Gas Chromatography-Mass Spectrometry Determination of Organochlorine Pesticides in Various Plant Leaves Used as Biomonitors in Environmental Pollution, Ergene River Basin, Turkey

Year 2018, Volume: 18 Issue: 1, 222 - 232, 30.04.2018

Cemile Özcan

Abstract

Ergene Basin is one of the 23 basins which identified the borders in Turkey. This Basin covers a large part of the province of Tekirdağ, Edirne and Kırklareli.The various plant samples (Urtica dioica L., Melissa officinalis, Verbascum sinuatum, Typha latifolia L., Pinus nigra L., Cupressus arizonica L., Populus nigra L., Cedrus libani L., Paliurus aculeatus L., Mentha pulegium L., Plantago major L., Laurus nobilis L.) collected from ten point in Ergene River Basin during 2012 year were extracted by using the quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction method. The concentrations of organochlorine pesticides having high toxicity were determined by using gas chromatography-mass spectrometry with electron impact ionization-possitive mode (GC-MS-EI (+)). The LOD, LOQ and RSD% were between 0.02- 0.21 μg L-1 , 0.06-0.71 μg L-1 , below 10%. for pesticides, respectively. Recoveries of pesticides in plant samples ranged from 78.9% to 99.9%, respectively. The ΣHCH and Dieldrin concentrations were not exceeded the tolerable daily intake limit accordingly serving as likely threat to humans

Keywords

Ergene River Basin, plant samples, pesticides, GC-MS, QuEChERS

Türkiye, Ergene Nehir Havzası'nda, Çevre Kirliliğinde Biomonitör Olarak Kullanılan Çeşitli Bitki Yapraklarındaki Organoklorlu Pestisitlerin Gaz Kromatografisi-Kütle Spektroskopisi ile Tayini

Abstract

Ergene Havzası Türkiye'de sınırları belirlenmiş olan 23 havzadan birisidir. Ergene Havzası, Tekirdağ, Edirne ve Kırklareli illerinin büyük bir kısmını kapsamaktadır. 2012 yılı süresince Ergene Nehir Havzasında on noktadan toplanan çeşitli bitki örnekleri (Urtica dioica L., Melissa officinalis, Verbascum sinuatum, Typha latifolia L., Pinus nigra L., Cupressus arizonica L., Populus nigra L., Cedrus libani L., Paliurus aculeatus L., Mentha pulegium L., Plantago major L., Laurus nobilis L.) hızlı, kolay, ucuz, etkili, dayanıklı ve güvenli (QuEChERS) ekstraksiyon metodu kullanılarak ekstrakte edilmiştir. Yüksek toksisiteye sahip organik klorlu pestisitlerin konsantrasyonları gaz kromatografi-kütle spektroskopisi-elektron impact iyonlaştırma-pozitif mod (GC-MS-EI (+)) kullanılarak tayin edilmiştir. Pestisitler için sırasıyla LOD, LOQ ve RSD% değerleri 0.02-0.21 μg L-1, 0.06-0.71 μg L-1 ve altında %10 bulunmuştur. Bitki örneklerindeki pestisitlerin geri dönüşüm çalışmaları sırasıyla 78.9-99.9% aralığında değişmektedir. İnsan sağlığını tehlikeye sokan ΣHCH ve Dieldrin konsantrasyonlarında izin verilen günlük alım sınırını aşmadığı belirlenmiştir.

Keywords

Ergene Nehir Havzası, bitki örnekleri, pestisitler, GC-MS; QuEChERS.

