Food Analytical Methods

, Volume 13, Issue 1, pp 222–229 | Cite as

Development of Method Based on Dispersive Liquid-Liquid Microextraction Air-Assisted for Multi-Element Determination of Cadmium and Manganese in Sugarcane Spirit (Brazilian cachaça) by FAAS

  • Adrielle S. Fontes
  • Julia C. Romero
  • Leonardo B. Guimarães
  • Erik G. P. da Silva
  • Daniel de C. Lima
  • Fábio Alan C. AmorimEmail author


In this work, a new method was developed for multi-element determination of Cd and Mn in samples of sugarcane spirit (cachaça) by FAAS using the air-assisted dispersive liquid-liquid microextraction (AA-DLLME). After univariate and multivariate optimizations (mixture design), the experimental conditions were as follows: 5.2 mL of sample at pH 8.5, 0.7 mL 10% (w/v) NaCl solution, 120 μL of trichlorethylene (extraction solvent) containing 1-(2-pyridylazo)-2-naphthol (PAN) at 0.05% (w/v) as chelating agent, six cycles of stirring the mixture with a glass syringe, and 3 min of centrifugation. In these conditions, the calibration curve obtained for Cd was Abs = 0.0158CCd + 0.0333, with R2 0.9951 and for Mn was Abs = 0.0011CMn + 0.0142 and R2 0.9911. The limits of detection, enrichment factor, and consumption index were, respectively, 0.51 μg L−1, 79 and 0.07 mL for Cd, and 1.64 μg L−1, 18, and 0.28 mL for Mn. Precision was evaluated at concentrations of 5 and 10 μg L−1, and RSD% (N = 10) was 0.97% and 6.6% for Cd and 2.8% and 4.5% for Mn, respectively. Addition and recovery tests in samples of Brazilian cachaça were performed to evaluate the accuracy, and recoveries were 87% to 120%, with concentrations found between 1.20 and 3.05 μg L−1 for Cd and between 6.98 and 14.4 μg L−1 for Mn. The developed method proved to be sensitive, efficient, simple, fast, and having low reagent consumption, and of applicability not previously reported in the literature.


AA-DLLME Cadmium Manganese Mixture design cachaça 



This research was supported by the Fundação de Amparo à Pesquisa do Estado da Bahia (FAPESB), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Financiadora de Estudos e Projetos (FINEP), and Santa Cruz State University (UESC).

Compliance with Ethics Requirements

Conflict of Interest

Adrielle S. Fontes has received research grants from Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES). Leonardo B. Guimarães has received research grants from Fundação de Amparo à Pesquisa do Estado da Bahia (FAPESB). Erik G. P. da Silva has received research grants from Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq).

Adrielle S. Fontes declares that she has no conflict of interest. Julia A. Romero declares that she has no conflict of interest. Leonardo B. Guimarães declares that he has no conflict of interest. Erik G. P. da Silva declares that he has no conflict of interest. Daniel de C. Lima declares that he has no conflict of interest.

Ethics Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed Consent

Informed consent was obtained from all individual participants included in the study.

Supplementary material

12161_2019_1600_MOESM1_ESM.docx (14 kb)
ESM 1 (DOCX 14 kb)


