CN103760288B - Test method of banned azo-dye in cigarette paper - Google Patents
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Abstract
The invention discloses a test method of a banned azo-dye in cigarette paper and belongs to the technical field of physical and chemical inspection of harmful substance residues in lined paper, tipping paper and carton packaging paper for cigarettes. The test method is characterized by comprising the following steps: cutting a cigarette paper sample, adding a reduction solution, reducing an azo substance into aromatic amine by sodium hydrosulfite in a citric acid buffer solution, extracting aromatic amine from the solution by a liquid-liquid extraction method, concentrating, redissolving by methanol, testing by a liquid chromatography-tandem mass spectrometry combined instrument, and quantifying by an internal standard method. According to the method, the deficiencies of a sample treatment method in the prior art are overcome, and a sample pre-treatment method and instrument test conditions are optimized for the tipping paper, the lined paper and the carton packaging paper for the cigarettes; as a solid-phase extraction column does not need to be passed, cumbersome purification and concentration steps such as rotary evaporation are not required, and the method has the advantages of accuracy for operation, high recovery rate, quickness, simplicity, convenience, high sensitivity and the like.
Description
Technical field
The invention belongs to the physical and chemical inspection technical field that in tobacco lining paper, tipping paper, bar box packaging paper, objectionable impurities is residual, relate generally to the determination techniques of azo dyes in tobacco lining paper, tipping paper, bar box packaging paper, that azo material is reduced into aromatic amine by sodium hydrosulfite in citric acid solution specifically, then the aromatic amine in solution is extracted by the method for liquid-liquid extraction, redissolve with methyl alcohol after concentrated, measure with Liquid Chromatography-Tandem Mass Spectrometry combined instrument, inner mark method ration.
Background technology
Cigarette paper comprises in the production run of internal lining paper, tipping paper, bar box packaging paper etc., needs to add various chemicals as chemicals such as bleaching agent, processing aid, printing-ink, anticorrosion and bactericidal agents, to improve its packaging character and aesthetic property.But research finds, these chemicals can remain in paper, and then move in cigarette, some of them migration thing has toxicity even carcinogenesis, forms harm to the health of consumer.The developed countries such as the U.S., European Union, Japan all formulate corresponding regulation and limit standard to the wrappage of Food Contact, and implement strict market access management.Azo dyes is exactly the dyestuff containing azo group-N=N-in molecular structure.Number according to azo group number can be divided into monoazo, bisazo dye and polyazo dye.The synthetic dyestuffs of about 70% are the azo dyes based on azo structure in the market, and it extensively comes across among the synthetic dyestuffs such as direct dyes, acid dyes, reactive dye, premetallized dye, disperse dyes, the dye of positive ion and the condensation dye.
Usual research is thought, its structure of azo dyes itself can not produce deleterious effect to human body usually, but there is the azo dyes that some synthesize with " arylamine class intermediate ", after itself and human body skin Long Term Contact, can because of the weakly acidic condition of people's surface skin, very easily there is reduction reaction and azo group is ruptured, generating a large amount of aromatic amine compounds.Its reaction equation is as follows:
And this compounds often also exists serious carcinogenicity, very easily make human body cell bring out pathology, to human body skin even the organ such as bladder, ureter can produce extremely serious carcinogenic infringement, should be prohibited.This violated azo dyes, is also referred to as " carcinogenic aromatic amine dyestuff ", while i.e. the decomposable asymmetric choice net aromatic amine dyestuff that prohibits the use of standard GB/T 18401-2010.1994, German Government was promulgated a decree the 118 kinds of azo dyess prohibitting the use and can produce 20 kinds of harmful aromatic amines.European Union issued 97/548/EEC instruction in 1997, was that European Union member countries forbid using cleavable in textiles and leathers goods and the decree discharging the azo dyes of some carcinogenic aromatic amine, comprised 22 carcinogenic aromatic amines altogether.European Union issued the instruction of 2001/C 96E/18 on March 27th, 2001, and this directives prescribe detection method of 3 prohibitive dye, requires that the detected level of carcinogenic aromatic amine must not exceed 30 mg/kg simultaneously.On July 19th, 2002, European Union announces the 2002/61st command, points out that every azo dyes discharging carcinogenic aromatic amine is under the reducing conditions all disabled.In China's " national textile product keystone specification ", the limitation of carcinogenic aromatic amine is required to be 20 mg/kg." technical requirement of GB/T18885-2009 ecological textile " requires to be 20 mg/kg to the limitation of aromatic amine.
