{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,8]],"date-time":"2026-03-08T10:10:58Z","timestamp":1772964658427,"version":"3.50.1"},"reference-count":45,"publisher":"MDPI AG","issue":"6","license":[{"start":{"date-parts":[[2025,3,10]],"date-time":"2025-03-10T00:00:00Z","timestamp":1741564800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100012190","name":"Ministry of Science and Higher Education of the Russian Federation","doi-asserted-by":"publisher","award":["FSRU-2024-0003"],"award-info":[{"award-number":["FSRU-2024-0003"]}],"id":[{"id":"10.13039\/501100012190","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Nitrogen-containing heterocyclic compounds (NHCs) are common environmental pollutants that need to be monitored due to their high toxicity. Typically, gas or liquid chromatography combined with mass spectrometric detection is used for this task. However, many NHCs are highly polar compounds, which can cause difficulties when using these methods. On the other hand, supercritical fluid chromatography is well-established in the analysis of polar compounds and could provide an alternative to conventional techniques. The presented work proposes an approach to the simultaneous determination of 20 NHCs in soils by supercritical fluid chromatography\u2013tandem mass spectrometry with the limits of quantification in the range 0.08\u20131.23 mg kg\u22121. The separation is carried out in gradient mode on a cyanopropyl stationary phase in 6 min. The approach was validated and tested on real objects\u2014peat and sandy soils contaminated with rocket fuel transformation products.<\/jats:p>","DOI":"10.3390\/molecules30061236","type":"journal-article","created":{"date-parts":[[2025,3,10]],"date-time":"2025-03-10T06:59:59Z","timestamp":1741589999000},"page":"1236","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Simultaneous Determination of 20 Nitrogen-Containing Heterocyclic Compounds in Soil by Supercritical Fluid Chromatography\u2013Tandem Mass Spectrometry"],"prefix":"10.3390","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1042-2915","authenticated-orcid":false,"given":"Sergey A.","family":"Vakhrameev","sequence":"first","affiliation":[{"name":"Laboratory of Environmental Analytical Chemistry, Core Facility Center \u201cArktika\u201d, Northern (Arctic) Federal University, Arkhangelsk 163002, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9313-2448","authenticated-orcid":false,"given":"Denis V.","family":"Ovchinnikov","sequence":"additional","affiliation":[{"name":"Laboratory of Environmental Analytical Chemistry, Core Facility Center \u201cArktika\u201d, Northern (Arctic) Federal University, Arkhangelsk 163002, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4796-9313","authenticated-orcid":false,"given":"Nikolay V.","family":"Ul\u2019yanovskii","sequence":"additional","affiliation":[{"name":"Laboratory of Environmental Analytical Chemistry, Core Facility Center \u201cArktika\u201d, Northern (Arctic) Federal University, Arkhangelsk 163002, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5223-6857","authenticated-orcid":false,"given":"Dmitry S.","family":"Kosyakov","sequence":"additional","affiliation":[{"name":"Laboratory of Environmental Analytical Chemistry, Core Facility Center \u201cArktika\u201d, Northern (Arctic) Federal University, Arkhangelsk 163002, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2025,3,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"46858","DOI":"10.1039\/C7RA09858H","article-title":"Design, synthesis, and herbicidal activity of pyrazole benzophenone derivatives","volume":"7","author":"Fu","year":"2017","journal-title":"RSC Adv."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"342","DOI":"10.1016\/j.bmc.2015.09.031","article-title":"Discovery of pyridine-based agrochemicals by using intermediate derivatization methods","volume":"24","author":"Guan","year":"2016","journal-title":"Bioorg. Med. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Matin, M.M., Matin, P., Rahman, M.R., Ben Hadda, T., Almalki, F.A., Mahmud, S., Ghoneim, M.M., Alruwaily, M., and Alshehri, S. (2022). Triazoles and Their Derivatives: Chemistry, Synthesis, and Therapeutic Applications. Front. Mol. Biosci., 9.","DOI":"10.3389\/fmolb.2022.864286"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"109238","DOI":"10.1016\/j.carres.2024.109238","article-title":"Synthesis, characterization and antifungal activity of imidazole chitosan derivatives","volume":"544","author":"Wu","year":"2024","journal-title":"Carbohydr. Res."