Application of The Principles of Green Chemistry in Residues Analysis of Pesticide Chemicals in Water: 20years Experiences in Egypt
M Khalifa1*, M Abbassy2, A Massoud1*
1 Kafr El Sheikh University, Faculty of Agriculture, Department of Pesticides Chemistry and Toxicology, Kafr El Sheikh, Egypt.
2 Damanhour University, Faculty of Agriculture, Department of Plant Protection, Damanhour, Egypt.
*Corresponding Author:M Khalifa, Drug and Food Quality Control Laboratories, Ministry of Health, Kuwait, Tel: 1810005; Fax: 1810005; E-mail: email@example.com
Citation: M Khalifa, M Abbassy, A Massoud (2020) Application of The Principles of Green Chemistry in Residues Analysis of Pesticide Chemicals in Water: 20years Experiences in Egypt. Pharmacol biomol res 3 (1): 114.
Received: August 10, 2020; Accepted: September 18, 2020; Published: September 22, 2020.
Residues analysis of pesticide chemicals in water is necessary for solving various environmental problems, as natural water are usually contaminated with a large number of these chemicals . Analysis of these chemicals in water usually is carried out using GC, HPLC, GC-MS and HPLC-MS and required ppb levels [1-3]. Analysis with such low levels is complicating problems which can be solved by using a concentration step (trace enrichment for residues of pesticide chemicals) prior to the chromatographic analysis. Before 1989, liquid-liquid extraction (LLE) as a tool for trace enrichment was frequently used in our laboratories for analysis of pesticide residues in water samples. In LLE there are some problems such as: a large sample volume may have be processed to yield analyses concentration to be sufficient for chromatographic detection, it requires large amounts from extraction solvents (generate a waste from toxic solvents), it is laborious, slow, difficult to automate (energy consuming) and it gives different extraction efficiencies for various compounds, finally LLE is environmentally friendless. Because of the increasing demand for eco-friendly methods for trace enrichment of pesticides residues from water samples is a major incentive to improve the classical procedures which have been mentioned previously and is an important step on the way of using "greener" analytical methods for analysis of pesticides residues in water. Considering the previously mentioned problems we present here a short review about some eco-friendly procedures that have been developed, validated and elaborated in our laboratories science 1989 for trace enrichment of pesticide residues from water samples. These procedures such as micro liquid liquid extraction ( mLLE) and solid phase extraction (SPE, using different sorbent materials and different formats, such as: porous polymer Amberlite XAD2 (bulk form packed in glass column, Figure 1. [4,5], C18bonded silica cartridges , graphitized carbon black cartridges(GBC) and C 18 Empore membrane disk, Figure 2 and Figure 3).
Figure 1: Schematic diagram showing SPE using porous polymer Amberlite XAD2 (bulk form packed in glass column) for extractions of pesticides residues from water samples under investigations.
Figure 2: Schematic diagram showing steps involved in SPE using Empore disk C-18 for trace enrichment of pesticides residues in water samples under investigations.
Figure 3: Schematic diagram showing apparatus for Empore Disk- C 18 SPE technique for trace enrichment of pesticide residues in water samples under investigations.
An analytical method for analysis of 15 chlorophenoxy acetic acids herbicides residues in water based on amber lite XAD2 as SPE sorbent for trace enrichment was developed and validated by [4,5]. Residue analysis for 13organochlrine insecticides (OC) in surface water of Tanta area (Figure 4), was done using Amber lite XAD2 as SPE sorbent for trace enrichment . Residues analysis for 10 OC and 2 organophosphates (OPs) in surface waters in some agricultural irrigation canal and some adjacent irrigation drains in Kafr El- Sheikh area, Figure 4B, were done using C18 cartridge as SPE sorbent for trace enrichment by [7,8].
Graphitized carbon black cartridges (GPC) were used as efficient SPE sorbent for trace enrichment 0f 10 OPs (polar compounds) in surface waters . C 18 Empore membrane disk, Figure 2, were used by  for analysis of 10 OCs in surface and tap waters.
C18 bonded silica cartridges, C 18 Empore membrane disc-C18 bonded silica, Figure 3 and Micro liquid extraction (mLLE), Figure 5 were used by [11-13] for analysis of 18 OCs and 10 OPs in surface and drainage waters of agricultural intensive area at Damanhur, El-Behira Governorate (Figure 4C) Egypt. For mLLE, a handmade extraction apparatus as shown in Figure 5 was constructed according to . For water samples extraction a 500 mL of samples were transferred into a 500-mL separating funnel and then 0.5 mL of n-hexane was added, the mixture was mechanically shaken for 2 min.
The supernatant organic phase was raised up to the bottleneck of the separating funnel (Figure 5) by raising a communicating vessel filled with deionized water. Raising of the level ensures the collection of the liquid with a Pasteur micropipette, the extract being thus ready for analysis.
Figure 4: Areas map for sampling of water.
Figure 5: Handmade apparatus for mLLE and trace enrichment of pesticide residues in water samples under investigations.
