TY - JOUR T1 - Accurate, Simple and Rapid Determination of Climbazole as Fungicide in Tap Water Samples by Gas Chromatography-Mass Spectrometry TT - Gaz Kromatografisi-Kütle Spektrometresi ile Musluk Suyu Örneklerinde Fungisit Olarak Klimbazolün Doğru, Basit ve Hızlı Tayini AU - Göver, Tuğçe PY - 2025 DA - July Y2 - 2025 DO - 10.7212/karaelmasfen.1642535 JF - Karaelmas Fen ve Mühendislik Dergisi PB - Zonguldak Bülent Ecevit Üniversitesi WT - DergiPark SN - 2146-7277 SP - 68 EP - 75 VL - 15 IS - 2 LA - en AB - This study describes the identification and quantification of climbazole, a fungicide, by using gas chromatography-mass spectrometry (GC-MS). A proper temperature program was applied for the efficient separation in the gas chromatography system for precise and accurate determination of climbazole. The analysis time for climbazole detection was 7.20 minutes. The identifier and quantifier ions were determined the ion peak with the highest relative abundance for climbazole in the National Institute of Standards and Technology (NIST) library, and the sharp peak at minute 4.95 in the chromatogram obtained in this ion peak was confirmed to belong to climbazole in the library. The analytical system provides linear working range between 2.05 and 99.37 mg/kg. Under the constant instrumental conditions, the limit of detection and limit of quantitation of climbazole were recorded as 0.60 and 2.01 mg/kg, respectively. Accuracy of the method was validated by performing recovery experiments on tap water samples. The climbazole was not detected in the two different tap water samples used in the recovery experiments. On the other hand, percent recovery results were calculated for spiked tap water samples by using an external calibration technique. The recovery values obtained for different climbazole concentrations were in the range of 87.7% - 114.4%. These results indicate the applicability and accuracy of the developed method in the determination of climbazole at water samples. KW - Climbazole KW - fungicide KW - gas chromatography KW - tap water N2 - Bu çalışmada, bir fungisit olan klimbazolün gaz kromatografisi-kütle spektrometrisi (GC-MS) kullanılarak belirlenmesi ve miktar tayini anlatılmaktadır. Klimbazolün hassas ve doğru tayini için gaz kromatografi sisteminde etkin bir ayırmanın yapılabilmesi amacıyla uygun sıcaklık programı uygulandı. Klimbazolün tayini için hızlı analiz süresi (7.20 dk) gerçekleştirildi. Tanımlayıcı ve niceleyici iyonlar, Ulusal Standartlar ve Teknoloji Enstitüsü (NIST) kütüphanesinde klimbazol için en yüksek bağıl bolluğa sahip iyon piki belirlendi ve bu iyon pikinde elde edilen kromatogramda 4.95 dakikadaki keskin pikin kütüphanede klimbazole ait olduğu doğrulandı. Analitik sistem 2.05 ile 99.37 mg/kg arasında oldukça iyi doğrusal çalışma aralığı sağlamaktadır. Sabit enstrümantal koşullar altında, klimbazolün gözlenebilme sınırı (LOD) ve tayin sınırı (LOQ) sırasıyla 0.60 ve 2.01 mg/kg olarak belirlendi. Yöntemin doğruluğu musluk suyu örneklerinde geri kazanım deneyleri yapılarak doğrulandı. Geri kazanım deneylerinde kullanılan iki farklı musluk suyu örneğinde klimbazol belirlenmedi. Öte yandan, standart ilaveli musluk suyu numuneleri için harici kalibrasyon tekniği