Malaysian Journal of Analytical Sciences, Vol 27 No 5 (2023): 956 – 970

EXPERIMENTAL AND THEORETICAL OPTIMIZATION OF EMULSIFICATION LIQUID-LIQUID MICROEXTRACTION FOR DETERMINATION OF HERBICIDES USING FATTY ACID DEEP EUTECTIC SOLVENTS

(Pengoptimuman Secara Eksperimen dan Teori bagi Pengemulsi Mikroekstraksi Cecair-Cecair untuk Penentuan Racun Perosak Menggunakan Pelarut Eutektik Terdalam

Asid Lemak)

Nur Hidayah Sazali, Nur Amanina Ajman, Wan Nazwanie Wan Abdullah, and Nurul Yani Rahim^*

School of Chemical Sciences, Universiti Sains Malaysia, 11800 USM Pulau Pinang, Malaysia

^*Corresponding author: nurulyanirahim@usm.my

Received: 20 July 2023; Accepted: 7 September 2023; Published: 30 October 2023

Abstract

Fatty acid deep eutectic solvents (DES) became known as a promising alternative to traditional organic solvents for various extraction processes. In this study, a hydrophobic DES comprising a mixture of lauric acid ( ) and pelargonic acid ( ) at a molar ratio of 1:3, was utilized to extract 2,4-D and MCPA herbicides from aqueous solutions. FTIR and TGA were utilized in order to characterize the synthesized DES. Emulsification liquid-liquid microextraction (ELLME) technique is employed to enhance the efficiency of extraction. Furthermore, response surface methodology (RSM) was applied to optimize the extraction process of these herbicides while considering parameters such as volume of DES and emulsifying agent and pH. RSM method has various advantages, including its simplicity, fast, low cost, and great extraction efficiency. It also helps in selecting the optimum condition method to analyze the relationship between the variable, where pH 2, 265 μL volume of DES and 200 μL volume of tetrahydrofuran (THF) were the optimal conditions obtained in this study. Under these conditions, the coefficients of determination ( ) were obtained between 65% and 79%. In addition, the results obtained from the experiment are comparable to or closely aligned with RSM, hence there was a good fit between the two methods. These results revealed that the fatty acid-based DES demonstrated remarkable efficiency in extracting 2,4-D and MCPA herbicides as well as contributing to the development of environmentally friendly extraction techniques.

Keywords: response surface methodology, 2,4-Dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, hydrophobic DES, emulsification liquid-liquid microextraction, pesticides

Abstrak

Pelarut eutektik terdalam asid lemak (DES) dikenali sebagai alternatif kepada pelarut organik tradisional untuk digunakan dalam pelbagai proses pengekstrakan. Dalam kajian ini, DES hidrofobik yang terdiri daripada campuran asid laurik ( ) dan asid pelargonik ( ) pada nisbah molar 1:3, telah digunakan untuk mengekstrak racun herba 2,4-D dan MCPA daripada larutan akueus. FTIR dan TGA telah digunakan untuk mengenalpasti DES yang disintesis. Teknik pengekstrakan mikro cecair-cecair pengemulsi (ELLME) digunakan untuk meningkatkan kecekapan pengekstrakan. Tambahan pula, metodologi permukaan tindak balas (RSM) digunakan bertujuan untuk mengoptimumkan proses pengekstrakan racun herba ini dan mempertimbangkan parameter seperti isipadu DES dan agen pengemulsi dan pH. Kaedah RSM ini mempunyai pelbagai kelebihan, termasuk kesederhanaan, pantas, kos rendah, dan kecekapan pengekstrakan yang hebat. RSM juga membantu dalam memilih keadaan kaedah yang optimum untuk menganalisis hubungan antara pembolehubah, di mana pH 2, 265 μL isipadu DES dan 200 μL isipadu tetrahydrofuran (THF) adalah keadaan optimum yang diperolehi dalam kajian ini. Dengan keadaan ini, pekali penentuan ( ) diperoleh antara 65% dan 79%. Di samping itu, keputusan yang diperoleh daripada data eksperimen adalah setanding atau sejajar rapat dengan data RSM, oleh itu terdapat kesesuaian yang baik antara kedua-dua kaedah. Keputusan ini mendedahkan bahawa DES berasaskan asid lemak menunjukkan kecekapan yang luar biasa dalam mengekstrak racun herba 2,4-D dan MCPA serta menyumbang kepada pembangunan teknik pengekstrakan mesra alam.

Kata kunci: metodologi permukaan tindak balas, 2,4-Dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, DES hidrofobik, pengekstrakan mikro cecair-cecair pengemulsi, racun herba

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