS + c APCI corona Full ms [100.00-1000.00] ESI 13-012162_ESI#334-371 RT: 199.1 5.08-5.64 AV: 38 T: FTMS + p Hybrid Ion Trap-Orbitrap MS) for petroleum analysis. A comparative analysis was made 100 549.2574 ESI Full ms [100.00-1400.00] Max ion source platform. The complementary nature of the application of each 551.3303 278.2 50 on ionization efficiency, ion distributions, and ionization competition. The three 80 264.2 290.2 332.3 550.3103 ionization method is summarized in Figure 1, which shows the APPI has more broader 374.3 ionization method are electrospray (ESI), atmosphere pressure chemical ionization 60 AGC: 5E4 549.1189 549.4412 549.8009 550.5292 551.1538 551.6119 552.1885 application than APCI, typically for the non-polar compounds. The advantage of using 390.3 0 236.2 416.3 550.4507 NL: 4.45E5 (APCI) and atmosphere pressure photo ionization (APPI). 40 444.4 100 185.1 13-012162 _apci#1-500 RT: APPI on non-polar compounds has recently been accepted for petroleum analysis. 486.4 20 526.5 APCI 0.00-6.85 AV: 500 T: FTMS +
Relative Abundance Relative 183.1 Methods: The extracted petroleum samples were directly injected by syringe pump 570.5 622.5 FIGURE 1. The targeted compounds of three different ionization techniques with 664.6 722.7 758.7 801.7 892.2 967.5 p APCI corona Full ms into the mass spectrometer. Three different ionization sources (ESI, APCI, APPI) were 0 50 551.4586 [100.00-1400.00] regard to the polarity and molecular weight of analytes. (Ref.1) 100 200 300 400 500 600 700 800 900 1000 549.4429 m/z 549.5942 used and the data were collected and analyzed by Thermo Scientific™ Xcalibur 548.8722 549.3443 549.8323 550.3567 550.5976 550.9258 551.3259 551.5524 552.1808
Relative Abundance 0 00-offset lens 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e5 #1-50 RT: 0.00-0.71 AV: 50 NL: 1.52E6 551.4594 NL: 1.10E3 software. 100 T: FTMS + c APCI corona Full ms [100.00-1000.00] 550.4515 13-012162_appi#1-269 RT: 199.1 100 APPI 0.01-3.88 AV: 269 T: FTMS + p APCI corona Full ms Results: APPI is the most promising ionization method for petroleum analysis because 549.5950 80 AGC: 5E5 50 [100.00-1400.00] nonpolar compounds can be ionized more efficiently than by APCI and ESI. The 551.3012 FIGURE 4. The impact of 00-offset potential on the ion distribution of petroleum 60 absence of radical ions in the APPI method enables efficient data processing and 548.6190 549.3376 549.7366 550.3263 550.5983 551.1261 551.5531 552.0343 264.2 0 sample. APCI was used to ionize sample and linear ion trap was the mass analyzer. 40 185.1 278.2 236.2 549.0 549.5 550.0 550.5 551.0 551.5 552.0 formula prediction. 332.3 20 105.1 157.1 360.3 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_0 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.06E7 Abundance Relative 402.3 444.4 500.4 540.5 580.5 624.6 664.6 706.6 748.7 802.7 836.6 904.8 934.9 991.2 T: ITMS + p APCI corona Full ms [100.00-1000.00] 0 106.1 100 100 200 300 400 500 600 700 800 900 1000 FIGURE 8. The mass spectrum of petroleum sample over 600 – 650 m/z ionized Introduction m/z 80 by APCI and APPI. The ionized ions from APCI and APPI are identical. 00-offset: 0 V 2-Ring_FTMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6_AGC_5e6 #1-50 RT: 0.01-0.90 AV: 50 NL: 2.90E6 The mass spectrometer has proven itself in the petroleum industry as an essential 60 T: FTMS + c APCI corona Full ms [100.00-1000.00] 108.1 153.1 199.1 199.1 100 NL: 3.27E5 analytical and process control instrument. The instrument is touted as a means to 40 105.1 606.5132 100 620.5288 13-012162 _apci#1-500 RT: 80 analyze and separate crude oil and petroleum samples that contain complicated 20 109.1 185.1 106.1 200.1 622.5444 647.4194 0.00-6.85 AV: 500 T: FTMS Relative Abundance Relative 250.2 618.5131 278.2 304.2 80 604.4976 + p APCI corona Full ms 346.3 400.3 442.3 484.3 530.4 570.4 612.5 662.6 704.6 742.6 810.7 856.7 896.8 931.0 966.9 60 AGC: 