SIMULTANEOUS DETERMINATION OF FLUORIDE, ACETATE, FORMATE, CHLORIDE, NITRATE, AND SULFATE IN DISTILLED ALCOHOLIC BEVERAGES WITH ION CHROMATOGRAPHY/CONDUCTIVITY DETECTOR

Abstract

A novel ion chromatography with suppressed conductivity detection method was developed for simultaneous determination of fluoride, acetate, formate, chloride, nitrate, and sulphate in distilled alcoholic beverages. In this study, bromide was used as an internal standard. The separation of the anions was accomplished by utilising an anion exchange column with gradient eluent program. The chromatographic conditions were as follows: the suppressor current was 31 mA; the flow rate of the mobile phase was 0.25 mL min-1; the column and detector compartment temperature were 35 °C and 40 °C, respectively; sample loop volume was 10 μL. All the calibration curves showed good linearity (r2 ≥ 0.999). The limits of detection (LOD) values were between 0.56 and 13.2 μg L-1 while the limits of quantification (LOQ) values were between 1.80 and 43.9 μg L-1. To evaluate the accuracy, a raki sample was spiked with standard solutions at three different concentration levels and the average recoveries were found in the range of 94.90% - 101.71%. Intra-day and inter-day precision studies were also investigated and the relative standard deviations (RSDs %) were less than 5.99%. The validated method was applied to the three kinds of commercial samples: Turkish raki, vodka, and gin.

Keywords

• Ion chromatography
• anion analysis
• distilled alcoholic beverages

Supporting Institution

Istanbul Technical University

Project Number

Scientific Research Project of Istanbul Technical University (ITU-BAP) via Grant No. 40254.

Thanks

This paper was produced by associated with a Msc. Thesis titled as "Simultaneous determination of fluoride, acetate, formate, chloride, nitrate, and sulphate in distilled alcoholic beverages with ion chromatography/ conductivity detector" funded by the Unit for Scientific Research Project of Istanbul Technical University (ITU-BAP) via Grant No. 40254. The authors would like to thank the Unit for Scientific Research Project of Istanbul Technical University (ITU-BAP) for financial support. The authors are grateful to Professor Dr. Mustafa ÖZCAN, Istanbul Technical University (ITU), Department of Chemistry, for his kind permission to use HS-GC/MS instrumentation.

References

1. 1. Destanoğlu O, Ateş İ. Determination and Evaluation of Methanol, Ethanol and Higher Alcohols in Legally and Illegally Produced Alcoholic Beverages. Journal of the Turkish Chemical Society, Section A: Chemistry. 2019;6(1):21-8.
2. 2. Hovda KE, Urdal P, Jacobsen D. Increased serum formate in the diagnosis of methanol poisoning. Journal of analytical toxicology. 2005;29(6):586-8.
3. 3. Zakharov S, Navrátil T, Pelclova D. Analysis of serum anion gap and osmolal gap in diagnosis and prognosis of acute methanol poisoning: clinical study in 86 patients. Monatshefte für Chemie-Chemical Monthly. 2015;146(5):787-94.
4. 4. Destanoğlu O, İsmail A. Evaluation of Formic Acid Concentrations in Postmortem Blood Samples Using Hs-GcMs System. Türkiye Klinikleri Journal of Forensic Medicine and Forensic Sciences. 2019;16(3):155-63.
5. 5. Treichel JL, Henry MM, Skumatz CM, Eells JT, Burke JM. Antioxidants and ocular cell type differences in cytoprotection from formic acid toxicity in vitro. Toxicological sciences. 2004;82(1):183-92.
6. 6. Grzybowski A, Zülsdorff M, Wilhelm H, Tonagel F. Toxic optic neuropathies: an updated review. Acta ophthalmologica. 2015;93(5):402-10.
7. 7. US.EPA. Provisional Peer-Reviewed Toxicity Values for Formic Acid. 2010. Contract No.: EPA/690/R-10/015F
8. 8. Cortés S, Gil ML, Fernández E. Volatile composition of traditional and industrial Orujo spirits. Food Control. 2005;16(4):383-8.

