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User Benefits Application News Fig. 1 ELEM-SPOT We have signed a comprehensive clean-energy research collaboration agreement with TotalEnergies, Université de Pau et des Pays de l’Adour (UPPA), and the University of Oviedo (UO). This system merges jointly owned patented technology from TotalEnergies, UPPA, and UO with our analytical technology. Detection Principle Analysis Mode Settings ELEM-SPOT provides two analysis modes: (i) GC-Combustion-MS (Comb) mode, in which compounds are oxidatively decomposed and N- and/or O-compounds are selectively detected. (ii) MS Direct (MS) mode, in which measurements are performed in the same manner as a conventional GC-MS without passing through EL-30. If high-abundance components (e.g., the solvent peak or major constituents) are introduced to EL-30, reactor degradation may be accelerated and analytical stability may decrease. Therefore, the analysis is started in MS mode and then switched to Comb mode after solvent elution. Fig. 2 Detection Principle of N-Compounds Expectations for algal biomass are growing as a next-generation key resource toward a carbon-neutral, low-carbon society. In addition to its high CO₂-reduction potential, algal biomass has attracted attention because it can be cultivated without competing with food resources, and its utilization is expected across a wide range of fields including fuels and materials. Unlike fossil resources, algal biomass contains many amino-acid- derived N-compounds. Because these compounds can cause catalyst poisoning in downstream refining processes, accurate determination of their content and optimization of the process are essential. However, selective and highly sensitive detection of compounds containing heteroatoms (e.g., N and O) in a complex matrix has been challenging with conventional technologies. Our proprietary ELEM-SPOT system combines a GC-MS with the combustion catalytic reactor EL-30, enabling the world’s first selective and highly sensitive analysis of N- and O-compounds in complex samples. In this article, we present an application example of analyzing N-compounds in algae-based bio-oil using ELEM-SPOT. Introduction Even in samples with complex matrices, nitrogen-containing compounds (N-compounds) can be detected selectively and with high sensitivity, enabling analysis with an equimolar response. With the same setup, qualitative analysis can also be performed as a conventional GC-MS system. By using the Gas Selector, oxygen-containing compounds (O-compounds) can also be analyzed using the same setup. Quantification of Nitrogen-Containing Compounds in Algae-Based Bio-Oil Using ELEM-SPOT Element Selective Gas Chromatograph Mass Spectrometer 1 Shimadzu Corporation, 2 University of Oviedo, 3 TotalEnergies, 4 Université de Pau et des Pays de l’Adour, 5 International Joint Laboratory iC2MC: Complex Matrices Molecular Characterization In this system, after organic compounds are separated by GC, they are oxidatively decomposed in the combustion catalytic reactor EL-30, and the resulting species are detected by MS operated in SIM mode. By monitoring the signal at m/z 30, corresponding to nitric oxide (NO), a nitrogen-derived combustion product, N-compounds can be detected selectively. The analytical conditions are summarized in Table 1. In ELEM- SPOT, in addition to parameters such as the EL-30 combustion furnace temperature and combustion gas flow rate, there are additional settings that are not available in conventional GC-MS. All these parameters can be easily configured using the LabSolutions software. Analytical Conditions GC-Combustion-MS mode EL-30 MS Direct mode Fig. 3 Two Analysis Modes of ELEM-SPOT Combustion Gas Settings ¹⁶O₂/He (1% v/v) was used for the combustion gas of the oxidative decomposition reaction. In addition, by connecting ¹⁸O₂/He (1% v/v) using the Gas Selector, the system can be switched to O-compound analysis as needed without changing the hardware configuration. *Sales are limited to areas where utilities can be procured and systems can be supported. Combustion Emiko Shimbo 1 , Shota Hayakawa 1 , Takamasa Suzuki 1 , Hanamichi Miyabayashi 1 , Gregory King 1 , Jorge Ruiz Encinar 2 , Mariella Moldovan 2 , Montserrat Redondo-Velasco 2 , Pierre Giusti 3,5 , Marco Piparo 3,5 , Gaëtan Burnens 3,5 , and Brice Bouyssiere 4,5
Application News As a real sample, algae-based bio-oil was analyzed. The sample was diluted 1:300 in hexane, and N,N-diethylaniline was added as a standard of known concentration. ELEM-SPOT exhibits an equimolar response, i.e., a linear response proportional to the number of atoms (C, H, and N; and O when ¹⁸O₂ is used as the combustion gas) introduced into the detector. Therefore, it is not necessary to prepare a calibration curve for each compound; the N concentration of other peaks can be calculated using a standard of known concentration. Figure 4 shows the extracted ion chromatogram at m/z 30 and m/z 44 obtained in Comb mode. The m/z 30 signal corresponds to NO, indicating N concentration, enabling detection of N- compounds. In contrast, the m/z 44 signal corresponds to CO₂, indicating C concentration, and provides a chromatographic profile similar to those obtained using GC-FID or GC-MS. The m/z 44 chromatogram demonstrates that the sample is a complex m Table 1 Analytical Conditions for Comb Mode [GC] Inj. Temp. : 250 ˚C Inj. Mode : Splitless Sampling Time : 1.5 min Carrier Gas : He Flow Mode : Column Flow (1.5 mL/min) Purge