تلفیق روش کچرز با میکرواستخراج مایع-مایع پخشی مبتنی بر مایعات یونی مغناطیسی برای استخراج آفت‌کش‌های کارباماتی از نمونه‌های سیب و اندزه‌گیری آن ها با کروماتوگرافی مایع با کارایی بالا
محورهای موضوعی : کنترل کیفی مواد غذایی
سجاد فرج‌پور
1
,
محمدرضا افشار مقدم
2
,
جلیل خندقی
3
1 - دانش‌آموخته کارشناسی ارشد علوم و صنایع غذایی، واحد سراب، دانشگاه آزاد اسلامی ، سراب، ایران
2 - استادیار مرکز ایمنی غذا و دارو، دانشگاه علوم پزشکی تبریز، تبریز، ایران , استادیار مرکز آنالیز دارویی، دانشگاه علوم پزشکی تبریز، تبریز، ایران
3 - استادیار گروه علوم و صنایع غذایی، واحد سراب، دانشگاه آزاد اسلامی، سراب، ایران
, استادیار گروه بیوتکنولوژی مواد غذایی، مرکز تحقیقات بیوتکنولوژی، واحد تبریز، دانشگاه آزاد اسلامی، تبریز، ایران
کلید واژه: آفت‌کش‌های کارباماتی, میکرواستخراج مایع-مایع پخشی, کروماتوگرافی مایع با کارایی بالا, کچرز,
چکیده مقاله :
مقدمه: امروزه استفاده از آفت‌کش‌ها به بخشی ضروری از فعالیت‌های کشاورزی تبدیل شده است. در این بین کاربامات‌ها به علت طول عمر نسبتاً کوتاه، اثرگذاری قوی و طیف گسترده فعالیت‌های بیولوژیکی، کاربردهای گسترده‌ای به‌عنوان حشره‌کش دارند. به‌دلیل اینکه باقیمانده این ترکیبات در محصولات غذایی تهدید جدی برای سلامت مصرف کنندگان است، لزوم پایش باقیمانده‌های این آفت‌کش در مواد غذایی به‌خوبی احساس می‌شود.مواد و روش‌ها: در تحقیق حاضر تلفیقی از روش کچرز و میکرواستخراج مایع-مایع پخشی برای استخراج آفت‌کش‌های آلدی‌کارب، کارباریل و پریمی‌کارب از نمونه‌های سیب توسعه داده شده و اندازه‌گیری آن‌ها با کروماتوگرافی مایع با کارایی بالا مجهز به آشکارساز ماورای بنفش انجام گرفت. برای این منظور تاثیر عوامل موثر در دو مرحله روش استخراج پیشنهادی بررسی و بهینه‌سازی شد. همچنین اعتبارسنجی روش توسعه داده شده با محاسبه ارقام شایستگی مانند محدوده خطی، حدود تشخیص و اندازه‌گیری، تکرارپذیری، فاکتور تغلیظ و راندمان استخراج ارزیابی گردید.یافته‌ها: روش پیشنهادی از قابلیت بالایی در استخراج باقیمانده آفت‌کش‌های هدف از نمونه‌های سیب برخوردار بود به‌طوریکه از محدوده خطی وسیعی برخوردار بوده (2000-7/10 نانوگرم در گرم) و تکرارپذیری روش بر اساس درصد انحراف استاندارد نسبی 6/2 تا 8/4 بود. تحت شرایط بهینه، کارایی روش پیشنهادی در استخراج آنالیت‌ها 75-67 درصد، فاکتور تغلیظ بیش از 335 و حدود تشخیص و اندازه‌گیری به ترتیب کمتر از 2/4 و 14 نانوگرم در گرم بدست آمدند که کمتر از حد مجاز باقیمانده تعیین شده برای این آفت‌کش‌ها در میوه و سبزیجات می‌باشد. همچنین روش مذکور به‌طور موفقیت‌آمیزی بر روی نمونه‌های حقیقی سیب انجام و نتایج نشان‌داد که هیچکدام از آفت‌کش‌های کارباماتی مورد نظر در نمونه های سیب مورد بررسی وجود ندارد.نتیجه‌گیری: در مجموع روش توسعه داده شده از قابلیت لازم برای تشخیص آفت‌کش‌های کارباماتی در نمونه‌های سیب برخوردار است. از مزایای این روش می‌توان ساده و قابل اعتماد بودن، مصرف حلال های سبز و زمان آنالیز کوتاه را نام برد.
