Abstract
A new method of cloud point preconcentration coupled with ultrasound-assisted back extraction of fludioxonil, fenarimol, metalaxyl for determination by gas chromatography with flame ionization detection (GC-FID) in fruits was developed. Some parameters with an effect on the extraction, such as the concentration of Triton X-114, pH influence, incubation time, equilibration temperature and centrifuging parameters were studied and optimized. When using solutions of Triton X-114 for extraction of 0.5% (w/v), the complete extraction of fungicides is observed in the pH range 5.2–8.0 under the conditions of the existence of their neutral molecular forms at an equilibrium phase separation temperature of 45 °C. Surfactant-rich phases were formed by centrifuging solutions at 4000 rpm for 15 min. The method was validated and characterized by the following metrological parameters: the limit of detection (LOD, 3σ) of fludioxonil is 0.06 μg⋅mL−1, the limit of quantitation (LOQ, 10σ) – 0.21 μg⋅mL−1, working range 0.21–10.0 μg⋅mL−1; for fenarimol LOD – 0.10 μg⋅mL−1, LOQ – 0.33 μg⋅mL−1, working range – 0.33–10.0 μg⋅mL−1; for metalaxyl LOD – 0.15 μg⋅mL−1, LOQ – 0.50 μg⋅mL−1, working range – 0.50–10.0 μg⋅mL−1. The procedure was used for determination of fludioxonil, fenarimol, metalaxyl in grapes after their treatment with commercial preparations of fungicides. The results show that the sensitivity, metrological characteristics, ecological safety, simplicity and convenience of the suggested procedure exceed its analogs based on extraction using organic solvents.
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Altunay N, Gürkan R (2016) Separation/preconcentration of ultra-trace levels ofinorganic Sb and Se from different sample matrices by charge transfersensitized ion-pairing using ultrasonic-assisted cloud point extraction priorto their speciation and determination by hydride generation AAS. Talanta 159:344–355. https://doi.org/10.1016/j.talanta.2016.06.054
Anastassiadou M, Bernasconi G, Brancato A, Carrasco Cabrera L, Ferreira L, Greco L, Jarrah S, Kazocina A, Leuschner R, Oriol Magrans J, Miron I, Nave S, Pedersen R, Reich H, Rojas A, Sacchi A, Santos M, Pia Scarlato A, Theobald A, Vagenende B, Verani A (2021) Review of the existing maximum residue levels for sulfuryl fluoride according to Article 12 of Regulation (EC) No 396/2005. EFSA J 19(1):6390. https://doi.org/10.2903/j.efsa.2021.6390
Asensio-Ramos M, Ravelo-Pérez LM, González-Curbelo MÁ, Hernández-Borges J (2011) Liquid phase microextraction applications in food analysis. J Chromatogr A 1218(42):7415–7437. https://doi.org/10.1016/j.chroma.2011.05.096
Bermúdez-Couso A, Fernández-Calviño D, Pateiro-Moure M, Garrido-Rodríguez B, Nóvoa-Muñoz JC, Estévez MA (2011) Adsorption and desorption behavior of metalaxyl in intensively cultivated acid soils. J Agric Food Chem 59:7286–7293. https://doi.org/10.1021/jf201028q
Brycht M, Burnat B, Skrzypek S, Guzsvány V, Gutowska N, Robak J, Nosal-Wiercińska A (2015) Voltammetric and corrosion studies of the fungicide fludioxonil. Electrochim Acta 158:287–297. https://doi.org/10.1016/j.electacta.2015.01.130
Bulgurcuoğlu AE, Durak BY, Chormey DS, Bakırdere S (2021) Development of a switchable solvent liquid phase extraction method for the determination of chlorthiamid, ethyl parathion, penconazole and fludioxonil pesticides in well, tap and lake water samples by gas chromatography mass spectrometry. Microchem J 168:106381. https://doi.org/10.1016/j.microc.2021.106381
Caixeta-Neta A, Ribeiro GC, De Amorim KP, Andrade LS (2020) Electrochemical determination of thiabendazole pesticide extracted and preconcentrated from tomato samples by cloud point extraction. Anal Methods 12:5823–5832. https://doi.org/10.1039/D0AY01918F
Campone L, Piccinelli AL, Celano R, Rastrelli L (2011) Application of dispersive liquid–liquid microextraction for the determination of aflatoxins B1, B2, G1 and G2 in cereal products. J Chromatogr A 1218(42):7648–7654. https://doi.org/10.1016/j.chroma.2011.05.028
Chen H, Luo J, Wang Q, Zhang D, Jiang R (2014) Psoralen and Isopsoralen’s cloud-point extraction from Psoralea corylifolia L. Sep Sci Technol 49:2169–2174. https://doi.org/10.1080/01496395.2014.908217
