Ion-Pair Based Dispersive Liquid-Liquid Microextraction for Spectrophotometric Analysis of Carmoisine in Food: A BAGI and AGREE Study

Authors

  • Araf Ismael Jabbar Ministry of Education, Directorate of Education of Anbar, Iraq
  • Adel Ismael Jabbar Ministry of Education, Directorate of Education of Anbar, Iraq.
  • Arwa Mahmoud Hussain Chemistry Department, College of Science, Mustansiriyah University, Baghdad, Iraq.
  • Ruba Fahmi Abbas Chemistry Department, College of Science, Mustansiriyah University, Baghdad, Iraq.
  • Adrián Fuente-Ballesteros Analytical Chemistry Group (TESEA), I. U. CINQUIMA, Faculty of Sciences, University of Valladolid, Valladolid 47011, Spain https://orcid.org/0000-0003-4150-4611

DOI:

https://doi.org/10.22401/

Keywords:

Microextraction, DLLME, Carmoisine, TTC reagent, AGREE, BAGI

Abstract

This paper discusses the identification of a new dispersive Liquid-liquid microextraction method for evaluating carmoisine dye using spectrophotometry. It has been established that Carmoisine dye is an anionic azo food dye used in the food industry in some countries such as Iraq. This method involves the extraction of carmoisine from aqueous solutions using chloroform as the extraction solvent in a DLLME procedure. Parameters influencing the DLLME efficiency, including pH, type and volume of extraction as well as dispersive solvents (chloroform and ethanol), under a centrifugation conditions, were thoroughly optimized to complete extraction conditions. Moreover, the method showed a linear calibration curve in the range of 1.0-10.0 mg/L. The low values of both the limit of quantification (0.297 mg/L) and the limit of detection (0.099 mg/L) indicate a more sensitive DLLME method. The applicability and environmental impact of the developed method were assessed using the Blue Applicability Grade Index (BAGI) and the Analytical Greenness metric (AGREE), yielding scores of 70.0 and 0.55, respectively, indicating a practical method with moderate adherence to green analytic chemistry principles. The optimized DLLME procedure was successfully applied to the determination of carmoisine dye in various food samples.

References

[1] Chakraborty, A.; Jayaseelan, K. "Analytical quality by design aided RP-HPLC method for the estimation of sunset yellow in commercial food samples employing green ultrasound assisted extraction: Greenness, blueness and whiteness evaluation". Green Anal. Chem., 12, 100183, 2025.

[2] Alahmad, W.; Kaya, S. I.; Cetinkaya, A.; Varanusupakul, P.; Ozkan, S. A. "Green chemistry methods for food analysis: Overview of sample preparation and determination". Adv. Sample Prep., 5, 100053, 2023.

[3] Leulescu, M.; Rotaru, A.; Moanţă, A.; Iacobescu, G.; Pălărie, I.; Cioateră, N.; Rotaru, P. "Azorubine: physical, thermal and bioactive properties of the widely employed food, pharmaceutical and cosmetic red azo dye material". J. Therm. Anal. Calorim., 143, 3945–3967, 2021.

[4] Sultana, S.; Rahman, M. M.; Aovi, F. I.; Jahan, F. I.; Hossain, M. S.; Brishti, S. A.; Sharma, R. "Food color additives in hazardous consequences of human health: An overview". Curr. Trends Med. Chem., 23(14), 1380–1393, 2023.

[5] Miller, M. D.; Steinmaus, C.; Golub, M. S.; Castorina, R.; Thilakartne, R.; Bradman, A.; Marty, M. A. "Potential impacts of synthetic food dyes on activity and attention in children: a review of the human and animal evidence". Environ. Health, 21(1), 45, 2022.

[6] Amchova, P.; Siska, F.; Ruda-Kucerova, J. "Food safety and health concerns of synthetic food colors: an update". Toxics, 12(7), 466, 2024.

[7] Amin, K. A.; Hameid II, H. A.; AbdElsttar, A. H. "Effect of food azo dyes tartrazine and carmoisine on biochemical parameters related to renal, hepatic function and oxidative stress biomarkers in young male rats". Food Chem. Toxicol., 48(10), 2994–2999, 2010.