5E6 hydrocarbons which have very similar masses. Because the organic composition of the 0 128.1 634.5444 [100.00-1400.00] 60 610.5445 630.5131 100 200 300 400 500 600 700 800 900 1000 636.5600 polar components of petroleum is so complex, its characterization was until recently The ionization mechanism of ESI, APCI and APPI was illustrated in Figure 2. APPI ion 40 185.1 624.5601 644.5288 m/z 236.2 40 source uses a Krypton lamp, which emits photons at 10.0 eV and 10.6 eV. Photon 20 264.2 638.5758 APCI limited to bulk properties (such as color, viscosity and density) until the emergence of 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_5 #1-50 RT: 0.00-0.19 AV: 50 NL: 1.17E5 Abundance Relative 290.2 614.4818 628.4974 332.2 20 642.5131 T: ITMS + p APCI corona Full ms [100.00-1000.00] 388.3 430.4 470.4 524.4 564.5 632.5 664.6 703.5 770.2 796.3 868.7 915.4 961.0 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) which energy from Krypton lamp is sufficient to ionize most analytes, and is lower than the 0 Abundance Relative 199.2 100 200 300 400 500 600 700 800 900 1000 100 0 NL: 4.60E3 ionization potentials of common reversed-phase solvents such as water, methanol, m/z 622.5454 offers the highest available, mass resolving power, and mass accuracy. The need to 00-offset: 5 V 100 608.5297 13-012162_appi#1-300 RT: 80 634.5453 and acetonitrile. 264.2 292.3 647.4202 0.01-4.32 AV: 300 T: FTMS volatilize the sample limited the obtainable molecular weight range (especially for 318.3 80 610.5453 618.5139 624.5610 632.5296 + p APCI corona Full ms 60 346.3 Comparison of ESI, APCI and APPI 390.3 [100.00-1400.00] heteroatom containing species). Since electron impact ionization produced extensive FIGURE 2. The ionization mechanism of (a) ESI source (HESI II), (b) APCI, and (c) 236.2 60 604.4983 638.5767 40 185.2 418.3 fragmentation (especially of alkyl chains), electrospray ionization (ESI) is a soft 456.3 616.4984 631.5218 644.5296 APPI. Positive charge (protonation) is added by potential through (a) ESI probe, 183.2 498.4 With the same mass spec settings (00-offset: 6 and AGC: 5E4), three different 40 20 540.4 APPI Relative Abundance Relative 580.5 622.5 ionization technique and more useful to characterize polar compounds. But ESI has the (b) corona discharge needle, (c) Krypton lamp. (Ref. 2) 664.5 718.6 776.7 804.7 856.8 890.9 938.8 978.9 ionization techniques were studied and compared. 20 limited reach for petroleum analysis since petroleum crude oils typically contain 90% 0 100 200 300 400 500 600 700 800 900 1000 As shown in Figure 6 and 7, the ion distributions were observed from the three 0 hydrocarbons, nonpolar compounds. m/z 600 605 610 615 620 625 630 635 640 645 650 m/z 2-Ring_ITMS_VT_350_SG_80_AG_25_CT_275_SL_30_00offset_6 #1-201 RT: 0.00-0.76 AV: 201 NL: 1.55E5 ionization techniques. Briefly, ESI is much more efficient for polar molecules and An ion trap based hybrid mass spectrometer (Orbitrap Elite MS) , with sufficiently high T: ITMS + c APCI corona Full ms [100.00-1000.00] 292.3 typically ionized many highly polar compound, heteroatom-containing components 100 199.2 278.3 320.3 362.3 – mass resolving power (m/Δm 240,000 @ m/z 400) and a m/z range up to 2000 Da was 390.4 (NnOoSs) of the petroleum sample. APCI shows the capability of ionizing the As shown in Figure 8, APCI and APPI produced identical ions from 600 650 m/z 404.4 80 250.3 00-offset: 6 V which indicated all ions generated by APPI are protonated ions like those from APCI utilized to analyze petroleum samples extracted from crude oil which were injected 430.4 petroleum components, both polar and non-polar compounds, but mainly focusing on 60 456.4 and that radical ions were not generated by APPI. The absence of radical ions directly by syringe. Three ionization methods, electrospray ionization (ESI), 236.3 484.4 nonpolar compounds. APPI gives access to many of the remaining 90% of petroleum 