Determination of Textile Dyes by Means of Non-Aqueous Capillary Electrophoresis With Electrochemical Detection
Determination of Textile Dyes by Means of Non-Aqueous Capillary Electrophoresis With Electrochemical Detection
Determination of Textile Dyes by Means of Non-Aqueous Capillary Electrophoresis With Electrochemical Detection
Abstract
Eight textile dye compounds including five cationic dyes, namely, basic blue 41, basic blue 9, basic green 4, basic violet 16 and basic violet 3,
and three anionic dyes, acid green 25, acid red 1 and acid blue 324, were separated and detected by non-aqueous capillary electrophoresis (NACE)
with electrochemical detection. Simultaneous separations of acid and basic dyes were performed using an acetonitrile-based buffer. Particular
attention was paid to the determination of basic textile dyes. The optimized electrophoresis buffer for the separation of basic dyes was a solvent
mixture of acetonitrile/methanol (75:25, v/v) containing 1 M acetic acid and 10 mM sodium acetate. The limits of detection for the basic dyes were
in the range of 0.1–0.7 g mL−1 . An appropriate solid-phase extraction procedure was developed for the pre-treatment of aqueous samples with
different matrices. This analytical approach was successfully applied to various water samples including river and lake water which were spiked
with textile dyes.
© 2008 Elsevier B.V. All rights reserved.
Keywords: Textile dyes; Non-aqueous capillary electrophoresis; Electrochemical detection; Environmental analysis; Solid-phase extraction
0039-9140/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2008.01.049
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peak shapes. Non-aqueous capillary electrophoresis (NACE) is 2.2. Detector configuration and capillary specifications
an attractive alternative which can diminish these problems. In
NACE organic solvent systems are used instead of conventional The electrochemical detector cell used for the present work
aqueous buffers. In particular, the manipulation of selectivity has been described in detail elsewhere [24]. Briefly, the detec-
by varying the organic solvents choices and ratios can help to tor cell consists of an inert PTFE cell body with two stainless
solve complicated separation problems. This forms the basis steel tubes which guide the separation capillary and the work-
for interesting possibilities to adjust performance characteristics ing electrode to the right axial position. The working electrode
like selectivity, resolution, and analysis time. Among the sol- was a 25-m platinum microdisk electrode. Fused-silica capil-
vents that can be used for NACE acetonitrile exhibits the largest laries with an i.d. of 75 m and an o.d. of 360 m (Polymicro
ratio of dielectric constant to viscosity which leads to a high Technologies, Phoenix, AZ, USA) were used throughout this
electro-osmotic velocity and fast separations. It has been demon- work. Before initial use, new capillaries were washed with 0.1 M
strated that electrochemical methods are well suited for analyte NaOH for 10 min, with distilled water for 5 min, for 15 min with
detection in conjunction with NACE [23]. In acetonitrile-based pure acetonitrile and for 25 min with the buffer used. After use,
buffers electrochemical detection exhibits a very good stability the capillaries were flushed with pure acetonitrile. The capillary
of the detection response within an extended accessible poten- and working electrode are kept in place by PTFE adapters fitted
tial range and low limits of detection (LOD) can be achieved to the stainless steel tubes. The capillary-to-electrode distance of
[18]. 75 ± 5 m was adjusted under a stereomicroscope by carefully
The aim of this work was to investigate the applicability of pushing the separation capillary towards the tip of the working
NACE–ED to the determination of cationic and anionic textile electrode. One of the stainless steel tubes served as counter elec-
dyes which represent common dye classes in textile effluents. trode and high-voltage ground. The cell was ready for operation
Particular attention was paid to the adaptation of the analyti- after filling it with 1.5 mL of the separation buffer and plac-
cal approach to the necessary matrix change from an aqueous ing a PTFE cap with an attached silver/silver chloride reference
sample to the NACE buffer system. electrode on top of it. As internal solution of the reference elec-
trode a non-aqueous acetonitrile-based buffer containing 1 M
2. Experimental acetic acid and 10 mM sodium acetate was used which ensured
that the drift of the reference electrode potential was less than
2.1. Electrophoretic and electrochemical equipment 1 mV h−1 . All potentials given in this work were measured with
respect to this reference system. In the presence of a high volt-
A high-voltage supply (Model HCN 7E-35000, F.u.G. Elek- age of 20 kV a shift of the working electrode potential of about
tronik, Rosenheim–Langenpfunzen, Germany) was used for 300 mV towards more negative potentials occurred [25] that had
measurements in conjunction with a home-made CE system. to be taken into consideration for a suitable potential setting.
Care was taken to ensure that the hydrostatic levels of the input
and output reservoirs were identical. Sample injection was done 2.3. Chemicals
by elevating the sample vial up to a difference in height of 10 cm
above the detector cell electrolyte level for a duration of 10 s. A Acetonitrile (99.9% HPLC grade, water <0.02%) and acetic
commercial CE system PrinCE model 255 (Prince Technologies, acid (99.99%) were obtained from Sigma–Aldrich (Stein-
Emmen, The Netherlands) equipped with a UV–vis detector heim, Germany), methanol (LiChrosolv) and sodium acetate
(Bischoff model lambda 1010, Leonberg, Germany) operated (Suprapur) were purchased from Merck (Darmstadt, Germany).