[8] Alimoradian, A.; Ansari Asl, B.; Asadi, S.; Abdollahi, M.; Moradzadeh, R.; Alimoradian, K.; Khansari, N. "Risk assessment of colorant additives and heavy metal content of jelly products targeting pediatric populations in Arak market, Iran". Iran. J. Toxicol., 19(2), 112-120, 2025.

[9] Karimi, F.; Demir, E.; Aydogdu, N.; Shojaei, M.; Taher, M. A.; Asrami, P. N.; Cheraghi, S. "Advancement in electrochemical strategies for quantification of Brown HT and Carmoisine (Acid Red 14) From Azo Dyestuff class". Food Chem. Toxicol., 165, 113075, 2022.

[10] Lipskikh, O. I.; Korotkova, E. I.; Dorozhko, E. V.; Derina, K. V.; Voronova, O. A. "Voltammetric determination of carmoisine in soft drinks". Inorg. Mater., 53, 1427–1431, 2017.

[11] Chanlon, S.; Joly-Pottuz, L.; Chatelut, M.; Vittori, O.; Cretier, J. L. "Determination of Carmoisine, Allura red and Ponceau 4R in sweets and soft drinks by Differential Pulse Polarography". J. Food Compos. Anal., 18(6), 503–515, 2005.

[12] Chakraborty, A.; Jayaseelan, K. "Eco-Friendly Simultaneous Estimation of Ponceau 4R and Carmoisine Employing an Analytical Quality by Design-Aided RP-HPLC Method in Commercial Food Samples Utilizing a Green Ultrasound-Assisted Extraction Technique". J. - Assoc. Off. Anal. Chem., 107(3), 430–442, 2024.

[13] Iammarino, M.; Mentana, A.; Centonze, D.; Palermo, C.; Mangiacotti, M.; Chiaravalle, A. E. "Chromatographic determination of 12 dyes in meat products by HPLC-UV-DIODE array detection". MethodsX, 6, 856–861, 2019.

[14] Martin, F.; Oberson, J. M.; Meschiari, M.; Munari, C. "Determination of 18 water-soluble artificial dyes by LC–MS in selected matrices". Food Chem., 197, 1249–1255, 2016.

[15] Ryvolová, M.; Táborský, P.; Vrábel, P.; Krásenský, P.; Preisler, J. "Sensitive determination of erythrosine and other red food colorants using capillary electrophoresis with laser-induced fluorescence detection". J. Chromatogr. A, 1141(2), 206–211, 2007.

[16] Kara, D. "Spectrophotometric determination of tartrazine, riboflavine and carmoisine in drinks by zero-order spectrophotometric method using determinant calculation and first derivative spectrophotometric method". Int. J. Chem. Environ. Eng., 2005.

[17] Asadpour-Zeynali, K.; Manafi-Khoshmanesh, S. "Simultaneous standard addition method for novel determination of components in a single step: application in analysis of Sunset yellow and Carmoisine by a spectrophotometric technique". Anal. Methods, 6(15), 6110–6115, 2014.

[18] Saadati, M. "Smartphone-based digital image analysis for determination of some food dyes in commercial products". Food Anal. Methods, 14(11), 2367–2374, 2021.

[19] Antela, K. U.; Sáez-Hernández, R.; Morales-Rubio, Á.;Cervera, M. L.; Luque, M. J. "Smartphone-based procedure to determine content of single synthetic dyes in food using the arata-possetto extraction method".Talanta, 270, 125537, 2024.

[20] Turak, F.; Dinç, M.; Dülger, Ö.;Özgür, M. U. "Four derivative spectrophotometric methods for the simultaneous determination of carmoisine and ponceau 4R in drinks and comparison with high performance liquid chromatography". IInt. J. Anal. Chem., 2014, 650465, 2014.

[21] Karatepe, A.; Akalın, Ç.;Soylak, M. "Spectrophotometric determination of carmoisine after cloud point extraction using Triton X-114". Turk. J. Chem., 41(2), 256–262, 2017.

[22] Pourreza, N.; Ghomi, M. "Simultaneous cloud point extraction and spectrophotometric determination of carmoisine and brilliant blue FCF in food samples". Talanta, 84(1), 240–243, 2011.