530.5 40 185.3 atmosphere pressure chemical ionization (APCI) and atmosphere pressure photo 554.5 – significantly reduced the workload of predicting the formula of each ions. 582.5 components hydrocarbon compounds including benzo- and dibenzothiophenes, 20 183.3 624.6 ionization (APPI) were used and ion distribution and polarity of compounds were Abundance Relative 664.6 708.7 128.3 752.7 806.8 854.8 892.9 946.9 furans, cycloalkanes, and polycyclic aromatic hydrocarbons (PAHs) not observed by 0 studied. Various MS scan modes and ion transfer optical potentials were investigated 100 200 300 400 500 600 700 800 900 1000 ESI. Conclusion to determine the approaches that provided high quality information with a wide m/z m/z FIGURE 6. The ion distribution of petroleum sample ionized by ESI, APCI and The performance of ultrahigh mass-resolution Orbitrap Elite mass spectrometer and range. (a) (c) As shown in Figure 4, the adjustment of the 00-offset potential from 0 to 6 V led to an APPI separately. Orbitrap was the mass analyzer with the AGC setting of 5E4 three ionization techniques on the petroleum analysis were investigated in this study. intensity decrease for low m/z ions and the accumulation of high m/z ions. The access and the 00-offset of 6. . The adjustment on 00-offset lens and AGC is needed to get the correct ion (b) of the 00-offset is important for petroleum analysis because it can control the low m/z Methods 13-012162_ESI #338-360 RT: 5.14-5.48 AV: 23 NL: 6.50E4 distribution from petroleum samples. ions entering the mass analyzer, thereby allowing the capacity of analyzer (ion trap T: FTMS + p ESI Full ms [100.00-1400.00] 288.17 Sample Preparation 100 . and/or Orbitrap analyzer) to be fully used by the targeted high m/z ions. As shown in 273.16 ESI The compounds ionized by ESI are the polar compounds having a relatively low Figure 4, 00-offset was optimized at 6 and used for data collection in experiments. 80 181.10 molecular mass. Samples: The extracted samples from refinery pipelines supplied by Taxon Bioscience 304.17 60 363.21 . Samples were dissolved into 1 mg/mL by Toluene, then diluted to 250 µg/mL by In order to obtain optimal performance in the trapping device, the ion population needs 40 The nonpolar compounds in petroleum samples can be ionized by APCI and 394.22 to be kept within a certain range. Therefore, a procedure is needed to predict the 20 APPI, and APPI shows an advantage over APCI in ionizing the large nonpolar different solvent based on the ionization method prior to direct injection. 470.28
Relative Abundance Relative 547.34 663.45 748.60 888.92 944.44 1029.91 1190.50 1304.57 appropriate accumulation time. Automatic control of the number of ions in the Orbitrap 0 compounds. Dilution solvent analyzer is achieved by measuring the total ion charge from a pre-scan and by 200 400 600 800 1000 1200 1400 m/z . Only protonated ions are generated from APPI and radical ions were not • calculating the ion injection time. Automatic Gain Control (AGC™) ensures that the ion For APPI and APCI: Toluene 13-012162 _apci #375-400 RT: 5.13-5.48 AV: 26 NL: 1.04E7 observed, which simplified the data processing and formula prediction. trap is always filled with the optimum number of ions for any scan type. T: FTMS + p APCI corona Full ms [100.00-1400.00] • For ESI: 1% Formic Acid and 5% DCM in 50:50 Toluene:Methanol 406.36 APCI 418.36 As shown in Figure 5, the AGC optimization was studied along with ion distribution. 