References

• Ahlborg U. G., L. Lipworth, L. Titus-Ernstoff, C. C. Hsieh, A. Hanberg, J. Baron, D. Trichopoulos, H. A. Adami (1995). Organochlorine compounds in relation to breast cancer, endometrial cancer, and endometriosis: an assessment of the biological and epidemiological evidence, Critical Reviews in Toxicology 25:463-531.
• Anonymous (1980) EEC Council Directive 80/778/EEC. 1980. Official Journal of European Communities, Vol. 229, pp.11.
• Anonymous (1980a) USEPA (United States Environmental Protection Agency). In: Watts RR, editor. Analysis of pesticide residues in human and environmental samples—a compilation of methods selected for use in pesticide monitoring programs; 1980. EPA-600/80-038.
• Anonymous (1996) Canada H. Provisional tolerable dietary intake (PTDI) values presently used by contaminants toxicology section. Ottawa, Ontario, Canada: Food Directorate, 1996.
• Anonymous (2007) U.S.E.P.A: Method 3535a solid-phase extraction (SPE). Ohio: USEPA, 2007.
• Attia S., K. Lebdi Grissa, G. Lognay, E. Bitume, T. Hance, A. Catherine Mailleux (2013). A review of the major biological approaches to control the worldwide pest Tetranychus urticae (Acari: Tetranychidae) with special reference to natural pesticides: Biological approaches to control Tetranychus urticae, Journal of Pest Science 86:361-386.
• Bakan G., S. Ariman (2004). Persistent organochlorine residues in sediments along the coast of mid-Black Sea region of Turkey, Marine Pollution Bulletin 48:1031-1039.
• Balkis N., A. Aksu, A. K. Balkis, M. Ş. Balkis (2015) Kromatografi ve Uygulamaları, Yalın Yayıncılık, İstanbul 2015, 1-96.
• Barr D. B. (2008). Biomonitoring of exposure to pesticides, Journal of Chemical Health and Safety 15:20–29.
• Barriada-Pereira M., E. Concha-Grana, M. J. Gonzalez-Castro, S. Muniategui-Lorenzo, P. Lopez-Mahia, D. Prada-Rodriguez, E. Fernandez-Fernandez (2005).
• Organochlorine pesticides accumulation and degradation products in vegetation samples of a contaminated area in Galicia (NW Spain), Chemosphere 58:1571-1578.
• Beard J., S. Marshall, K. Jong, R. Newton, T. Triplett-McBride, B. Humphries, R. Bronks (2000). 1,1-trichloro-2,2-bis (p-chlorophenyl)ethane (DDT) and reduced bone mineral density, Archives of Environ Health 55:177-180.
• Borga K., G. W. Gabrielsen, J. U. Skaare (2004). Biomagnification of organochlorines along a Barents Sea food chain, Environmental Pollution 113:187-198.
• Bruzzoniti M. C., L. Checchini, R. M. De Carlo, S. Orlandini, L. Rivoira, M. Del Bubba (2014). QuEChERS sample preparation for the determination of pesticides and other organic residues in environmental matrices: a critical review, Analytical and Bioanalytical Chemistry 406:4089–4116.
• Chowdhury M. T. I., M. A. Razzaque, M. S. I. Khan (2011). Chlorinated pesticide residue status in tomato, potato and carrot, Journal of Experimental Sciences 2:1-5.
• Darko G., O. Akoto, C. Oppong (2008). Persistent organochlorine pesticide residues in fish, sediments and water from Lake Bosomtwi, Ghana, Chemosphere 72:21-24.
• De´vier M. H., P. Mazellier, S. Aı¨t-Aı¨ssa, H. Budzinski (2011). New challenges in environmental analytical chemistry: Identification of toxic compounds in complex mixtures, Comptes Rendus Chimie 14:766–779.
• El-Shahawi M. S., A. Hamza, A. S. Bashammakh, W. T. Al-Saggaf (2010). Review: An overview on the accumulation, distribution, transformations, toxicity and analytical methods for the monitoring of persistent organic pollutants, Talanta 80:1587–1597.
• Erarslan C., Y. Örgün, E. Bozkurtoğlu (2014).Geochemistry of trace elements in the Keşan coal and its effect on the physicochemical features of ground- and surface waters in the coal fields, Edirne, Thrace Region, Turkey International Journal of Coal Geology 133:1-12.
• Güneş E.H., Y. Güneş, İ. Talınlı (2008). Toxicity evaluation of industrial and land base sources in a river basin, Desalination 226:348-356.