At present, the main vapor-phase chromatography of method (GC-ECD), gas chromatography tandem mass spectrometry (GC-MS) (Li Ying, Zhang Yan, Jing Ruijun etc., the aromatic amine compound in Gas Chromatography-Mass Spectrometry textile of aromatic amine is detected.Printing and dyeing, 2006(3): 40-42), liquid phase chromatography (HPLC-DAD) (Wang Huihui, Niu Zengyuan, Ye Xiwen etc., the high effective liquid chromatography for measuring of 23 kinds of forbidding azo dyes in dyed textiles and leather and fur products.Analytical test journal, 28(8): 944-948) and liquid chromatography tandem mass spectrometry (LC-MS/MS) (Wen Yuyun, Ou Ting, He Ming are superfine.The carcinogenic aromatic amine of azo dyes release in Ultra Performance Liquid Chromatography-tandem mass spectrometry Fast Measurement textiles and leathers.Chromatogram, 31(4): 380-385; Qian Weijun, Ruan Yong, Shi Dongliang etc.In dyed textiles, the High performance liquid chromatography-electrospray ionization mass spectrometry coupling method of forbidding azo dyes measures.Textile journal, 31 (12): 89-92).These methods all need loaded down with trivial details pretreatment process, and the partial aromatic amine recovery is low.GC, HPLC method requires low to instrument and equipment, but is vulnerable to the impact of impurity interference, causes false positive.And aromatic amine polarity is comparatively large, thermal stability is poor, when adopting GC-MS method to analyze, sensitivity is not high and chromatogram peak-to-peak type is poor.
summary of the invention:
Object of the present invention is intended to overcome prior art defect, there is provided a kind of after being shredded by sample, add reducing solution, then liquid-liquid extraction is carried out, extract concentrates, it is rear direct with the assay method of aromatic amine in liquid chromatography tandom mass spectrometry determination paper to redissolve, the method energy detects aromatic amine in paper fast, accurately, and measurement result is accurate, mensuration interference is few.
The object of the invention is to be achieved through the following technical solutions: the assay method of forbidding azo dyes in a kind of Cigarette paper, add reducing solution after being shredded by Cigarette paper sample, azo material is made to be reduced into aromatic amine by sodium hydrosulfite in citric acid solution, then the aromatic amine in solution is extracted by the method for liquid-liquid extraction, redissolve with methyl alcohol after concentrated, measure with Liquid Chromatography-Tandem Mass Spectrometry combined instrument, inner mark method ration, concrete steps are as follows:
A, Cigarette paper sample is carried out cutting, Cigarette paper sample comprises tobacco lining paper, tipping paper, bar box packaging paper, the specific requirement of cutting is as follows: the cutting method of cigarette tipping paper carries out according to the regulation of YC 171-2008, namely the tipping paper sample (should comprise monolateral) of long 200 mm, wide 40 mm is accurately cut; The cutting method of tobacco lining paper carries out according to the regulation of YC 264-2008, i.e. cutting area about 170 cm
2(be namely equivalent to the soft box of regular-size cigarette and pack the internal lining paper area adopted); The cutting method of tobacco shred and box packaging paper carries out according to the regulation of YC/T 207-2006, namely to rigid pack paper, master package face is accurately cut with reference to printing impression, area is 22.0 cm × 5.5 cm, to soft box packaging paper, gets a soft box packaging paper, area is 15.5 cm × 10.0 cm, to bar wrapping paper, at packaging front middle section, accurately cut the sample of 22.0 cm × 5.5 cm.
