Matrix Effect Assessment of an Ion Chromatographic Method to Determine Inorganic Anions in Wastewater

  • Rachel B. CostaEmail author
  • Priscila R. Camiloti
  • Carolina A. Sabatini
  • Carla E. D. dos Santos
  • Paulo C. F. Lima Gomes
  • Maria Ângela T. Adorno


Inorganic anion monitoring is essential for bioreactor operation and is related for pollution control or energy and products recovery. However, there is a lack of studies validating methods for inorganic anions analyses in conditions compatible to those in bioreactor operations treating different types of wastewater. This paper provides a systematic statistical study and matrix-effect assessment for sugarcane vinasse, leachate, sewage and synthetic sewage. Sample preparation consisted of only a filtration and sample dilution. Cl, NO2, NO3, PO43− and SO42− were determined in a Dionex ICS 5000® equipped with a chemical conductivity suppressor. Calibration curves were linear and well-adjusted between 2.5 and 50 mg L−1 for all the anions in all the tested matrices, except PO43− and SO42− in vinasse. A calibration range for PO43− in all tested matrices was 5.0 to 100 mg L−1, whereas a range from 5.0 mg L−1 to 50 mg L−1 was obtained for SO42− in vinasse. All the anions yielded recoveries in the range of 85–115% for all the tested matrices. Relative standard deviations lower than 10 and 2% were achieved for peak areas and retention times, respectively. A signal enhancement was observed for all the tested matrices and all the anions. The matrix effect level varied from −1.7 (NO2 in vinasse) to −33.9% (Cl in leachate). Sewage was the less affected matrix, while leachate gave higher matrix effects. Validation results and the matrix effect assessment showed that a simple sample preparation is suitable for multi-elemental analyses of inorganic anions for complex environmental samples.


Inorganic anion determination Complex matrices Standard addition method Environmental chemistry 



The authors acknowledge the Fundação de Amparo à Pesquisa no Estado de São Paulo (FAPESP 2009/15984-0) and Professor Marcelo Zaiat for his kind suggestions.

Compliance with Ethical Standards

Conflict of interest

The authors declare that they do not have any conflict of interest.