  1. Al-Saidi HM, Emara AAA (2014) The recent developments in dispersive liquid–liquid microextraction for preconcentration and determination of inorganic analytes. J Saudi Chem Soc 18:745–761. CrossRefGoogle Scholar
  2. Alves VN, Borges SSO, Coelho NMM (2011) Direct zinc determination in brazilian sugar cane spirit by solid-phase extraction using moringa oleifera husks in a flow system with detection by FAAS. Int J Anal Chem 2011:1–8. CrossRefGoogle Scholar
  3. Amorim FAC, Costa VC, Guedes WN, Sá IP, Santos MC, Silva EGP, Lima DC (2016) Multivariate optimization of method of slurry sampling for determination of iron and zinc in starch samples by flame atomic absorption spectrometry. Food Anal Methods 9:1719–1725. CrossRefGoogle Scholar
  4. Amorim FAC, Costa VC, Silva EGP, Lima DC, Jesus RM, Bezerra MA (2017) Multivariate optimization of simple procedure for determination of Fe and Mg in cassava starch employing slurry sampling and FAAS. Food Chem 227:41–47. CrossRefGoogle Scholar
  5. ANVISA – Agência Nacional de Vigilância Sanitária. Resolução RDC N° 42, de 29 de agosto de 2013. Accessed 5 April 2019
  6. Böck FC, Helfer GA, Costa AB, Dessuy MB, Ferrão MF (2018) Rapid determination of ethanol in sugarcane spirit using partial least squares regression embedded in smartphone. Food Anal Methods 11:1951–1957. CrossRefGoogle Scholar
  7. Bortoletto AM, Alcarde AR (2015) Assessment of chemical quality of Brazilian sugar cane spirits and cachaças. Food Control 54:1–6. CrossRefGoogle Scholar
  8. Capobiango M, Oliveira ES, Cardeal ZL (2013) Evaluation of methods used for the analysis of volatile organic compounds of sugarcane (cachaça) and fruit spirits. Food Anal Methods 6:978–988. CrossRefGoogle Scholar
  9. Costa VC, Silva EGP, Lima DC, Franco M, Jesus RM, Bezerra MA, Amorim FAC (2018) Use of mixture design with minimal restrictions to optimize an extraction procedure employing diluted acids assisted by ultrasound and microwave for nutrient element determination in vegetable samples. J Braz Chem Soc 29:1189–1198. CrossRefGoogle Scholar
  10. Do Carmo DR, Bicalho UO, Silveira TF, Dias Filho NL, Paim LL (2013) Determination of copper in different ethanolic matrices using a chloropropyl silica gel modified with a nanostructured cubic octa(3-aminopropyl)octasilsesquioxane. J Chem 2013:1–11. CrossRefGoogle Scholar
  11. El-Shahawi MS, Al-Saidi HM (2013) Dispersive liquid-liquid microextraction for chemical speciation and determination of ultra-trace concentrations of metal ions. Trends Anal Chem 44:12–24. CrossRefGoogle Scholar
  12. Ezoddin M, Abdi K, Esmaeili N (2016) Ultrasound enhanced air-assisted surfactant liquid–liquid microextraction based on the solidification of an organic droplet for the determination of chromium in water, air and biological samples. Microchem J 129:200–204. CrossRefGoogle Scholar
  13. Ezoddin M, Lamei N, Siami F, Abdi K, Karimi MA (2018) Deep eutectic solvent based air assisted ligandless emulsification liquid–liquid microextraction for preconcentration of some heavy metals in biological and environmental samples. Bull Environ Contam Toxicol 101:814–819. CrossRefPubMedGoogle Scholar
  14. Fakhriyan G, Mousavi HZ, Sajjadi SM (2016) One-step determination of lead over a higher linear range by an artificial neural network after air-assisted liquid–liquid microextraction coupled to flame atomic absorption spectrometry. Anal Methods 8:995–1002. CrossRefGoogle Scholar
  15. Farajzadeh MA, Mogaddam MRA (2012) Air-assisted liquid-liquid microextraction method as a novel microextraction technique; application in extraction and preconcentration of phthalate esters in aqueous sample followed by gas chromatography-flame ionization detection. Anal Chim Acta 728:31–38. CrossRefPubMedGoogle Scholar
  16. Franco MOK, Suarez WT, Santos VB (2017a) Digital image method smartphone-based for furfural determination in sugarcane spirits. Food Anal Methods 10:508–515. CrossRefGoogle Scholar
  17. Franco MOK, Suarez WT, Maia MV, Santos VB (2017b) Smartphone application for methanol determination in sugar cane spirits employing digital image-based method. Food Anal Methods 10:2102–2109. CrossRefGoogle Scholar
  18. Kinaree S, Chanthai S (2014) Ultra-trace determination of Pb(II) and Cd(II) in drinking water and alcoholic beverages using homogeneous liquid–liquid extraction followed by flame atomic absorption spectrometry. Chem Pap 68:342–351. CrossRefGoogle Scholar