Introduction: Today, the use of pesticides has become an essential part of agricultural activities. Due to their relatively short lifespan, strong effect, and extensive variety of biological activities, carbamates are one of those that are frequently utilized as insecticides. The need to monitor the presence of pesticides in food products is a major concern because of their major risk on consumers' health.Materials and Methods: In the current research, Aldicarb, Carbaryl, and Primicarb insecticides were extracted from apple samples using a combination of QuEChERS technique with dispersive liquid-liquid microextraction, and their determination was carried out using HPLC-DAD. For this purpose, the effect of the effective factors in the two stages of the proposed extraction process was investigated and optimized. Also, merit figures including linear range, limits of detection and quantification, repeatability, enrichment factor, and extraction recovery were calculated in order to validate the developed method.Results: Concerned with the broad linear range (10.7-2000 ng/g) and the repeatability based on RSD% of 2.6 to 4.8, the proposed method proved highly capable of extracting the desired pesticide residues from apple samples. Under optimal conditions, the suggested approach had an extraction efficiency of 67–75%, an enrichment factor of greater than 335, and limits of detection and quantification of less than 4.2 and 14 ng/ml, respectively, which were less than the MRLs set for these pesticides in fruits and vegetables. The mentioned method was successfully performed on real apple samples and the results revealed that the samples did not contain any of the expected carbamates.Conclusion: In general, the developed method has the necessary ability to detect carbamate insecticides in apple samples. This method offers several advantages of being simple and reliable, employing green solvents, and short analysis time.
Ahmadzadeh Anvar, S., Torbati, M., Farajzadeh, M. A. & Afshar Mogaddam, M. R. (2020). Elevated temperature homogeneous liquid phase extraction coupled to ionic liquid–based dispersive liquid–liquid microextraction followed by high-performance liquid chromatography: application of water-miscible ionic liquids as extraction solvent in determination of carbamate pesticides. Food Analytical Methods, 13(6), 1282-1291.
Baig, S. A., Akhtera, N. A., Ashfaq, M. & Asi, M. R. (2009). Determination of the organophosphorus pesticide in vegetables by high-performance liquid chromatography. American-Eurasian Journal of Agriculture and Environmental Science, 6(5), 513-519.
Bhanti, M. & Taneja, A. (2007). Contamination of vegetables of different seasons with organophosphorous pesticides and related health risk assessment in northern India. Chemosphere, 69(1), 63-68.
Daghi, M. M., Nemati, M., Abbasalizadeh, A., Farajzadeh, M. A., Mogaddam, M. R. A. & Mohebbi, A. (2022). Combination of dispersive solid phase extraction using MIL–88A as a sorbent and deep eutectic solvent–based dispersive liquid–liquid microextraction for the extraction of some pesticides from fruit juices before their determination by GC–MS. Microchemical Journal, 183, 107984.
Dias, E., e Costa, F. G., Morais, S. & de Lourdes Pereira, M. (2015). A review on the assessment of the potential adverse health impacts of carbamate pesticides. Topics in public health, 197-212.
EU Pesticides database (2005). Part A of Annex I to Reg. 396/2005, http://ec.europa.eu/food/plant/pesticides/eu-pesticides-database.
Fakhim Rasoolzadeh, R., Afshar Moghaddam, M. & Khandaghi, J. (2020). Application of a novel microextraction method for determination of organophosphorous pesticides from fruit juice using high performance liquid chromatography. Food Hygiene, 10(2 (38)), 31-43. [In Persian]
Farajzadeh, M. A., Afshar Mogaddam, M. R. & Alizadeh Nabil, A. A. (2015). Polyol‐enhanced dispersive liquid–liquid microextraction coupled with gas chromatography and nitrogen phosphorous detection for the determination of organophosphorus pesticides from aqueous samples, fruit juices, and vegetables. Journal of separation science, 38(23), 4086-4094.
