{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,10]],"date-time":"2026-07-10T20:12:38Z","timestamp":1783714358450,"version":"3.55.0"},"reference-count":56,"publisher":"MDPI AG","issue":"5","license":[{"start":{"date-parts":[[2022,4,27]],"date-time":"2022-04-27T00:00:00Z","timestamp":1651017600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"UJI-FISABIO Calls","award":["UGP-20-309"],"award-info":[{"award-number":["UGP-20-309"]}]},{"name":"European Regional Development Funds (ERDF) Operational Programme of the Valencian Region (2014\u20132020)","award":["UGP-20-309"],"award-info":[{"award-number":["UGP-20-309"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Toxics"],"abstract":"<jats:p>A fast and automated strategy has been developed for identifying unknown substances in the atmosphere (concretely, in the particulate matter, PM10) using LC-HRMS (MS3). A total of 15 samples were collected in three different areas (rural, urban and industrial). A sampling flow rate of 30 m3 h\u22121 was applied for 24 h, sampling a total volume of around 720 m3. A total of 49 compounds were tentatively identified using very restrictive criteria regarding exact mass, retention time, isotopic profile and both MS2 and MS3 spectra. Pesticides, pharmaceutical active compounds, drugs, plasticizers and metabolites were the most identified compounds. To verify whether the developed methodology was suitable, 11 substances were checked with their analytical standards and all of them were confirmed. Different profiles for industrial, rural and urban areas were examined. The Principal Component Analysis (PCA) model allowed us to separate the obtained data of the three assessed area. When the profiles obtained in the three evaluated areas were compared using a Volcano plot (the rural area was taken as reference), 11 compounds were confirmed as being discriminant: three of them (3-hydroxy-2-methylpyridine, 3-methyladenine and nicotine) were more likely to be found in industrial sites; ten compounds (3-hydroxy-2-methylpyridine, 3-methyladenine, azoxystrobin, cocaine, cotinine, ethoprophos, imidacloprid, metalaxyl-M, nicotine and pyrimethanil) were more probable in the case of urban sites; finally, triisopropanolamine was more likely to be detected in rural locations.<\/jats:p>","DOI":"10.3390\/toxics10050220","type":"journal-article","created":{"date-parts":[[2022,4,27]],"date-time":"2022-04-27T22:20:20Z","timestamp":1651098020000},"page":"220","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Identification of Unknown Substances in Ambient Air (PM10), Profiles and Differences between Rural, Urban and Industrial Areas"],"prefix":"10.3390","volume":"10","author":[{"given":"Antonio","family":"L\u00f3pez","sequence":"first","affiliation":[{"name":"Foundation for the Promotion of Health and Biomedical Research in the Valencian Region, FISABIO-Public Health, 21, Avenida Catalunya, 46020 Valencia, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Esther","family":"Fuentes","sequence":"additional","affiliation":[{"name":"Foundation for the Promotion of Health and Biomedical Research in the Valencian Region, FISABIO-Public Health, 21, Avenida Catalunya, 46020 Valencia, Spain"},{"name":"Environmental and Public Health Analytical Chemistry, Research Institute for Pesticides and Water, University Jaume I, S\/N, Avenida Sos Baynat, 12071 Castell\u00f3 de la Plana, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vicent","family":"Yus\u00e0","sequence":"additional","affiliation":[{"name":"Foundation for the Promotion of Health and Biomedical Research in the Valencian Region, FISABIO-Public Health, 21, Avenida Catalunya, 46020 Valencia, Spain"},{"name":"Public Health Laboratory of Valencia, 21, Avenida Catalunya, 46020 Valencia, Spain"},{"name":"Analytical Chemistry Department, University of Valencia, Edifici Jeroni Mu\u00f1oz, Dr. Moliner 50, 46100 Burjassot, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4930-8933","authenticated-orcid":false,"given":"Mar\u00eda","family":"Ib\u00e1\u00f1ez","sequence":"additional","affiliation":[{"name":"Environmental and Public Health Analytical Chemistry, Research Institute for Pesticides and Water, University Jaume I, S\/N, Avenida Sos Baynat, 12071 Castell\u00f3 de la Plana, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5914-9721","authenticated-orcid":false,"given":"Clara","family":"Coscoll\u00e0","sequence":"additional","affiliation":[{"name":"Foundation for the Promotion of Health and Biomedical Research in the Valencian Region, FISABIO-Public Health, 21, Avenida Catalunya, 46020 Valencia, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,4,27]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Kumar, A. (2010). Anthropogenic Air Pollution Sources. Air Quality, InTech.","DOI":"10.5772\/259"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3897","DOI":"10.1002\/2017GL072602","article-title":"The global nonmethane reactive organic carbon budget: A modeling perspective","volume":"44","author":"Safieddine","year":"2017","journal-title":"Geophys. Res. Lett."