ISSN 1061-9348, Journal of Analytical Chemistry, 2006, Vol. 61, No. 2, pp. 172178. Pleiades Publishing, Inc., 2006.

. Original Russian Text A.V. Pirogov, A.V. Yurev, O.A. Shpigun, 2006, published in Zhurnal Analiticheskoi Khimii, 2006, Vol. 61, No. 2, pp. 184191.

ARTICLES

Determination of Optical Bleaching Agents (Belofors) in Writing Paper by Capillary Electrophoresis

A. V. Pirogov, A. V. Yurev, and O. A. Shpigun
Department of Chemistry, Moscow State University, Vorobevy gory, Moscow, 119992 Russia
Received December 17, 2004

AbstractCapillary electrophoresis was used for determining Belofors, which are used as optical bleaching agents for improving the whiteness of writing paper. Sodium dodecyl sulfate (SDS) was used as a modier of capillary walls in the separation of water-soluble Belofors. An optimum buffer electrolyte for separating and determining Belofors was as follows: 0.5 mM sodium hydrogen phosphate, 12.2 mM sodium tetraborate, and 30 mM SDS; pH 9.1. Bleaching agents in 39 samples of paper manufactured in Russia, Finland, Sweden, France, the Czech Republic, and Austria were determined and characterized. Common features for classifying paper types in accordance with brands and manufacturers were found. DOI: 10.1134/S1061934806020146

The use of optical bleaching agents (Belofors) in the manufacture of writing paper is preferable over other whitening processes because it does not have an adverse effect on the physical properties of paper. Belofors are used in very small amounts (from 0.005 to 0.15 wt % in paper). In this case, they increase the apparent whiteness of paper to a high extent that cannot be attained in either the chemical bleaching of brous prepared raw materials or the use of white pigments or dyes for paper whitening [1]. Stilbene derivatives, which exhibit space isomerism, are used as paper whitening agents. In a number of studies, ammonium acetate [2], sodium tetraborate [3], and borate or phosphate buffer solutions with TTAB additives in concentrations lower than the critical micelle concentration (CMC) [4, 5] were used as running buffers for separating Belofors and stilbene derivatives by capillary zone electrophoresis (CZE). The triazine group is the main group in the stilbene molecule. In a number of studies, triazines were efciently separated by micellar electrokinetic chromatography (MEKC) [6, 7]. A 15 mM aqueous solution of tetrabutylammonium bromide (TBAB) served as a buffer electrolyte. However, it was found that sulfo groups that are the constituents of stilbene derivatives are insufcient for the efcient separation of optical bleaching agents. The use of sodium dodecyl sulfate (SDS) as an additive to the running buffer facilitates the complete separation of Belofors, paper components, and impurities. Information obtained in studies of printed matter (primarily, the presence and composition of optical bleaching agents, paper components, and impurities) is used for various forensic purposes, for example, for determining the quality of paper and the possible site of its manufacture.

In this work, we studied 39 samples of paper manufactured in Russia, Finland, Sweden, France, Czech Republic, and Austria. The aim of this work was to determine water-soluble optical bleaching agents and their impurities in papers from various manufacturers and to nd regularities that can help in the classication of paper in accordance with brands and manufacturers. EXPERIMENTAL The study was performed on an HP3D instrument from Agilent (Waldbronn, Germany). The instrument was equipped with a diode-array detector and the HP3D CE ChemStation software for control and data acquisition and processing. The separation was performed on a fused-silica capillary from Polymicro Technologies (Phoenix, United States) with a total length of 80.5 cm (effective length of 72 cm) and an inner diameter of 50 m. Before use, a new capillary was washed with 0.1 M NaOH and HCl solutions, water, and a buffer electrolyte for 10 min. The capillary was washed with the working buffer electrolyte for 2 min before each subsequent sample injection. The sample was injected into the capillary at a pressure of 50 mbar for 4 s. The applied voltage was 200400 nm. Mixtures of optical bleaching agents were prepared from commercially available individual bleaching agents. For the preparation of a buffer solution, SDS (Aldrich), sodium tetraborate, and sodium hydrogen phosphate (of chemically pure grade) were used. All of the solutions were ltered through a membrane lter with a pore diameter of 0.22 m and outgassed in a vacuum produced by a water-jet pump for 5 min.