  1. APHA. Standard Methods for the Examination of Water and Wastewater. 20 th edit ed. [s.l.] American Public Health Association, American Water Works Association, Water Environment Federation, 2005.Google Scholar
  2. Araujo, P. (2009). Key aspects of analytical method validation and linearity evaluation. Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, 877(23), 2224–2234. Scholar
  3. Camiloti, P. R., Mockaitis, G., Rodrigues, J. A. D., Damianovic, M. H. R. Z., Foresti, E., & Zaiat, M. (2013). Innovative anaerobic bioreactor with fixed-structured bed (ABFSB) for simultaneous sulfate reduction and organic matter removal. Journal of Chemical Technology and Biotechnology, 89(7), 1044–1050. Scholar
  4. Camiloti, P. R., Oliveira, G. H. D., & Zaiat, M. (2016). Sulfur recovery from wastewater using a micro-aerobic external silicone membrane reactor (ESMR). Water, Air and Soil Pollution., 227(1).
  5. Chiu, Y. C., Lee, L. L., Chang, C. N., & Chao, A. C. (2007). Control of carbon and ammonium ratio for simultaneous nitrification and denitrification in a sequencing batch bioreactor. International Biodeterioration Biodegradation, 59(1), 1–7. Scholar
  6. Christofoletti, C. A., Escher, J. P., Correia, J. E., Marinho, J. F. U., & Fontanetti, C. S. (2013). Sugarcane vinasse: environmental implications of its use. Waste Management, 33(12), 2752–2761. Scholar
  7. Economou, A., Botitsi, H., Antoniou, S., & Tsipi, D. (2009). Determination of multi-class pesticides in wines by solid-phase extraction and liquid chromatography-tandem mass spectrometry. Journal of Chromatography A, 1216(31), 5856–5867. Scholar
  8. Fuess, L. T., & Garcia, M. L. (2015). Bioenergy from stillage anaerobic digestion to enhance the energy balance ratio of ethanol production. Journal of Environmental Management, 162, 102–114. Scholar
  9. Gade, B. (1993). Ion chromatographic investigations of leachates from a hazardous-waste landfill. Journal of Chromatography A, 640-1(2), 227–230. Scholar
  10. García, D., Alcántara, C., Blanco, S., Pérez, R., Bolado, S., & Muñoz, R. (2017). Enhanced carbon, nitrogen and phosphorus removal from domestic wastewater in a novel anoxic-aerobic photobioreactor coupled with biogas upgrading. Chemical Engineering Journal, 313, 424–434. Scholar
  11. Jackson, L. K., Joyce, R. J., Laikhtman, M., & Jackson, P. E. (1998). Determination of trace level bromate in drinking water by direct injection ion chromatography. Journal of Chromatography A, 829-1(2), 187–192. Scholar
  12. Jackson, P. E. (2006). Ion chromatography in environmental analysis. In Encyclopedia of analytical chemistry (pp. 2779–2801). Chichester: John Wiley & Sons Ltd.Google Scholar
  13. Jackson, P. E., Thomas, D. H., Donovan, B., Pohl, C. A., & Kiser, R. E. (2001). New block-grafted anion exchanger for environmental water analysis by ion chromatography. Journal of Chromatography A, 920(1–2), 51–60. Scholar
  14. Kiyuna, L. S. M., Fuess, L. T., & Zaiat, M. (2017). Unraveling the influence of the COD/sulfate ratio on organic matter removal and methane production from the biodigestion of sugarcane vinasse. Bioresource Technology, 232, 103–112. Scholar
  15. Kjeldsen, P., Barlaz, M. A., Rooker, A. P., Baun, A., Ledin, A., & Christensen, T. H. (2002). Present and long-term composition of MSW landfill leachate: A review. Critical Reviews in Environmental Science and Technology, 32(4), 297–336. Scholar
  16. Kruve, A., Rebane, R., Kipper, K., Oldekop, M. L., Evard, H., Herodes, K., Ravio, P., & Leito, I. (2015). Tutorial review on validation of liquid chromatography-mass spectrometry methods: part I. Analytica Chimica Acta, 870(1), 8–28. Scholar
  17. Lacerda, C. V., Ritter, E., Costa Pires, J. A., & Castro, J. A. (2014). Migration of inorganic ions from the leachate of the Rio Das Ostras landfill: a comparison of three different configurations of protective barriers. Waste Management, 34(11), 2285–2291. Scholar
  18. Lopez-Moreno, C., Viera, I., & Urbano, A. M. (2010). Validation of an ion chromatographic method for the quantification of anions in water. Desalination, 261(1–2), 111–116. Scholar
  19. Martins, T. H., Souza, T. S. O., & Foresti, E. (2017). Ammonium removal from landfill leachate by Clinoptilolite adsorption followed by bioregeneration. Journal of Environmental Chemical Engineering., 5, 63–68. Scholar
  20. Matuszewski, B. K., Constanzer, M. L., & Chavez-Eng, C. M. (2003). Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS. Analytical Chemistry, 75(13), 3019–3030 Scholar