at 200 nm, was used for comparative measurements with UV Ferrocene was from Riedel-de-Haën AG (Seelze–Hannover,
detection. Germany) and was purified by sublimation. For solid-phase
In case of electrochemical detection the implementation of an extraction (SPE), the cartridges ENVI-Chrom P (0.25 and
isolating transformer ensured galvanic separation between the 0.50 g—6 ml) and ENVI-18 (0.50 g—6 ml) were purchased
high-voltage supply and the potentiostat. The electrochemical from Supelco (Bellefonte, PA, USA). The chemicals used for
detector cell was placed in a Faraday cage so as to minimize inter- SPE were of analytical-reagent grade and were used as received.
ference from external noise. All electrochemical measurements The following textile dyes were used in this work: San-
were performed in the three-electrode mode with the aid of a docryl blue (basic blue 41), sandocryl red (basic violet 16),
voltammetric analyzer Model Autolab PGSTAT10 (Eco Chemie, sandocryl green (basic green 4), sandolan green (acid green
Utrecht, The Netherlands) equipped with a low current amplifier 25), sandolan red (acid red 1) and nylosan blue (acid blue 324)
module ECD system. The current signal was filtered through a which were kindly provided by Clariant (México). The dye com-
third-order Sallen–Key filter having a time constant of 100 ms. pounds crystal violet (basic violet 3) and methylene blue (basic
The interval time of the current measurements for amperometric blue 9) were analytical-reagent grade and were obtained from
recordings of the electropherograms was 0.3 s when the analy- Feinchemie K.-H., Kallies KG (Sebnitz, Germany) and Riedel-
sis time was shorter than 1000 s and when the analysis time was de-Haën (Seelze, Germany), respectively. All dye substances
longer, it was 0.5 s. Before running a new electropherogram, a were used as received without further purification. Table 1 sum-
working electrode potential of 3.0 V was applied for 5 s followed marizes specifications of the dye compounds used.
by −1.0 V for 5 s to ensure long-term stability of the detector Sample pre-treatment for aqueous solutions was based on
response. SPE using ENVI-Chrom P cartridges. The SPE cartridges were
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Table 1
Overview of basic and acid dyes used in this work
Name Color index (code) Chemical structure Chemical classification
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Table 1 (Continued )
Name Color index (code) Chemical structure Chemical classification
activated immediately prior to use by passing through 3 ml shows the cyclic voltammograms for the basic and acid dyes in
methanol followed by 6 ml of distilled water. The sample was acetonitrile solution. All target analytes can be oxidized within
applied to the cartridge and drawn through at a flow-rate of the accessible potential range. However, the oxidation mech-
3 mL min−1 . The cartridges were then rinsed with 12 mL of dis- anisms are rather complex involving typically more than one
tilled water and 2 mL of pure acetonitrile. Thereafter the dyes oxidation step and following reactions. In the context of this
were eluted with 3–5 mL of acetonitrile/tetrahydrofuran (2:1, work no further efforts were undertaken to investigate details of
v/v) solution at a flow-rate of 1 mL min−1 and investigated by the oxidation processes. All dye compounds allow the recording
NACE–ED by injecting directly the extracted solution. of mass transport controlled detection signals within the poten-
tial window from 1.5 to 1.7 V. In order to obtain information
3. Results and discussion regarding problems due to electrode fouling five consecutive
cyclic voltammograms were recorded for the respective dye
3.1. Voltammetric behaviour of textile dyes in non-aqueous compounds. Without an electrochemical pre-treatment between
solutions the successive recordings decreasing and changing signals were
typically obtained. This indicates the presence of reaction prod-
In order to investigate the applicability of ED in non-aqueous ucts on the electrode surface causing changes in the electrode
media for the determination of textile dyes the voltammetric response. However, an electrochemical activation procedure
behaviour of the individual dye compounds was studied. Fig. 1 which applied an anodic pulse of 3.0 V for 5 s and a cathodic
pulse of −1.0 V for 5 s was sufficient to restore the initial
electrode behaviour. Fig. 2 exemplifies this situation for basic
blue 9 illustrating the positive effect of an electrochemical pre-
Fig. 1. (a) Cyclic voltammograms of basic dyes: 1, basic violet 3 (408 g mL−1 );
2, basic green 4 (418.5 g mL−1 ); 3, basic blue 9 (320 g mL−1 ); 4, basic blue 41
(451 g mL−1 ); 5, basic violet 16 (369 g mL−1 ) and acetonitrile-based back-
ground electrolyte (BGE) containing 1 M acetic acid and 10 mM sodium acetate. Fig. 2. Repetitive cyclic voltammograms of basic blue 9 (320 g mL−1 ) in
(b) Cyclic voltammograms of saturated solutions of acid dyes 6, acid blue 324; acetonitrile containing 1 M acetic acid and 10 mM sodium acetate (a) without
7, acid green 25; 8, acid red 1 and acetonitrile-based background electrolyte con- pre-treatment between successive runs and (b) with an electrochemical pre-
taining 1 M acetic acid and 10 mM sodium acetate. A 25-m platinum microdisk treatment (3 V and −1 V for 5 s) between successive runs. Other conditions
electrode was used as working electrode and the scan rate was 25 mV/s. were as in Fig. 1.
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Table 2
Analytical characteristics of determinations of basic textile dyes by means of non-aqueous capillary electrophoresis with electrochemical detection (ED)/ultraviolet
detection (UV)
Compound Concentration (g mL−1 ) Migration time (s) (RSDa , %) Peak height (nA) (RSDa , %) LODb (ED) (g mL−1 ) LODb (UVc ) (g mL−1 )
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