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The oxidation of benzoic acid by reactive nitrous acid (HONO) was negligible, and the reactivity of the H2O2\/NO2\u2013 system decreased with a decrease in temperature under aqueous conditions. However, freezing markedly accelerated the chemical reaction. Based on Raman microscope measurements, concentrated species were confirmed in certain regions of the ice. We proposed that the change in nitrite speciation (accordingly, a decrease in the pH below pKa), derived from the freezing concentration effect, was the reason for the accelerated reactions. The oxidation characteristics of the system were monitored under varying conditions, such as initial pH, dosage ratio, benzoic acid concentration, and reaction with various benzene derivatives. The ultrahigh-performance liquid chromatography\/electrospray ionization\/mass spectrometry (UHPLC\/ESI\/MS) measurement showed that peroxynitrous acid (HOONO)-mediated oxidation generated hydroxylated and nitrated byproducts. Additionally, decarboxylated products were detected, indicating direct electron transfer from the organic compounds to HOONO. As freezing is a global phenomenon, and H2O2 and NO2\u2013 are ubiquitous in the environment, the transformation of aromatic compounds with H2O2\/NO2\u2013 in cold environments must be considered in environmental chemistry.<\/jats:p>","DOI":"10.1021\/acs.est.1c05705","type":"journal-article","created":{"date-parts":[[2021,12,14]],"date-time":"2021-12-14T09:12:56Z","timestamp":1639473176000},"page":"2323-2333","source":"Crossref","is-referenced-by-count":38,"title":["Frozen\nHydrogen Peroxide and Nitrite Solution: The\nAcceleration of Benzoic Acid Oxidation via the Decreased pH in Ice"],"prefix":"10.1021","volume":"56","author":[{"given":"Yong-Yoon","family":"Ahn","sequence":"first","affiliation":[{"name":"Korea Polar Research Institute (KOPRI) , ,","place":["Incheon, Republic of Korea, 21990"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7804-7587","authenticated-orcid":true,"given":"Jungwon","family":"Kim","sequence":"additional","affiliation":[{"name":"Hallym University , , , ,","place":["Chuncheon, Gangwon-do, Republic of Korea, 24252"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0803-3547","authenticated-orcid":true,"given":"Kitae","family":"Kim","sequence":"additional","affiliation":[{"name":"Korea Polar Research Institute (KOPRI) , ,","place":["Incheon, Republic of Korea, 21990"]},{"name":"University of Science of Technology (UST) , , ,","place":["Incheon, Republic of Korea, 21990"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2021,12,14]]},"reference":[{"key":"2026081414103421300_cit1","doi-asserted-by":"publisher","first-page":"18971","DOI":"10.1039\/C9RA02457C","article-title":"Mechanism\nand kinetic study of the reaction of benzoic acid with OH, NO3 and\nSO4\u2013 radicals in the atmosphere","volume":"9","author":"Zhang","year":"2019","journal-title":"RSC\nAdv."},{"key":"2026081414103421300_cit2","doi-asserted-by":"publisher","first-page":"7410","DOI":"10.1021\/acs.est.9b00950","article-title":"Abiotic Formation of\nHumic-Like Substances through Freezing-Accelerated\nReaction of Phenolic Compounds and Nitrite","volume":"53","author":"Min","year":"2019","journal-title":"Environ. 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Catal."},{"key":"2026081414103421300_cit33","doi-asserted-by":"publisher","first-page":"869","DOI":"10.1042\/bj3140869","article-title":"Peroxynitrite-mediated\nformation of free radicals in human plasma: EPR detection of ascorbyl,\nalbumin-thiyl and uric acid-derived free radicals","volume":"314","author":"Va\u0301squez-Vivar","year":"1996","journal-title":"Biochem. J."},{"key":"2026081414103421300_cit34","doi-asserted-by":"crossref","DOI":"10.1016\/S0076-6879(08)36004-2","article-title":"The Chemistry\nof Peroxynitrite: Implications for Biological Activity","volume-title":"Methods Enzymology","author":"Goldstein","year":"2008"},{"key":"2026081414103421300_cit35","doi-asserted-by":"publisher","first-page":"928","DOI":"10.1039\/jr9520000928","article-title":"168. Pernitrous acid. The reaction between hydrogen\nperoxide and nitrous acid, and the properties of an intermediate product","author":"Halfpenny","year":"1952","journal-title":"J. Chem. Soc."},{"key":"2026081414103421300_cit36","doi-asserted-by":"publisher","first-page":"419","DOI":"10.1042\/bj2810419","article-title":"Production of hydroxyl\nradicals from the simultaneous generation of superoxide and nitric\noxide","volume":"281","author":"Hogg","year":"1992","journal-title":"Biochem. J."},{"key":"2026081414103421300_cit37","doi-asserted-by":"publisher","first-page":"71","DOI":"10.3109\/10715769709097786","article-title":"Peroxynitrite-Dependent Aromatic\nHydroxylation and Nitration of Salicylate and Phenylalanine. 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Chem."},{"key":"2026081414103421300_cit46","volume-title":"Detection in Biological\nMedia: Challenges and Advances","author":"Koppenol","year":"2016"},{"key":"2026081414103421300_cit47","doi-asserted-by":"publisher","first-page":"330","DOI":"10.1016\/j.jhazmat.2017.01.031","article-title":"Accelerated redox reaction\nbetween chromate and phenolic pollutants during freezing","volume":"329","author":"Ju","year":"2017","journal-title":"J. Hazard. Mater."},{"key":"2026081414103421300_cit48","doi-asserted-by":"publisher","DOI":"10.1016\/j.seppur.2020.117233","article-title":"Freezing-accelerated\nremoval of chromate by biochar\nsynthesized from waste rice husk","volume":"250","author":"Han","year":"2020","journal-title":"Sep. Purif.\nTechnol."},{"key":"2026081414103421300_cit49","doi-asserted-by":"publisher","DOI":"10.1016\/j.seppur.2020.117377","article-title":"Enhanced reduction\nof hexavalent chromium by hydrogen sulfide in frozen solution","volume":"251","author":"Nguyen","year":"2020","journal-title":"Sep. Purif. Technol."},{"key":"2026081414103421300_cit50","doi-asserted-by":"publisher","first-page":"1277","DOI":"10.1021\/jp0553683","article-title":"Enhanced Protonation\nof Cresol Red in Acidic Aqueous Solutions Caused by Freezing","volume":"110","author":"Heger","year":"2006","journal-title":"J. Phys. Chem. B"},{"key":"2026081414103421300_cit51","doi-asserted-by":"publisher","first-page":"8270","DOI":"10.1021\/acs.jpcb.1c04414","article-title":"Proton Transport and\nRelated Chemical Processes of Ice","volume":"125","author":"Lee","year":"2021","journal-title":"J. Phys.\nChem. 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