10 Mass Spectrometry 472.40 References Optimization of Orbitrap Elite MS The AGC setting was found to have a significant impact on ion distribution. Although 540.47 662.44 Ionization Source: the higher AGC setting allowed more ions to enter the Orbitrap mass analyzer, 2.9E6 5 391.33 566.48 1. Product specification of APPI/APCI combination ion source, Thermo Scientific Orbitrap Elite MS is a high performance hybrid mass spectrometer 165.07 (AGC: 5E6) vs 1.52E6 (AGC: 5E5) vs 1.8oE5 (AGC: 5E4), the ion distribution of the 269.23 674.58 http://www.thermoscientific.fr/com/cda/product/detail/0,1055,19246,00.html 756.65 Electrospray (HESI II) combining the use of an Orbitrap analyzer with a linear ion trap. The DC potential of the Abundance Relative 838.73 923.01 1021.12 1106.22 1220.36 1306.44 petroleum sample was poor because more low m/z ions entered the Orbitrap mass 0 2. Application note 347: Mechanism of [M+H]+ Formation in Atmospheric Pressure optic lens in the first vacuum stage can be optimized to the ion distribution of petroleum analyzer. To maximize a broad m/z range distribution the low AGC setting of 5E4 is 200 300 400 500 600 700 800 900 1000 1100 1200 1300 Atmosphere Pressure Chemical Ionization (APCI) – m/z Photoionization Mass Spectrometry, Thermo Fisher Scientific Inc. compounds which typically cover the mass range 200 1000 m/z. By optimizing the DC preferred. The package of ions is collected in the ion trap and the number of ions was Atmosphere Pressure Photo ionization (APPI) potential, the kinetic energy of ions was controlled, which means the ions could be 13-012162_appi #208-226 RT: 3.00-3.26 AV: 19 NL: 5.35E4 controlled by AGC. The ion package is send to C-Trap and cooled down, focused and T: FTMS + p APCI corona Full ms [100.00-1400.00] accelerated or slowed down as appropriate. Ion Trap and Orbitrap Elite (Mass Resolution = 240,000) sent to the Orbitrap analyzer for analysis. C-trap, like all RF devices, has an m/z 688.59 APPI 871.95 Acknowledgements 552.47 702.61 In this study, the setting of 00-offset in Figure 3 was observed to have a significant dependent potential well to trap ions. So if a mix of ions is sent into C-trap, the lower 10 Positive scan 622.55 956.05 We would like to thank Jean Jacques Dunyach from Thermo Fisher Scientific for impact on the intensity of ions from petroleum. Ions have the same velocity from the m/z ions are trapped by a deeper well and the high m/z ions are trapped by a 998.10 1068.17 5 206.24 supplying the APPI source information. AGC: 5E4 - 5E6 vacuum drop in the first vacuum stage after the ion beam passes through the transfer shallower well. If a mix of ions fills up C-trap such that space charge starts to be of the 1161.28 1246.38 130.88 335.06 tube. The increasing of the 00-offset potential slows down the ions, allowing the low m/z same order as the well depth, then the high m/z ions will be spilled out firstly. By Abundance Relative 223.68 474.42 1349.49 Mass Spectrum (average of 100-200 scans) 0 All trademarks are the property of Thermo Fisher Scientific and its subsidiaries. ions to be prevented from entering the linear trap mass analyzer and Orbitrap mass reducing the number of ions via setting a low AGC value, more high m/z ions could be 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 obtained on spectrum. m/z This information is not intended to encourage use of these products in any manners that might infringe the Data Collection and Analysis analyzer. intellectual property rights of others. Xcalibur software PO64143-EN 0614S
6 Petroleum Analysis by Orbitrap Elite Mass Spectrometer with Multiple Ionization Methods www.thermoscientific.com ©2014 Thermo Fisher Scientific Inc. All rights reserved. ISO is a trademark of the International Standards Organization. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This information is presented as an exam- ple of the capabilities of Thermo Fisher Scientific products. It is not intended to encourage use of these products in any manners Thermo Fisher Scientific, that might infringe the intellectual property rights of others. Specifications, terms and pricing are subject to change. San Jose, CA USA is ISO 9001:2008 Certified. Not all products are available in all countries. Please consult your local sales representative for details.
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