Ghasemi, R., Mirzaei, H., Mogaddam, M. R. A., Khandaghi, J. & Javadi, A. (2022). Application of magnetic ionic liquid-based air–assisted liquid–liquid microextraction followed by back-extraction optimized with centroid composite design for the extraction of antibiotics from milk samples prior to their determination by HPLC–DAD. Microchemical Journal, 181, 107764.
Gholizadeh, S., Mirzaei, H., Khandaghi, J., Mogaddam, M. R. A. & Javadi, A. (2022). Ultrasound–assisted solvent extraction combined with magnetic ionic liquid based-dispersive liquid–liquid microextraction for the extraction of mycotoxins from tea samples. Journal of Food Composition and Analysis, 114, 104831.
Jalili, V., Barkhordari, A. & Ghiasvand, A. (2020). New extraction media in microextraction techniques. A review of reviews. Microchemical Journal, 153, 104386.
Lehotay, S., Stajnbaher, D., Schenck, F. & Anastassiades, M. (2003). Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. Journal of AOAC International, 86, 412-431.
Limoei Khosrowshahi, B., Marzi Khosrowshahi, E., Afshar Mogaddam, M. & KHandaghi, J. (2022). Use of Dispersive Solid-Phase Extraction in Combination with Dispersive Liquid-Liquid Microextraction for the Assessment of Organophosphorus Pesticides in Fruit Juice Samples Using Gas Chromatography-Nitrogen-Phosphorus Detector. Iranian Journal of Nutrition Sciences & Food Technology, 87-98. [In Persian]
Llompart, M., Celeiro, M. & Dagnac, T. (2019). Microwave-assisted extraction of pharmaceuticals, personal care products and industrial contaminants in the environment. TrAC Trends in Analytical Chemistry, 116, 136-150.
Meshkini, K., AfsharMogaddam, M. & Khandaghi, J. (2021). Development of Homogeneous Liquid-Liquid Extraction in Combination with Dispersive Liquid-Liquid Microextraction Based on Deep Eutectic Solvents for the Extraction and Assessment of Phytosterols in Animal Cream Samples using Gas Chromatography Equipped with Flame Ionization Detector. Iranian Journal of Nutrition Sciences & Food Technology, 16(2), 57-67. [In Persian]
Mitra, S. & Brukh, R. (2003). Sample preparation: an analytical perspective. John Wiley pub. New Jersey, pp. 12-35.
Msagati, T. A. & Mamba, B. B. (2012). Monitoring of N-methyl carbamate pesticide residues in water using hollow fibre supported liquid membrane and solid phase extraction. Physics and Chemistry of the Earth, Parts A/B/C, 50, 149-156.
Rastpour, N., Khandaghi, J., Farajzadeh, M. A. & Mogaddam, M. R. A. (2022). Deep eutectic solvent-based QuEChERS method combined with dispersive liquid–liquid microextraction for extraction of benzoylurea insecticides in cabbage leaves samples. International Journal of Environmental Analytical Chemistry, 102(12), 2778-2791.
Rezaee, M., Assadi, Y., Hosseini, M.-R. M., Aghaee, E., Ahmadi, F. & Berijani, S. (2006). Determination of organic compounds in water using dispersive liquid–liquid microextraction. Journal of Chromatography a, 1116(1-2), 1-9.
Salvatierra-stamp, V., Muñiz-Valencia, R., Jurado, J. M. & Ceballos-Magaña, S. G. (2018). Hollow fiber liquid phase microextraction combined with liquid chromatography-tandem mass spectrometry for the analysis of emerging contaminants in water samples. Microchemical Journal, 140, 87-95.
Sheikhzadeh, F., Mogaddam, M. R. A., Farajzadeh, M. A. & Khandaghi, J. (2020). Development of microwave radiations-induced homogeneous liquid-liquid microextraction method for extraction of pyrethroid pesticides in fruit and vegetable samples. International Journal of Environmental Analytical Chemistry, 1-12.