For qualitative and quantification analysis in our laboratories GC-ECD/FID/FPD, GC-MS (ITD) were used as analytical tools. On the basis of these analytical tools and the previously mentioned procedures for trace enrichment, several muliti- residual analytical methods were developed and validated in our laboratories according to the international rules . These analytical methods were simple and demonstrates good accuracy, sensitivity selectivity, precision to be applied successfully for analysis of pesticide residues of some Ops and OCs in water samples [4-13]. The resulting residues data were compared with the maximum residual levels (MRLs) set by WHO .
In conclusion our analytical methods are fulfills the principles of green chemistry (green analytical chemistry) according to [16,17], we are using a small amounts of solvent ,waste generation is low, doing fast and easy, save time and money, safe for analytsts, using multiresidues technique is consuming low energy, in our laboratories the overall performance of analysis was improved. Finally it can be said that our analytical methods for residues analysis of pesticide chemicals in water samples in our laboratories is suitable for sustainable development of agriculture in Egypt.
WHO (1993) Guidelines for drinking water quality, 2ndEdition, Geneva.
PAM (1994) Pesticides Analytical Manual, U.S Food and Drug Administration, U.S. Department of Health and Human Services, Washington, DC, USA.
Khalifa MA, El-Mmeshaan M, Al-Sharifi FA, Abbassy MA, Alkalf B, et al. (2002) New trends in analysis ,of organic chemical pollutants in water, Kuwait Environmental Protection Society , Book No.11,ISBN 99906-607-3-5 (in arabic with english summary).
Khalifa MA, Nolte J, Linscheid M (1989a) Analysis of chlorophenoxy acetic acid herbicides in water. 1- - Gas chromatography- - ion trap detector (GC- ITD) as analytical tool.. 2nd Int.. Symposium on New Trends In chemistry (The Role of Analytical Chemistry In National Development In Egypt), January 2-7, 1989, Cairo Univ., Cairo, Egypt.
Khalifa MA, Nolte J, Linscheid M (1989b) Analysis of chlorophenoxy acetic acid herbicides in water. 2- Development a method for multiresidue analysis in water at pictogram levels. 2nd Int. Symposium on New Trends In chemistry (The Role of Analytical Chemistry In National Development In Egypt), January 2-7, 1989, Cairo Univ, Cairo, Egypt.
Khalifa MA (1991) Residue analysis of pesticide chemicals in surface water: 1- Organochlorine insecticides in surface water of El-Kassed irrigation canal at Tanta region, Egypt. Egyptian J.Apple.Sci 6: 654-669.
Hamed SA (1997) Toxicological studies on some side effects on some environmental pollutants in water. M Sc thesis supervised by Masoud A . & Khalifa M.A. (1992-1997), Department of Pesticides Chemistry and Toxicology, Faculty of Agriculture, Tanta University, Egypt (now Kafr El -Sheikh University, Kafr El -Sheikh).
Khalifa MA, Massoud A, El-Diken T, Al-Khulifah B, Hamed SA, et al. (2000) Residues analysis of pesticide chemicals in surface water . Residues level of some insecticides in Meet Yazid agricultural irrigation canal and some adjacent irrigation drains in Kafr El-sheikh governorate, Egypt. Manusoura J.Forensic.Med.Clin.Toxicol III: 129-150.
Al-Sharifi FA, Al-Mutairi NZ, Al Shamari SB, Dawood W, Khalifa MA, et al. (2006) A multi residue analysis of ten organophosphorous insecticides in water based on solid phase extraction and Gas Chromatography- Mass Spectrometry. J.Agric. & Env. Sci. Alex. Univ 5: 59-77.
El-Mmeshaan M, Al-Sharifi FA, Khalifa MA (2002) Analysis of ten organochlorine chemicals in water using solid phase extraction technique and Gas-Chromatography Mass Spectrometry. J.Agric. & Env. Sci.. Alex. Univ 1: 20-29.
Noor El- Deen E (2010) Toxicity of pesticide residues in some of the water resources in El-Behira Governorate, Egypt .MSc thesis., supervised by Abbassy, M.A., M.A. Marzouk and M.A. Khalifa (2007-2010 ), Faculty of Agriculture at Damanhur, Alexandria University, Egypt.
Abbassy MA, Marzouk MA, Al-Khulifah B, Khalifa MA, Noor – Eldeen E, et al. (2010) Monitoring of pesticide residues in drainage, canal and tap water at Damanhur, El-Behira Governorate, Egypt. J. Agric. & Env. Sci. Dam. Univ. 9: 88-103.
Noor El-Deen E (2017) Studies on analysis and toxicity of pesticide residues in water environment. PhD thesis supervised by Abbassy M.A. & Khalifa M. A. (2010-2017), Faculty of Agriculture, Damanour University, Damanhour, Egypt
Fernandez - Gutierrez A, Martinez-Vidal JL, Arrebola-Liebanas FJ, Genozalez-Casado A, Vilchez JL (1998) Determination of endosulfan and some pyrethroides in waters by micro liquid-liquid extraction and GC-MS. Fresenius J.Anal.Chem 360: 568-572.
ICH (2005) International Conference On Harmonization , Q2 R1 . www//ICH.com.
Anstas PT (1998) Green chemistry .Oxford University Press.