• Güyer G. T., K. Nadeem, N. Dizge (2016). Recycling ofpad-batch washing textile wastewater through advanced oxidation processes and its reusability assessment for Turkish textile industry, Journal of Cleaner Production 139:488-494.
• Huang Z., Y. Li, B. Chen, S. Yao (2007). Simultaneous determination of 102 pesticide residues in Chinese teas by gas chromatography-mass spectrometry, Journal of Chromatography B 853: 154-162.
• Huo F., H. Tang, X. Wu, D. Chen, T. Zhao, P. Liu, L. Li (2016). Utilizing a novel sorbent in the solid phase extraction for simultaneous determination of 15 pesticide residues in green tea by GC/MS, Journal of Chromatography B 1023-1024: 44-54.
• Jacobsen A. M., B. Halling-Sørensen, F. Ingerslev, S. H. Hansen (2004). Simultaneous extraction of tetracycline, macrolide and sulfonamide antibiotics from agricultural soils using pressurised liquid extraction, followed by solid-phase extraction and liquid chromatography–tandem mass spectrometry, Journal of Chromatography A 1038:157-170.
• Kurt P. B., H. B. Ozkoc (2004). A survey to determine levels of chlorinated pesticides and PCBs in mussels and seawater from the Mid-Black Sea Coast of Turkey, Marine Pollution Bulletin 48:1076-1083.
• Lino C. M., M. I. N. da Silveira (1997). Extraction and clean-up methods for the determination of organochlorine pesticide residues in medicinal plants, Journal of Chromatography A 769:275-283.
• Lu C., R. A. Fenske (1998). Air and surface chlorpyrifos residues following residential broadcast and aerosol pesticide applications, Environmental Science and Technology 32:1386-1390.
• Mantzos N., A. Karakitsou, I. Zioris, E. Leneti, I. Konstantinou (2013). QuEChERS and solid phase extraction methods for the determination of energy crop pesticides in soil, plant and runoff water matrices, International Journal of Environmental Analytical Chemistry 93:1566–1584.
• Nerin C., R. Batlle, M. Saraguda, C. Pedrocchi (2002). Supercritical fluid extraction of organochlorine pesticides and some metabolites in frogs from National Park of Ordesa and Monte Perdido, Analytica Chimica Acta 464:303-312.
• Nikolaou A.D., S. Meric, D.F. Lekkas, V. Naddeo, V. Belgiorno, S. Groudev, A. Tanik (2008). Multi-parametric water quality monitoring approach according to the WFD application in Evros trans-boundary river basin: priority pollutants, Desalination 226:306-320.
• Ordu S, A Demir (2009). Determination of Land Data of Ergene Basin (Turkey) by Planning Geographic Information Systems. Journal of Environmental Science and Technology 2: 80-87.
• Ozcan C (2016). Determination of Organochlorine Pesticides in Some Vegetable Samples Using GC-MS. Polish Journal of Environmental Studies, 25(3), 1141-1147.
• Ozcan C (2015). Pollution evaluation of organochlorine pesticides and heavy metals from cheese samples in Kirklareli, Turkey, Journal of Food, Agriculture & Environment 13:70-75.
• Ozcan C., Y. Dilgin, M. Yaman (2012). Determination of Quercetin in Medicinal Plants Such as Rose Hip (Rosa canina), Bettle (Urtica dioica), Terebinth (Terebinthina chica) and Purslane (Portulace oleracea) using HPLC-MS Method, Asian Journal of Chemistry 24:3396-3400.
• Ozcan C, Yaman M (2013). Determination of Kaempferol in Rosa canina, Urtica Dioica, Terebinthina Chica and Portulace Oleracea by HPLC-MS, Asian Journal of Chemistry 25:9758-9762.
• Ozcan C., M. Yaman (2015). Determination of Myricetin in Medicinal Plants by High-Performance Liquid Chromatography, Instrumentation Science & Technology 43:44-52.
• Ozcan S., N. Satiroglu, M. Soylak (2010). Column solid phase extraction of iron(III), copper(II), manganese(II) and lead(II) ions food and water samples on multiwalled carbon nanotubes, Food and Chemical Toxicology 48:2401–2406.
