Seasonal variability of nitrite and nitrate molar concentrations in fine and coarse particulate matter in coastal urban-industrial environments, and the effect of meteorological conditions on molar ratios

Öz

The present study investigates the seasonal variation, atmospheric transformation, and source attribution of nitrite (NO2-) and nitrate (NO3-) in fine (PM2.5) and coarse (PM2.5-10) particulate matter collected over a period of one year in a coastal urban-industrial area characterised by diverse emission sources. A comprehensive measurement programme was conducted to analyse the seasonal dynamics and correlations of nitrogen species. The measurement of molar concentrations (nmol/m³) and nitrate/nitrite molar ratios, as well as meteorological parameters (including temperature, relative humidity, solar radiation, and rainfall), were the scientific basis of this study. The findings indicate that nitrate and nitrite concentrations are notably elevated during the winter months, particularly in the fine fraction. These concentrations exhibit a strong correlation with combustion emissions associated with heating and cold weather conditions, characterised by low-radiation atmospheric conditions. The nitrate/nitrite molar ratios were elevated during the winter months, indicating enhanced oxidative transformation processes influenced by thermodynamic conditions and primary emissions. Pearson's correlation coefficient analysis confirmed a substantial negative relationship between temperature and nitrogen species. This finding emphasises enhanced secondary formation under cold conditions, as well as the significant impact of insolation. The findings of this study provide valuable insights into the complex interplay between anthropogenic emissions, atmospheric chemistry, and meteorological factors in coastal industrial environments. The study under scrutiny here demonstrates the pivotal function of fine-mode nitrate contamination during the heating season and its attendant health ramifications, thus engendering a comprehensive comprehension of paramount importance for the effective management of air quality in such regions.

Anahtar Kelimeler

• Nitrite
• Nitrate
• Molar Concentrations
• Molar Ratios
• Meteorological Effects

Kıyı kentsel-endüstriyel ortamlarda ince ve kaba partikül maddelerdeki nitrit ve nitrat molar konsantrasyonlarının mevsimsel değişkenliği ve meteorolojik koşulların molar oranları üzerindeki etkisi

Öz

Bu çalışma, çeşitli emisyon kaynaklarının bulunduğu bir kıyı kentsel-endüstriyel alanda bir yıl boyunca toplanan ince (PM2,5) ve kaba (PM2,5-10) partikül maddelerdeki nitrit (NO2-) ve nitrat (NO3-) bileşiklerinin mevsimsel değişimi, atmosferik dönüşümü ve kaynak atıflarını incelemektedir. Azot türlerinin mevsimsel dinamiklerini ve korelasyonlarını analiz etmek için kapsamlı bir ölçüm programı yürütülmüştür. Mol konsantrasyonlarının (nmol/m³) ve nitrat/nitrit mol oranlarının yanı sıra meteorolojik parametrelerin (sıcaklık, bağıl nem, güneş radyasyonu ve yağış dahil) ölçümü, bu çalışmanın bilimsel temelini oluşturmuştur. Bulgular, nitrat ve nitrit konsantrasyonlarının kış aylarında, özellikle ince fraksiyonda belirgin şekilde yükseldiğini göstermektedir. Bu konsantrasyonlar, düşük radyasyonlu atmosferik koşullarla karakterize edilen ısıtma ve soğuk hava koşullarıyla ilişkili yanma emisyonlarıyla güçlü bir korelasyon sergilemektedir. Nitrat/nitrit molar oranları kış aylarında yükseldi, bu da termodinamik koşullar ve birincil emisyonların etkisiyle oksidatif dönüşüm süreçlerinin arttığını gösterdi. Pearson korelasyon katsayısı analizi, sıcaklık ve azot türleri arasında önemli bir negatif ilişki olduğunu doğruladı. Bu bulgu, soğuk koşullarda ikincil oluşumun arttığını ve güneş ışınımının önemli etkisini vurgulamaktadır. Bu çalışmanın bulguları, kıyı sanayi ortamlarında antropojenik emisyonlar, atmosfer kimyası ve meteorolojik faktörler arasındaki karmaşık etkileşime ilişkin değerli bilgiler sağlamaktadır. Burada incelenen çalışma, ısıtma mevsiminde ince mod nitrat kirliliğinin ve bunun sağlık üzerindeki etkilerinin önemli rolünü ortaya koyarak, bu tür bölgelerde hava kalitesinin etkin yönetimi için büyük önem taşıyan kapsamlı bir anlayış sağlar.