Chen Y, Du K, Li J, Bai Y, An M, Tan Z, Chang Y-x (2018) A Green and efficient method for the preconcentration and determination of Gallic acid, bergenin, quercitrin, and embelin from Ardisia japonica Using nononic surfactant genapol X-080 as the extraction solvent. Int J Anal Chem 2018:1707853. https://doi.org/10.1155/2018/1707853
Dağdeviren S, Altunay N, Sayman Y, Gürkan R (2018) A new method of UA_CPE coupled with spectrophotometry for the faster and cost-effective detection of proline in fruit juice, honey, and wine. Food Chem 255:31–40. https://doi.org/10.1016/j.foodchem.2018.02.046
Demir Ö, Ulusoy Hİ, Özer ET, Osman B (2020) Development of a new solid phase extraction method for sensitive determination of some carbamate pesticides in water using poly(EGDMA-MATrp) microbeads. Microchem J 158:105317. https://doi.org/10.1016/j.microc.2020.105317
Doroschuk VO, Kulichenko SA, Lelyushok SO (2005) The influence of substrate charge and molecular structure on interphase transfer in cloud point extraction systems. J Colloid Interface Sci 291(1):251–255. https://doi.org/10.1016/j.jcis.2005.04.107
Doroshchuk VA, Levchik VM, Mandzyuk ES (2015) Cloud-point extraction preconcentration of sym-triazine herbicides to determination by gas chromatography. J Anal Chem 70:119–124. https://doi.org/10.1134/S106193481412003X
European Food Safety Authority (2011) Modification of the existing MRLs for fenarimol in various crops. EFSA J 9(9):2350. https://doi.org/10.2903/j.efsa.2011.2350
European Food Safety Authority (2016) Modification of the existing maximum residue levels for metalaxyl in various crops. EFSA J 14(7):e04521. https://doi.org/10.2903/j.efsa.2016.4521
Farajzadeh MA, Nemati M, Altunay N, Tuzen M, Kaya S, Kheradmand F, Mogaddam MRA (2022) Experimental and density functional theory studies during a new solid phase extraction of phenolic compounds from wastewater samples prior to GC–MS determination. Microchem J 177:107291. https://doi.org/10.1016/j.microc.2022.107291
Fernández-Calviño D, Bermúdez-Couso A, Nóvoa-Muñoz JC, Arias-Estévez M (2015) Metalaxyl mobility in acid soils: evaluation using different methods. Int J Environ Sci Technol 12:2179–2190. https://doi.org/10.1007/s13762-014-0612-1
Fontana AR, Silva MF, Martínez LD, Wuilloud RG, Altamirano JC (2009) Determination of polybrominated diphenyl ethers in water and soil samples by cloud point extraction-ultrasound-assisted back-extraction-gas chromatography-mass spectrometry. J Chromatogr A 1216(20):4339–4346. https://doi.org/10.1016/j.chroma.2009.03.029
Hagarova I (2017) Cloud point extraction utilizable for separation and preconcentration of (ultra)trace elements in biological fluids before their determination by spectrometric methods: a brief review. Chem Pap 71:869–879. https://doi.org/10.1007/s11696-016-0014-6
Hengel MJ, Miller D, Jordan R (2016) Development and validation of a method for the determination of pesticide residues in beer by liquid chromatography-mass spectrometry. J Am Soc Brew Chem 74(1):49–52. https://doi.org/10.1094/ASBCJ-2016-1115-01
Hernández AF, Gil F, Lacasaña M, Rodríguez-Barranco M, Tsatsakis AM, Requena M, Alarcón R (2013) Pesticide exposure and genetic variation in xenobiotic-metabolizing enzymes interact to induce biochemical liver damage. Food Chem Toxicol 61:144–151. https://doi.org/10.1016/j.fct.2013.05.012
Jankulovska MS, Velkoska-Markovska L, Petanovska-Ilievska B, Ilievski U (2019) Application of high performance liquid chromatography for determination of metalaxyl, acetamiprid and azoxystrobine in tomato samples. J Anal Chem 74:339–344. https://doi.org/10.1134/S1061934819040075
Ji Y, Wu L, Lv R, Wang H, Song S, Cao M (2021) Facile cloud point extraction for the separation and determination of phenolic acids from dandelion. ACS Omega 6(20):13508–13515. https://doi.org/10.1021/acsomega.1c01768
Kamrin MA (1997) Pesticide profiles. Toxicity environmental impact and fate. CRC Press, Boca Raton
Khan S, Bhatia T, Trivedi P, Satyanarayana GNV, Mandrah K, Saxena PN, Mudiam MKR, Roy SK (2016) Selective solid-phase extraction using molecularly imprinted polymer as a sorbent for the analysis of fenarimol in food samples. Food Chem 199:870–875. https://doi.org/10.1016/j.foodchem.2015.12.091
