CCD-Optimized UA-DMSPE Combined with DFT Assisted Selection of a Novel Anthraquinone-Based Sorbent for Pb(II) and Cd(II) Determination in Rice and Paddy Soil

Mumcu T., Öncüoğlu S., Mumcu A., Yılmaz Ü.

ACS OMEGA, cilt.1, sa.1, ss.1-29, 2026 (SCI-Expanded, Scopus)

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 1 Sayı: 1
  • Basım Tarihi: 2026
  • Doi Numarası: 10.1021/acsomega.6c05694
  • Dergi Adı: ACS OMEGA
  • Derginin Tarandığı İndeksler: Scopus, Science Citation Index Expanded (SCI-EXPANDED), Chemical Abstracts Core, Directory of Open Access Journals
  • Sayfa Sayıları: ss.1-29
  • Dokuz Eylül Üniversitesi Adresli: Evet

Özet

In this study, a novel ultrasound-assisted dispersive micro

solid-phase extraction (UA-DMSPE) method coupled with flame

atomic absorption spectrometry (FAAS) was developed for the rapid,

reliable, low-cost, and environmentally friendly determination of Pb(II)

and Cd(II) ions in rice and paddy soil samples. Three novel

anthraquinone-derived ligands, not previously reported in the literature,

were synthesized and their metal-binding behaviors were evaluated

through density functional theory (DFT) calculations. Based on

Frontier molecular orbital (FMO), molecular electrostatic potential

(MEP), and global reactivity descriptor analyses, Derivative 2, exhibiting

the lowest HOMO−LUMO energy gap (ΔE = 2.1284 eV) together

with the highest softness (σ = 347.8739) and electrophilicity index (ω =

28.2323), was identified as the most promising ligand for Pb(II) and

Cd(II) coordination. Accordingly, Derivative 2 was selected and loaded onto silica to prepare a novel anthraquinone-functionalized

sorbent and employed throughout all experimental studies. The principal parameters affecting extraction efficiency were optimized

using a six-factor central composite design (CCD) coupled with response surface methodology (RSM), enabling statistical

evaluation of the relationships between experimental variables and extraction recovery. Under optimized conditions, the developed

method exhibited low limits of detection of 0.19 and 0.28 μg L−1 for Pb(II) and Cd(II), respectively, wide linear working ranges

(0.8−500 and 1.0−500 μg L−1), and satisfactory precision (%RSD < 2.2). The proposed method demonstrated high tolerance

toward coexisting ions and satisfactory recovery values in rice and paddy soil samples. Moreover, the simultaneous evaluation of rice

and paddy soil samples enabled a reliable assessment of the potential transfer of heavy metals from soil to plant systems. The

environmental performance of the proposed method was assessed using Analytical Eco-Scale, GAPI, and AGREE metrics,

demonstrating high environmental compatibility owing to low reagent consumption, solvent-free operation, and minimal waste

generation (AGREE score ≈ 0.84). Overall, the developed method combines DFT-assisted sorbent selection, CCD-based

optimization, high selectivity, low detection limits, and strong green analytical performance, providing an effective and reliable

analytical platform for the determination of Pb(II) and Cd(II) in rice and paddy soil samples.