},{"key":"ref_3","first-page":"147","article-title":"Pesticides and related toxicants in the atmosphere","volume":"247","author":"Woodrow","year":"2018","journal-title":"Part Rev. Environ. Contam. Toxicol. Book Ser."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1525","DOI":"10.1126\/science.1180353","article-title":"Evolution of Organic Aerosols in the Atmosphere","volume":"326","author":"Jimenez","year":"2009","journal-title":"Science"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"439","DOI":"10.1016\/j.scitotenv.2015.11.064","article-title":"Long-term monitoring and seasonal analysis of polycyclic aromatic hydrocarbons (PAHs) measured over a decade in the ambient air of Porto, Portugal","volume":"543","author":"Alburquerque","year":"2016","journal-title":"Sci. Total Environ."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"724","DOI":"10.1016\/j.scitotenv.2016.08.149","article-title":"Risk assessment of airborne pesticides in a Mediterranian Region of Spain","volume":"574","author":"Vera","year":"2017","journal-title":"Sci. Total Environ."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"128902","DOI":"10.1016\/j.chemosphere.2020.128902","article-title":"Dioxins and dioxin-like PCBs in the ambient air of the Valencian Region. Levels, human exposure and risk assessment","volume":"267","author":"Pardo","year":"2021","journal-title":"Chemosphere"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chroma.2013.10.081","article-title":"Design of experiment approach for the optimization of polybrominated diphenyl ethers determination in fine airborne particulate matter by microwave-assisted extraction and gas chromatography coupled to tandem mass spectrometry","volume":"1323","author":"Beser","year":"2014","journal-title":"J. Chromatogr. A"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"484","DOI":"10.1289\/ehp.1509676","article-title":"Ambient particulate matter air pollution exposure and mortality in the NIH-AARP Diet and Health Cohort","volume":"124","author":"Thurston","year":"2016","journal-title":"Environ. Health Perspect."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"790","DOI":"10.1016\/j.envpol.2017.06.022","article-title":"Association between air pollution and cardiovascular mortality in Hefei, China: A time-series analysis","volume":"229","author":"Zhang","year":"2017","journal-title":"Environ. Pollut."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"126668","DOI":"10.1016\/j.chemosphere.2020.126668","article-title":"Maternal air pollution exposure and congenital heart defects in offspring: A systematic review and meta-analysis","volume":"253","author":"Hu","year":"2020","journal-title":"Chemosphere"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1494","DOI":"10.1021\/es970890r","article-title":"Octanol-Air Partition Coefficient for describing particle\/gas partitioning of aromatic compounds in urban air","volume":"32","author":"Harner","year":"1998","journal-title":"Environ. Sci. Technol."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3596","DOI":"10.1021\/es980994h","article-title":"Gas-particle partitioning of atmospheric PCDD\/Fs: Measurements and observations on modeling","volume":"33","author":"Lee","year":"1998","journal-title":"Environ. Sci. Technol."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"243","DOI":"10.1016\/j.atmosres.2007.11.022","article-title":"Atmospheric concentrations of PAHs, their possible sources and gas-to-particle partitioning at a residential site of Bursa, Turkey","volume":"88","author":"Esen","year":"2008","journal-title":"Atmos. Res."},{"key":"ref_15","first-page":"838","article-title":"Health and respirable particulate (PM10) air pollution: A causal or statistical association?","volume":"104","author":"Gamble","year":"1996","journal-title":"Environ. Health Perspect."