Simultaneous Determination of Cationic and Anionic Surfactants in Environmental Water Samples by Ion-Pair Liquid Chromatography/Mass Spectrometry

Author(s): Atsuko Nishigaki*, Kana Miyazaki, Nobuko Suzuki, Kazushige Kojima, Kazunori Saitoh, Masami Shibukawa

Journal Name: Current Chromatography

Volume 7 , Issue 1 , 2020


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Abstract:

Background: Cationic surfactants (CSs) such as quaternary ammonium compounds are used as fabric softeners, anti-bacterial agents, and human hair cosmetics. Accurate determination of CSs in environmental water samples is very difficult because of their very low concentration and strong adsorptivity to not only glassware but also to plasticware due to strong hydrophobic and electrostatic attractions. Linear alkylbenzene sulfonates (LASs), anionic surfactants, are produced in the largest quantity as the main components of laundry detergents, dishwashing liquids, and other cleaning formulations. In this study, a liquid chromatography/mass spectrometry (LC/MS) method was developed for simultaneous determination of CSs, cetyltrimethylammonium ion (CTMA) and trimethylstearylammonium ion (TMSA), and LASs in environmental water samples.

Materials and Methods: This method involves a solid-phase extraction of CSs and LASs from the water samples using a solid-phase extraction cartridge, InertSep Slim-J PLS-3. A hydrophilic polymer column, Shodex MSpak GF-310 4D was used for the separation of CSs and LASs with a mobile phase gradient from 36 to 44 % (v/v) acetonitrile-water containing 0.8 mM di-nbutylammonium acetate and 0.2 M acetic acid. Di-n-butylammonium ion acts as the ion-pair reagent for retention of LASs on the column, while it makes the retention of CSs moderate. Positive and negative electrospray ionization modes were used for the MS detection for CSs and LASs, respectively.

Results and Discussion: Instrument detection limits of the developed method based on selected ion monitoring technique for the mixed standard solutions of CSs and LASs were 3 and 6 ng L-1 for CTMA and TMSA, respectively and 13 – 47 ng L-1 for the C10-C14 LASs. The total concentration of the CSs was determined to be 6.6 μg L-1 for river water (Ebi river, Japan) and 0.028 μg L-1 for seawater (Tokyo Bay, Japan) samples. The concentration of total LAS was determined to be 1122 μg L-1 for the river and 10.8 μg L-1 for the seawater samples.

Conclusion: These results demonstrate that the solid-phase extraction and the LC/MS method developed in this study are useful for the simultaneous determination of trace amounts of CSs and LASs in environmental water samples.

Keywords: Cationic surfactants, anionic surfactants, liquid chromatography, mass spectrometry, river water, seawater.