Tudi, M., Daniel Ruan, H., Wang, L., Lyu, J., Sadler, R., Connell, D. & Phung, D. T. (2021). Agriculture development, pesticide application and its impact on the environment. International journal of environmental research and public health, 18(3), 1112.
van der Hoff, G. R. & van Zoonen, P. (1999). Trace analysis of pesticides by gas chromatography. Journal of Chromatography a, 843(1-2), 301-322.
Zahiri, E., Khandaghi, J., Farajzadeh, M. A. & Mogaddam, M. R. A. (2020). Combination of dispersive solid phase extraction with solidification organic drop–dispersive liquid–liquid microextraction based on deep eutectic solvent for extraction of organophosphorous pesticides from edible oil samples. Journal of Chromatography a, 1627, 461390.
Zare Sani, M., Mogaddam, M. R. A. & Khandaghi, J. (2021). Combination of cold induced HLLME with an effervescence-assisted DLLME based on deep eutectic solvent decomposition; application in extraction of some pyrethroid and carbamate pesticides from edible oils. International Journal of Environmental Analytical Chemistry, 1-16.
_||_Ahmadzadeh Anvar, S., Torbati, M., Farajzadeh, M. A. & Afshar Mogaddam, M. R. (2020). Elevated temperature homogeneous liquid phase extraction coupled to ionic liquid–based dispersive liquid–liquid microextraction followed by high-performance liquid chromatography: application of water-miscible ionic liquids as extraction solvent in determination of carbamate pesticides. Food Analytical Methods, 13(6), 1282-1291.
Baig, S. A., Akhtera, N. A., Ashfaq, M. & Asi, M. R. (2009). Determination of the organophosphorus pesticide in vegetables by high-performance liquid chromatography. American-Eurasian Journal of Agriculture and Environmental Science, 6(5), 513-519.
Bhanti, M. & Taneja, A. (2007). Contamination of vegetables of different seasons with organophosphorous pesticides and related health risk assessment in northern India. Chemosphere, 69(1), 63-68.
Daghi, M. M., Nemati, M., Abbasalizadeh, A., Farajzadeh, M. A., Mogaddam, M. R. A. & Mohebbi, A. (2022). Combination of dispersive solid phase extraction using MIL–88A as a sorbent and deep eutectic solvent–based dispersive liquid–liquid microextraction for the extraction of some pesticides from fruit juices before their determination by GC–MS. Microchemical Journal, 183, 107984.
Dias, E., e Costa, F. G., Morais, S. & de Lourdes Pereira, M. (2015). A review on the assessment of the potential adverse health impacts of carbamate pesticides. Topics in public health, 197-212.
EU Pesticides database (2005). Part A of Annex I to Reg. 396/2005, http://ec.europa.eu/food/plant/pesticides/eu-pesticides-database.
Fakhim Rasoolzadeh, R., Afshar Moghaddam, M. & Khandaghi, J. (2020). Application of a novel microextraction method for determination of organophosphorous pesticides from fruit juice using high performance liquid chromatography. Food Hygiene, 10(2 (38)), 31-43. [In Persian]
Farajzadeh, M. A., Afshar Mogaddam, M. R. & Alizadeh Nabil, A. A. (2015). Polyol‐enhanced dispersive liquid–liquid microextraction coupled with gas chromatography and nitrogen phosphorous detection for the determination of organophosphorus pesticides from aqueous samples, fruit juices, and vegetables. Journal of separation science, 38(23), 4086-4094.
Ghasemi, R., Mirzaei, H., Mogaddam, M. R. A., Khandaghi, J. & Javadi, A. (2022). Application of magnetic ionic liquid-based air–assisted liquid–liquid microextraction followed by back-extraction optimized with centroid composite design for the extraction of antibiotics from milk samples prior to their determination by HPLC–DAD. Microchemical Journal, 181, 107764.
Gholizadeh, S., Mirzaei, H., Khandaghi, J., Mogaddam, M. R. A. & Javadi, A. (2022). Ultrasound–assisted solvent extraction combined with magnetic ionic liquid based-dispersive liquid–liquid microextraction for the extraction of mycotoxins from tea samples. Journal of Food Composition and Analysis, 114, 104831.
Jalili, V., Barkhordari, A. & Ghiasvand, A. (2020). New extraction media in microextraction techniques. A review of reviews. Microchemical Journal, 153, 104386.