172

DETERMINATION OF OPTICAL BLEACHING AGENTS (BELOFORS) IN WRITING PAPER H N N H H C C SO3Na SO3Na H N N

173

CH3O N

N N

OCH3 Belofor KB

HNPh H H C C SO3Na
2

HN Ph

Tinopal CBS-X

SO3Na H N N N N N(C2H4OH)2 SO3Na H N SO3Na N N N H N H N

SO3Na C H Belofor TsBV

C H SO3Na
2

Belofor 2510

HNC2H4OH SO3Na H N SO3Na N N N N(C2H4OH)2 H N SO3Na N H N N N(C2H4OH)2 H N C H SO3Na

Belofor 2512

C H SO3Na
2

Belofor OB

Fig. 1. Structural formulas of the test Belofors (stilbene derivatives).

RESULTS AND DISCUSSION Belofors with the trade names Belofor 2510, Belofor 2512, and Belofor OBLiquid were separated and determined by CZE with SDS additives (to prevent the adsorption of bleaching agents on capillary walls). A buffer electrolyte containing 0.5 mM sodium hydrogen phosphate, 12.2 mM sodium tetraborate, and 30 mM
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SDS (pH 9.1) was chosen as an optimum buffer solution. Figure 1 shows the structural formulas of bleaching agents. The high efciency of the separation of both a model mixture of bleaching agents (Fig. 2) and bleaching agents in extracts from paper surfaces (Figs. 3, 4) allowed us to classify paper sources based on the data of on chemical analysis for bleaching agents.
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PIROGOV et al. Signal, arb. units 2 2.5 2.0 1.5 1.0 0.5 0 7 t, min 1 2 3 4 5 6 7 8 t, min 3 1

Fig. 2. MEKC separation of (1) Belofor KB, (2) Tinopal CBS-X, (3) Belofor TsBV, (4) Belofor 2512, and (5) Belofor 2510. Analytical conditions: 0.5 mM phosphate, 3 mM tetraborate, and 30 mM SDS; pH 9.1; applied voltage of 30 kV; hydrodynamic sample injection; 50 mbar; 4 s; 25C.

Fig. 3. Electropherogram of the extract of paper no. 22: (1, 3) Belofor OB isomers and (2) Belofor OB; the other peaks correspond to paper components. Analytical conditions: 0.5 mM phosphate, 12.2 mM tetraborate, and 30 mM SDS; pH 9.1; applied voltage of 30 kV; hydrodynamic sample injection; 50 mbar; 4 s; 25C.

In this study, we analyzed 39 aqueous extracts from various brands of paper. For this purpose, fragments of size 10 10 cm2 were cut from the test papers and placed in Petri dishes, and 5-mL portions of distilled water were added. Extraction was performed using continuous stirring for 10 min at 20C. The resulting extracts were separated from suspensions by centrifugation (5 min; 12 000 rps). The mobile phase (200 L) was added to 500 L of an extract, and the mixture was injected into the instrument for capillary electrophoresis. The effect of temperature on the recovery of bleaching agents from paper surfaces was studied. It was noted that an increase in the temperature from 20 to 50C in the course of extraction did not increase the recovery of Belofors considerably (an increase by about 5%), whereas the concentration of paper components in the extract increased signicantly. The recovery of Belofors was about 80%. The concentration of bleaching agents in papers was about 0.0050.05 wt %. The detection limits of Belofor OBLiquid and Belofor 2512 in papers were equal to 0.05 and 0.07 mg/L, respectively. A comparison between the experimental results indicates that the optical bleaching agent and its isomers and impurities are the most important characteristics of similarity between papers. Paper components are important and necessary additions; however, papers cannot always be unambiguously characterized based on these components. One or another type of paper be adequately characterized by individually studying the structure of paper using other analytical techniques and by supplementing these data with information on the optical bleaching agent. As a rule, wood from papermanufacturing countries is used for the manufacture of paper, but optical bleaching agents can be purchased from various vendors. The processes of the synthesis of

optical bleaching agents are similar; however, the concentrations of particular isomeric species in the bleaching agents are different. This is a characteristic sign of paper, as found experimentally. Belofor OBLiquid and Belofor 2512 were detected as optical bleaching agents in 30 and 2 (paper nos. 14 and 36) instances, respectively. In seven instances, Belofors were not detected because optical dyes (such as Direct White) were used as whitening agents according to manufacturers specications. Note that, under the given conditions of analysis, a standard solution of Belofor OBLiquid usually gave three peaks. Of these peaks, the second (main) peak corresponds to Belofor OBLiquid and the rst and third peaks are due to its isomeric forms. The ratio between the peaks depends on the site of paper manufacture. Not all of the extracts analyzed exhibited the third peak. Two series of experiments were performed. In the rst series, papers from various manufacturers with
Signal, arb. units 2 5 4 3 2 1 0 2 4 6 8