Khani R, Sheykhi R, Bagherzade G (2019) An environmentally friendly method based on micro-cloud point extraction for determination of trace amount of quercetin in food and fruit juice samples. Food Chem 293:220–225. https://doi.org/10.1016/j.foodchem.2019.04.099
Khosrowshahi EM, Mogaddam MRA, Javadzadeh Y, Altunay N, Tuzen M, Kaya S, Ghalkhani M, Farajzadeh MA, Nemati M (2022) Experimental and density functional theoretical modeling of triazole pesticides extraction by Ti2C nanosheets as a sorbent in dispersive solid phase extraction method before HPLC-MS/MS analysis. Microchem J 178:107331. https://doi.org/10.1016/j.microc.2022.107331
Kolachi NF, Kazi TG, Khan S, Wadhwa SK, Baig JA, Afridi HI, Shah AQ, Shah F (2011) Multivariate optimization of cloud point extraction procedure for zinc determination in aqueous extracts of medicinal plants by flame atomic absorption spectrometry. Food Chem Toxicol 49(10):2548–2556. https://doi.org/10.1016/j.fct.2011.06.065
Mercader JV, Abad-Fuentes A, Agulló C, Abad-Somovilla A, Esteve-Turrillas FA (2014) Development of a sensitive and specific enzyme-linked immunosorbent assay for the determination of fludioxonil residues in fruit juices. Anal Methods 6(22):8924–8929. https://doi.org/10.1039/C4AY01756K
Milcheva NP, Genç F, Racheva PV, Delchev VB, Andruch V, Gavazov K (2021) An environmentally friendly cloud point extraction–spectrophotometric determination of trace vanadium using a novel reagent. J Mol Liq 334:116086. https://doi.org/10.1016/j.molliq.2021.116086
Mortada WI (2020) Recent developments and applications of cloud point extraction: a critical review. Microchem J 157:105055. https://doi.org/10.1016/j.microc.2020.105055
Nemati M, Tuzen M, Farajzadeh MA, Kaya S, Mogaddam MRA (2022) Development of dispersive solid-liquid extraction method based on organic polymers followed by deep eutectic solvents elution; application in extraction of some pesticides from milk samples prior to their determination by HPLC-MS/MS. Anal Chim Acta 1199:339570. https://doi.org/10.1016/j.aca.2022.339570
Noorashikin MS, Sohaimi NM, Suda N, Aziz HZ, Zaini SRM, Kandasamy S, Suresh K (2017) The application of cloud point extractionin environmental analysis. J Sustain Sci Manag 12(1):79–95
Ojeda CB, Rojas FS (2009) Separation and preconcentration by a cloud pointextraction procedure for determination of metals: an overview. Anal Bioanal Chem 394:759–782. https://doi.org/10.1007/s00216-009-2660-9
Oliva J, Navarro S, Barba A, Navarro G (1999) Determination of chlorpyrifos, penconazole, fenarimol, vinclozolin and metalaxyl in grapes, must and wine by on-line microextraction and gas chromatography. J Chromatogr A 833(1):43–51. https://doi.org/10.1016/s0021-9673(98)00860-7
Paleologos EK, Giokas DL, Karayannis MI (2005) Micelle-mediated separation and cloud-point extraction. TrAC Trends Anal Chem 24(5):426–436. https://doi.org/10.1016/j.trac.2005.01.013
Proenca P, Marques EP, Teixeira H, Castanheira F, Barroso M, Avila S, Vieira D (2003) A fatal forensic intoxication with fenarimol: analysis by HPLC/DAD/MSD. Forensic Sci Int 133(1–2):95–100. https://doi.org/10.1016/S0379-0738(03)00054-9
Quina FH, Hinze WL (1999) Surfactant-mediated cloud point extractions: an environmentally benign alternative separation approach. Ind Eng Chem Res 38(11):4150–4168. https://doi.org/10.1021/ie980389n
Ridgway K, Lalljie SP, Smith RM (2007) Sample preparation techniques for the determination of trace residues and contaminants in foods. J Chromatogr A 1153(1):36–53. https://doi.org/10.1016/j.chroma.2007.01.134
Rietveld R, Quirijns J (1994) On-line liquid chromatography-gas chromatography for determination of fenarimol in fruiting vegetables. J Chromatogr A 683(1):151–155. https://doi.org/10.1016/S0021-9673(94)89111-7
Safdarian M, Hashemi P, Ghiasvand A (2021) A fast and simple method for determination of β-carotene in commercial fruit juice by cloud point extraction-cold column trapping combined with UV–Vis spectrophotometry. Food Chem 343:128481. https://doi.org/10.1016/j.foodchem.2020.128481
Samaddar P, Sen K (2014) Cloud point extraction: a sustainable method of elemental preconcentration and speciation. J Ind Eng Chem 20(4):1209–1219. https://doi.org/10.1016/j.jiec.2013.10.033