[1]
Hummel, D.O. Handbook of Surfactant Analysis: Chemical, Physico-chemical and Physical Methods; Wiley: Chichester, 2000.
[2]
Bressan, M.; Brunetti, R.; Casellato, S.; Fava, G.C.; Givo, P.; Negrisolo, P.; Tallandini, L.; Thomann, S.; Tosoni, L.; Turchetto, M. Effects of linear alkylbenzene sulfonate (LAS) on benthic organisms. Tenside Deterg., 1989, 26, 148-158.
[3]
Argese, E.; Marcomini, A.; Miana, P.; Bettiol, C.; Perrin, G. Submitochondrial particle response to linear alkylbenzenesulfonates, nonylphenol polyethoxylates and their biodegradation derivatives. Environ. Toxicol. Chem., 1994, 13, 737-742.
[http://dx.doi.org/10.1002/etc.5620130507]
[4]
Schroder, H.F. Surfactants: non-biodegradable, significant pollutants in sewage treatment plant effluents: Separation, identification and quantification by liquid chromatography, flow-injection analysis—mass spectrometry and tandem mass spectrometry. J. Chromatogr. A, 1993, 647, 219-234.
[http://dx.doi.org/10.1016/0021-9673(93)83404-G]
[5]
Eichhorn, P.; Flavier, M.E.; Paje, M.L.; Kneppe, T.P. Occurrence and fate of linear and branched alkylbenzenesulfonates and their metabolites in surface waters in the Philippines. Sci. Total Environ., 2001, 269(1-3), 75-85.
[http://dx.doi.org/10.1016/S0048-9697(00)00825-1] [PMID: 11305345]
[6]
Eichhorn, P.; Rodrigues, S.V.; Baumann, W.; Knepper, T.P. Incomplete degradation of linear alkylbenzene sulfonate surfactants in Brazilian surface waters and pursuit of their polar metabolites in drinking waters. Sci. Total Environ., 2002, 284(1-3), 123-134.
[http://dx.doi.org/10.1016/S0048-9697(01)00873-7] [PMID: 11846157]
[7]
Nishigaki, A.; Kuroiwa, C.; Shibukawa, M. Characterization and determination of linear alkylbenzenesulfonates in environmental water samples by high-performance liquid chromatography with a hydrophilic polymer column and electrospray ionization mass spectrometric detection. Anal. Sci., 2004, 20(1), 143-147.
[http://dx.doi.org/10.2116/analsci.20.143] [PMID: 14753273]
[8]
Donalo, J.V.; Shirley, J.S. Effect of organic carbon on the uptake and toxicity of quaternary ammonium compounds to the fathead minnow, Pimephales promelas. Environ. Toxicol. Chem., 1992, 11, 571-580.
[http://dx.doi.org/10.1002/etc.5620110415]
[9]
Li, X.; Brownawell, B.J. Analysis of quaternary ammonium compounds in estuarine sediments by LC-ToF-MS: very high positive mass defects of alkylamine ions as powerful diagnostic tools for identification and structural elucidation. Anal. Chem., 2009, 81(19), 7926-7935.
[http://dx.doi.org/10.1021/ac900900y] [PMID: 19739657]
[10]
Merino, F.; Rubio, S.; Pérez-Bendito, D. Mixed aggregate-based acid-induced cloud-point extraction and ion-trap liquid chromatography-mass spectrometry for the determination of cationic surfactants in sewage sludge. J. Chromatogr. A, 2003, 998(1-2), 143-154.
[http://dx.doi.org/10.1016/S0021-9673(03)00565-X] [PMID: 12862380]
[11]
Norberg, J.; Thordarson, E.; Mathiasson, L.; Jönsson, J.A. Microporous membrane liquid-liquid extraction coupled on-line with normal-phase liquid chromatography for the determination of cationic surfactants in river and waste water. J. Chromatogr. A, 2000, 869(1-2), 523-529.
[http://dx.doi.org/10.1016/S0021-9673(99)01219-4] [PMID: 10720266]
[12]
Radke, M.; Behrends, T.; Förster, J.; Herrmann, R. Analysis of cationic surfactants by microbore high-performance liquid chromatography-electrospray mass spectrometry. Anal. Chem., 1999, 71(23), 5362-5366.
[http://dx.doi.org/10.1021/ac990453q] [PMID: 21662732]
[13]
Larson, J.R.; Pfelffer, C.D. Determination of alkyl quaternary ammonium compounds by liquid chromatography with indirect photometric detection. Anal. Chem., 1983, 55, 393-396.