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"56","DOI":"10.1016\/j.jhazmat.2018.05.012","article-title":"Understanding re-distribution of road deposited particle-bound pollutants using a Bayesian Network (BN) approach","volume":"355","author":"Liu","year":"2018","journal-title":"J. Hazard. Mater."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"S23","DOI":"10.1016\/S1352-2310(01)00122-4","article-title":"Some ideas about the sources of PM10","volume":"35","author":"Lenschow","year":"2001","journal-title":"Atmos. Environ."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1308","DOI":"10.1016\/j.atmosenv.2009.12.011","article-title":"A European aerosol phenomenologye: Physical and chemical characteristics of particulate matter from 60 rural, urban, and kerbside sites across Europe","volume":"44","author":"Putaud","year":"2004","journal-title":"Atmos. Environ."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"184","DOI":"10.5094\/APR.2010.024","article-title":"Analysis and interpretation of particulate matter-PM10, PM2.5 and PM1 emissions from the hetergoneous traffic near an urban roadway","volume":"1","author":"Bathmanabhan","year":"2010","journal-title":"Atmos. Pollut. Res."},{"key":"ref_20","first-page":"13","article-title":"Particulate matter air pollution (PM10 and PM2.5) in urban and industrial areas","volume":"5","author":"Chuturkova","year":"2015","journal-title":"J. Sci. Educ. Innov."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"150083","DOI":"10.1016\/j.scitotenv.2021.150083","article-title":"Analyzing the spatio-temporal variation of the CO2 emissions from district heating systems with \u201cCoal-to-Gas\u201d transition: Evidence from GTWR model and satellite data in China","volume":"803","author":"Zhang","year":"2022","journal-title":"Sci. Total Environ."},{"key":"ref_22","unstructured":"EEA (2012). Air Quality in Europe-2012 Report. European Environmental Agency Report. No 4\/2012, EEA."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"4474","DOI":"10.1021\/es040302r","article-title":"Using passive air samplers to assess Urban-Rural trends for Persistent Organic Pollutants. Polychlorinated Biphenyls and Organochlorine Pesticides","volume":"38","author":"Harner","year":"2004","journal-title":"Environ. Sci. Technol."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"3852","DOI":"10.1007\/s11356-012-1328-8","article-title":"Persistent organic pollutants in the atmosphere from urban and industrial environments in the Rhine Valley: PCBs, PCDD\/Fs","volume":"20","author":"Stille","year":"2013","journal-title":"Environ. Sci. Pollut. Res. Int."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"158","DOI":"10.1016\/j.atmosenv.2017.12.029","article-title":"Black carbon emissions from biomass and coal in rural China","volume":"176","author":"Zhang","year":"2018","journal-title":"Atmos. Environ."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.trac.2016.12.006","article-title":"Trends in LC-MS and LC-HRMS analysis and characterization of polyphenols in food","volume":"88","author":"Lucci","year":"2016","journal-title":"Trac-Trends Anal. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"191","DOI":"10.1016\/j.trac.2018.10.035","article-title":"An overview of non-targeted screening strategies based on high resolution accurate mass spectrometry for the identification of migrants coming from plastic food packaging materials","volume":"110","author":"Bauer","year":"2019","journal-title":"Trac-Trends Anal. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"36","DOI":"10.1016\/j.talanta.2019.05.078","article-title":"Determination of phosphodiesterase 5 (PDE5) inhibitors in instant coffee premixes using liquid chromatography-high-resolution mass spectrometry (LC-HRMS)","volume":"204","author":"Yusop","year":"2019","journal-title":"Talanta"},{"key":"ref_29","first-page":"1052526","article-title":"Analysis of unknowns in recycled LDPE plastic by LC-Orbitrap Tribrid HRMS using MS3 with an intelligent data acquisition mode","volume":"158","author":"Dualde","year":"2020","journal-title":"Microchem. J."