Abstract
A simple and rapid method for determination of azinphos-methyl, parathion-methyl and ethoprofos, group of organophosphorus pesticides in wastewater matrices, is presented. A chemometric approach for the optimisation of vortex-assisted dispersive liquid–liquid microextraction experimental conditions prior to liquid chromatography–mass spectrometry detection was applied. In this method, a high-density organic solvent (chloroform) was used as the extractant, with acetone as the disperser solvent. Vortexing was applied prior to centrifugation for phase separation of the organic phase (sedimented layer of extractant) and the aqueous layer. A two-level full factorial design (24) was employed initially for the screening process, and final optimisation of the significant parameters was performed using response surface methodology based on central composite design. The method performance characteristics investigated included linear dynamic range (LDR, 5–100 µg L−1) with a good correlation coefficient (> 0.999). The method precision expressed as intra-day and inter-day relative standard deviation (%RSD) was in the range of 7.8–8.2% and 8.1–9.4%, respectively. The influence of matrix was found to be negligible with recoveries ranging from 99.9 to 106.7%. The proposed method was then applied in real wastewater samples. Extraction recoveries performed at two spiking levels (25 and 100 µg L−1) in untreated (influent) and treated (effluent) wastewater matrices ranged between 94.95 and 119.47%.
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References
Baugros J-B, Giroud B, Dessalces G, Grenier-Loustalot M-F, Cren-Olivé C (2008) Multiresidue analytical methods for the ultra-trace quantification of 33 priority substances present in the list of REACH in real water samples. Anal Chim Acta 607:191–203. https://doi.org/10.1016/j.aca.2007.11.036
Berijani S, Assadi Y, Anbia M, Hosseini M-RM, Aghaee E (2006) Dispersive liquid–liquid microextraction combined with gas chromatography-flame photometric detection: very simple, rapid and sensitive method for the determination of organophosphorus pesticides in water. J Chromatogr A 1123:1–9. https://doi.org/10.1016/j.chroma.2006.05.010
Brito NM, Navickiene S, Polese L, Jardim EFG, Abakerli RB, Ribeiro ML (2002) Determination of pesticide residues in coconut water by liquid–liquid extraction and gas chromatography with electron-capture plus thermionic specific detection and solid-phase extraction and high-performance liquid chromatography with ultraviolet detection. J Chromatogr A 957:201–209. https://doi.org/10.1016/S0021-9673(02)00351-5
Cai Z, Wang D, Ma WT (2004) Gas chromatography/ion trap mass spectrometry applied for the analysis of triazine herbicides in environmental waters by an isotope dilution technique. Anal Chim Acta 503:263–270. https://doi.org/10.1016/j.aca.2003.10.038
Cháfer-Pericás C, Herráez-Hernández R, Campíns-Falcó P (2007) In-tube solid-phase microextraction-capillary liquid chromatography as a solution for the screening analysis of organophosphorus pesticides in untreated environmental water samples. J Chromatogr A 1141:10–21. https://doi.org/10.1016/j.chroma.2006.11.105
Dimpe KM, Mpupa A, Nomngongo PN (2018) Microwave-assisted solid phase extraction for separation preconcentration sulfamethoxazole in wastewater using tyre based activated carbon as solid phase material prior to spectrophotometric determination. Spectrochim Acta Part A Mol Biomol Spectrosc 188:341–348. https://doi.org/10.1016/j.saa.2017.07.039
Farajzadeh MA, Bahram M, Vardast MR, Bamorowat M (2011) Dispersive liquid-liquid microextraction for the analysis of three organophosphorus pesticides in real samples by high-performance liquid chromatography–ultraviolet detection and its optimization by experimental design. Microchim Acta 172:465–470. https://doi.org/10.1007/s00604-010-0451-9
Gervais G, Brosillon S, Laplanche A, Helen C (2008) Ultra-pressure liquid chromatography–electrospray tandem mass spectrometry for multiresidue determination of pesticides in water. J Chromatogr A 1202:163–172. https://doi.org/10.1016/j.chroma.2008.07.006
Hamedi R, BG Aghaie A, Hadjmohammadi MR (2018) Magnetic core micelles as a nanosorbent for the efficient removal and recovery of three organophosphorus pesticides from fruit juice and environmental water samples. J Sep Sci 41:2037–2045. https://doi.org/10.1002/jssc.201701090
Jiménez JJ, Bernal JL, Nozal MJd, Alonso C (2004) Liquid-liquid extraction followed by solid-phase extraction for the determination of lipophilic pesticides in beeswax by gas chromatography–electron-capture detection and matrix-matched calibration. J Chromatogr A 1048:89–97. https://doi.org/10.1016/j.chroma.2004.07.034
John H, Worek F, Thiermann H (2008) LC-MS-based procedures for monitoring of toxic organophosphorus compounds and verification of pesticide and nerve agent poisoning. Anal Bioanal Chem 391:97–116. https://doi.org/10.1007/s00216-008-1925-z
Khalili-Zanjani MR, Yamini Y, Yazdanfar N, Shariati S (2008) Extraction and determination of organophosphorus pesticides in water samples by a new liquid phase microextraction–gas chromatography-flame photometric detection. Anal Chim Acta 606:202–208. https://doi.org/10.1016/j.aca.2007.11.032
Liang P, Guo L, Liu Y, Liu S, Zhang T-z (2005) Application of liquid-phase microextraction for the determination of phoxim in water samples by high-performance liquid chromatography with diode array detector. Microchem J 80:19–23. https://doi.org/10.1016/j.microc.2004.07.004
