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Journal of Wood Chemistry and Technology

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The Analysis of Optical Brightening Agents in Paper Samples Using Liquid Chromatography with HighResolution Mass Spectrometry
Farzad Shadkami , Robert Helleur & Bruce B. Sithole
a b a a

Analytical Chemistry Group, Department of Chemistry, Memorial University of Newfoundland, St. John's, Newfoundland, Canada
b

Pulp and Paper Research Institute of Canada, Pointe-Claire, Quebec, Canada Available online: 03 Mar 2011

To cite this article: Farzad Shadkami, Robert Helleur & Bruce B. Sithole (2011): The Analysis of Optical Brightening Agents in Paper Samples Using Liquid Chromatography with High-Resolution Mass Spectrometry, Journal of Wood Chemistry and Technology, 31:1, 42-57 To link to this article: http://dx.doi.org/10.1080/02773811003725695

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Journal of Wood Chemistry and Technology, 31: 4257, 2011 Copyright Taylor & Francis Group, LLC ISSN 0277-3813 print / 1532-2319 online DOI: 10.1080/02773811003725695

The Analysis of Optical Brightening Agents in Paper Samples Using Liquid Chromatography with High-Resolution Mass Spectrometry
Farzad Shadkami,1 Robert Helleur,1 and Bruce B. Sithole2

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Analytical Chemistry Group, Department of Chemistry, Memorial University of Newfoundland, St. Johns, Newfoundland, Canada 2 Pulp and Paper Research Institute of Canada, Pointe-Claire, Quebec, Canada

Abstract: There is limited information available on the analysis and characterization

of optical brightening agents (OBA) commonly used in the pulp and paper industry. The available literature provides only a few reports on suitable chromatographic methods of analysis of OBA compounds present in paper products. The choice of suitable extraction solvents for OBA is also debatable. Some advocate using organic solvents, whereas others use water. The extracted OBAs are usually characterized by uorescence spectroscopy or liquid chromatography with UV detection. These methods are not selective and do not yield information on the chemical structures of the compounds. We have characterized OBA compounds by liquid chromatography with high-resolution mass spectrometry, specically liquid chromatographyquadrupole time-of-ightmass spectrometry (LC-QTOF-MS). Preliminary extraction results show that boiling water is effective for characterizing OBAs from commercial papers. Positive-ion and negativeion electrospray ionization allowed for observation of straightforward mass spectra for OBA standards and OBA extracts from paper products. The ESI-MS results for the most common OBA in the industry, TOBA (a tetrasulfonated stilbene derivative), gave a prominent m/z value of 1075.1797 in the negative-ion mode and 1077.1941 in the positive-ion mode corresponding to the [M 1] and [M + 1]+ species of tetrasulfonated optical brightening agent in the full acidic form. The LC-MS analysis of OBAs in paper extracts showed that they can exist in both cis and trans forms, an important parameter for proper quantitative analysis of OBAs. Preliminary experiments found that isomerization can actually occur when certain OBAs in solution are exposed to natural light. Keywords: Optical brightening agents, uorescent whitening agents, QTOF, LCQTOF-MS, optical brighteners, uorescent brightening agents, extraction Address correspondence to Farzad Shadkami, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 3H6. E-mail: shadkami@ mun.ca 42

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INTRODUCTION Optical brightening agents (OBAs), sometimes called uorescent whitening agents (FWAs), are now widely used to achieve a higher standard of whiteness in paper and board used for packaging and writing papers. They inuence the optical properties of the paper directly by means of chemicophysical interactions. The compounds absorb light in the UV range, 290400 nm, and emit visible blue light, 400480 nm, thereby enhancing the optical impression of higher whiteness and brightness. Consequently, the yellowish tinge of the bers shifts toward bluish-white. Thus, the degree of whiteness can be increased quite signicantly, especially if the OBAs are combined with shading dyestuffs.[1] This in turn leads to sharper contrasts in the printed image and helps to reduce toner consumption. OBAs can be added in the stock preparation, wet end, size press, and coater. High- or medium-substantivity compounds are used in stock applications, whereas medium- or low-substantivity compounds are used in the size press and coaters. The dosages used are 1% in stock applications and 1.5% in size press or coaters.[2] Lately, higher dosages, up to 3.5%, have been used to achieve even higher brightness properties in paper products. The OBA stilbene derivatives are widely used in the paper industry and include (1) disulfur (or 4,4 -bis[[4-[bis(2-hydroxyethyl)amino]-6-anilino1,3,5-triazin-2-yl]amino]stilbene-2,2 -disulfonic acid [DOBA]), (2) tetrasulfur (or tetrasodium 4,4 -bis[[4-[bis(2-hydroxyethyl)amino]-6-(4-sulfonate anilino)-1,3,5-triazin-2-yl]amino]stilbene-2,2 -disulfonate salt [TOBA]), and (3) hexasulfur (or hexasodium 4,4 -bis[[4-[bis(2-hydroxyethyl)amino]6-(2,5-disulfonate anilino)-1,3,5-triazin-2-yl]amino]stilbene-2,2 -disulfonate salt [HOBA]) derivatives (Figure 1). Among them, tetrasulfur (TOBA) is the most commonly used. In addition to the pulp and paper industry, OBAs are widely used in the textile industry and in the manufacture of household detergents. However, there