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"92","DOI":"10.1016\/j.chroma.2014.12.038","article-title":"Identification of two novel brominated contaminants in water samples by ultra-high performance liquid chromatography-Orbitrap Fusion Tribrid mass spectrometer","volume":"1377","author":"Liu","year":"2015","journal-title":"J. Chromatogr. A"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"102","DOI":"10.1016\/j.chroma.2019.01.077","article-title":"The quantification of chlorinated paraffins in environmental samples by ultra-high-performance liquid chromatography coupled with Orbitrap Fusion Tribrid mass spectrometry","volume":"1593","author":"Wu","year":"2019","journal-title":"J. Chromatogr. A"},{"key":"ref_32","unstructured":"Thermo Scientific (2020, June 18). SN65392-EN 0119M. AcquireX, 2019. Available online: https:\/\/www.thermofisher.com\/es\/es\/home\/industrial\/mass-spectrometry\/liquid-chromatography-mass-spectrometry-lc-ms\/lc-ms-software\/lc-ms-data-acquisition-software\/acquirex-intelligent-data-acquisition-workflow.html."},{"key":"ref_33","unstructured":"(2020, June 16). Thermo Scientific. Available online: https:\/\/www.thermofisher.com\/es\/es\/home\/industrial\/mass-spectrometry\/liquid-chromatography-mass-spectrometry-lcms\/lc-ms-software\/multi-omics-data-analysis\/compound-discoverer-software.html."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1016\/j.talanta.2015.11.068","article-title":"Retrospective screening of pesticide metabolites in ambient air using liquid chromatography coupled to high-resolution mass spectrometry","volume":"150","author":"Millet","year":"2016","journal-title":"Talanta"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1071\/EN19089","article-title":"Quantification of known and unknown terpenoid organosulfates in PM10 using untargeted LC-HRMS\/MS: Contrasting summertime rural Germany and the North China Plain","volume":"16","author":"Wang","year":"2019","journal-title":"Environ. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"11353","DOI":"10.1021\/acs.est.9b03839","article-title":"2D Liquid chromatographic fractionation with ultra-high resolution MS analysis resolves a vast molecular diversity of trophospheric particle organics","volume":"53","author":"Spranger","year":"2019","journal-title":"Environ. Sci. Technol."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1740","DOI":"10.1021\/acs.analchem.0c04426","article-title":"Online Counter Gradient LC-FT-ICR-MS Enables Detection of Highly Polar Natural Organic Matter Fractions","volume":"93","author":"Han","year":"2021","journal-title":"Anal. Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"7365","DOI":"10.1021\/acs.est.0c08208","article-title":"An Automated Methodology for Non-targeted Compositional Analysis of Small Molecules in High Complexity Environmental Matrices Using Coupled Ultra Performance Liquid Chromatography Orbitrap Mass Spectrometry","volume":"55","author":"Pereira","year":"2021","journal-title":"Environ. Sci. Technol."},{"key":"ref_39","first-page":"84","article-title":"Nontarget screening using passive air and water sampling with a level II fugacity model to identify unregulated environmental contaminants","volume":"62","author":"Chung","year":"2017","journal-title":"Int. J. Environ. Sci."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"114834","DOI":"10.1016\/j.envpol.2020.114834","article-title":"Organic contaminants formed during fire extinguishing using different firefighting methods assessed by nontarget analysis","volume":"265","author":"Dubocq","year":"2020","journal-title":"Environ. Pollut."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"116052","DOI":"10.1016\/j.trac.2020.116052","article-title":"Passive air sampling and nontargeted analysis for screening POP-like chemicals in the atmosphere: Opportunities and challenges","volume":"132","author":"Zhang","year":"2020","journal-title":"Trends Anal. Chem."},{"key":"ref_42","first-page":"6654611","article-title":"Identification of 24 Unknown Substances (NIAS\/IAS) from Food Contact Polycarbonate by LC-Orbitrap Tribrid HRMS-DDMS3: Safety Assessment","volume":"2021","author":"Dualde","year":"2021","journal-title":"Int. J. Anal. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"20150202","DOI":"10.1098\/rsta.2015.0202","article-title":"Principal component analysis: A review and recent developments","volume":"374","author":"Jolliffe","year":"2016","journal-title":"Philos. Trans. R. Soc. A"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"565","DOI":"10.1039\/c3np20111b","article-title":"A global approach to analysis and interpretation of metabolic data for plant natural product discovery","volume":"30","author":"Hur","year":"2013","journal-title":"Nat. Prod. Rep."