• Ozen O. A., A. Songur, M. Sarsilmaz, M. Yaman, I. Kus (2003). Zinc, Copper And Iron concentrations In cerebral cortex of Male Rats exposed To Formaldehyde inhalation, Journal of Trace Elements in Medicine and Biology 17:207-209.
• Ozmen M., Z. Ayas, A. Güngördü, G. F. Ekmekci, S. Yerli (2008). Ecotoxicological assessment of water pollution in Sariyar Dam Lake, Turkey, Ecotoxicology and Environmental Safety 70:163-173.
• Pang G-F., Y-M. Liu, C-L. Fan, J-J. Zhang, Y-Z. Cao, X-M. Li, Z-Y. Li, Y-P. Wu, T-T. Guo (2006). Simultaneous determination of 405 pesticide residues in grain by accelerated solvent extraction then gas chromatography-mass spectrometry or liquid chromatography-tandem mass spectrometry, Analytical and Bioanalytical Chemistry 384:1366-1408.
• Pastor A., E. Vazquez, R. Ciscar, M. de la Guardia (1997). Efficiency of the microwave-assisted extraction of hydrocarbons and pesticides from sediments, Analytica Chimica Acta 344:241-249.
• Ratola N., V. Homem, J. A. Silva, R. Araújo, J. M. Amigo, L. Santos, A. Alves (2014). Biomonitoring of pesticides by pine needles—Chemical scoring, risk of exposure, levels and trends, Science of the Total Environment 476–477:114–124.
• Sarigiannis D. A., P. Kontoroupis, E. S. Solomou, S. Nikolaki, A. J. Karabelas (2013). Inventory of pesticide emissions into the air in Europe, Atmospheric Environment 75:6–14.
• Shrivastava A., V. B. Gupta (2011). Methods for the determination of limit of detection and limit of quantitation of the analytical methods, Chronicles of Young Scientists 2:21-25.
• Singh R. P (2001). Comparison of Organochlorine Pesticide Levels in Soil and Groundwater of Agra, India. Bulletin of Environmental Contamination and Toxicology 67:126-132.
• Smeds A., P. Saukko (2001). Identification and quantification of polychlorinated biphenyls and some endocrine disrupting pesticides in human adipose tissue from Finland, Chemosphere 44:1463-1471.
• Sojinu O. S., O. O. Sonibare, O. O. Ekundayo, E. Y. Zeng (2012). Assessment of organochlorine pesticides residues in higher plants from oil exploration areas of Niger Delta, Nigeria, Science of the Total Environment 433:169–177.
• Stefanelli P., A. Santilio, L. Cataldi, R. Dommar (2009). Multiresidue analysis of organochlorine and pyrethroid pesticides in ground beef meat by gas chromatographymass spectrometry, Journal of Environmental Science and Health, Part B 44:350-356.
• Tokatli C (2015). Assessmet of water quality in the Meriç River as an ecosystem element in Turkey’s Thrace Region. Pol. J. Environ. Stud. 24 (5): 2205-2211.
• Tremolada P., V. Burnett, D. Calamari, K. C. Jones (1996). Spatial distribution of PAHs in the U.K. atmosphere using pine needles, Environmental Science & Technology 30:3570-3477.
• Yaman M., S. Gucer (1988). Determination of Nickel in Vegetable Matrices by Atomic Absorption Spectrometry After Precocentration on Activated Carbon, (Annali Di Chimica)(Rome) 88: 555-565.
• Yaman M (2000). Speciation of copper in soils and relation with its concentration in fruits, Communications In Soil Science and Plant Analysis 31:3205-3215.
• Yilmaz G.B., D. Atik, N. Sivri (2017) Agricultural Diffuse Pollution and Sustainability in Ergene Basin, European Journal of Sustainable Development Research (EJSDR) 2(1): 127-134.
• Xu D., W. Zhong, L. Deng, Z. Chai, X. Mao (2004). Regional distribution of organochlorinated pesticides in pine needles and its indication for socioeconomic development, Chemosphere 54:743–752.
• Yao Y., T. Harner, P. Blanchard, L. Tuduri, D. Waite, L. Poissant, C. Murphy, W. Belzer, F. Aulagnier, E. Sverko (2008). Pesticides in the atmosphere across Canadian agricultural regions, Environmental Science & Technology 42:5931–5937.
• Yeo H. G., M. Choi, Y. Sunwoo (2004). Seasonal variations in atmospheric concentrations of organochlrine pesticides in urban and rural areas of Korea, Atmospheric Environment 38:4779-4788.