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Figure 1. Original forms (structures) of optical brightening standards as received. Shown are the structures of (1) DADS, (2a) DOBA, (2b) TOBA, and (2c) HOBA.

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are concerns about toxicity and the environmental effects of these products. Governmental agencies such as the U.S. Food and Drug Administration (FDA) require assurance that food packaging will not release OBAs into food. Consequently, such food packaging should not contain OBAs, and food packaging made from recycled bers should be tested to ensure that there is no migration of OBAs into food.[3] Because the compounds are soluble in water, they can accumulate in natural ground and surface waters and they are not easily degradable by environmental biological systems.[4] Hence, their analysis and determination in various matrices is important. OBAs were originally analyzed by thin-layer chromatography (TLC) and spectrophotometric techniques.[5,6] However, these techniques are affected by various interfering species and suffer from low selectivity. Gas chromatography (GC) has limited applications in the analysis of the OBAs used in the pulp and paper industry because of their high molecular weights and low volatility induced by the presence of hydroxyl, amino, and disulfonate groups, even after extensive derivatization. Capillary zone electrophoresis (CZE) with UV and uorescence detectors has also been used in the analysis of aromatic sulfonates[7] and for the determination of FWAs in paper and board packaging after using hot water extraction.[8] We have previously used spectrouorometry to measure the migration of OBAs from food packaging made from recycled bers.[9] The method works well for monitoring of total OBAs but cannot identify the chemistries of the present OBAs. Liquid chromatographymass spectrometry (LC-MS) has been used for better characterization of the chemistries of OBAs. Ogura et al.[10] developed a technique for characterization of optical brighteners from ve groups of stilbene, biphenyl stilbene, pyrazoline, oxazole, and coumarin derivatives using LC-MS. Nageswara Rao et al.[11] analyzed OBA compounds such as 4,4 -dinitrostilbene-2,2 -disulfonic acid, 4-amino-4 -nitrostilbene-2,2 disulfonic acid, and 4,4 -diaminostilbene-2,2 -disulfonic acid and studied their degradation products using electrospray ionizationmass spectrometry (ESIMS). They also studied[12] separation and determination of aromatic sulfonates in an aquatic environment using ESI-MS. In another study,[13] OBAs were investigated qualitatively and quantitatively by solid-phase extraction following by high-performance liquid chromatography (HPLC)-ESI-MS (ion trap) applying di-n-hexylammonium acetate as the ion-pairing reagent in the mobile phase. Chen and Ding[14] used hot water and solid-phase extraction followed by mass spectrometric analysis to measure OBAs in paper and clothes. All of the above ESI-MS detections used negative-ion modes. Stoll and Giger[15] developed a method for the extraction and quantitative determination of three detergent-derived OBA isomers in lake sediments and surface waters by HPLC and uorescence detection after postcolumn UV irradiation. LC-QTOF-MS, which is a hybrid of LC interfaced to a mass spectrometer containing two mass analyzers in parallel, a quadrupole (Q), and time of ight (TOF) analyzer, provides good mass accuracy and sensitivity for determinations

