Abstract
Membrane-based continuous liquidliquid extraction combined on-line with normal-phase liquid chromatography is
proposed for the determination of cationic surfactants in complex aqueous samples. The technique has the potential for
complete automation. Selective enrichment of cationic surfactants from spiked river water and waste-water samples with
simultaneous removal of matrix constituents, followed by a quantitative transfer of the extract onto a liquid chromatographic
column and separation of the surfactant homologues yielding low detection limits, has been realised. The homologues of
alkyldimethylbenzylammonium chloride (Dodigen 226) were chosen as model compounds in the method development.
Dodigen homologues were ion-paired with heptanoic acid and extracted into chlorobutane by means of microporous
membrane liquidliquid extraction. It was thereby possible to attain an enrichment of over 250 times for one of the
homologues, viz. the concentration in the organic liquid is 250 times higher than in the original sample. Detection limits for
the three best-detected homologues of the mixture were in the range 0.75 mg / l in spiked river water samples. Ion-pair
normal-phase liquid chromatography, again with heptanoic acid as counter-ion, gave the necessary separation of the
surfactant homologues. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Microporous membrane liquidliquid extraction; Extraction methods; Water analysis; Environmental analysis;
Surfactants
1. Introduction
Cationic surfactants are widely used as, for example, fabric softeners, anti-static agents and antiseptic
components. Hence, they may be present in wastewater in large amounts. Although more than 90% of
all surfactants are removed in waste-water treatment
plants, trace amounts may be released into the
environment [1]. Cationic surfactants have rather low
toxicity for mammals, except in high doses, but they
*Corresponding author. Tel.: 146-46-222-8169; fax: 146-46222-4544.
0021-9673 / 00 / $ see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S0021-9673( 99 )01219-4
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2. Experimental
2.1. Chemicals
The cationic surfactant used as model compound
were the commercial product Dodigen 226, obtained
from Hoechst (Frankfurt, Germany). According to
the producer, Dodigen 226 is a dimethyl alkyl benzyl
ammonium chloride and has five homologues with
chain-lengths C 10 (2%), C 12 (57%), C 14 (23%), C 16
(11%), C 18 (7%), see Fig. 1. The content of the
commercial product is 30100% of surfactant. For
quantitative measurements in this work, a range of
concentrations is given, corresponding to this interval.
As the chromatographic eluent a mixture of chloroform, ammonia, both analytical-reagent grade
(Merck, Darmstadt, Germany), heptanoic acid (ICN
Biomedicals, Aurora, OH, USA) and ethanol (ETAX
2.3. Apparatus
A schematic system configuration is shown in Fig.
2. The LC system consisted of a model 2150 HPLCpump (LKB, Bromma, Sweden), a two-position tenport high-pressure valve (Valco, Houston, TX, USA)
and a UV detector (Spectroflow 757, Kratos, Ramsey, NJ, USA). The monitoring wavelength was 264
nm. Chromatographic software (JCL6000 Chromatography Data System, Jones Chromatography, Hengoed, UK) was used for collection of data and
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Fig. 2. Experimental set-up with the high pressure valve in position for MMLLE extraction.
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3.1. Extraction
3.1.1. Organic solvent and ion-pairing agent
Quaternary ammonium ions can be extracted from
an aqueous solution to an organic solution as ion
pairs with anions as counter-ions. The counter ion
may be solvated in the organic solvent:
2
1
2
NR 1
4(aq) 1 X (org ) NR 4 X (org)
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Fig. 3. Enrichment factor, Ee , versus the extracted volume, V, for three of the homologues of Dodigen 226 (C 16 j, C 14 m, C 12 d) in reagent
grade water.
3.3. Detection
For Dodigen, which contains a UV-absorbing
benzene ring, detection is conveniently made using a
UV detector at 264 nm. However, most cationic
surfactants do not absorb UV radiation and, therefore, the detection is not straightforward [8]. In a
non-aqueous eluent in normal-phase chromatography, conductometric detection can be used for
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Table 1
Limits of detection for Dodigen homologues in spiked river water.
The results are given in ranges, due to the uncertainty in the
concentration of the reference material (see Section 2.1)
Homologue
LOD
(mg / l)
C 12
C 14
C 16
14
0.72
15
3.5. Application
Processed real samples included spiked river water
Fig. 4. Enrichment of 10 mg / l Dodigen (25 mg / l of the C 12 homologue and 0.72 mg / l of the C 14 homologue) in natural water followed
by NP-HPLC with UV detection. No peaks were found in the corresponding blank.
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Fig. 5. Enrichment of 12.5 mg / l Dodigen (27 mg / l of the C 12 homologue) in waste-water followed by NP-HPLC with UV detection. No
peaks were found in the corresponding blank.
4. Conclusions
A system for sensitively and selectively enriching
and separating cationic surfactants even at homologue level from complex matrices, with detection
limits in the low mg / l region has been demonstrated.
The cumbersome adsorption of cationic surfactants
has been circumvented both in the extraction as well
as in the chromatographic procedure.
Acknowledgements
The authors thank the undergraduate students
Katarina Borg and Eva Palm, involved in the project,
for their contribution to this work and also Hoechst
for providing us with cationic surfactants. Financial
support from the European Union (project number
ENV4-CT95-0016) is acknowledged.
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