kullanılarak yüzde geri kazanım sonuçları hesaplandı. Klimbazolün farklı konsantrasyonları için geri kazanım sonuçlarının %87.7 ile %114.4 arasında değiştiği görüldü. Bu sonuçlar, klimbazol tayini için geliştirilen yöntemin kompleks su örneklerinde bile uygulanabilirliğini ve doğruluğunu göstermektedir. CR - Abubakar, Y., Tijjani, H., Egbuna, C., Adetunji, CO., Kala, S., Kryeziu, TL., Ifemeje, J. C., Patrick-Iwuanyanwu, KC. 2020. Pesticides, History, and Classification (Chapter 3). Natural Remedies for Pest, Disease and Weed Control, Elsevier, pp. 29–42. https://doi.org/10.1016/B978-0-12-819304-4.00003-8 CR - Aktaş, Ş., Aminzai, MT., Tegin, İ., Yabalak, E., Acar, O. 2024. Determination of pesticide residues in varieties of pepper sold at different periods and provinces in Turkey and investigation of their adverse effects on human health and the environment. Int. J. Environ. Health Res., 34(6): 2491–2503. Doi: 10.1080/09603123.2023.2254720 CR - Arabkhani, B., Goudarzi, N., Chamjangali, MA. 2025. Development of a sensitive and accurate method for the simultaneous determination of climbazole and clotrimazole using β‑cyclodextrin assisted liquid–liquid microextraction based on switchable solvent. Chemical Papers. 79:1945–1957. https://doi.org/10.1007/s11696-025-03900-4 CR - Blair, A., Ritz, B., Wesseling, C., Beane Freeman, L. 2015. Pesticides and human health. Occup. Environ. Med., 72(2): 81–82. Doi: 10.1136/oemed-2014-102454 CR - Blasco, C., Picó, Y., Mañes, J., Font, G. 2002. Determination of fungicide residues in fruits and vegetables by liquid chromatography–atmospheric pressure chemical ionization mass spectrometry. J. Chromatogr. A, 947(2): 227–235. Doi: 10.1016/S0021-9673(02)00009-2 CR - Boxall, ABA., Rudd, MA., Brooks, BW., Caldwell, DJ., Choi, K., Hickmann, S., Innes, E., Ostapyk, K., Staveley, JP., Verslycke, T., Ankley, GT., Beazley, KF., Belanger, S. E., Berninger, JP., Carriquiriborde, P., Coors, A., DeLeo, PC., Dyer, SD., Ericson, J. F., … Van Der Kraak, G. 2012. Pharmaceuticals and Personal Care Products in the Environment: What Are the Big Questions? Environ. Health Perspect., 120(9): 1221–1229. Doi: 10.1289/ehp.1104477 CR - Casado, J., Rodríguez, I., Ramil, M., Cela, R. 2014. Selective determination of antimycotic drugs in environmental water samples by mixed-mode solid-phase extraction and liquid chromatography quadrupole time-of-flight mass spectrometry. J. Chromatogr. A, 1339: 42–49. Doi: 10.1016/j.chroma.2014.02.087 CR - Chen, G., Hoptroff, M., Fei, X., Su, Y., Janssen, HG. 2013. Ultra-high-performance liquid chromatography–tandem mass spectrometry measurement of climbazole deposition from hair care products onto artificial skin and human scalp. J. Chromatogr. A, 1317: 155–158. Doi: 10.1016/j.chroma.2013.08.032 CR - Chen, ZF., Ying, GG., Ma, YB., Lai, HJ., Chen, F., Pan, CG. 2013. Occurrence and dissipation of three azole biocides climbazole, clotrimazole and miconazole in biosolid-amended soils. Sci. Total Environ., 452–453: 377–383. Doi: 10.1016/j.scitotenv.2013.03.004 CR - Chow, R., Scheidegger, R., Doppler, T., Dietzel, A., Fenicia, F., Stamm, C. 2020. A review of long-term pesticide monitoring studies to assess surface water quality trends. Water Res. X., 9: 100064. Doi: 10.1016/j.wroa.2020.100064 CR - Daughton, CG., Ternes, TA. 1999. Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ. Health Perspect., 107(suppl 6): 907–938. Doi: 10.1289/ehp.99107s6907 CR - Ejigu, A., Tefera, M., Guadie, A. 2024. Electrochemical detection of pesticides: A comprehensive review on voltammetric determination of malathion, 2,4-D, carbaryl, and glyphosate. Electrochem. commun., 169: 107839. Doi: 10.1016/j.elecom.2024.107839 CR - Gonçalves, RFS., Madalena, DA., Fernandes, JM., Marques, M., Vicente, AA., Pinheiro, AC. 2022. Application of nanostructured delivery systems in food: From incorporation to detection and characterization. Trends Food Sci. Technol., 129: 111–125. Doi: 10.1016/j.tifs.2022.09.016 CR - Holvoet, KMA., Seuntjens, P., Vanrolleghem, PA. 2007. Monitoring and modeling pesticide fate in surface waters at the catchment scale. Ecol. Modell., 209(1): 53–64. Doi: 10.1016/j.ecolmodel.2007.07.030 CR - Ichihara, K., Kohsaka, C., Yamamoto, Y. 2021. Determination of proteinaceous free amino acids by gas chromatography. Anal. Biochem., 633(114): 423. https:// doi.org/10.1016/j.ab.2021.114423 CR - Keikavousi Behbahan, A., Mahdavi, V., Gordan, H., Bagheri, H. 2024. Fabrication of neem tree seed shell biochar polyamide composite for determination of pesticides in environmental water samples by GC-ECD: A comparison of various hard shell nuts’ biochar in thin-film microextraction setup. J. Food Compos. Anal., 125: 105743. Doi: 10.1016/j.jfca.2023.105743 CR - Li, WK., Shi, YP. 2024. Recent advances of carbon materials on pesticides removal and extraction based determination from polluted water. TrAC, Trends Anal. Chem., 171: 117534. Doi: 10.1016/j.trac.2024.117534 CR - Liu, WR., Ying, GG., Zhao, JL., Liu, YS., Hu, LX., Yao, L., Liang, YQ., Tian, F. 2016. Photodegradation of the azole fungicide climbazole by ultraviolet irradiation under different conditions: Kinetics, mechanism and toxicity evaluation. J. Hazard. Mater., 318: 794–801. Doi: 10.1016/j.jhazmat.2016.06.033 CR - Mahmood, I., Imadi, SR., Shazadi, K., Gul, A., Hakeem, KR. 2016. Effects of Pesticides on Environment. In Plant, Soil and Microbes, Springer International Publishing, pp. 253–269. https://doi.org/10.1007/978-3-319-27455-3_13 CR - Oflu, S., Erarpat, S., Zaman, BT., Günkara, ÖT., Bakırdere, S., Turak, F. 2023. Combination of quadrupole isotope dilution mass spectrometry with simultaneous derivatization and spray assisted droplet formation-liquid phase microextraction for the determination of methamphetamine in human urine and serum samples by gas chromatography mass spectrometry. J. Pharmacol. Toxicol. Methods. 119: 107207 CR - Paz-Alvarez, M., Pudney, PDA., Hadgraft, J., Lane, ME. 2018. Topical delivery of climbazole to mammalian skin. Int. J. Pharm., 549(1–2): 317–324. Doi: 10.1016/j.ijpharm.2018.07.058 CR - Pople, JE., Moore, AE., Talbot, DCS., Barrett, KE., Jones, DA., Lim, FL. 2014. Climbazole increases expression of cornified envelope proteins in primary keratinocytes. Int. J. Cosmet. Sci., 36(5): 419–426. Doi: 10.1111/ics.12137 Popp, J., Pető, K., Nagy, J. 2013. Pesticide productivity and food security. A review. Agron. Sustain. Dev., 33(1): 243–255. Doi: 10.1007/s13593-012-0105-x CR - Pramod, SK., Navnath, KA., Pramod, SM. 2021. A Review on Gas Chromatography-Mass Spectrometry(GC-MS). World J. Pharm. Res. 10(3): 741-763. CR - Rana, RA., Siddiqui, Md. N., Skalicky, M., Brestic, M., Hossain, A., Kayesh, E., Popov, M., Hejnak, V., Gupta, DR., Mahmud, NU., Islam, T. 2021. Prospects of Nanotechnology in Improving the Productivity and Quality of Horticultural Crops. Hortic., 7(10), 332. Doi: 10.3390/horticulturae7100332 CR - Rasheed, T. 2023. Carbon dots as robust class of sustainable and environment friendlier nano/optical sensors for pesticide recognition from wastewater. TrAC, Trends Anal. Chem., 160: 116957. Doi: 10.1016/j.trac.2023.116957 CR - Rasmussen, HT., Huang, K. 2012. 8.7 Chromatographic Separations and Analysis: Chromatographic Separations and Analysis of Enantiomers. Comprehensive Chirality, Elsevier, pp. 96–114. https://doi.org/10.1016/B978-0-08-095167-6.00831-4 CR - Richardson, JR., Fitsanakis, V., Westerink, RHS., Kanthasamy, AG. 2019. Neurotoxicity of pesticides. Acta Neuropathol., 138(3): 343–362. Doi: 10.1007/s00401-019-02033-9 CR - Scaroni, I., Previati, MP., Bovolenta, A. 1996. Handbook of Food Analysis. In Marcel Dekker & L. M. L. Nollet (Eds.), Handbook of Food Analysis, pp. 1461–1500. CR - Scientific Committee on Consumer Products (SCCP). 2009. Opinion on climbazole, SCCP/1204/08 (Scientific Committee on Consumer Products, Ed.). https://ec.europa.eu/health/ph_risk/committees/04_sccp/docs/sccp_o_164.pdf Accessed on Feb 05, 2025. CR - Serbest, H. 2024. Accurate and Sensitive Determination of Mefenpyr-diethyl in Barley, Oat and Corn Silk Matrices by Gas Chromatography – Flame Ionization Detector (GC–FID). Karaelmas Fen ve Müh. Derg., 14(1): 23–27. Doi: 10.7212/karaelmasfen.1393684 CR - Strózyñska, M., Schuhen, K. 2019. Dispersive solid-phase extraction followed by triethylsilyl derivatization and gas chromatography mass spectrometry for perfluorocarboxylic acids determination in water samples. J. Chromatogr. A, 1597: 1–8. https://doi.org/10.1016/j.chroma.2019.03.008 CR - Sun, X., Wang, M., Peng, J., Yang, L., Wang, X., Wang, F., Zhang, X., Wu, Q., Chen, R., Chen, J. 2019. Dummy molecularly imprinted solid phase extraction of climbazole from environmental water samples. Talanta, 196: 47–53. Doi: 10.1016/j.talanta.2018.12.017 CR - Tefera, M., Tessema, M., Admassie, S., Iwuoha, E. I., Waryo, TT., Baker, PGL. 2018. Electrochemical determination of phenothrin in fruit juices at graphene oxide-polypyrrole modified glassy carbon electrode. Sens. Bio-Sens. Res., 21: 27–34. Doi: 10.1016/j.sbsr.2018.09.003 CR - Zhang, QQ., Ying, GG., Chen, ZF., Liu, YS., Liu, WR., Zhao, JL. 2015. Multimedia fate modeling and risk assessment of a commonly used azole fungicide climbazole at the river basin scale in China. Sci. Total Environ., 520: 39–48. Doi: 10.1016/j.scitotenv.2015.03.038 CR - Zhong, Y., Chen, ZF., Liu, SS., Dai, X., Zhu, X., Zheng, G., Liu, S., Liu, G., Cai, Z. 2017. Analysis of azole fungicides in fish muscle tissues: Multi-factor optimization and application to environmental samples. J. Hazard. Mater., 324, Part B: 535–543. Doi: 10.1016/j.jhazmat.2016.11.024 UR - https://doi.org/10.7212/karaelmasfen.1642535 L1 - https://dergipark.org.tr/tr/download/article-file/4621622 ER -