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of low- and high-molecular-weight compounds. The instrument is also capable of MS-MS analysis in which high-molecular-weight compounds can be selected as their precursor ions by the quadrupole mass analyzer and fragmented in a collision cell to produce and identify its fragment ions in a time-of-ight mass analyzer. This technique has been applied to the analysis of a wide range of functionally complex compounds including phosphorylated peptides,[16] protein tyrosine-O-sulfated peptides,[17] alkaloids,[18] and avonoids,[19] but it has not yet been applied in the investigation of OBAs. In the present study we describe for the rst time the separation and accurate mass determination of four stilbene derivative OBAs including 4,4 -diamino-2,2 -stilbene-disulfonic acid (DADS), DOBA, TOBA, and HOBA in the molecular range of 3701369 Da in both negative- and positive-ion modes by LC-ESI-QTOF-MS. The extraction and analysis of OBAs present in different commercial copy-grade papers containing OBAs and the observation of isomerization occurring in some structures under natural light were also undertaken.

EXPERIMENTAL Chemicals Ammonium acetate (98%), DADS (85%), and uorescent brightener 28 (DOBA) were purchased from Sigma Chemical Co. (St. Louis, MO). Tetrasulfonated OBA (TOBA), which was a commercial formulation, KalBitec, was kindly supplied by Kalamazoo Chemicals (Richland, MI), and hexasulfonated OBA (Leucophor BCS), or HOBA, was kindly supplied by Clariant Inc. (Charlotte, NC; material number: 15363624156). LC-MS-grade acetonitrile, ethanol, and water were obtained from Honeywell Burdick & Jackson (Muskegon, MI). The concentrations of the standards were 8 mg/10 g of acetonitrile/water (35%/65%). However, because of the low solubility of DADS and the possibility of clogging the LC syringe, the standard solutions were ltered on polytetrauoroethylene (PTFE) lters (0.20 m pore size); therefore, the concentration of DADS was lower than expected.

OBA Extraction from Paper Samples Hot water extraction of OBAs from paper products was initially chosen because other studies[8,14] have shown satisfactory spike recoveries of OBAs from paper. The present study goes further by examining aqueous alcoholic and aqueous acetonitrile as extraction solvents as well. Paper samples were cut into small pieces and known weights were extracted using a SoxtecTM 2050 extraction apparatus (FOSS North America, Inc., Eden Prairie, MN). Operation

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and use of a Soxtec apparatus has been described previously.[20] Several solvents, namely, ethanol/water (50/50%), methanol/water (50/50%), acetonitrile/water (50/50%), water, and ethanol, were evaluated to ascertain the best extraction efciency for characterizing OBA present in real samples. The nal paper extracts were analyzed by LC-QTOF-MS. Three different paper samples with differing brightness levels were analyzed for OBAs including copy-grade printing paper with a brightness of 92, a card paper with a brightness of 86, and a darker paper with a brightness of 79. LC-QTOF-MS An accurate-mass LC-QTOF LC/MS (Model 6520, Agilent Technologies, Mississauga, ON, Canada) was used for analysis. The OBAs were separated on a C18 HPLC column (Zorbax Eclipse plus, 2.1 50 mm, 1.8 m, Agilent Technologies, Mississauga, ON, Canada). The chromatographic system was an Agilent liquid chromatograph, 1200 Series, using a gradient elution with solution A (water, 5 mM ammonium acetate, pH = 7.2) and solution B (50% acetonitrile:50% methanol) at a ow rate of 0.2 mL/min. The gradient program used was as follows: 10% B increased to 60% B in 16 min, then 90% B in 25 min, and nally 95% B in 27 min. The ion source was an ESI. The source and other MS parameters were as follows: gas temperature = 350 C; drying gas ow = 10 L/min; nebulizer gas pressure = 40 psig; Vcap = 4000 V; MS TOF fragmentor = 200 V; skimmer voltage kept at 65 V. The mass spectrometer was operated in both positive and negative modes. MS data were acquired in both centroid and prole modes and processed using Agilent MassHunter software. In MS/MS studies, a xed collision energy of 60 V was applied and the reference masses (112.0509 and 922.0092) were excluded. Exposure of OBA Standards to Light Irradiation All four OBA standards (DADS, DOBA, TOBA, and HOBA) in concentrations of 10, 100, and 1000 ppm in water were exposed to light for one month. The source of the light was normal sunlight exposure during the day and cool white uorescence lamp at night. The goal was to examine the chemical stability of OBA standards in the light and the occurrence of isomerization. RESULTS AND DISCUSSION Mass Spectral Characterization of OBAs As shown in Figure 1, two of the OBA standards were sodium salts of sulfonic acid (TOBA and HOBA) and the other two were sulfonic acids (DADS and

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Figure 2. LC-QTOF-MS: (a) total ion chromatogram for mixture of four optical brightening standards including DOBA-U (an unknown impurity along with DOBA) and (b) extracted ion (+ mode) chromatogram for HOBA.