  19. Kocot K, Pytlakowska K, Zawisza B, Sitko R (2016) How to detect metal species preconcentrated by microextraction techniques? Trends Anal Chem 82:412–424. CrossRefGoogle Scholar
  20. Leong MI, Fuh MH, Huang SD (2014) Beyond dispersive liquid–liquid microextraction. J Chromatog A 1335:2–14. CrossRefGoogle Scholar
  21. MAPA (2005) Ministério da Agricultura, Pecuária e Abastecimento. Instrução Normativa n° 13. Accessed 5 April 2019
  22. Penteado JCP, Masini JC (2009) Multivariate analysis for the classification differentiation of brazilian sugarcane spirits by analysis of organic and inorganic compounds. Anal Lett 42:2747–2757. CrossRefGoogle Scholar
  23. Płotka-Wasylka J, Owczarek K, Namieśnik J (2016) Modern solutions in the field of microextraction using liquid as a medium of extraction. Trends Anal Chem 85:46–64. CrossRefGoogle Scholar
  24. Ribeiro GC, Coelho LM, Coelho NMM (2013) Determination of nickel in alcoholic beverages by FAAS after online preconcentration using mandarin peel (Citrus reticulata) as biosorbent. J Braz Chem Soc 24(6):1072–1078. CrossRefGoogle Scholar
  25. Sampaio OM, Reche RV, Franco DW (2008) Chemical profile of rums as a function of their origin: the use of chemometric techniques for their identification. J Agri Food Chem 56:1661–1668. CrossRefGoogle Scholar
  26. Serafim FAT, Pereira-Filho ER, Franco DW (2016) Chemical data as markers of the geographical origins of sugarcane spirits. Food Chem 196:196–203. CrossRefPubMedGoogle Scholar
  27. Škrlíková J, Andruch V, Sklenářová H, Chocholouš P, Solich P, Balogh IS (2010) An air-assisted liquid–liquid extraction using a dual-valve sequential injection manifold (DV-SIA): Determination of copper. Anal Methods 2:1134. CrossRefGoogle Scholar
  28. Sorouraddin SM (2016) Simultaneous separation and preconcentration of ultra-trace of Cu(II), Pb(II) and Zn(II) in water samples by air-assisted liquid–liquid microextraction prior to determination by graphite furnace atomic absorption spectrometry. J Iran Chem Soc 13:2219–2227. CrossRefGoogle Scholar
  29. Sorouraddin SM, Farajzadeh MA, Nouri S, Afshar Moghaddam MR (2017) Air-assisted liquid liquid microextraction combined with graphite furnace atomic absorption spectrometry for preconcentration and determination of trace amount of co(II) and Ni(II) ions in water samples. Anal Bioanal Chem Res 4:227–238. CrossRefGoogle Scholar
  30. Souza LM, Alcarde AR, Lima FV, Bortoletto AM (2013) Produção de cachaça de qualidade. ESALQ, PiracicabaGoogle Scholar
  31. Suarez WT, Gabriel WL, Junior BRA, Franco MOK, Santos VB (2018) A simplistic portable led-based photometer for in situ determination of copper in sugarcane spirits. Food Anal Methods 11:3324–3330. CrossRefGoogle Scholar
  32. Tavares FL, Okumura LL, Cardoso MG, Oliveira MF, Magriotis ZM, Saczk AA (2012) An alternative method for the simultaneous determination of copper and lead for quality control of sugar cane spirit using a nanotube-based sensor. J Braz Chem Soc 23(9):1614–1622. CrossRefGoogle Scholar
  33. Villis PCM, Gomes WC, Silva FB, Dos Santos DR, Silveira G, De Morais A, Blasques RV, Nunes GS, Pissetti FL, Gushikem Y, Lucho AMS (2018) Copper(II) trace determination in aqueous/ethanolic medium using an ionic imprinted hybrid. Int J Electrochem Sci 13:10564–10586. CrossRefGoogle Scholar
  34. Wang X, Xu G, Chen P, Liu X, Fang Y, Yang S, Wang G (2016) Arsenic speciation analysis in environmental water, sediment and soil samples by magnetic ionic liquid-based air-assisted liquid–liquid microextraction. RSC Adv 6:110247–110254. CrossRefGoogle Scholar
  35. Zgoła-Grześkowiak A, Grześkowiak T (2011) Dispersive liquid-liquid microextraction. Trends Anal Chem 30:1382–1399. CrossRefGoogle Scholar
  36. Zounr RA, Tuzen M, Khuhawar MY (2018) A simple and green deep eutectic solvent based air assisted liquid phase microextraction for separation, preconcentration and determination of lead in water and food samples by graphite furnace atomic absorption spectrometry. J Mol Liq 259:220–226. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Exact Sciences and TechnologyState University of Santa CruzIlhéusBrazil
  2. 2.Departamento de Ciências Exatas e TecnológicasUniversidade Estadual de Santa CruzIlhéusBrazil

Personalised recommendations