Anahtar Kelimeler

• Nitrit
• Nitrat
• Molar Konsantrasyonlar
• Meteorolojik Etkiler
• Molar Oranlar

Kaynakça

1. V.J. Erpenbeck, R.A. Jörres, M. Discher, H. Krentel, D. Tsikas, B. Luettig, N. Krug, J.M. Hohlfeld, Local nitric oxide levels reflect the degree of allergic airway inflammation after segmental allergen challenge in asthmatics, Nitric Oxide, 13, 2005, 125-133.
2. A.M. Wilson, J.C. Salloway, C.P. Wake, T. Kelly, Air pollution and the demand for hospital services: a review, Environ Int, 30, 2004, 1109-1118.
3. B. Gürler Akyüz, M. Akyüz, Seasonal variations, source apportionment, and health risk assessment of nitrosamines in inhalable particulate matter (PM10) in the atmosphere of Zonguldak, Türkiye, Environ Sci Pollut Res, 32, 2025,11083-11096.
4. O.R. Abou Chakra, M. Joyeux, E. Nerrière, M.-P. Strub, D. Zmirou-Navier, Genotoxicity of organic extracts of urban airborne particulate matter: An assessment within a personal exposure study, Chemosphere, 66, 2007, 1375-1381.
5. R. Pozzi, B. De Berardis, L. Paoletti, C. Guastadisegni, Winter urban air particles from Rome (Italy): Effects on the monocytic–macrophagic RAW 264.7 cell line, Environ Res, 99, 2005, 344-354.
6. A.I. Calvo, C. Alves, A. Castro, V. Pont, A.M. Vicente, R. Fraile, Research on aerosol sources and chemical composition: Past, current and emerging issues, Atmos Res, 120-121, 2013, 1-28.
7. R.M. Harrison, J. Yin, Particulate matter in the atmosphere: which particle properties are important for its effects on health, Sci Total Environ, 249, 2000, 85-101.
8. S. Biswas, B. Chowdhury, B.C. Ray, A novel spectrofluorimetric method for the ultra trace analysis of nitrite and nitrate in aqueous medium and its application to air, water, soil and forensic samples, Talanta 64, 2004, 308-312.

