Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness Evaluation

An ultrasound-assisted dispersive liquid–liquid microextraction (DLLME) method was developed to concentrate and quantify rare earth elements (REEs) (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in acidic aqueous solutions. Tetrachloroethylene (PCE) was used as the diluent, di-(...

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Main Authors: Milica Delić, Mirjana Ristić, Maja Đolić, Aleksandra Perić-Grujić, Antonije Onjia
Format: Article
Language:English
Published: MDPI AG 2025-01-01
Series:Metals
Subjects:
Online Access:https://www.mdpi.com/2075-4701/15/1/52
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author Milica Delić
Mirjana Ristić
Maja Đolić
Aleksandra Perić-Grujić
Antonije Onjia
author_facet Milica Delić
Mirjana Ristić
Maja Đolić
Aleksandra Perić-Grujić
Antonije Onjia
author_sort Milica Delić
collection DOAJ
description An ultrasound-assisted dispersive liquid–liquid microextraction (DLLME) method was developed to concentrate and quantify rare earth elements (REEs) (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in acidic aqueous solutions. Tetrachloroethylene (PCE) was used as the diluent, di-(2-ethyl hexyl) phosphoric acid (D2EHPA) as the extracting agent, and acetone as the dispersant solvent. The method was optimized at pH = 2.3, T = 25 °C, and V<sub>S</sub> = 400 µL of a PCE ÷ D2EHPA mixture (10 ÷ 1) using the response surface methodology (RSM) with a Box–Behnken design. Under optimal conditions, the method proved efficient for the DLLME of most REEs (Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), where the achieved recoveries were in the range of 61–109%, while relative standard deviations were in the range 11–28%. The proposed method was applied to recover REEs from real coal ash leachate samples. A greenness evaluation using the Green Analytical Procedure Index (GAPI), Analytical GREEnness (AGREE), and Analytical Eco-Scale (AES) methodologies revealed acceptable metric scores of 74, 0.61, and 26.6–79.8, respectively.
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spelling doaj-art-daa23aa804c44c4a92c2c098af4edc132025-01-24T13:41:31ZengMDPI AGMetals2075-47012025-01-011515210.3390/met15010052Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness EvaluationMilica Delić0Mirjana Ristić1Maja Đolić2Aleksandra Perić-Grujić3Antonije Onjia4Faculty of Technology and Metallurgy, University of Belgrade, 11120 Belgrade, SerbiaFaculty of Technology and Metallurgy, University of Belgrade, 11120 Belgrade, SerbiaFaculty of Technology and Metallurgy, University of Belgrade, 11120 Belgrade, SerbiaFaculty of Technology and Metallurgy, University of Belgrade, 11120 Belgrade, SerbiaFaculty of Technology and Metallurgy, University of Belgrade, 11120 Belgrade, SerbiaAn ultrasound-assisted dispersive liquid–liquid microextraction (DLLME) method was developed to concentrate and quantify rare earth elements (REEs) (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in acidic aqueous solutions. Tetrachloroethylene (PCE) was used as the diluent, di-(2-ethyl hexyl) phosphoric acid (D2EHPA) as the extracting agent, and acetone as the dispersant solvent. The method was optimized at pH = 2.3, T = 25 °C, and V<sub>S</sub> = 400 µL of a PCE ÷ D2EHPA mixture (10 ÷ 1) using the response surface methodology (RSM) with a Box–Behnken design. Under optimal conditions, the method proved efficient for the DLLME of most REEs (Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), where the achieved recoveries were in the range of 61–109%, while relative standard deviations were in the range 11–28%. The proposed method was applied to recover REEs from real coal ash leachate samples. A greenness evaluation using the Green Analytical Procedure Index (GAPI), Analytical GREEnness (AGREE), and Analytical Eco-Scale (AES) methodologies revealed acceptable metric scores of 74, 0.61, and 26.6–79.8, respectively.https://www.mdpi.com/2075-4701/15/1/52REEscoal ash leachateDLLMED2EHPABox–Behnkenresponse surface methodology
spellingShingle Milica Delić
Mirjana Ristić
Maja Đolić
Aleksandra Perić-Grujić
Antonije Onjia
Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness Evaluation
Metals
REEs
coal ash leachate
DLLME
D2EHPA
Box–Behnken
response surface methodology
title Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness Evaluation
title_full Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness Evaluation
title_fullStr Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness Evaluation
title_full_unstemmed Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness Evaluation
title_short Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness Evaluation
title_sort dispersive liquid liquid chelate microextraction of rare earth elements optimization and greenness evaluation
topic REEs
coal ash leachate
DLLME
D2EHPA
Box–Behnken
response surface methodology
url https://www.mdpi.com/2075-4701/15/1/52
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AT majađolic dispersiveliquidliquidchelatemicroextractionofrareearthelementsoptimizationandgreennessevaluation
AT aleksandrapericgrujic dispersiveliquidliquidchelatemicroextractionofrareearthelementsoptimizationandgreennessevaluation
AT antonijeonjia dispersiveliquidliquidchelatemicroextractionofrareearthelementsoptimizationandgreennessevaluation