DOBA). Under the chromatographic conditions employed, it is expected that all of the structural forms would be in their full acidic form. The MS data support this. The chromatographic conditions (mobile phases, gradient elution, and column type) were optimized to achieve adequate resolution of the OBA compounds as illustrated in Figure 2a. However, coelutions of DADS and HOBA could not be resolved. Figure 2b demonstrates that the extracted ion chromatogram for an m/z value of 1237.1060 isolates the HOBA peak. This chromatogram is the result of LC separation and ESI-QTOF mass detection in the positive mode, which is in contrast to other studies in which only the negative mode was used.[1012] The different retention times of the OBA standards can be explained by the differences in the molecular weights of the compounds, the interaction of acidic sites of the OBA with the C18 nonpolar column, and the interaction of polar hydroxyl and amino groups with the column and their different behaviors in multicomponent gradient elution.

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Figure 3. QTOF mass spectra of DADS in (a) positive-ion and (b) negative-ion mode.

The anticipated mass spectrum of DADS was observed in both positive and negative modes as shown in Figure 3. The mass-to-charge ratios corresponding to [M + H]+, 371.0376, and [M H], 369.0211, were observed. The molar mass of the chemical, based on its empirical formula (C14 H14 N2 O6 S2 ), is 370.0293. The mass accuracy of observed vs. calculated data obtained with the QTOF-MS for all observed ions are given in Table 1. Two chromatographic peaks for the standard DOBA were observed: DOBA and DOBA-U (DOBA-unknown; Figure 2a). The molar mass of DOBA, with the empirical formula of C40 H44 N12 O10 S2 , is 916.2745. Analysis of the DOBA peak (actual DOBA) in the positive-ion ESI mode showed m/z adducts of 917.2845 and 459.1456, which represent a singly charged ion of [M + H]+ and

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Table 1. Mass spectra data and assignments

Compound 370.0293 916.2745

Retention time (min) Molecular weight Assignment m/z (Observed) m/z (Calculated) Error (ppm)

Polarity

DADS

1.01

DOBA

16.50

371.0372 369.0215 917.2818 459.1451 915.2661 457.1299

1.1 1.1 2.9 1.1 0.76 1.3

[M + H]+ [M H] [M + H]+ [M + 2H]2+ [M H] [M 2H]2

DOBA-U

14.30

928.2901

TOBA

9.89

1076.1881

Precursor ion MS/MS of 1077.1941 of TOBA HOBA 1236.1017 1237.1060 619.0580

371.0376 369.0211 917.2845 459.1456 915.2654 457.1305 929.3031 465.1562 927.2911 463.1423 1077.1941 539.1016 1075.1797 537.0877 1043.1710 963.1002 1077.1959 539.1019 1075.1803 537.0861 1043.1742 963.1040 1237.1096 619.0587 1.7 0.56 0.56 2.9 3.1 3.9 2.9 1.1 [M + H]+ [M + 2H]2+ [M H] [M 2H]2 [M 2OH + H] [1043.1710 SO3 ] [M + H]+ [M + H]2+

(+) () (+) (+) () () (+) (+) () () (+) (+) () () (+) MS/MS (+) MS/MS (+) (+)

1.01

49

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Figure 4. QTOF mass spectra of DOBA: (a) positive-ion and (b) negative-ion mode.

a doubly charged ion of [M + 2H]2+ (Figure 4a), respectively. In the negativeion mode DOBA yielded two ions with m/z of 915.2654 and 457.1305 that correspond to [M H] and [M 2H]2 (Figure 4b), respectively. On the other hand, for DOBA-U, negative-ion ESI yielded a simple spectrum with ions of m/z 927.2911 and 463.1423 (Figure 5a). A similar pattern was observed in the positive-ion mode but with the addition, instead of subtraction, of a proton (Figure 5b). This nding suggests that the molecular weight of DOBA-U can be 928.2901. This structure is unknown, but because of its molecular weight and chromatographic behavior it is considered an impurity in the industrial production of DOBA; however, the molecular weight could correspond to [M 2OH + 2Na]. The chromatographic results for TOBA with a molar mass of 1076.1881 (C40 H44 N12 O16 S4 ) is shown in Figure 2a. The standard TOBA sodiated salt converts to its acidic form when injected into the LC mobile phase. The mass