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"117815","DOI":"10.1016\/j.molliq.2021.117815","article-title":"Imidazole derivatives as efficient and potential class of corrosion inhibitors for metals and alloys in aqueous electrolytes: A review","volume":"345","author":"Ouakki","year":"2022","journal-title":"J. Mol. Liq."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"133609","DOI":"10.1016\/j.colsurfa.2024.133609","article-title":"Effects of pyrazine and its derivatives as inhibitors on copper film chemical-mechanical polishing properties for ruthenium-based copper interconnect","volume":"688","author":"Zhan","year":"2024","journal-title":"Colloids Surf. A Physicochem. Eng. Asp."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"139139","DOI":"10.1016\/j.chemosphere.2023.139139","article-title":"Mechanistic insights into pyridine exposure induced toxicity in model Eisenia fetida species: Evidence from whole-animal, cellular, and molecular-based perspectives","volume":"335","author":"He","year":"2023","journal-title":"Chemosphere"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"466","DOI":"10.1016\/j.ecoenv.2019.05.048","article-title":"Chronic toxicity of treated and untreated aqueous solutions containing imidazole-based ionic liquids and their oxydized by-products","volume":"180","author":"Siciliano","year":"2019","journal-title":"Ecotoxicol. Environ. Saf."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"151177","DOI":"10.1016\/j.scitotenv.2021.151177","article-title":"A comprehensive review of 1,2,4-triazole fungicide toxicity in zebrafish (Danio rerio): A mitochondrial and metabolic perspective","volume":"809","author":"Huang","year":"2022","journal-title":"Sci. Total Environ."},{"key":"ref_10","first-page":"309","article-title":"Degradation of pyridines in the environment","volume":"19","author":"Sims","year":"1989","journal-title":"Crit. Rev. Environ. Sci. Technol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"228","DOI":"10.1016\/j.chroma.2008.05.078","article-title":"Thermal extraction\u2013two-dimensional gas chromatography\u2013mass spectrometry with heart-cutting for nitrogen heterocyclics in biomass burning aerosols","volume":"1200","author":"Ma","year":"2008","journal-title":"J. Chromatogr. A"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1865","DOI":"10.5194\/acp-15-1865-2015","article-title":"Identification and quantification of gaseous organic compounds emitted from biomass burning using two-dimensional gas chromatography\u2013time-of-flight mass spectrometry","volume":"15","author":"Hatch","year":"2015","journal-title":"Atmos. Chem. Phys."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"4029","DOI":"10.1016\/j.biortech.2007.01.047","article-title":"Heterocyclic nitrogenous pollutants in the environment and their treatment options\u2013an overview","volume":"99","author":"Padoley","year":"2008","journal-title":"Bioresour. Technol."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"163377","DOI":"10.1016\/j.scitotenv.2023.163377","article-title":"Urban areas as sources of the groundwater contaminants N, N-dimethylsulfamide (N,N-DMS) and 1,2,4-triazole","volume":"881","author":"Albers","year":"2023","journal-title":"Sci. Total Environ."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"123","DOI":"10.1016\/j.chroma.2018.05.056","article-title":"Validation of an analytical method for 1,2,4-triazole in soil using liquid chromatography coupled to electrospray tandem mass spectrometry and monitoring of propiconazole degradation in a batch study","volume":"1562","author":"Blondel","year":"2018","journal-title":"J. Chromatogr. A"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"128708","DOI":"10.1016\/j.jhazmat.2022.128708","article-title":"Unsymmetrical dimethylhydrazine and related compounds in the environment: Recent updates on pretreatment, analysis, and removal techniques","volume":"432","author":"Hu","year":"2022","journal-title":"J. Hazard. Mater."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"32","DOI":"10.1016\/j.aca.2010.05.040","article-title":"Screening of transformation products in soils contaminated with unsymmetrical dimethylhydrazine using headspace SPME and GC\u2013MS","volume":"674","author":"Kenessov","year":"2010","journal-title":"Anal. Chim. Acta"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"78","DOI":"10.1016\/j.scitotenv.2012.04.017","article-title":"Transformation products of 1,1-dimethylhydrazine and their distribution in soils of fall places of rocket carriers in Central Kazakhstan","volume":"427\u2013428","author":"Kenessov","year":"2012","journal-title":"Sci. Total. Environ."