The extraction of b, sample: fragment sample being cut into 5 mm × 5 about mm, mixes; Take 0.5 g sample and (be accurate to 0.0001 g); Fragment is placed in 50 mL tool plug triangular flasks, adds the citrate buffer solution that 15 mL are preheated to 70 ± 2 DEG C, fiercely shake, make liquid immersion sample, in 70 ± 2 DEG C of water-baths, place 30 min; Add hydrosulfurous acid sodium water solution 3 mL, keep 70 ± 2 DEG C, react 30 min; Then cold water conical flask being placed in flowing is cooled to room temperature in 2min;
C, sample purification: the sodium hydroxide solution adding 1 mL 20% in triangular flask respectively, mark (D9-4-aminobphenyl) solution, 10 mL t-butyl methyl ether and appropriate (8-10g) anhydrous sodium sulfate in 100 μ L, vibrate 10 min, then leaves standstill 5 min.Get the supernatant of 1 mL, add the acetum that 2-3 drips, nitrogen blows to dry to the greatest extent, redissolves with the methyl alcohol of 1 mL, enters LC-MS/MS and analyzes;
D, preparation standard working solution: take in 10 mL volumetric flasks in the various aromatic amine standard items of 0.01g respectively, be also finally mixed with the standard working solution with concentration gradient with methanol dilution;
E, liquid chromatography tandom mass spectrometry determination: the standard working solution drawing the variable concentrations prepared, inject liquid chromatography-tandem mass spectrometer;
The calculating of f, aromatic amine measurement result
The quantitative test of residual quantity is carried out with internal standard method, namely with each aromatic amine and interior target quota ion, to its respective concentration, regretional analysis is carried out to peak area, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record and detect aromatic amine and interior target quota ion to peak area ratio, substitute into typical curve, try to achieve the residual quantity of the aromatic amine in sample.
The manner of formulation of standard working solution is as follows in the present invention: take 10 mg standard items in 10 mL volumetric flasks, be accurate to 0.0001g, use methanol dilution constant volume, be mixed with the hybrid standard storing solution that concentration is about 1.0 mg/mL; Pipette hybrid standard storing solution 1mL in 100mL volumetric flask, use methanol dilution constant volume, obtain the hybrid working solution that concentration is about 10 μ g/mL; Pipette the hybrid working solution of certain volume respectively in 10 mL volumetric flasks, and add 100 μ L inner mark solutions.Use methanol dilution constant volume, be namely mixed with the standard working solution of variable concentrations, series standard working solution concentration is respectively: 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL, 500 ng/mL and 1000 ng/mL;
The liquid phase chromatogram condition adopted is: chromatographic column: phenyl post (150 mm* 4.6 mm, 3 μm); Mobile phase: methyl alcohol/
5 mmol/L ammonium acetate aqueous solutions, flow velocity: 200 μ L/min; Gradient elution program is in table 1; Column temperature: 30 DEG C; Sample size: 5 μ L; The Mass Spectrometry Conditions adopted: scan mode: positive ion scans; Electric spray ion source (ESI); Atomization gas flow is 50 psi; Gas curtain airshed 15 psi; Auxiliary heating airshed is 50 psi; Ionization temperature 550 DEG C; Impinging air flows amount is 10 psi; 4 kinds of gases are nitrogen; The residence time is 50 msec; Ionization voltage 5500 V, detection mode: polyion reaction monitoring (MRM), MRM parameter is in table 2.
Method of the present invention overcomes the deficiency of prior art sample treatment, optimizes sample-pretreating method and instrument testing conditions for cigarette tipping paper, internal lining paper and tobacco shred and box packaging paper sample.Compared with prior art the inventive method has following excellent results:
(1) the present invention takes the pretreatment mode that shreds sample, and make solvent better contact sample, experimental result shows, process can improve the extraction efficiency of reduction effect and aromatic amine like this.
(2) in extract, add NaOH after the present invention's reduction, solution is adjusted to alkalescence, is conducive to the extraction of organic solvent to object.
(3) the present invention blows in journey at nitrogen and adds acetic acid, and aromatic amine is existed in the form of an ion, aromatic amine can be avoided to blow lose in process at nitrogen, improve the recovery.