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Figure 5. QTOF mass spectra of DOBA-U (unknown DOBA standard) in (a) negativeion and (b) positive-ion mode.

spectrum of the TOBA peak at the retention time of 9.89 min gives m/z = 1075.1797 in the negative-ion mode and m/z = 1077.1941 in the positive-ion mode. In the negative-ion mode m/z = 1075.1797 could correspond to [M H], whereas m/z = 537.0877 would correspond to a doubly charged ion of [M 2H]2 (Figure 6b). Also, in the positive-ion mode the m/z = 1077.1941 could correspond to [M + H]+ and m/z = 539.1016 would correspond to [M + 2H]2+ (Figure 6a). Mass-to-charge values of 1075.1797 in the negative-ion mode and 1077.1941 in the positive-ion mode are strong markers of TOBA. The molar mass of HOBA, based on the empirical formula of C40 H44 N12 O22 S6 , is 1236.1017. The HOBA assignment in the positive-ion mode gave m/z values of 1237.1060 and 619.0580 (Figure 6c). These m/z values would correspond to [M + H]+ and [M + H]2+.

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Figure 6. QTOF mass spectra of TOBA in (a) positive-ion and (b) negative-ion mode and (c) HOBA in positive-ion mode.

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In Table 1 all calculated masses were reported using QTOF software mass calculator, and the ppm mass error was calculated based on [(Observed mass Calculated mass)/Calculated mass] 106.

MS-MS of OBA Standards A representative precursor ion MS-MS mass spectrum in this study was TOBA in the positive-ion mode. The precursor ion at 1077.1941 was selected and subjected to low-energy collision showing two major ions at m/z = 1043.1710 and m/z = 963.1002. These ions are believed to correspond to [M 2OH + H] and [1043.1710 SO3 ], respectively (Figure 7). Thus, the structural information that can be obtained by MS-MS data of these OBA compounds is due to the presence of hydroxyl and sulfone groups.

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Figure 7. (a) QTOF mass spectrum of TOBA in positive-ion mode and (b) precursor ion MS/MS of m/z 1077.1941 of TOBA.

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Exposure of OBA Standards to Light All four OBA standards (DADS, DOBA, TOBA, and HOBA) were exposed to light for one month. The standards were analyzed by LC-QTOF-MS after exposure. DADS and HOBA did not show any isomerization; however, the chromatogram of DOBA showed an isomer at retention time of 16.0 min. TOBA also showed an isomer (TOBA ) at retention time of 5.3 min in a chromatogram similar to that shown in Figure 8. The mass spectra of trans and cis isomers were the same. Only the peak area for the main TOBA and DOBA peaks were decreased by about 30% after exposure to light. This is important for papermaking because the cis and trans forms of OBAs affect the brightness of the papers.[17] Also, this is important for quantitative measurements of OBAs wherein the presence of both cis and trans forms of the OBAs may not be taken into account. This will lead to erroneous calculations if the quantitation is done based on only one form of the OBAs.

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Extraction of OBAs from Paper Samples The extraction efciency was calculated based on the sum of the peak areas for both TOBA and its TOBA isomers (Figure 8) relative to the peak area of a reference TOBA standard (TOBA). Afterwards, the weight percentage of TOBA and TOBA in a known weight of paper sample was calculated after considering the concentration factor. All extraction solvents except ethanol were able to qualitatively extract the OBAs present in the paper. The only OBAs found in the paper products under study were TOBA or TOBA . The amounts extracted

Figure 8. LC-QTOF-MS total ion chromatogram for a printing paper extract (TOBA and TOBA are two isomers).

