Year 2017, Volume 4 , Issue 1, Pages 415 - 432 2017-01-09

Simultaneous Determination of Different Anions in Milk Samples Using Ion Chromatography with Conductivity Detection

Orhan Destanoğlu [1] , Gülçin Gümüş Yılmaz [2]

The description of a simple method for simultaneous determination of chloride, nitrate, sulfate, iodide, phosphate, thiocyanate, perchlorate, and orotic acid in milk samples was outlined. The method involves the use of dialysis cassettes for matrix elimination, followed by ion chromatography on a high capacity anion exchange column with suppressed conductivity detection. The novelty of dialysis process was that it did not need any chemical and organic solvent for elimination of macromolecules such as fat, carbohydrates and proteins from milk samples. External standard calibration curves for these analytes were linear with great correlation coefficients. The relative standard deviations of analyte concentrations were acceptable both inter-day and intra-day evaluations. Under optimized conditions, the limit of detection (Signal-to-Noise ratio = 3) for chloride, phosphate, thiocyanate, perchlorate, iodide, nitrate, sulfate, and orotate was found to be 0.012, 0.112, 0.140, 0.280, 0.312, 0.516, 0.520, and 0.840 mg L−1, respectively. Significant results were obtained for various spiked milk samples with % recovery in the range of 93.88 - 109.75 %. The proposed method was successfully applied to milk samples collected from Istanbul markets. The advantages of the method described herein are reagent-free, simple, and reliable.