},{"key":"ref_19","first-page":"106821","article-title":"Rapid quantification and screening of nitrogen-containing rocket fuel transformation products by vortex assisted liquid-liquid microextraction and gas chromatography\u2014High-resolution Orbitrap mass spectrometry","volume":"17","author":"Kosyakov","year":"2021","journal-title":"Microchem. J."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"33645","DOI":"10.1007\/s11356-021-17844-1","article-title":"Quantification of trace transformation products of rocket fuel unsymmetrical dimethylhydrazine in sand using vacuum-assisted headspace solid-phase microextraction","volume":"29","author":"Zhakupbekova","year":"2022","journal-title":"Environ. Sci. Pollut. Res. Int."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"109833","DOI":"10.1016\/j.microc.2023.109833","article-title":"Direct quantification of 1,1-dimethylhydrazine transformation products in sandy soil by thermal desorption gas chromatography\u2013Tandem mass spectrometry","volume":"197","author":"Popov","year":"2024","journal-title":"Microchem. J."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"2400383","DOI":"10.1002\/jssc.202400383","article-title":"Analysis of nitrogen-containing rocket fuel transformation products in loamy soil by thermal desorption gas chromatography-tandem mass spectrometry","volume":"47","author":"Popov","year":"2024","journal-title":"J. Sep. Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1321","DOI":"10.1080\/03067319.2015.1090569","article-title":"Rapid determination of 1,1-dimethylhydrazine transformation products in soil by accelerated solvent extraction coupled with gas chromatography\u2013tandem mass spectrometry","volume":"95","author":"Kosyakov","year":"2015","journal-title":"Int. J. Environ. Anal. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"226","DOI":"10.1016\/j.talanta.2015.05.045","article-title":"Determination of 1-methyl-1H-1,2,4-triazole in soils contaminated by rocket fuel using solid-phase microextraction, isotope dilution and gas chromatography-mass spec-trometry","volume":"143","author":"Yegemova","year":"2015","journal-title":"Talanta"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"4","DOI":"10.15328\/cb1014","article-title":"Quantification of transformation products of unsymmetrical dimethylhydrazine in aqueous extracts from soil based on vacuum-assisted headspace solid-phase microextraction","volume":"89","author":"Orazbayeva","year":"2018","journal-title":"Chem. Bull. Kaz."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"332","DOI":"10.1016\/j.talanta.2018.02.047","article-title":"Quantification of transformation products of rocket fuel unsymmetrical dimethylhydrazine in soils using SPME and GC-MS","volume":"184","author":"Bakaikina","year":"2018","journal-title":"Talanta"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"4921","DOI":"10.1007\/s00216-020-02665-x","article-title":"Development of an LC-MS method for determination of nitrogen-containing heterocycles using mixed-mode liquid chromatography","volume":"412","author":"Abdighahroudi","year":"2020","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"891","DOI":"10.1007\/s10337-018-3522-4","article-title":"Determination of 1,1-dimethylhydrazine and its transformation products in soil by zwitterionic hydrophilic interaction liquid chromatography\/tandem mass spectrometry","volume":"81","author":"Kosyakov","year":"2018","journal-title":"Chromatographia"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1254","DOI":"10.1080\/03067319.2014.940342","article-title":"Simultaneous determination of 1,1-dimethylhydrazine and products of its oxidative transformations by liquid chromatography\u2013tandem mass spectrometry","volume":"94","author":"Kosyakov","year":"2014","journal-title":"Int. J. Environ. Anal. Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1089","DOI":"10.1080\/03067310500191454","article-title":"Ion chromatography as a tool for the investigation of unsymmetrical hydrazine degradation in soils","volume":"85","author":"Smolenkov","year":"2005","journal-title":"Int. J. Environ. Anal. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"510","DOI":"10.1134\/S1061934820040140","article-title":"Using a stationary phase based on porous graphitized carbon for the determination of 1,1-dimethylhydrazine transformation products by liquid chromatography\u2013mass spectrometry","volume":"75","author":"Kosyakov","year":"2020","journal-title":"J. Anal. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Ovchinnikov, D.V., Vakhrameev, S.A., Falev, D.I., Ul\u2019yanovskii, N.V., and Kosyakov, D.S. (2022). Rapid simultaneous quantification of 1-formyl-2,2-dimethylhydrazine and dimethylurea isomers in environmental samples by supercritical fluid chromatography-tandem mass spectrometry. Molecules, 27.","DOI":"10.3390\/molecules27155025"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"6970","DOI":"10.1016\/j.chroma.2009.07.043","article-title":"Separation and analysis of dimethylaniline isomers by supercritical fluid chromatography\u2014Electrospray ionization tandem mass spectrometry","volume":"1216","author":"Strife","year":"2009","journal-title":"J. Chromatogr. A"},{"key":"ref_34","doi-asserted-by":"crossref","unstructured":"Cafeo, G., Satira, A., Russo, M., Mondello, M., and Dugo, P. (2023). Determination of oxygen heterocyclic compounds in foods using supercritical fluid chromatography-tandem mass spectrometry. Foods, 12.","DOI":"10.3390\/foods12183408"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"6789","DOI":"10.1007\/s00216-016-9805-4","article-title":"SFC-MS\/MS as an orthogonal technique for improved screening of polar analytes in anti-doping control","volume":"408","author":"Parr","year":"2016","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"141","DOI":"10.1016\/j.chroma.2016.04.040","article-title":"Analysis of polar urinary metabolites for metabolic phenotyping using supercritical fluid chromatography and mass spectrometry","volume":"1449","author":"Sen","year":"2016","journal-title":"J. Chromatogr. A"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"54","DOI":"10.1016\/j.trd.2017.10.013","article-title":"The environmental impact of space transport","volume":"58","author":"Koroleva","year":"2018","journal-title":"Transp. Res. D"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"136","DOI":"10.1016\/j.chroma.2017.02.066","article-title":"Unravelling the effects of mobile phase additives in supercritical fluid chromatography. Part I: Polarity and acidity of the mobile phase","volume":"1492","author":"West","year":"2017","journal-title":"J. Chromatogr. A"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"30","DOI":"10.1016\/j.tca.2007.10.011","article-title":"Thermodynamics of mixtures containing amines: VII. Systems containing dimethyl or trimethylpyridines","volume":"467","author":"Gonzalez","year":"2008","journal-title":"Thermochim. Acta"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"4172","DOI":"10.1021\/jp022403m","article-title":"Electronic and vibrational polarizabilities and hyperpolarizabilities of azoles: A comparative study of the structure\u2212polarization relationship","volume":"107","author":"Jug","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"115","DOI":"10.1002\/jssc.200301672","article-title":"Elution and preliminary structure-retention modeling of polar and ionic substances in supercritical fluid chromatography using volatile ammonium salts as mobile phase additives","volume":"27","author":"Pinkston","year":"2004","journal-title":"J. Sep. Sci."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1016\/j.chroma.2011.11.052","article-title":"Ammonia as a preferred additive in chiral and achiral applications of supercritical fluid chromatography for small, drug-like molecules","volume":"1220","author":"Ventura","year":"2012","journal-title":"J. Chromatogr. A"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"6441","DOI":"10.1016\/j.chroma.2009.07.022","article-title":"Effect of increasing concentration of ammonium acetate as an additive in supercritical fluid chromatography using CO2-methanol mobile phase","volume":"1216","author":"Boughtflower","year":"2009","journal-title":"J. Chromatogr. A"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"307","DOI":"10.1016\/j.chroma.2009.11.050","article-title":"Determination of pyridine, 2-picoline, 4-picoline and quinoline from mainstream cigarette smoke by solid-phase extraction liquid chromatography\/electrospray ionization tandem mass spectrometry","volume":"1217","author":"Saha","year":"2010","journal-title":"J. Chromatogr. A"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"2708","DOI":"10.1080\/00032719.2015.1045593","article-title":"Determination of Imidazole, 4-Methylimidazole, and 2-Methylimidazole in Cigarette Additives by Ultra-High Performance Liquid Chromatography","volume":"48","author":"Zhu","year":"2015","journal-title":"Anal. Lett."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/6\/1236\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T16:49:55Z","timestamp":1760028595000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/6\/1236"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,3,10]]},"references-count":45,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2025,3]]}},"alternative-id":["molecules30061236"],"URL":"https:\/\/doi.org\/10.3390\/molecules30061236","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,3,10]]}}}