[http://dx.doi.org/10.1021/ac00253a054]
[14]
Wee, V.T.; Kennedy, J.M. Determination of trace levels of quaternary ammonium compounds in river water by liquid chromatography with conductometric detection. Anal. Chem., 1982, 54, 1631-1633.
[http://dx.doi.org/10.1021/ac00246a037]
[15]
Shibukawa, M.; Eto, R.; Kira, A.; Miura, F.; Oguma, K.; Tatsumoto, H.; Ogura, H.; Uchiumi, A. Separation and determination of quaternary ammonium compounds by high-performance liquid chromatography with a hydrophilic polymer column and conductometric detection. J. Chromatogr. A, 1999, 830, 321-328.
[http://dx.doi.org/10.1016/S0021-9673(98)00939-X]
[16]
Radke, M.; Behrends, T.; Förster, J.; Herrmann, R. Analysis of cationic surfactants by microbore high-performance liquid chromatography-electrospray mass spectrometry. Anal. Chem., 1999, 71(23), 5362-5366.
[http://dx.doi.org/10.1021/ac990453q] [PMID: 21662732]
[17]
Peng, X.T.; Shi, Z.G.; Feng, Y.Q. Rapid and high-throughput determination of cationic surfactants in environmental water samples by automated on-line polymer monolith microextraction coupled to high performance liquid chromatography-mass spectrometry. J. Chromatogr. A, 2011, 1218(23), 3588-3594.
[http://dx.doi.org/10.1016/j.chroma.2011.04.009] [PMID: 21514936]
[18]
Bassarab, P.; Williams, D.; Dean, J.R.; Ludkin, E.; Perry, J.J. Determination of quaternary ammonium compounds in seawater samples by solid-phase extraction and liquid chromatography-mass spectrometry. J. Chromatogr. A, 2011, 1218(5), 673-677.
[http://dx.doi.org/10.1016/j.chroma.2010.11.088] [PMID: 21194696]
[19]
Thurman, E.M.; Mills, M.S. Solid-Phase Extraction: Principles and Practice; Wiley: Chichester, 1998.
[20]
Akter, F.; Saito, S.; Tasaki-Handa, Y.; Shibukawa, M. Partition/ion-exclusion chromatographic ion stacking for analysis of trace anions in water and salt samples by ion chromatography. Anal. Sci., 2018, 34(3), 369-373.
[http://dx.doi.org/10.2116/analsci.34.369] [PMID: 29526907]
[21]
Akter, F.; Ogiyama, Y.; Saito, S.; Shibukawa, M. Mechanism of ion stacking in aqueous partition chromatographic processes. J. Sep. Sci., 2017, 40(16), 3205-3213.
[http://dx.doi.org/10.1002/jssc.201700081] [PMID: 28590082]
[22]
Shibukawa, M.; Kondo, Y.; Ogiyama, Y.; Osuga, K.; Saito, S. Interfacial water on hydrophobic surfaces recognized by ions and molecules. Phys. Chem. Chem. Phys., 2011, 13(35), 15925-15935.
[http://dx.doi.org/10.1039/c1cp20704k] [PMID: 21818466]
[23]
Baba, T.; Sakamoto, R.; Shibukawa, M.; Oguma, K. Solute retention and the states of water in polyethylene glycol and poly(vinyl alcohol) gels. J. Chromatogr. A, 2004, 1040(1), 45-51.
[http://dx.doi.org/10.1016/j.chroma.2004.03.065] [PMID: 15248424]
[24]
Shibukawa, M. Dependence of retention of ionic solutes on the composition of the mobile phase electrolytes in partition chromatography. J. Chromatogr. A, 1993, 655, 199-205.
[http://dx.doi.org/10.1016/0021-9673(93)83224-G]
[25]
Shibukawa, M.; Ohta, N. Model for partition chromatography of ionic solutes in the presence of eluent electrolytes. Chromatographia, 1986, 22, 261-267.
[http://dx.doi.org/10.1007/BF02268770]
[26]
Sello, S.B.; Stevens, C.V. Antistatic treatments.Handbook of fiber science and technology: Volume II. Chemical processing of fibers and fabrics. Functional finishes Part B; Lewin, M.; Sello, S. B., Eds.; Marcel Dekker Inc: New York:, 1984.


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Article Details

VOLUME: 7
ISSUE: 1
Year: 2020
Page: [57 - 64]
Pages: 8
DOI: 10.2174/2213240606666190701103503

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