Milk, Dialysis, Chloride, Nitrate, Sulfate, Iodide, Phosphate, Thiocyanate, Perchlorate, Orotic acid, Ion chromatography
  • Martinelango PK, Gümüş G, Dasgupta PK. Matrix interference free determination of perchlorate in urine by ion association–ion chromatography–mass spectrometry. Analytica Chimica Acta. 2006 May;567(1):79–86. DOI:10.1016/j.aca.2006.02.022
  • Niemann RA, Anderson DL. Determination of iodide and thiocyanate in powdered milk and infant formula by on-line enrichment ion chromatography with photodiode array detection. Journal of Chromatography A. 2008 Jul;1200(2):193–7. DOI: 10.1016/j.chroma.2008.05.064.
  • Leung AM, Pearce EN, Braverman LE. Best Practice & Research Clinical Endocrinology & Metabolism Perchlorate , iodine and the thyroid. Best Pract Res Clin Endocrinol Metab. Elsevier Ltd; 2010;24(1):133–41. DOI: 10.1016/j.beem.2009.08.009.
  • Bhagat PR, Pandey AK, Acharya R, Nair AGC, Rajurkar NS, Reddy AVR. Selective preconcentration and determination of iodine species in milk samples using polymer inclusion sorbent. Talanta 2007;71:1226–32. DOI: 10.1016/j.talanta.2006.06.018.
  • Dorea JG. Iodine nutrition and breast feeding. Journal of Trace Elements in Medicine and Biology. 2002 Jan;16(4):207–20. DOI: 10.1016/S0946-672X(02)80047-5.
  • Tonacchera M, Pinchera A, Dimida A, Ferrarini E, Agretti P, Vitti P, et al. Relative Potencies and Additivity of Perchlorate, Thiocyanate, Nitrate, and Iodide on the Inhibition of Radioactive Iodide Uptake by the Human Sodium Iodide Symporter. Thyroid. 2004 Dec;14(12):1012–9. DOI:10.1089/thy.2004.14.1012.
  • Iannece P, Motta O, Tedesco R, Carotenuto M, Proto A. Determination of Perchlorate in Bottled Water from Italy. Water. 2013 Jun 13;5(2):767–79. DOI: 10.3390/w5020767.
  • Sungur Ş, Atan MM. Determination of nitrate, nitrite and perchlorate anions in meat, milk and their products consumed in Hatay region in Turkey. Food Additives and Contaminants: Part B. 2013 Mar;6(1):6–10. DOI:10.1080/19393210.2012.717108
  • Lin S-L, Lo C-Y, Fuh M-R. Quantitative determination of perchlorate in bottled water and tea with online solid phase extraction high-performance liquid chromatography coupled to tandem mass spectrometry. Journal of Chromatography A. 2012 Jul;1246:40–7. DOI:10.1016/j.chroma.2012.02.014.
  • Kirk AB, Dyke JV, Martin CF, Dasgupta PK. Temporal Patterns in Perchlorate, Thiocyanate, and Iodide Excretion in Human Milk. Environmental Health Perspectives. 2006 Nov 20;115(2):182–6. DOI:10.1289/ehp.9558.
  • Chen L, Chen H, Shen M, Zhou Z, Ma A. Analysis of Perchlorate in Milk Powder and Milk by Hydrophilic Interaction Chromatography Combined with Tandem Mass Spectrometry. Journal of Agricultural and Food Chemistry. 2010 Mar 24;58(6):3736–40. DOI: 10.1021/jf903801m.
  • Jiang S, Li Y-S, Sun B. Determination of trace level of perchlorate in Antarctic snow and ice by ion chromatography coupled with tandem mass spectrometry using an automated sample on-line preconcentration method. Chinese Chemical Letters. 2013 Apr;24(4):311–4. DOI:10.1016/j.cclet.2013.02.011.
  • Licata P, Naccari F, Di Bella G, Lo Turco V, Martorana V, mo Dugo G. Inorganic anions in goat and ovine milk from Calabria (Italy) by suppressed ion chromatography. Food Additives & Contaminants: Part A. 2013 Mar;30(3):458–65. DOI: 10.1080/19440049.2012.747222.
  • Cataldi TRI, Nardiello D, Ciriello R, Guerrieri A. Pulsed electrochemical detection of orotic acid by an activated potential waveform at a gold working electrode following anion-exchange chromatography. Journal of Chromatography A. 2006 Feb;1107(1–2):130–8. DOI: 10.1016/j.chroma.2005.12.049.
  • Manjeshwar S, Rao P, Rajalakshmi S, Sarma D. The regulation of ribonucleoside diphosphate reductase by the tumor promoter orotic acid in normal rat liver in vivo. Molecular Carcinogenesis. 1999;24(3):188–96. URL:;2-%23/full.
  • Noël L, Carl M, Vastel C, Guérin T. Determination of sodium, potassium, calcium and magnesium content in milk products by flame atomic absorption spectrometry (FAAS): A joint ISO/IDF collaborative study. International Dairy Journal. 2008 Sep;18(9):899–904. DOI:10.1016/j.idairyj.2008.01.003.
  • Arnaud J, Bouillet MC, Alary J, Favier A. Zinc determination in human milk by flameless atomic absorption spectrometry after dry ashing. Food Chemistry. 1992 Jan;44(3):213–9. DOI: 10.1016/0308-8146(92)90190-D.
  • Kjellström S, Appels N, Ohlrogge M, Laurell T, Marko-Varga G. Microdialysis—a membrane based sampling technique for quantitative determination of proteins. Chromatographia. 1999 Nov;50(9–10):539–46.. DOI: 10.1007/BF02493658.
  • Buldini PL, Mevoli A, Quirini A. On-line microdialysis–ion chromatographic determination of inorganic anions in olive-oil mill wastewater. Journal of Chromatography A. 2000 Jun;882(1–2):321–8. DOI: 10.1016/S0021-9673(00)00434-9.
  • Sam AK, Osman MM, El-Khangi FA. Determination of protein and trace elements in human milk using NAA and XFR techniques. Journal of Radioanalytical and Nuclear Chemistry. 1998 May;231(1–2):21–3. DOI: 10.1007/BF02387999.
  • Cunha IIL, de Oliveira RM. Phosphorus determination in milk and bone samples by neutron activation analysis. Journal of Radioanalytical and Nuclear Chemistry. 1996 Jun;213(3):185–92. DOI: 10.1007/BF02165689.
  • Bjergegaard C, Møller P, Sørensen H. Determination of thiocyanate, iodide, nitrate and nitrite in biological samples by micellar electrokinetic capillary chromatography. Journal of Chromatography A. 1995 Nov;717(1–2):409–14. DOI: 10.1016/0021-9673(95)00554-1.
  • Han F, He Y-Z, Li L, Fu G-N, Xie H-Y, Gan W-E. Determination of benzoic acid and sorbic acid in food products using electrokinetic flow analysis–ion pair solid phase extraction–capillary zone electrophoresis. Analytica Chimica Acta. 2008 Jun;618(1):79–85. DOI: 10.1016/j.aca.2008.04.041.
  • Buldini PL, Cavalli S, Sharma JL. Matrix removal for the ion chromatographic determination of some trace elements in milk. Microchemical Journal. 2002 Sep;72(3):277–84. DOI:10.1016/S0026-265X(02)00039-5.
  • Magnusson B. The fitness for purpose of analytical methods: A laboratory guide to method validation and related topics. Eurachem; 2014. 57 p. (Eurachem Guide). URL: .
  • González AG, Herrador MA, Asuero AG. Intra-laboratory testing of method accuracy from recovery assays. Talanta. 1999 Mar;48(3):729–36. DOI: 10.1016/S0039-9140(98)00271-9.
  • Silveira ELC, de Caland LB, Tubino M. Simultaneous quantitative analysis of the acetate, formate, chloride, phosphate and sulfate anions in biodiesel by ion chromatography. Fuel. 2014 May;124:97–101. DOI: 10.1016/j.fuel.2014.01.095.
  • AOAC International, Guidelines for standard methods performance requirements, appendix F, AOAC official methods of analysis 2012.
Journal Section Articles

Author: Orhan Destanoğlu

Author: Gülçin Gümüş Yılmaz


Application Date : November 3, 2016
Acceptance Date : July 10, 2020
Publication Date : January 9, 2017

Vancouver Destanoğlu O , Gümüş Yılmaz G . Simultaneous Determination of Different Anions in Milk Samples Using Ion Chromatography with Conductivity Detection. Journal of the Turkish Chemical Society Section A: Chemistry. 2017; 415-432.