(4) the inventive method utilizes LC-MS/MS to measure the content of aromatic amine in paper, can carrying out quantitatively and qualitative analysis simultaneously, carrying out qualitative analysis without the need to re-using other instruments.
(5) the inventive method was not owing to needing solid-phase extraction column, and without the need to the loaded down with trivial details purifications such as rotary evaporation and concentrated step, the method is had, and operation is accurate, the recovery is high, fast and convenient and sensitivity advantages of higher.
1. the detectability of the inventive method:
The aromatic amine standard working solution of variable concentrations is injected LC-MS/MS, and calculate detectability (LOD) with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), detectability is in table 3.
2. the repeatability of the inventive method and recovery of standard addition:
In blank sample, add the standard solution of aromatic amine, then carry out pre-treatment and LC-MS/MS analysis by method of the present invention, and calculate its recovery according to adding scalar sum measured value, the results are shown in Table 3.Method has good stability as can be seen from Table 3, and average relative standard's deviation (RSD) is less than 6.5%, illustrates that the present invention is reproducible.
Accompanying drawing explanation
Fig. 1 is assay method process flow diagram of the present invention (this figure is as Figure of abstract).
Embodiment
The present invention is described further below in conjunction with example, but is not restriction the present invention.
Example 1:
1. instrument and reagent:
T-butyl methyl ether, methyl alcohol, acetic acid is chromatographic grade reagent; Distilled water, meets the requirement of one-level water in GB/T 6682.
API 4000 quadrupole rod tandem mass spectrometer; Water-bath constant temperature oscillator; Switzerland Mettler AE 163 electronic balance (sensibility reciprocal: 0.0001g).
2. sample preparation:
First sample is carried out cutting: the cutting method of cigarette tipping paper carries out according to the regulation of YC 171-2008, namely accurately cut the tipping paper sample (should comprise monolateral) of long 200 mm, wide 40 mm; The cutting method of tobacco lining paper carries out according to the regulation of YC 264-2008, i.e. cutting area about 170 cm
2(be namely equivalent to the soft box of regular-size cigarette and pack the internal lining paper area adopted); The cutting method of tobacco shred and box packaging paper carries out according to the regulation of YC/T 207-2006; namely to rigid pack paper; master package face is accurately cut with reference to printing impression; area is 22.0 cm × 5.5 cm, to soft box packaging paper, gets a soft box packaging paper; area is 15.5 cm × 10.0 cm; to bar wrapping paper, at packaging front middle section, accurately cut the sample of 22.0 cm × 5.5 cm;
Sample is cut into the fragment of 5 mm × 5 about mm, mixes; Take 0.5 g sample and (be accurate to 0.01 g); Fragment is placed in 50 mL tool plug triangular flasks, adds the citrate buffer solution that 17 mL are preheated to 70 ± 2 DEG C, fiercely shake, make liquid immersion sample, in 70 ± 2 DEG C of water-baths, place 30 min; Add hydrosulfurous acid sodium water solution 3 mL, keep 70 ± 2 DEG C, react 30 min; Then conical flask is cooled to room temperature in 2min;
In triangular flask, add the sodium hydroxide solution of 1 mL20% respectively, the anhydrous sodium sulfate of 100 μ L inner mark solutions, 10 mL t-butyl methyl ether and 8-10 g, vibrate 10 min, then leaves standstill 5 min.Get the supernatant of 1 mL, add the acetum that 2-3 drips, nitrogen blows to dry to the greatest extent.Redissolve with the methyl alcohol of 1 mL, enter LC-MS/MS and analyze;
3. prepare standard working solution: take the various aromatic amine standard items of 10 mg to 10 mL volumetric flasks in, be accurate to 0.0001g, use methanol dilution constant volume, be mixed with the hybrid standard storing solution that concentration is about 1.0 mg/mL; Pipette hybrid standard storing solution 1mL in 100mL volumetric flask, use methanol dilution constant volume, obtain the hybrid working solution that concentration is about 10 μ g/mL; Pipette the hybrid working solution of certain volume respectively in 10 mL volumetric flasks, and add 100 μ L inner mark solutions.Use methanol dilution constant volume, be namely mixed with the pesticide standard working solution of variable concentrations, series standard working solution concentration is respectively: 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL, 500 ng/mL and 1000 ng/mL;
4. assay method: the quantitative test carrying out residual quantity with internal standard method, namely with each aromatic amine and interior target quota ion, to its respective concentration, regretional analysis is carried out to peak area, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record and detect aromatic amine and interior target quota ion to peak area ratio, substitute into typical curve, try to achieve the residual quantity of the aromatic amine in sample, try to achieve biphenylamine in sample, 4, the content of 4-diaminodiphenylmethane and 2,4-diaminotoluene is 2.08 μ g/g, 1.01 μ g/g and 0.85 μ g/g respectively.