Lehotay, S., Stajnbaher, D., Schenck, F. & Anastassiades, M. (2003). Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. Journal of AOAC International, 86, 412-431.
Limoei Khosrowshahi, B., Marzi Khosrowshahi, E., Afshar Mogaddam, M. & KHandaghi, J. (2022). Use of Dispersive Solid-Phase Extraction in Combination with Dispersive Liquid-Liquid Microextraction for the Assessment of Organophosphorus Pesticides in Fruit Juice Samples Using Gas Chromatography-Nitrogen-Phosphorus Detector. Iranian Journal of Nutrition Sciences & Food Technology, 87-98. [In Persian]
Llompart, M., Celeiro, M. & Dagnac, T. (2019). Microwave-assisted extraction of pharmaceuticals, personal care products and industrial contaminants in the environment. TrAC Trends in Analytical Chemistry, 116, 136-150.
Meshkini, K., AfsharMogaddam, M. & Khandaghi, J. (2021). Development of Homogeneous Liquid-Liquid Extraction in Combination with Dispersive Liquid-Liquid Microextraction Based on Deep Eutectic Solvents for the Extraction and Assessment of Phytosterols in Animal Cream Samples using Gas Chromatography Equipped with Flame Ionization Detector. Iranian Journal of Nutrition Sciences & Food Technology, 16(2), 57-67. [In Persian]
Mitra, S. & Brukh, R. (2003). Sample preparation: an analytical perspective. John Wiley pub. New Jersey, pp. 12-35.
Msagati, T. A. & Mamba, B. B. (2012). Monitoring of N-methyl carbamate pesticide residues in water using hollow fibre supported liquid membrane and solid phase extraction. Physics and Chemistry of the Earth, Parts A/B/C, 50, 149-156.
Rastpour, N., Khandaghi, J., Farajzadeh, M. A. & Mogaddam, M. R. A. (2022). Deep eutectic solvent-based QuEChERS method combined with dispersive liquid–liquid microextraction for extraction of benzoylurea insecticides in cabbage leaves samples. International Journal of Environmental Analytical Chemistry, 102(12), 2778-2791.
Rezaee, M., Assadi, Y., Hosseini, M.-R. M., Aghaee, E., Ahmadi, F. & Berijani, S. (2006). Determination of organic compounds in water using dispersive liquid–liquid microextraction. Journal of Chromatography a, 1116(1-2), 1-9.
Salvatierra-stamp, V., Muñiz-Valencia, R., Jurado, J. M. & Ceballos-Magaña, S. G. (2018). Hollow fiber liquid phase microextraction combined with liquid chromatography-tandem mass spectrometry for the analysis of emerging contaminants in water samples. Microchemical Journal, 140, 87-95.
Sheikhzadeh, F., Mogaddam, M. R. A., Farajzadeh, M. A. & Khandaghi, J. (2020). Development of microwave radiations-induced homogeneous liquid-liquid microextraction method for extraction of pyrethroid pesticides in fruit and vegetable samples. International Journal of Environmental Analytical Chemistry, 1-12.
Tudi, M., Daniel Ruan, H., Wang, L., Lyu, J., Sadler, R., Connell, D. & Phung, D. T. (2021). Agriculture development, pesticide application and its impact on the environment. International journal of environmental research and public health, 18(3), 1112.
van der Hoff, G. R. & van Zoonen, P. (1999). Trace analysis of pesticides by gas chromatography. Journal of Chromatography a, 843(1-2), 301-322.
Zahiri, E., Khandaghi, J., Farajzadeh, M. A. & Mogaddam, M. R. A. (2020). Combination of dispersive solid phase extraction with solidification organic drop–dispersive liquid–liquid microextraction based on deep eutectic solvent for extraction of organophosphorous pesticides from edible oil samples. Journal of Chromatography a, 1627, 461390.
Zare Sani, M., Mogaddam, M. R. A. & Khandaghi, J. (2021). Combination of cold induced HLLME with an effervescence-assisted DLLME based on deep eutectic solvent decomposition; application in extraction of some pyrethroid and carbamate pesticides from edible oils. International Journal of Environmental Analytical Chemistry, 1-16.