10

12 t, min

Fig. 4. Electropherogram of the extract of paper no. 36: (1, 2) paper Belofor and (3) paper component. Analytical conditions are specied in Fig. 3. Vol. 61 No. 2 2006

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DETERMINATION OF OPTICAL BLEACHING AGENTS (BELOFORS) IN WRITING PAPER Table 1. Normalized peak areas (S) of substances at migration times (t) for various types of paper; wavelength 270 nm Migration time, t (min) Paper no. Paper brand and manufacturer 3.64 4.11

175

4.87 5.65* 6.38* 7.16* 14.87** 16.20** Peak area, S

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Kama Ofce, Krasnokamsk Paper Mill of Goznak Ballet, OAO Svetogorsk, Russia Amicus Professional, Finland Chaika, Finland (manufactured before 2001) KYMPLUX, Finland ECO Copy, Sweden Heinzel, Lux Copy, Austria Mega Copy Ofce, Austria KMT paper, St. Petersburg paper mill Offset no. 1, OAO Syktyvkar LPK, Komi Republic

3.37 0.31 0.67

3.37 9.03 9.33 2.11 5.35 8.51

3.31

16.2

6.35 11.51 75.40 5.17 27.47 58.02 3.53 20.77 65.70

1.05 6.79 10.83 59.90 19.32 21.39 11.23 19.52 42.51

3.13 11.95 17.34 25.32 33.75

28.13 21.60 36.30 13.97 4.91 49.14 45.95 7.05 7.93 4.57 1.70

CARTBLANK, OAO Syktyvkar LPK, Komi Republic 2.69 3.04 21.42 47.63 18.16 Snegurochka, OAO Syktyvkar LPK, Komi Republic Writing No. 1, OAO Kotlas TsBK, Russia MAESTRO GUTENBERG extra, Czech Republic 5.71 54.73 31.63

3.45 10.19 17.27 69.08

MAESTRO GUTENBERG standard, Czech Republic 7.13 5.66 17.19 36.76 33.26 MAESTRO GUTENBERG classic, Czech Republic MAESTRO GUTENBERG special, Czech Republic Chaika, OAO Svetogorsk, Russia (manufactured since late 2001) Photocopying paper, Serpukhov Paper Mill 6.60 11.68 35.03 29.19 17.51 3.59 5.34 22.65 49.22 14.63 3.16 2.50 6.15 65.98 20.51

4.94 2.41 14.58 36.74 41.33

Notes: No peak. * Migration times of Belofor OBLiquid and its derivatives. ** Migration times of Belofor 2512 and its derivatives.

known brands were studied; however, the year of paper manufacture was unknown (Table 1). In the second series, papers from the Svetogorsk Pulp-and-Paper Mill (Russia), Data Copy (Sweden, France, and Finland), and Xerox (Finland and Russia) with known years of manufacture and paper brands were studied (Table 2).
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Based on the results of the rst series, data on the types of bleaching agents were obtained. Electropherograms gave information on paper components and the derivatives of bleaching agents used. However, we failed to group papers based on any sign in order to characterize the type of paper and the site of manufac2006