Liu Y, Zhang C, Liao X, Luo Y, Wu S, Wang J (2015) Hydrolysis mechanism of methyl parathion evidenced by Q-Exactive mass spectrometry. Environ Sci Pollut Res 22:19747–19755. https://doi.org/10.1007/s11356-015-5169-0
Matuszewski B, Constanzer M, Chavez-Eng C (2003) Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC − MS/MS. Anal Chem 75:3019–3030. https://doi.org/10.1021/ac020361s
Nagaraju D, Huang S-D (2007) Determination of triazine herbicides in aqueous samples by dispersive liquid–liquid microextraction with gas chromatography–ion trap mass spectrometry. J Chromatogr A 1161:89–97. https://doi.org/10.1016/j.chroma.2007.05.065
Peyrovi M, Hadjmohammadi M (2017) Alkanol-based supramolecular solvent microextraction of organophosphorus pesticides and their determination using high-performance liquid chromatography. J Iran Chem Soc 14:995–1004. https://doi.org/10.1007/s13738-017-1049-5
Rakić T, Kasagić-Vujanović I, Jovanović M, Jančić-Stojanović B, Ivanović D (2014) Comparison of full factorial design, central composite design, and box-Behnken design in chromatographic method development for the determination of fluconazole and its impurities. Anal Lett 47:1334–1347. https://doi.org/10.1080/00032719.2013.867503
Rezaee M, Assadi Y, Milani Hosseini M-R, Aghaee E, Ahmadi F, Berijani S (2006) Determination of organic compounds in water using dispersive liquid–liquid microextraction. J Chromatogr A 1116:1–9. https://doi.org/10.1016/j.chroma.2006.03.007
Rezaee M, Yamini Y, Faraji M (2010) Evolution of dispersive liquid–liquid microextraction method. J Chromatogr A 1217:2342–2357. https://doi.org/10.1016/j.chroma.2009.11.088
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
Sereshti H, Karimi M, Samadi S (2009) Application of response surface method for optimization of dispersive liquid–liquid microextraction of water-soluble components of Rosa damascena Mill. essential oil. J Chromatogr A 1216:198–204. https://doi.org/10.1016/j.chroma.2008.11.081
Snyder LR, Kirkland JJ, Glajch JL (2012) Practical HPLC method development. Wiley, Hoboken
Soisungnoen P, Burakham R, Srijaranai S (2012) Determination of organophosphorus pesticides using dispersive liquid–liquid microextraction combined with reversed electrode polarity stacking mode—micellar electrokinetic chromatography. Talanta 98:62–68. https://doi.org/10.1016/j.talanta.2012.06.043
Stalikas C, Fiamegos Y, Sakkas V, Albanis T (2009) Developments on chemometric approaches to optimize and evaluate microextraction. J Chromatogr A 1216:175–189. https://doi.org/10.1016/j.chroma.2008.11.060
Tankiewicz M, Fenik J, Biziuk M (2010) Determination of organophosphorus and organonitrogen pesticides in water samples. Trends Analyt Chem 29:1050–1063. https://doi.org/10.1016/j.trac.2010.05.008
Tian F, Liu W, Fang H, An M, Duan S (2014) Determination of six organophosphorus pesticides in water by single-drop microextraction coupled with GC-NPD. Chromatographia 77:487–492. https://doi.org/10.1007/s10337-013-2609-1
Wu C, Liu H, Liu W, Wu Q, Wang C, Wang Z (2010) Determination of organophosphorus pesticides in environmental water samples by dispersive liquid–liquid microextraction with solidification of floating organic droplet followed by high-performance liquid chromatography. Anal Bioanal Chem 397:2543–2549. https://doi.org/10.1007/s00216-010-3790-9
**a J, **ang B, Zhang W (2008) Determination of metacrate in water samples using dispersive liquid–liquid microextraction and HPLC with the aid of response surface methodology and experimental design. Anal Chim Acta 625:28–34. https://doi.org/10.1016/j.aca.2008.07.020
Yin Q, Zhu Y, Yang Y (2018) Dispersive liquid–liquid microextraction followed by magnetic solid-phase extraction for determination of four parabens in beverage samples by ultra-performance liquid chromatography–tandem mass spectrometry. Food Anal Method 11:797–807. https://doi.org/10.1007/s12161-017-1051-7
Zhou Q, Bai H, **e G, **ao J (2008) Trace determination of organophosphorus pesticides in environmental samples by temperature-controlled ionic liquid dispersive liquid-phase microextraction. J Chromatogr A 1188:148–153. https://doi.org/10.1016/j.chroma.2008.02.094
Zohrabi P, Shamsipur M, Hashemi M, Hashemi B (2016) Liquid-phase microextraction of organophosphorus pesticides using supramolecular solvent as a carrier for ferrofluid. Talanta 160:340–346. https://doi.org/10.1016/j.talanta.2016.07.036
Acknowledgements
The authors acknowledge the University of Johannesburg and Water Research Commission (WRC) Project No. K5/2563 for funding of this work and for providing scholarship funds to Vallerie A. Muckoya to pursue her PhD programme. Professor Patrick Njobeh from Food and Biotechnology Department, University of Johannesburg, Dr Riaan Meyer and Mr Darryl Harris from Shimadzu South Africa are also acknowledged for their technical assistance.
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Muckoya, V.A., Nomngongo, P.N. & Ngila, J.C. Determination of organophosphorus pesticides in wastewater samples using vortex-assisted dispersive liquid–liquid microextraction with liquid chromatography–mass spectrometry. Int. J. Environ. Sci. Technol. 17, 2325–2336 (2020). https://doi.org/10.1007/s13762-020-02625-z
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DOI: https://doi.org/10.1007/s13762-020-02625-z