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based on sample weight were low; the highest was 0.048% using hot water. Our study did not quantitatively measure the remaining OBA on the paper. This could be accomplished in future studies using a uorescence spectrometer capable of reectance to quantify the amount of remaining uorescent OBAs. The percentage extraction for the various solvents were water (0.048 0.002%) > methanol/water (50%) (0.030 0.004%) > acetonitrile/water (50%) (0.025 0.003%) > ethanol/water (50%) (0.015 0.003%). The values in parentheses indicate the weight percentage of TOBA and TOBA in printing paper (brightness 92) for seven replicates. The relative polarity of the OBAs, based on their different functional groups, supports the descending order of extraction efciency from lower organic content (i.e., water) to higher organic content (i.e., ethanol); however, it should be noted that other researchers[21] have mentioned the use of dimethylformamide (DMF) to extract OBAs from paper samples. Further studies should be undertaken on paper products where aluminum sulfate and other additives are used as cationic xatives for OBAs onto bers and, therefore, OBAs maybe more difcult to extract. The employment of acidic extraction conditions could thus be a good solution to overcome the chemical xation and to assist in weakening the hydrogen bonds between OBAs and cellulose. Analysis of OBAs in high-brightness paper (brightness 92) showed that the paper contained two stereochemical isomers of the acidic form of tetrasulfonated OBA (TOBA and TOBA ) as illustrated in Figure 8. Seven replicated analyses indicated that the paper contained 0.048 0.002% OBA (w/w%). Two lower brightness papers, B-86 and B-79, contained the same OBA at 0.008 0.001% and 0.002 0.001%. Surprisingly, a signicant amount of DOBA (0.053 w/w%) was found in the paper with the lowest brightness (B-79). This is because the paper was made from mechanical pulp, unlike the other papers that were made from fully bleached kraft pulps. The result illustrates that addition of OBAs to mechanical pulps is less efcient in induction of brightness than addition of similar dosages of OBAs to bleached kraft pulp.[22,23] Analysis of papers exposed to light for a month in a simulated, intense cool white uorescence chamber showed no further isomerization of the OBAs.

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CONCLUSIONS Optical brightening agents were separated and analyzed by LC-QTOF-MS. For all OBAs (DADS, DOBA, TOBA, and HOBA) the molecular ions corresponded mainly to [M + H]+ and [M H] in positive and negative-ion ESI, respectively. This work advances the applications of OBAs in industry in which OBAs can be qualitatively and quantitatively analyzed. Analysis of commercial copier-grade papers showed the presence of two stereochemical isomers of tetrasulfonated OBA or TOBA, which is the most economical OBA

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additive in the pulp and paper industry. It was found that, for the paper products used in this study, the descending order of extraction efciency was from lower organic content (i.e., water) to higher organic content (i.e., ethanol). However, in future work it may be prudent to explore acidic extraction conditions, or other organic solvents such as DMF, to ascertain their extraction efciency. Further research is required on extraction techniques and on a wider range of paper products before routine extraction and analysis of OBAs is established. This should include a method that can semiquantitatively measure the amount of OBA remaining on the paper after extraction by measuring uorescence; for example, a uorescence reectance spectrometer.

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REFERENCES
1. Branston, R. Fluorescent whitening agents (FWAs) and dyes in paper coating in 1998. In Coating Materials: Pigments, Binders, and Additives Short Course; TAPPI Press: Norfolk, Virginia, 1998; pp. 540555. 2. Murray, S.G. Dyes and uorescent whitening agents for paper. In Paper Chemistry; Roberts, J.C., Ed.; Blackie Academic & Professional: Glasgow, 1991; 132161. 3. Code of Federal Regulations, Foods and Drugs, Title 21, Parts 170199. Ofce of the Federal Register National Archives and Records Administration, U.S. Government Printing Ofce, Washington, DC, Revised April 1, 2007. 4. Hashm, M.A.; Kulandai, J.; Hassan, R.S. Biodegradability of branched alkylbenzene sulfonates. Journal of Chemical Technology & Biotechnology 1992, 54, 207214. 5. McPherson, B.P.; Omelczenko, N. The determination of optical brighteners in laundry detergents by reverse phase and ion pair high performance liquid chromatography. Journal of the American Oil Chemists Society 1980, 57, 388391. 6. Lepri, L.; Desideri, P.G.; Coas, W. High-performance thin-layer chromatography of uorescent whitening agents and their identication in detergents. Journal of Chromatography 1985, 322, 363370. 7. Loos, R.; Niessner, R. Analysis of aromatic sulfonates in water by solid-phase extraction and capillary electrophoresis. Journal of Chromatography A 1998, 822, 291303. 8. Damant, A.P.; Castle, L. Determination of uorescent whitening agents in paper and board packaging by capillary electrophoresis. Journal of Microcolumn Separations 1999, 11, 259262. 9. Milanova, E.; Sithole, B.B. Migration of uorescent whitening agents from food packaging made from recycled paper. Paper, Film & Foil Converter 2004, 78, 7883. 10. Ogura, I.; DuVal, D.L.; Miyajima, K. Characterization of brighteners in detergents by high-performance liquid chromatography/mass spectrometry/ultraviolet/uorescence and three-dimensional high-performance liquid chromatography. Journal American Oil Chemists Society 1995, 72, 827833. 11. Nageswara Rao, R.; Venkateswarlu, N.; Khalid, S.; Narsimha, R. LC-PDA and LCESI-MS separation and determination of process-related substances arising from