[23] Heydari, R.; Hosseini, M.; Zarabi, S. "A simple method for determination of carmine in food samples based on cloud point extraction and spectrophotometric detection". Spectrochim. Acta, Part A, 150, 786–791, 2015.

[24] Güray, T. "A novel method for simultaneous analysis of tartrazine and indigo carmine by cloud point extraction using spectrophotometric technique". Int. J. Chem. Stud., 7(6), 17–23, 2019.

[25] Erek, F. "A comparative study on magnetic solid phase extraction and magnetic colloidal gel based-dispersive solid phase extraction methods for preconcentration of carmoisine (E 122) in food samples". J. Food Compos. Anal., 139, 107091, 2025.

[26] Abbas, R. F.; Hassan, M. J. M.; Rheima, A. M. "Magnetic solid phase extraction for determination of dyes in food and water samples". Indones. J. Chem., 23(4), 1181–1198, 2023.

[27] Mazdeh, F. Z.; Khorrami, A. R.; Moradi-Khatoonabadi, Z.; EsmaeiliAftabdari, F.; Ardekani, M. R. S.; Moghaddam, G.; Hajimahmoodi, M. "Determination of 8 synthetic food dyes by solid phase extraction and reversed-phase high performance liquid chromatography". Trop. J. Pharm. Res., 15(1), 173–181, 2016.

[28] Khan, W. A.; Varanusupakul, P.; Haq, H. U.; Arain, M. B.; Boczkaj, G. "Applications of nanosorbents in dispersive solid phase extraction/microextraction approaches for monitoring of synthetic dyes in various types of samples: A review". Microchem. J., 208, 112419, 2025.

[29] Smirnova, S. V.; Lyskovtseva, K. A.; Pletnev, I. V. "Extraction and determination of synthetic food dyes using tetraalkylammonium based liquid-liquid extraction". Microchem. J., 162, 105833, 2021.

[30] Uzcan, F.; Yilmaz, E.; Soylak, M. "Development and factorial experimental design optimization of deep eutectic solvent‐based microextraction of carmoisine (E122) in candy and water samples". Anal. Lett., 56(13), 2172–2181, 2023.

[31] Amini, P.; Faraji, M. "Development and validation of dispersive liquid-liquid microextraction coupled to spectrophotometry for extraction and determination of carmoisine in foodstuff". Iran. J. Nutr. Sci. Food Technol., 11(1), 95–106, 2016.

[32] Dmitrienko, S. G.; Apyari, V. V.; Tolmacheva, V. V.; Gorbunova, M. V. "Dispersive liquid–liquid microextraction of organic compounds: An overview of reviews". J. Anal. Chem., 75, 1237–1251, 2020.

[33] Snigur, D.; Azooz, E. A.; Zhukovetska, O.; Guzenko, O.; Mortada, W. "Low-density solvent-based liquid-liquid microextraction for separation of trace concentrations of different analytes". TrAC, Trends Anal. Chem., 167, 117260, 2023.

[34] Jabbar, A. I.; Khaleel, A. I.; Thani, M. Z. "Determination of Cefixime inclusion complex with 2-hydroxypropyl-β-cyclodextrin and extraction using DLLME and SIHLLME". J. Univ. Anbar Pure Sci, 17(1), 97-106, 2023.

[35] Kareem, N. K.; Thani, M. Z.; Al-Rawi, K. F. "New microextraction methods for the evaluation of bromhexineHCl in pure and pharmacological formulations". Egypt. J. Chem., 65(4), 209–219, 2022.

[36] Špadina, M.; Dufrêche, J. F.; Pellet-Rostaing, S.; Marčelja, S.; Zemb, T. "Molecular forces in liquid–liquid extraction". Langmuir, 37(36), 10637–10656, 2021.

[37] Campone, L.; Piccinelli, A. L.; Celano, R.; Rastrelli, L. "pH-controlled dispersive liquid–liquid microextraction for the analysis of ionisable compounds in complex matrices: Case study of ochratoxin A in cereals". Anal. Chim. Acta, 754, 61–66, 2012.