For the accuracy of determination methods, add the biphenylamine of 1.0 μ g in this sample, 4, 4-diaminodiphenylmethane and 2, 4-diaminotoluene standard mixed solution, carry out the same sample pre-treatments, the Selective ion mode peak area of various aromatic amine is recorded with LC-MS/MS, substitute into typical curve, try to achieve the biphenylamine in now sample, 4, 4-diaminodiphenylmethane and 2, 4-diaminotoluene content is 3.0 μ g/g, 2.01 μ g/g and 1.80 μ g/g, i.e. biphenylamine, 4, 4-diaminodiphenylmethane and 2, the recovery of standard addition of 4-diaminotoluene is all greater than 96.0%, illustrate that the method is accurately.
Example 2:
Method as described in Example 1, selects another cigarette tipping paper sample, records various aromatic amine content in sample and is 0.
Example 3:
Method as described in Example 1, selects another tobacco lining paper sample, records various aromatic amine content in sample and is 0.
Claims (3)
1. the assay method of forbidding azo dyes in a Cigarette paper, it is characterized in that: be add reducing solution after being shredded by Cigarette paper sample, azo material is made to be reduced into aromatic amine by sodium hydrosulfite in citric acid solution, then the aromatic amine in solution is extracted by the method for liquid-liquid extraction, redissolve with methyl alcohol after concentrated, measure with Liquid Chromatography-Tandem Mass Spectrometry combined instrument, inner mark method ration, concrete steps are as follows:
A, Cigarette paper sample is carried out cutting;
The extraction of b, sample: fragment sample being cut into 5 mm × 5 about mm, mixes; Take 0.5 g sample; Fragment is placed in 50 mL tool plug triangular flasks, adds the citrate buffer solution that 15 mL are preheated to 70 ± 2 DEG C, fiercely shake, make liquid immersion sample, in 70 ± 2 DEG C of water-baths, place 30 min; Add hydrosulfurous acid sodium water solution 3 mL, keep 70 ± 2 DEG C, react 30 min; Then cold water conical flask being placed in flowing is cooled to room temperature in 2min;
C, sample purification: the sodium hydroxide solution adding 1 mL 20% in triangular flask respectively, mark in 100 μ L: the anhydrous sodium sulfate of D9-4-aminobphenyl solution, 10 mL t-butyl methyl ether and 8-10g, vibrate 10 min, then 5 min are left standstill, get the supernatant of 1 mL, add the acetum that 2-3 drips, nitrogen blows to dry to the greatest extent, redissolve with the methyl alcohol of 1 mL, enter LC-MS/MS and analyze;
D, preparation standard working solution: take the various aromatic amine standard items of 0.01g respectively in 10 mL volumetric flasks, be also finally mixed with the standard working solution with concentration gradient with methanol dilution;
E, liquid chromatography tandom mass spectrometry determination: the standard working solution drawing the variable concentrations prepared, inject liquid chromatography-tandem mass spectrometer; The liquid phase chromatogram condition adopted is: chromatographic column: phenyl post, specification 150 mm × 4.6 mm, 3 μm; Mobile phase: methyl alcohol/5mmol/L ammonium acetate aqueous solution, flow velocity: 200 μ L/min; Gradient elution; Column temperature: 30 DEG C; Sample size: 5 μ L; The Mass Spectrometry Conditions adopted: scan mode: positive ion scans; Electric spray ion source (ESI); Atomization gas flow is 50 psi; Gas curtain airshed 15 psi; Auxiliary heating airshed is 50 psi; Ionization temperature 550 DEG C; Impinging air flows amount is 10 psi; 4 kinds of gases are nitrogen; The residence time is 50 msec; Ionization voltage 5500 V, detection mode: polyion reaction monitoring (MRM); Gradient elution program sees the following form:
The calculating of f, aromatic amine measurement result
The quantitative test of residual quantity is carried out with internal standard method, namely with each aromatic amine and interior target quota ion, to its respective concentration, regretional analysis is carried out to peak area, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record and detect aromatic amine and interior target quota ion to peak area ratio, substitute into typical curve, try to achieve the residual quantity of the aromatic amine in sample.