  21. Michalski, R. (2006). Ion chromatography as a reference method for determination of inorganic ions in water and wastewater. Critical Reviews in Analytical Chemistry, 36(Sep), 107–127.CrossRefGoogle Scholar
  22. Michalski, R., Lyko, A., & Kurzyca, I. (2012). Matrix influences on the determination of common ions by using ion chromatography part 1—determination of inorganic anions. Journal of Chromatographic Science, 50(6), 482–493. Scholar
  23. Miller JM, Miller JC (2010) Statistics and Chemometrics for Analytical Chemistry. 6th ed.: Pearson Education Limited, Essex, England.Google Scholar
  24. Miskaki, P., Lytras, E., Kousouris, L., & Tzoumerkas, P. (2007). Data quality in water analysis: validation of ion chromatographic method for the determination of routine ions in potable water. Desalination, 213(1–3), 182–188. Scholar
  25. Moraes, B. S., Zaiat, M., & Bonomi, A. (2015). Anaerobic digestion of vinasse from sugarcane ethanol production in Brazil: challenges and perspectives. Renewable and Sustainable Energy Reviews, 44, 888–903. Scholar
  26. Moura, R. B., Damianovic, M. H. R. Z., & Foresti, E. (2012). Nitrogen and carbon removal from synthetic wastewater in a vertical structured-bed reactor under intermittent aeration. Journal of Environmental Management, 98, 163–167. Scholar
  27. Naveen, B. P., Mahapatra, D. M., Sitharam, T. G., Sivapullaiah, P. V., & Ramachandra, T. V. (2016). Physico-chemical and biological characterization of urban municipal landfill leachate. Environmental Pollution, 220, 1–12. Scholar
  28. Neele, J., Cleven, R., & Van De Wiel, H. (2002). Matrix effects in the determination of low anion concentrations using suppressed IC. International Journal of Environmental Analytical Chemistry, 82(1), 13–22. Scholar
  29. Paull, B., & Nesterenko, P. (2005). Novel ion chromatographic stationary phases for the analysis of complex matrices. Analyst, 130(2), 134–146. Scholar
  30. Philips, S., Laanbroek, H. J., & Verstraete, W. (2002). Origin, causes and effects of increased nitrite concentrations in aquatic environments. Reviews in Environmental Science and Biotechnology, 1, 115–141. Scholar
  31. Poggi-Varaldo, H. M., Munoz-Paez, K. M., Escamilla-Alvarado, C., et al. (2014). Biohydrogen, biomethane and bioelectricity as crucial components of biorefinery of organic wastes: a review. Waste Management and Research, 32(5), 353–365. Scholar
  32. Santos, C. E. D., Moura, R. B., Damianovic, M. H. R. Z., & Foresti, E. (2016) Influence of COD/N ratio and carbon source on nitrogen removal in a structured-bed reactor subjected to recirculation and intermittent aeration (SBRRIA). Journal of Environmental Management 166,519–524.
  33. Santos, J. D., Silva, A. L. L., Costa, J. L., Scheidt, G. N., Novak, A. C., Sydney, E. B., & Soccol, C. R. (2013). Development of a vinasse nutritive solution for hydroponics. Journal of Environmental Management, 114, 8–12.
  34. Singh, R. P., Abbas, N. M., & Smesko, S. A. (1996). Suppressed ion chromatographic analysis of anions in environmental waters containing high salt concentrations. Journal of Chromatography A, 733(1–2), 73–91. Scholar
  35. Tchobanoglous, G., Burton, F. L., & Stensel, H. D. (2003). Metcalf & Eddy: Wastewater engineering, treatment and reuse (4th ed.). New York: McGraw Hill Education.Google Scholar
  36. Thompson, M., Ellison, S. L. R., & Wood, R. (2002). Harmonized guidelines for single-laboratory validation of methods of analysis (IUPAC Technical Report). Pure Applied Chemistry, 74(5), 835–855.CrossRefGoogle Scholar
  37. USEPA.(1993) Method 300.1–1 - Determination of inorganic anions in drinking water by ion chromatography. Cincinnati, OH.Google Scholar
  38. Valdés, F., Camiloti, P. R., Rodriguez, R. P., Delforno, T. P., Carrillo-Reyes, J., & Zaiat, M. D. (2016). Sulfide-oxidizing bacteria establishment in an innovative microaerobic reactor with an internal silicone membrane for sulfur recovery from wastewater. Biodegradation, 27, 119–130.CrossRefGoogle Scholar
  39. Villagrán, C., Deetlefs, M., Pitner, R. W., & Hardacre, C. (2004). Quantification of halide in ionic liquids using ion chromatography. Analytical Chemistry, 76(7), 2118–2123. Scholar
  40. Von Sperling, M. (2007). Wastewater characteristics, treatment and disposal. London: IWA Publishing.Google Scholar

Copyright information

© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Laboratory of Biological Processes, Center for Research, Development and Innovations in Environmental Engineering, Sao Carlos School of EngineeringUniversity of Sao Paulo (EESC/USP)São CarlosBrazil
  2. 2.Department of Analytical ChemistrySao Paulo State University, UNESPAraraquaraBrazil

Personalised recommendations