[38] Kokosa, J. M. "Selecting an extraction solvent for a greener liquid phase microextraction (LPME) mode-based analytical method". TrAC, Trends Anal. Chem., 118, 238–247, 2019.

[39] Sajid, M.; Alhooshani, K. "Dispersive liquid-liquid microextraction based binary extraction techniques prior to chromatographic analysis: A review". TrAC, Trends Anal. Chem., 108, 167-182, 2018.

[40] Amraei, A.; Niazi, A.; Alimoradi, M.; Hosseini, M. "Cloud point extraction and simultaneous spectrophotometric determination of allura red and carmoisine using wavelet orthogonal signal correction–partial least squares method". J. Anal. Chem., 74, 93–99, 2019.

[41] Aparna, B.; Sudeepa, K.; Eshwari, K.; Md, J.; Reddy, P. R.; Devi, C. S. "Synthesis, structural interpretation, biological activity and DNA cleavage studies of Cu-II ternary complexes of 3-acyl 2-(2'-hydroxy-5-substituted phenyl) benzothiazolines and L-glycine". J. Indian Chem. Soc., 93(2), 133–149, 2016.

[42] Turak, F.; Dinç, M.; Dülger, Ö.;Özgür, M. U. "Four derivative spectrophotometric methods for the simultaneous determination of carmoisine and ponceau 4R in drinks and comparison with high performance liquid chromatography". Int. J. Anal. Chem., 2014, 650465, 2014.

[43] Nguyen, N. V. T.; Nguyen, K. N. H.; Dam, K. T. T.; Vo, H. T. T.; Nguyen, K. A. T.; Kim, K. H. "Simultaneous determination of 11 water-soluble dyes in food products and beverages by high performance liquid chromatography". Int. Food Res. J., 28(1), 120–128, 2021.

[44] Avazpour, M.; Shiri, S.; Delpisheh, A. "Simultaneous determination of Brilliant Blue FCF and carmoisine in food samples by aqueous two-phase system and spectrophometric detection". J. Basic Res. Med. Sci., 1(1), 56–65, 2014.

[45] Sorouraddin, M. H.; Saadati, M.; Mirabi, F. "Simultaneous determination of some common food dyes in commercial products by digital image analysis". J. Food Drug Anal., 23(3), 447–452, 2015.

[46] Peksa, V.; Jahn, M.; Stolcova, L.; Schulz, V.; Proska, J.; Prochazka, M.; Popp, J. "Quantitative SERS analysis of azorubine (E 122) in sweet drinks". Anal. Chem., 87(5), 2840–2844, 2015.

[47] Abbas, R. F.; Hassan, M. J. M.; Rheima, A. M. "Determination of AY 23 dye using magnetic solid-phase extraction coupled with spectrophotometry: Application of greenness and blueness assessment tools". Green Anal. Chem., 12, 100179, 2025.

[48] Manousi, N.; Wojnowski, W.; Płotka-Wasylka, J.; Samanidou, V. "Blue applicability grade index (BAGI) and software: a new tool for the evaluation of method practicality". Green Chem., 25(19), 7598–7604, 2023.

[49] Pena-Pereira, F.; Wojnowski, W.; Tobiszewski, M. "AGREE—Analytical GREEnness metric approach and software". Anal. Chem., 92(14), 10076–10082, 2020.

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Published

2026-03-16

Issue

Vol. 29 No. 1 (2026): March 2026

Section

Mathematics

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Copyright (c) 2026 Araf Ismael Jabbar, Adel Ismael Jabbar, Arwa Mahmoud Hussain, Ruba Fahmi Abbas, Adrián Fuente-Ballesteros

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This work is licensed under a Creative Commons Attribution 4.0 International License.

How to Cite

(1)
Ismael Jabbar, A. .; Ismael Jabbar, A. .; Mahmoud Hussain, A. .; Fahmi Abbas, R. .; Fuente-Ballesteros, A. . Ion-Pair Based Dispersive Liquid-Liquid Microextraction for Spectrophotometric Analysis of Carmoisine in Food: A BAGI and AGREE Study. Al-Nahrain J. Sci. 2026, 29 (1), 42-53. https://doi.org/10.22401/.