2. the assay method of forbidding azo dyes in Cigarette paper according to claim 1, it is characterized in that: described Cigarette paper sample comprises tobacco lining paper, tipping paper, bar box packaging paper, the specific requirement of cutting is as follows: the cutting method of cigarette tipping paper carries out according to the regulation of YC 171-2008, namely accurately cut long 200 mm, wide 40 mm tipping paper sample and should comprise one monolateral; The cutting method of tobacco lining paper carries out according to the regulation of YC 264-2008, i.e. cutting area about 170 cm
2namely be equivalent to the soft box of regular-size cigarette and pack the internal lining paper area adopted; The cutting method of tobacco shred and box packaging paper carries out according to the regulation of YC/T 207-2006, namely to rigid pack paper, master package face is accurately cut with reference to printing impression, area is 22.0 cm × 5.5 cm, to soft box packaging paper, gets a soft box packaging paper, area is 15.5 cm × 10.0 cm, to bar wrapping paper, at packaging front middle section, accurately cut the sample of 22.0 cm × 5.5 cm.
3. the assay method of forbidding azo dyes in Cigarette paper according to claim 1, it is characterized in that: the manner of formulation of standard working solution is as follows: take the various aromatic amine standard items of 10 mg in 10 mL volumetric flasks, use methanol dilution constant volume, be mixed with the hybrid standard storing solution that concentration is about 1.0 mg/mL; Pipette hybrid standard storing solution 1mL in 100mL volumetric flask, use methanol dilution constant volume, obtain the hybrid working solution that concentration is about 10 μ g/mL; Pipette the hybrid working solution of certain volume respectively in 10 mL volumetric flasks, and add 100 μ L inner mark solutions; Use methanol dilution constant volume, be namely mixed with the standard working solution of variable concentrations, series standard working solution concentration is respectively: 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL, 500 ng/mL and 1000 ng/mL.
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| CN105277552B (en) * | 2015-11-18 | 2018-10-30 | 福州大学 | A kind of device and its application method for azo colouring agent on-line checking |
| CN106226114A (en) * | 2016-07-25 | 2016-12-14 | 云南中烟工业有限责任公司 | A kind of device of Cigarette paper analysis detection sample cutting |
| CN106323687A (en) * | 2016-08-04 | 2017-01-11 | 福建中烟工业有限责任公司 | Method for extracting aromatic amine, detection method, kit and application |
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| JP5357598B2 (en) * | 2009-03-30 | 2013-12-04 | 株式会社住化分析センター | Analysis method of amines |
| RU2414702C1 (en) * | 2009-10-28 | 2011-03-20 | Государственное образовательное учреждение высшего профессионального образования "Воронежская государственная технологическая академия" | Method of identifying natural carmine dye in presence of sulphonated azo dyes |
| CN102798677B (en) * | 2012-08-27 | 2014-01-29 | 江苏出入境检验检疫局工业产品检测中心 | Method for quickly screening and detecting azo dyes forbidden in textile materials, leathers and dyes using gas chromatography mass spectrometry |
| CN103175931A (en) * | 2012-11-29 | 2013-06-26 | 泰州市产品质量监督检验所 | Method for determining harmful aromatic amine by liquid chromatogram-tandem mass spectrometry |
| CN103033579A (en) * | 2012-12-27 | 2013-04-10 | 通标标准技术服务(上海)有限公司 | Rapid determination method for content of banned azo dye |
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