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"72","DOI":"10.1007\/s11306-018-1367-3","article-title":"Guidelines and considerations for the use of system suitability and quality control samples in mass spectrometry assays applied in untargeted clinical metabolomic studies","volume":"14","author":"Broadhurst","year":"2018","journal-title":"Metabolomics"},{"key":"ref_46","unstructured":"(2021, July 31). Chemspider Webpage. Available online: http:\/\/www.chemspider.com\/."},{"key":"ref_47","unstructured":"Thermo Fisher Scientific (2020, October 19). Mass Frontier Spectral Interpretation Software. Available online: https:\/\/www.thermofisher.com\/es\/es\/home\/industrial\/mass-spectrometry\/liquid-chromatography-mass-spectrometry-lc-ms\/lc-ms-software\/multi-omics-data-analysis\/mass-frontier-spectral-interpretation-software.html."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"318","DOI":"10.1016\/j.chroma.2007.04.021","article-title":"Data processing for mass spectrometry-based metabolomics","volume":"1158","author":"Katajamaa","year":"2007","journal-title":"J. Chromatogr. A"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"547","DOI":"10.1016\/j.talanta.2016.07.065","article-title":"Retrospective analysis of pesticide metabolites in urine using liquid chromatography coupled to high-resolution mass spectrometry","volume":"160","author":"Dualde","year":"2016","journal-title":"Talanta"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"258","DOI":"10.1016\/j.atmosres.2008.12.002","article-title":"Annual variation of particulate organic compounds in PM10 in the urban atmosphere of Algiers","volume":"92","author":"Ladji","year":"2009","journal-title":"Atmos. Res."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"89","DOI":"10.1016\/j.atmosenv.2014.08.058","article-title":"Timeline trend profile and seasonal variations in nicotine present in ambient PM10 samples: A four year investigation from Delhi region, India","volume":"98","author":"Yadav","year":"2014","journal-title":"Atmos. Environ."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"187","DOI":"10.1016\/j.envint.2016.09.010","article-title":"Cocaine and cannabinoids in the atmosphere of Northern Europe cities, comparison with Southern Europe","volume":"97","author":"Balducci","year":"2016","journal-title":"Env. Int."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"e2498","DOI":"10.1038\/cddis.2016.376","article-title":"Systemic application of 3-methyladenine markedly inhibited atherosclerotic lesion in ApoE-\/- mice by modulation autophagy, foam cell formation and immune-negative molecules","volume":"7","author":"Dai","year":"2016","journal-title":"Cell Death Dis."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"681","DOI":"10.1002\/poc.3471","article-title":"Excited state deactivation channels via internal conversions in two positions isomers of hydroxyl-methyl-pyridine: A theoretical study","volume":"28","author":"Schterev","year":"2015","journal-title":"J. Phys. Org. Chem."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"344","DOI":"10.1016\/j.scitotenv.2015.06.027","article-title":"Comprehensive monitoring of the occurrence of 22 drugs and transformation products in airborne particulate matter in the city of Barcelona","volume":"532","author":"Mastroianni","year":"2015","journal-title":"Sci. Total Environ."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"549","DOI":"10.1002\/aoc.3330","article-title":"Incorporation of azo group at axial position of silatranes: Synthesis, characterization and antimicrobial activity","volume":"29","author":"Singh","year":"2015","journal-title":"Appl. Organometal. Chem."}],"container-title":["Toxics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2305-6304\/10\/5\/220\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T23:02:20Z","timestamp":1760137340000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2305-6304\/10\/5\/220"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,4,27]]},"references-count":56,"journal-issue":{"issue":"5","published-online":{"date-parts":[[2022,5]]}},"alternative-id":["toxics10050220"],"URL":"https:\/\/doi.org\/10.3390\/toxics10050220","relation":{},"ISSN":["2305-6304"],"issn-type":[{"value":"2305-6304","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,4,27]]}}}