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Table 2. Normalized peak areas (S) of substances at migration times (t) for various types of paper; wavelength 270 nm Migration time, t (min) Paper no. Paper brand and manufacturer 3.64 4.11 4.87 5.65* 6.38* 7.16* 9.68** 10.94** 12.71 Peak area, S SVETOGORSK 20 21 22 23 24 25 26 27 28 1996 SvetoCopy New, 20012002 International Paper Ballet, 2002 International Paper Print&Copy, 2002 Copying Paper, 19951996 1997 Offset Paper 80 g/m2, 145%, 1999 Offset Paper 70 g/m2, 145%, 1999 Offset Paper 90 g/m2, 145%, 1999 DATA COPY 29 30 31 32 33 34 80 g/m2, 97%, 1998 Original 80 g/m2, 97%, 1999 M-Real, 2004 2000 M-Real, late 2002 to early 2003 Modo Paper, 1999 XEROX 35 37 38 39 36 Business 80 g/m2, 93%, 2002 Rank Xerox Premier 120 g/m2, 20002001 Excel, 2001 Business 80 g/m2, new, 2003 Excel 80 g/m2, 96%, 2002 1.46 4.08 7.54 4.51 85.39 71.17 2.98 1.24 7.77 83.99 8.24 3.07 1.04 9.97 1.59 11.48 10.95 4.15 7.52 6.91 6.07 67.41 67.12 63.69 4.09 4.22 1.89 0.57 2.97 4.28 2.89 2.44 7.87 4.32 5.17 5.58 7.02 7.24 4.10 4.88 4.09 78.19 83.43 80.35 83.64 82.22 85.22 2.19 1.77 1.82 2.16 2.22 2.35

45.74 17.02 37.23 1.86 0.95 0.87 2.79 2.88 3.09 5.45 6.85 4.37

3.76 20.77 28.21 7.00 21.88 4.84 5.03 4.52 5.70 6.50

49.86 30.07 59.18 74.71 3.27 5.46

3.81 17.81

50.00 15.12 34.88

Notes: No peak. * Migration times of Belofor OBLiquid and its derivatives. ** Migration times of Belofor 2512 and its derivatives. JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 2 2006

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Table 3. Ratios between the retention times of paper components, Belofors, and their derivatives in various types of paper Ratio between retention times No. Paper brand and manufacturer I 4.87 ------------------------------( 3.64 4.11 ) SVETOGORSK 20 24 25 21 22 23 26 27 28 1996 Copying Paper, 19951996 1997 SvetoCopy New, 20012002 International Paper Ballet, 2002 International Paper Print & Copy, 2002 Offset Paper 80 g/m2, 145%, 1999 Offset Paper 70 g/m2, 145%, 1999 Offset Paper 90 g/m2, 145%, 1999 0.6 1.27 1.25 0.97 1.17 1.8 1.1 8.4 7.2 6.8 12.4 10.7 12.2 6.0 5.8 5.5 8.0 7.4 7.7 2.55 3.9 3.9 1.9 2.2 1.79 II 6.38 --------5.65 III 6.38 ------------------------------( 5.65 7.16 ) IV 5.65 --------7.16

DATA COPY 29 31 33 34 30 32 80 g/m2, 97%, 1998 M-Real, 2004 M-Real, 20022003 Modo Paper, 1999 Original 80 g/m2, 97%, 1999 2000 XEROX 35 38 37 39 Business 80 g/m2, 93%, 2002 Excel, 2001 Rank Xerox Premier 120 g/m2, 20002001 Business 80 g/m2, new, 2003 11.23 15.6 8.1 12.4 2.53 3.65 11.1 12.6 10.4 11.5 3.23 11.0 6.65 7.4 6.6 6.25 2.69 1.44 1.48 1.44 1.7 1.19 4.9 0.15

ture. A common characteristic based on the character of the bleaching agent and its derivatives can be found; however, it is insufcient for an unambiguous interpretation of the entire set of data. It is likely that only one type of bleaching agent is always used for paper whitening, because we did not detect the combined use of two, three, or more types of bleaching agents. Moreover, based on the results of the rst series of experiments, we can conclude that the results are difcult to interpret unambiguously in the absence of information on the years of paper manufacture.
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The results concerning paper from the Svetogorsk Pulp-and-Paper Mill allowed us to distinguish three groups of papers (Table 3). The rst group included paper nos. 2123. These papers belong to the same type because of similar distributions of Belofor OBLiquid and its isomers, as well as paper components, in these papers. The Belofor constituent of the test papers was additionally identied as Belofor OBLiquid using NMR spectroscopy. The paper components and bleaching agents detected in the aqueous extracts of these papers were identical, but their concentrations were dif2006