Santalad A, Srijaranai S, Burakham R, Glennon JD, Deming RL (2009) Cloud-point extraction and reversed-phase high-performance liquid chromatography for the determination of carbamate insecticide residues in fruits. Anal Bioanal Chem 394:1307–1317. https://doi.org/10.1007/s00216-009-2663-6
Seebunrueng K, Santaladchaiyakit Y, Soisungnoen P, Srijaranai S (2011) Catanionic surfactant ambient cloud point extraction and high-performance liquid chromatography for simultaneous analysis of organophosphorus pesticide residues in water and fruit juice samples. Anal Bioanal Chem 401:1703. https://doi.org/10.1007/s00216-011-5214-x
Sikalos TI, Paleologos EK (2005) Cloud point extraction coupled with microwave or ultrasonic assisted back extraction as a preconcentration step prior to gas chromatography. Anal Chem 77(8):2544–2549. https://doi.org/10.1021/ac048267u
Sun C, Liu W, Zhao P (2014) Micelle-mediated extraction and cloud point preconcentration of chlorophylls from spinach. Sep Sci Technol 49:2921–2926. https://doi.org/10.1080/01496395.2014.948557
Sürücü B, Ulusoy HI, Ulusoy S, Demir Ö, Gülle S (2022) Application of cloud point extraction for residues of chloramphenicol and amoxicillin in milk samples by HPLC–DAD. Eur Food Res Technol 248:437–445. https://doi.org/10.1007/s00217-021-03889-6
Tang X, Zhu D, Huai W, Zhang W, Fu C, Xie X, Quan S, Fan H (2017) Simultaneous extraction and separation of flavonoids and alkaloids from Crotalaria sessiliflora L. by microwave-assisted cloud-point extraction. Sep Purif Technol 175:266–273. https://doi.org/10.1016/j.seppur.2016.11.038
Tudi M, Daniel Ruan H, Wang L, Lyu J, Sadler R, Connell D, Chu C, Phung DT (2021) Agriculture development, pesticide application and its impact on the environment. Int J Environ Res Public Health 18:1112. https://doi.org/10.3390/ijerph18031112
Ulusoy Hİ, Köseoğlu K, Kabir A, Ulusoy S, Locatelli M (2020) Fabric phase sorptive extraction followed by HPLC-PDA detection for the monitoring of pirimicarb and fenitrothion pesticide residues. Microchim Acta 187:337. https://doi.org/10.1007/s00604-020-04306-7
Vinggaard AM, Jacobsen H, Metzdorff SB, Andersen HR, Nellemann C (2005) Anti androgenic effects in short-term in vivo studies of the fungicide fenarimol. Toxicology 207(1):21–34. https://doi.org/10.1016/j.tox.2004.08.009
Xie M, Hao X, Jiang X, Liu W, Liu T, Zheng H, Wang M (2021) Ultrasound-assisted dual-cloud point extraction with high-performance liquid chromatography-hydride generation atomic fluorescence spectrometry for mercury speciation analysis in environmental water and soil samples. J Sep Sci 44(12):2457–2464. https://doi.org/10.1002/jssc.202100088
Xing W, Chen L, Zhang F (2014) Separation of camptothecin from Camptotheca acuminate samples using cloud point extraction. Anal Methods 6:3644–3650. https://doi.org/10.1039/c3ay42289e
Yan H, Wang H, Qiao J, Yang G (2011) Molecularly imprinted matrix solidphase dispersion combined with dispersive liquid–liquid microextraction for the determination of four Sudan dyes in egg yolk. J Chromatogr A 1218(16):2182–2188. https://doi.org/10.1016/j.chroma.2011.02.042
Yang F, Wang Y, Liu S, He C, Tao X, Deng H, Tang G, Bian Z, Fan Z (2020) A green and effective method for the determination of metalaxyl enantiomers in tobacco and soil by supercritical fluid chromatography-tandem mass spectrometry. Chirality 32(5):505–514. https://doi.org/10.1002/chir.23184
Zhang H, Zhang A, Huang M, Yu W, Li Z, Wu S, Zheng K, Zhang K, Hu D (2018) Simultaneous determination of boscalid and fludioxonil in grape and soil under field conditions by gas chromatography/tandem triple quadrupole mass spectrometry. Biomed Chromatogr 32:e4091. https://doi.org/10.1002/bmc.4091
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Makarchuk, I.S., Klovak, V.O., Levchyk, V.M. et al. Cloud point extraction coupled with ultrasonic-assisted back-extraction for the determination of metalaxyl, fludioxonil and fenarimol in fruits by gas chromatography with flame ionization detection. Chem. Pap. 76, 7575–7584 (2022). https://doi.org/10.1007/s11696-022-02431-6
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DOI: https://doi.org/10.1007/s11696-022-02431-6