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12.

13.

Downloaded by [University of Guelph] at 22:46 29 February 2012

14.

15.

16.

17.

18.

19.

20. 21.

22.

23.

stilbene-type uorescent whitening agents. Application to monitoring of their photodegradation products in industrial efuents and aqueous environmental systems. Journal of Separation Science 2005, 28, 443452. Nageswara Rao, R.; Venkateswarlu, N.; Khalid, S.; Narsimha, R. Liquid chromatographic separation and determination of aromatic sulfonates in an aquatic environment using a photodiode array and electrospray ionization-mass spectrometer as detectors. Analytical Sciences 2003, 19, 611615. Chen, H.; Wang, S.; Ding, W. Determination of uorescent whitening agents in environmental waters by solid-phase extraction and ion pair liquid chromatographytandem mass spectrometry. Journal of Chromatography A 2006, 1102, 135142. Chen, H.; Ding, W. Hot water and solid-phase extraction of uorescent whitening agents in paper materials and infant clothes followed by unequivocal determination with ion-pair chromatographytandem mass spectrometry. Journal of Chromatography A 2006, 1108, 202207. Stoll, J.A.; Giger, W. Determination of detergent-derived uorescent whitening agent isomers in lake sediments and surface waters by liquid chromatography. Analytical Chemistry 1997, 69, 25942599. Bateman, R.H.; Carruthers, R.; Hoyes, J.B.; Jones, C.; Langridge, I.; Millar, A.; Vissers, J.P.C. A novel precursor ion discovery method on a hybrid quadrupole orthogonal acceleration time-of-ight mass spectrometer for studying protein phosphorylation. Journal of the American Society for Mass Spectrometry 2002, 13, 792803. Salek, M.; Costagliola, S.; Lehmann, W.D. Protein tyrosine-O-sulfation analysis by exhaustive product ion scanning with minimum collision offset in a NanoESI Q-TOF tandem mass spectrometry. Analytical Chemistry 2004, 76, 51365142. Zhang, J.; Jin, Y.; Dong, J.; Xiao, Y.; Feng, J.; Xue, X.; Zhang, X.; Liang, X. Systematic screening and characterization of tertiary and quaternary alkaloids from Corydalis yanhusuo W. T. Wang using ultra-performance liquid chromatographyquadrupole-time-of-ight mass spectrometry. Talanta 2009, 78, 513522. Kao, T.H.; Huang, S.C.; Inbaraj, B.S.; Chen, B.H. Determination of avonoids and saponins in Gynostemma pentaphyllum (Thunb.) Makino by liquid chromatographymass spectrometry. Analytica Chimica Acta 2008, 626, 200211. Sithole, B.B.; Vollstaedt, P.; Allen, L.H. Composition of Soxtec and Soxhlet systems for determining extractives content. Tappi Journal 1991, 74, 187191. Jao, M.L.; Liao, M.I.; Huang, C.T.; Cheng, C.C.; Chou, S.S. Studies on analytical method for determination of uorescent whitening agents in paper containers for food. Journal of Food and Drug Analysis 1999, 7, 5363. Zhang, H.; Hu, H.; He, Z.; Ni, Y.; Zhou, Y. Retention of optical brightening agents (OBA) and their brightening efciency on HYP-containing paper sheets. Journal of Wood Chemistry and Technology 2007, 27, 153167. Holmberg, M. Dyes and uorescent whitening agents. In Papermaking Science and Technology 4. Papermaking Chemistry; Gullichsen, J.; Paulapuro, H.; Neimo, H., Eds.; Faper Oy: Helsinki, Finland, 1999; 303320.