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ferent. In accordance with the above signs, paper nos. 2628 were assigned to the second group. The difference between the rst and second groups consists in different ratios between the Belofor and its derivatives. It is most likely that a bleaching agent manufactured or purchased from another lot, in which the process of Belofor synthesis was changed, was used in the manufacture of papers in 2002. The third group of papers included paper nos. 20, 24, and 25, which were free of Belofors. For Data Copy papers, one main group of paper nos. 2934 was distinguished in accordance with the concentration of the Belofor OBLiquid agent. The use of a single bleaching agent in the manufacture of structurally different papers is economically sound and reasonable, as demonstrated by the results of analysis. Paper nos. 29 and 30 were similar to one another in the composition of paper components; the difference consisted in the concentrations of various Belofor OBLiquid species. Paper nos. 30 and 32 were similar in paper components; however, there was no similarity in the bleaching agent and its derivatives. Note that paper of the Data Copy brand can be manufactured in Sweden, Finland, or France. The experimental results suggest that Belofor from a constant (single) manufacturer is used as an optical bleaching agent in this paper. The results of studying Xerox papers did not allow us to group these papers as in the two previous series. The absence of Belofor from paper nos. 37 and 39 was a common characteristic of these papers; however, paper components were fully different. Paper nos. 35 and 38 contained Belofor OBLiquid, probably, from different lots of synthesis. A Belofor optical bleaching agent similar to Belofor 2512 in UV spectrum and elution time was present in paper no. 36. All of the Xerox papers containing Belofors were characterized by higher Belofor concentrations; this can be due to either the higher concentrations of the bleaching agent or the technology of application and, correspondingly, the extraction of the bleaching agent and paper components. This difference is characteristic. We can assume that various bleaching agents are used in Xerox papers with no preference to a single agent synthesized at one site in accordance with the same technology. Paper from the Svetogorsk Pulp-and-Paper Mill exhibited the best result in terms of writing paper classication. This is likely due to the manufacture of paper at one site and the use of optical bleaching agents from a single source. In accordance with the experimental results, Finnish Xerox paper is characterized by either a wide range of raw materials used or a wide range of output products. Data Copy papers are manufactured in various countries.

The availability of reference samples is an important factor in the study of writing papers. The laboratory should have at hand a collection of the entire printed matter from a particular manufacturer over the entire period of its operation. Only in this case can reliable information be obtained in a study of one or another paper and it is possible to determine where and when paper was manufactured and which substances are present in it. Thus, for example, we can see that the composition of Belofor used at the Svetogorsk Pulpand-Paper Mill in 1999 was somewhat different from that used in 2002. In conclusion, comparing the results of the rst and second series, note that paper nos. 2 and 4 (the rst series of experiments) fell within the second group of the second series of Svetogorsk (Russia) and Data Copy (Finland), respectively. Paper manufactured in Austria occupies a separate place and does not fall within any group. Paper nos. 5, 11, 12, 17, and 18 from the rst series can be placed in one group in accordance with the concentrations of the bleaching agent; however, they were manufactured in different countries. CONCLUSIONS Thus, we studied 39 extracts from writing papers. We found that, in principle, water-soluble optical bleaching agents can be determined and paper constituents can be detected in extracts by capillary electrophoresis. Thus, capillary electrophoresis in combination with other techniques can be used for identifying paper types, paper constituents, and probable manufacturers. A particular paper can be attributed to a particular lot, brand, or manufacturer if the entire range of output printed matter from the manufacturer is available. REFERENCES
1. Flyate, D.M., Svoistva bumagi (Properties of Paper), Moscow: Lesnaya Prom-st, 1986. 2. Damat, A.P. and Castle, L., J. Microcolumn Sep., 1999, vol. 11, no. 4, p. 259. 3. Jandera, P., Fischer, J., and Stanek, V., J. Chromatogr., A, 1997, vol. 772, p. 385. 4. Lin, C.E., Hsueh, C.C., Wang, T.Z., et al., J. Chromatogr., A, 2000, vol. 878, p. 137. 5. Jandera, P., Fischer, J., Stanek, V., et al., J. Chromatogr., A, 1996, vol. 738, p. 201. 6. Lin, C-E., Hsueh, C.C., and Wang, T.Z., J. Chromatogr., A, 1999, vol. 835, p. 197. 7. Martinez, R.C. and Gonzalo, E.R., J. Chromatogr., A, 1996, vol. 733, p. 349.

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