Flow : 3.0 mL/min Oven Temp. : 40 ˚C (3 min) - 2 ˚C/min - 250 ˚C (20 min) Inj. Volume : 1 µL [Comb] Interface Temp. : 250 ˚C Oven Temp. : 1050 ˚C Makeup Gas Flow : He 0.6 mL/min Purge Gas Flow : He 0.6 mL/min Combustion Gas Flow : 0.4 mL/min (¹⁶O/He, 0.3% v/v) Mode Switch Time : 13.5 min [MS] Interface Temp. : 250 ˚C Ion Source Temp. : 200 ˚C Acquisition Mode : SIM (m/z 28, 30, 44) Event Time : 0.3 sec Ionization Voltage : 0.94 kV Detector Start Time : 14 min System : ELEM-SPOT (GCMS-QP2020 NX + EL-30) Auto-injector : AOC-30i Column : HP1-MS (50 m×0.25 mm I.D., 0.50 µm) Analysis of Algae-Based Bio-Oil Fig. 4 Chromatograms of Algae-Based Bio-Oil Analysis Table 2 List of Identified N-Compounds* (MS Mode) and Calculated N Concentrations (Comb Mode) * In Reference 1, after N-compound peaks were screened and quantified using ELEM-SPOT, further qualitative identification was performed by GC×GC-MS). As a result, compounds accounting for approximately 70% of the total N concentration were identified. multicomponent mixture, suggesting that it would be difficult to detect N-compounds using a universal detector. By monitoring m/z 30 in ELEM-SPOT Comb mode, N-compounds were selectively detected. The quantitative value calculated using the known- concentration standard was 11,140 ppmN. The total N concentration in the same sample determined by a chemiluminescence method was 11,000 ppm N, indicating good agreement. In addition, ELEM-SPOT enables calculation of not only the total N concentration but also that for each chromatographic peak. Furthermore, the same sample was measured in MS mode and qualitative identification of N-compounds was attempted with library searching. Among the peaks judged as N-compounds by Comb mode, 16 components could be identified as shown in Table 2. Peak Compound ppmN 1 4,6-dimethylpyrimidine, 5-methyl-2-pyridinamine, etc. - 2 Aniline 49 3 2,6-diethylpyrazine etc. - 4 N-ethylsuccinimide, 2-isobutyl-3-methylpyrazine etc. - 5 3,5-diethyl-2-methylpyrazine 34 6 2,5-dimethyl-3-propylpyrazine 61 7 5H-2,5-dimethyl-6,7-dihydrocyclopentapyrazine 164 8 3-ethyl-4-methyl-1H-Pyrrole-2,5-dione 53 9 2-butyl-3-methylpyrazine 52 10 2-methyl-3-propylpyrazine 57 11 3-methylquinoline 90 12 5-methylindole 86 13 1-(2’-phenylethyl)-pyrrole 64 14 5,6,7-trimethyl-1H-indole 16 15.0 30.0 45.0 60.0 75.0 90.0 105.0 120.0 1 2 4 5 6 7 8 12 13 14 9 3 10 11 m/z 30 (N-compounds) m/z 44 (Organic compounds) Standard of known concentration (N,N-diethylaniline)
Application News www.shimadzu.com/an/ Shimadzu Corporation © Shimadzu Corporation, 2026 For Research Use Only. Not for use in diagnostic procedures. This publication may contain references to products that are not available in your country. Please contact us to check the availability of these products in your country. The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu. See https://www.shimadzu.com/about/trademarks/index.html for details. Third party trademarks and trade names may be used in this publication to refer to either the entities or their products/services, whether or not they are used with trademark symbol “TM” or “”. Shimadzu disclaims any proprietary interest in trademarks and trade names other than its own. The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject to change without notice. First Edition: Jul. 2026 01-01223-EN Conclusion ELEM-SPOT, LabSolutions, and AOC are trademarks of Shimadzu Corporation or its affiliated companies in Japan and/or other countries. ELEM-SPOT sales are restricted to areas where utilities can be procured and systems can be supported. Biomass feedstocks derived from algae contain N-compounds, and removal processes are important when they are used for producing fuels and chemicals. In this article, we presented an application example in which N-compounds in algae-based bio- oil were selectively detected and quantified using ELEM-SPOT. With this system, we were able to specifically detect only N- compounds among hundreds of components. In addition, the total N concentration calculated using a standard of known concentration was in good agreement with the result obtained by a chemiluminescence method. <References> 1) García-Bellido, J.; Freije-Carrelo, L.; Redondo-Velasco, M.; Piparo, M.; Zoccali, M.; Mondello, L.; Moldovan, M.; Bouyssiere, B.; Giusti, P.; Encinar, J. R. “Potential of GC-Combustion-MS as a Powerful and Versatile Nitrogen-Selective Detector in Gas Chromatography” Anal. Chem., vol. 95, no. 31, pp. 11761– 11768. July. 2023. <Acknowledgements> We gratefully acknowledge the valuable support provided by TotalEnergies, Université de Pau et des Pays de l’Adour, and the University of Oviedo in the development of this instrument and the preparation of this application note. In the m/z 30 chromatogram acquired in Comb mode, minor unspecific signals may be observed even for compounds that do not contain N. The main cause is C¹⁸O (molecular weight of 30) generated from trace amounts of ¹⁸O present in the combustion gas, etc. To correct for this contribution, the following equation can be used: In this analysis, although we applied this correction, no noticeable differences were observed for peaks originating from non-N- containing compounds; therefore, uncorrected m/z 30 results were used. *Correction for C¹⁸O-Derived Peaks Molecular weight of C¹⁶O Isotopic abundance ratio of ¹⁸O and ¹⁶O (0.2/99.76) Molecular weight of N¹⁶O and C¹⁸O  ⁄  30 = ⁄  30 − ⁄ m z 28 × Ab¹⁸ Ab¹⁶
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