9. 9. Osobamiro T. Analysis of some contaminants commonly found in alcoholic beverages. Am-Eur J Sci Res. 2013;8(1):53-6.
10. 10. Kamphorst JJ, Chung MK, Fan J, Rabinowitz JD. Quantitative analysis of acetyl-CoA production in hypoxic cancer cells reveals substantial contribution from acetate. Cancer & metabolism. 2014;2(1):23.
11. 11. US.EPA. Reassessment of One Exemption from the Requirement of a Tolerance for Ethyl Acetate and One Exemption from the Requirement of a Tolerance for Amyl Acetate. 2006.
12. 12. Browne D, Whelton H, O'Mullane D. Fluoride metabolism and fluorosis. Journal of Dentistry. 2005;33(3):177-86.
13. 13. DenBesten P, Li W. Chronic fluoride toxicity: dental fluorosis. Fluoride and the oral environment. 22: Karger Publishers; 2011. p. 81-96.
14. 14. Martínez-Mier EA. Fluoride: its metabolism, toxicity, and role in dental health. Journal of Evidence-Based Complementary & Alternative Medicine. 2012;17(1):28-32.
15. 15. Buldini PL, Cavalli S, Trifirò A. State-of-the-art ion chromatographic determination of inorganic ions in food. Journal of Chromatography A. 1997;789(1-2):529-48.
16. 16. Jagadish R, Shanmugaselvan VA. Quantification of Inorganic Anions in Tea (Camellia Sinensis (L) O. Kuntze) Tissues and Soil Using Ion Chromatography Coupled with Conductivity Detector. Communications in soil science and plant analysis. 2018;49(8):875-88.
17. 17. Zhang F, Ma C, Wang Y, Liu W, Liu X, Zhang H. Fluorescent probes for chloride ions in biological samples. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2018;205:428-34.
18. 18. WHO. Chloride in Drinking-water. 2003. Contract No.: WHO/SDE/WSH/03.04/03
19. 19. Chow C, Hong C. Dietary vitamin E and selenium and toxicity of nitrite and nitrate. Toxicology. 2002;180(2):195-207.
20. 20. EFSA. Nitrites and nitrates added to food. 2017:[1-4 pp.].
21. 21. US.EPA. Drinking Water Advisory: Consumer Acceptability Advice and Health Effects Analysis on Sulfate. 2003. Contract No.: EPA 822-R-03-007
22. 22. WHO. Sulfate in Drinking-water 2004. Contract No.: WHO/SDE/WSH/03.04/114
23. 23. Jurado-Sánchez B, Ballesteros E, Gallego M. Gas chromatographic determination of 29 organic acids in foodstuffs after continuous solid-phase extraction. Talanta. 2011;84(3):924-30.
24. 24. Yang M-H, Choong Y-M. A rapid gas chromatographic method for direct determination of short-chain (C2–C12) volatile organic acids in foods. Food Chemistry. 2001;75(1):101-8.
25. 25. Brondz I. Development of fatty acid analysis by high-performance liquid chromatography, gas chromatography, and related techniques. Analytica Chimica Acta. 2002;465(1-2):1-37.
26. 26. Molnár-Perl I. Role of chromatography in the analysis of sugars, carboxylic acids and amino acids in food. Journal of Chromatography A. 2000;891(1):1-32.
27. 27. Viidanoja J. Determination of short chain carboxylic acids in vegetable oils and fats using ion exclusion chromatography electrospray ionization mass spectrometry. Journal of Chromatography A. 2015;1383:96-103.
28. 28. Kubáň P, Ďurč P, Bittová M, Foret F. Separation of oxalate, formate and glycolate in human body fluid samples by capillary electrophoresis with contactless conductometric detection. Journal of Chromatography A. 2014;1325:241-6.
29. 29. Balcerzak M, Kapica D. Fast ion chromatographic method for the determination of formates in alcoholic drinks. Food Analytical Methods. 2017;10(7):2358-64.
30. 30. Uzhel A, Zatirakha A, Smolenkov A, Shpigun O. Quantification of inorganic anions and organic acids in apple and orange juices using novel covalently-bonded hyperbranched anion exchanger with improved selectivity. Journal of Chromatography A. 2018;1567:130-5.
31. 31. Souza SR, Tavares MF, de Carvalho LR. Systematic approach to the separation of mono-and hydroxycarboxylic acids in environmental samples by ion chromatography and capillary electrophoresis. Journal of Chromatography A. 1998;796(2):335-46.
32. 32. Lachenmeier DW, Schmidt B, Bretschneider T. Rapid and mobile brand authentication of vodka using conductivity measurement. Microchimica Acta. 2008;160(1-2):283.
33. 33. Arbuzov V, Savchuk S. Identification of vodkas by ion chromatography and gas chromatography. Journal of Analytical Chemistry. 2002;57(5):428-33.
34. 34. Lachenmeier DW, Attig R, Frank W, Athanasakis C. The use of ion chromatography to detect adulteration of vodka and rum. European Food Research and Technology. 2003;218(1):105-10.
35. 35. Distilled Alcoholic Beverage Regulation, 2016/55 (2017).
36. 36. Suksom W, Wannachai W, Boonchiangma S, Chanthai S, Srijaranai S. Ion chromatographic analysis of monosaccharides and disaccharides in raw sugar. Chromatographia. 2015;78(13-14):873-9.
37. 37. Magnusson B, Örnemark U. Eurachem Guide: The Fitness for Purpose of Analytical Methods—A Laboratory Guide to Method Validation and Related Topics, ; Eurachem: Torino, Italy, 2014. Google Scholar.
38. 38. AOAC. AOAC Guidelines for Single Laboratory Validation of Chemical Methods for Dietary Supplements and Botanicals 2002.