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Spotting Targets Selectively







 Hydrocarbon compounds are first separated by GC and then oxidatively dissociated in the element-selective combustion
 unit. Then the separated compounds are detected by MS using the selected ion monitoring (SIM) mode. As a result, the
 difficult analysis of trace quantities of an oxygenated compound was enabled by using isotopic oxygen ( O2) as the   y
 18
 oxidation gas (Pat. No. WO 2017/114654). Furthermore, nitrogen-containing compounds can be detected selectively by   CxHyNzOw  xCO2 +  2  H2O  + zNO
 using regular oxygen ( O2) as the oxidation gas.
 16

                                                      If now-common CxHyNzOw hydrocarbons are directly detected by
                                         m/z  44(CO2)  FID or GC-MS after column separation, then they are detected
 GC-Comb-MS Mode            Oxidative                 based on a single peak. If that peak is detected by GC-MS after
                           dissociation  m/z  18(H2O)  column separation and oxidative dissociation, and further
 Comb-mode
 The GC-Comb-MS mode is a                             analyzed by m/z, then MS chromatograms are obtained for each
                                         m/z 30(NO)
 configuration where an                               product of oxidative dissociation. Since the dissociation
 element-selective combustion unit is                 products are unique for each element contained in the
 connected after the GC and before   CxHyNzOw  xCO2  +  (y/2)H2O  +  zNO  compound, a unique chromatogram is obtained for each
 the MS. In this mode,                                specific hetero-element contained in the compound.
 oxygen/nitrogen-containing
 compounds can be selectively   18 O2 in Helium
 detected. After separating
 hydrocarbon compounds with GC,   Principle of Detecting Oxygenated Compounds
 the compounds are oxidatively
 decomposed in the combustion   In the analysis of oxygenated compounds, oxidative decomposition is performed using isotopic oxygen ( O2) in the
                                                                                            18
 catalytic reactor and detected using   GC-MS  GC  EL-30  carrier gas, and screening is conducted to separate oxygen-containing compounds from other components.
 the SIM mode.   Dedicated data analysis tools are employed to accurately identify oxygen-containing compounds.



 MS Chromatogram from GC-Comb-MS  18 O2 (Isotopic) Oxidation Gas  16 O2 Oxidation Gas
 After screening
 4  Before screening  (Oxygen Content Analysis)
 2
                                                                                       16
                     16
                                                                                16
                                          16
                                               18
                                                      18
                                  16
                                                                  16
                                                   +
 11  14          CxHy O + 18 O2  C O2 +  H2 O + C O2 H2 O      CxHy O + 16 O2  C O2  + H2 O
 5  10  1 Cyclohexanone  8 Hexylbutyrate  m/z  44  18  48  20              m/z  44     18
 6
 1  3
 7  8  2 2-ethoxyethylacetate  9 Dodecane
 13
 12  3 Benzaldehyde  10 Phenethyl acetate
 9                                 Oxygen from  Oxygen from      Oxygen originating from oxygenated compounds cannot be
 4 Dimethyl malonate  11 Dimethyl phthalate  oxygenated compounds  oxidation gas  discriminated from oxygen originating from oxidation gas.
 5 2-pentyl butyrate  12 Acephatene
 6 Acetaldehyde  13 Dibenzofurane
 7 1-octanol  14 Eicosane
                                           CxHy
 Note: This provides a unique chromatogram that can be used
 to determine whether compounds contain oxygen.          CxHyNz
    Compounds 9, 12, and 14 do not contain oxygen.  CxHyOz
                             Intensity                             C O2 Oxidation product of organic compounds
                                                                    18
 MS Direct Mode                                                 NO Origin of nitrogen-containing compounds
                                                              16
                            m/z                              C O2 Origin of oxygen-containing compounds
                                         Retention Time
 The MS Direct mode is a common configuration in GC-MS. The ELEM-SPOT system enables analysis in a typical GC-MS
 setup without passing through the element-selective combustion unit by switching the configuration flow paths.
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