9. N.S. Bryan, M.B. Grisham, Methods to detect nitric oxide and its metabolites in biological samples, Free Radical Bio Med, 43, 2007, 645-657.
10. D. Tsikas, Review Methods of quantitative analysis of the nitric oxide metabolites nitrite and nitrate in human biological fluids, Free Radic Res, 39, 2005, 797-815.
11. D. Tsikas, F.-M. Gutzki, D.O. Stichtenoth, Circulating and excretory nitrite and nitrate as indicators of nitric oxide synthesis in humans: methods of analysis. Eur J Clin Pharmacol, 62, 2006, 51-59.
12. Y. Zuo, C. Wang, T. Van, Simultaneous determination of nitrite and nitrate in dew, rain, snow and lake water samples by ion-pair high-performance liquid chromatography, Talanta, 70, 2006, 281-285.
13. M. Grau, U.B. Hendgen-Cotta, P. Brouzos, , C. Drexhage, T. Rassaf, T. Lauer, A. Dejam, M. Kelm, P. Kleinbongard, Recent methodological advances in the analysis of nitrite in the human circulation: nitrite as a biochemical parameter of the L-arginine/NO pathway, J Chromatogr B, 851, 2007, 106-123.
14. D. Tsikas, Analysis of nitrite and nitrate in biological fluids by assays based on the Griess reaction: Appraisal of the Griess reaction in the L-arginine/nitric oxide area of research, J Chromatogr B, 851, 2007, 51-70.
15. A. Moriyama, A. Tabaru, H. Unoki, S. Abe, A. Masumoto, M. Otsuki, Plasma nitrite/nitrate concentrations as a tumor marker for hepatocellular carcinoma, Clin Chim Acta, 296, 2000, 181-191.
16. P.C. Pinto, J.L. Lima, M.L.M.F. de Sousa, Sequential injection analysis of nitrites and nitrates in human serum using nitrate reductase, Clin Chim Acta, 337, 2003, 69-76.
17. M.J. Moorcroft, J. Davis, R.G. Compton, Detection and determination of nitrate and nitrite: a review, Talanta, 54, 2001, 785-803.
18. A.S. Pannala, A.R. Mani, J.P. Spencer, V. Skinner, K.R. Bruckdorfer, K.P. Moore, C.A. Rice-Evans, The effect of dietary nitrate on salivary, plasma, and urinary nitrate metabolism in humans, Free Radical Bio Med, 34, 2003, 576-584.
19. L. Peri, D. Pietraforte, G. Scorza, A. Napolitano, V. Fogliano, M. Minetti, Apples increase nitric oxide production by human saliva at the acidic pH of the stomach: a new biological function for polyphenols with a catechol group, Free Radical Bio Med, 39, 2005, 668-681.
20. F. Romitelli, S.A. Santini, E. Chierici, D. Pitocco, B. Tavazzi, A.M. Amorini, G. Lazzarino, E. Di Stasio, Comparison of nitrite/nitrate concentration in human plasma and serum samples measured by the enzymatic batch Griess assay, ion-pairing HPLC and ion-trap GC–MS: the importance of a correct removal of proteins in the Griess assay, J Chromatogr B, 851, 2007, 257-267.
21. Y. Kono, H. Shibata, Y. Kodama, Y. Sawa, The suppression of the N-nitrosating reaction by chlorogenic acid, Biochem J, 312, 1995, 947-953.
22. B. Sırıken, M. Özdemir, H. Yavuz, S. Pamuk, The microbiological quality and residual nitrate/nitrite levels in turkish sausage (soudjouck) produced in Afyon Province, Turkey, Food Control, 17, 2006, 923-928.
23. D.C. Siu, A. Henshall, Ion chromatographic determination of nitrate and nitrite in meat products, J Chromatogr A, 804, 1998, 157-160.
24. Y. Zuo, Y. Deng, The near-UV absorption constants for nitrite ion in aqueous solution, Chemosphere, 36, 1998, 181-188.
25. M.A. Alam, Z. Ren, G. da Silva, Nitramine and nitrosamine formation is a minor pathway in the atmospheric oxidation of methylamine: A theoretical kinetic study of the CH3NH+ O2 reaction, Int J Chem Kinet, 51, 2019, 723-728.
26. M. Akyüz, Ş. Ata, Seasonal variations of particle-associated nitrosamines by gas chromatography–mass spectrometry in the atmospheric environment of Zonguldak, Turkey, Environ Sci and Pollut R, 20, 2013, 7398-7412.
27. S. Zhen, M. Luo, Y. Shao, D. Xu, L. Ma, Study on the source of nitrate in atmospheric particulate matter in Beijing using nitrogen and oxygen dual isotopes, Scientific Reports, 15:18174, 2025.
28. M. Gen, Z. Liang, R. Zhang, B. R. Go Mabato, C. K. Chan, Particulate nitrate photolysis in the atmosphere, Environ. Sci.: Atmos., 2, 2022, 111–127.
29. K. Xina, J. Chen, T.-O. Soyol-Erdene, Formation mechanism and source apportionment of nitrate in atmospheric aerosols, APN Science Bulletin, 13, 1, 2023, 102–111.
30. Y. Cao, Q. Ma, B. Chu, H. He, Homogeneous and heterogeneous photolysis of nitrate in the atmosphere: state of the science, current research needs, and future prospects, Front. Environ. Sci. Eng., 17(4), 2023, 48.
31. W. Song, X.-Y. Liu, C.-Q. Liu, New Constraints on Isotopic Effects and Major Sources of Nitrate in Atmospheric Particulates by Combining δ15N and Δ17O Signatures, JGR Atmospheres, 126, 2021, e2020JD034168.
32. Y. Yang, L. Huang, M. Zhao, Y. Wu,Y. Xu, Q. Li, W. Wang, L. Xue, Multiphase reactions of organic peroxides and nitrite as a source of atmospheric organic nitrates, Nature Communications 16, 2025, 5437.
33. S. N. Sinha, N.M. Desai, G.M. Patel, M.M. Mansuri, V. Shivgotra, Concentration of nitrite in respirable particulate matter of ambient air in Vadodara, Gujarat, India, Journal of Environmental Biology, 31, 2010, 375-378.
34. X. Shang, H. Kang, Y. Chen, M. Abdumutallip, L. Li, X. Li, H. Fu, X. Wang, L. Wang, X. Wang, H. Ouyang, X. Tang, H. Xiao, C. George, J. Chen, PM1.0-Nitrite Heterogeneous Formation Demonstrated via a Modified Versatile Aerosol Concentration Enrichment System Coupled with Ion Chromatography, Environ. Sci. Technol., 55, 2021, 9794−9804.