CN103760288A - 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
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Technical field
The invention belongs to the residual physical and chemical inspection technical field of objectionable impurities in tobacco lining paper, tipping paper, bar box packaging paper, 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 by the method for liquid-liquid extraction, extract the aromatic amine in solution, after concentrated, with methyl alcohol, redissolve, with Liquid Chromatography-Tandem Mass Spectrometry combined instrument, measure inner mark method ration.
Background technology
Cigarette paper comprises in the production run of internal lining paper, tipping paper, bar box packaging paper etc., need 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 discovery, these chemicals can remain in paper, and then move in cigarette, and some of them migration thing has even carcinogenesis of toxicity, and consumer's health is formed to harm.The developed countries such as the U.S., European Union, Japan are all to having formulated corresponding rules and limit standard with the wrappage of Food Contact, and have implemented strict market access management.Azo dyes is exactly the dyestuff that contains azo group-N=N-in molecular structure.According to the number of azo group number, can be divided into monoazo, bisazo dye and polyazo dye.The synthetic dyestuffs of 70% left and right are and take azo structure as basic azo dyes 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.
Conventionally research is thought, its structure of azo dyes itself can not produce deleterious effect to human body conventionally, but there are some to use " arylamine class intermediate " synthetic azo dyes, because of after itself and human body skin Long Term Contact, can be because of the weakly acidic condition of people's surface skin, very easily there is reduction reaction and make azo group fracture, generate a large amount of aromatic amine compounds.Its reaction equation is as follows:
And this compounds often 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 ", the decomposed aromatic amine dyestuff that namely standard GB/T 18401-2010 bans use of simultaneously.1994, German Government was promulgated a decree and is banned use of 118 kinds of azo dyess that can produce 20 kinds of harmful aromatic amines.European Union issued 97/548/EEC instruction in 1997, was the decree that European Union member countries forbid using cleavable in textiles and leathers goods and discharge the azo dyes of some carcinogenic aromatic amine, comprised altogether 22 carcinogenic aromatic amines.European Union has issued the instruction of 2001/C 96E/18 on March 27th, 2001, the detection method of 3 forbidding dyestuffs has been stipulated in this instruction, requires 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 that discharges carcinogenic aromatic amine under reducing condition is all disabled.In the textile product keystone specification > > of China < < country, for limiting the quantity of of carcinogenic aromatic amine, requiring is 20 mg/kg.It is 20 mg/kg that < < GB/T18885-2009 ecological textile technical requirement > > requires limiting the quantity of of aromatic amine.
At present, detect 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.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 dyess in dyed textiles and leather and fur products.Analytical test journal, 28(8): 944-948) and Liquid Chromatography-Tandem Mass Spectrometry method (LC-MS/MS) (Wen Yuyun, Ou Ting, He Ming are superfine.The carcinogenic aromatic amine that in Ultra Performance Liquid Chromatography-tandem mass spectrometry Fast Measurement textiles and leathers, azo dyes discharges.Chromatogram, 31(4): 380-385; Qian Weijun, Ruan Yong, Shi Dongliang etc.The High performance liquid chromatography-electrospray ionization mass spectrometry coupling method of forbidding azo dyes in dyed textiles is measured.Textile journal, 31 (12): 89-92).These methods all need loaded down with trivial details pretreatment process, and the part aromatic amine recovery is low.GC, HPLC method require low to instrument and equipment, but are vulnerable to the impact that impurity disturbs, and cause false positive.And aromatic amine polarity is large, thermal stability is poor, while 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, provide a kind of after sample is shredded, add reducing solution, then carry out liquid-liquid extraction, extract is concentrated, the rear direct assay method with aromatic amine in liquid chromatography tandom mass spectrometry determination paper of redissolution, the method can fast, accurately detect aromatic amine in paper, and measurement result is accurate, mensuration is disturbed 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, to add reducing solution after Cigarette paper sample is shredded, make azo material by sodium hydrosulfite, be reduced into aromatic amine in citric acid solution, then by the method for liquid-liquid extraction, extract the aromatic amine in solution, after concentrated, with methyl alcohol, redissolve, with Liquid Chromatography-Tandem Mass Spectrometry combined instrument, measure, inner mark method ration, concrete steps are as follows:
A, Cigarette paper sample is carried out to 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, accurately cut long 200 mm, the tipping paper sample of wide 40 mm (should comprise monolateral); The cutting method of tobacco lining paper carries out according to the regulation of YC 264-2008, i.e. cutting area approximately 170 cm
2(being equivalent to the internal lining paper area that the soft box packing of regular-size cigarette adopts); The cutting method of tobacco shred and box packaging paper carries out according to the regulation of YC/T 207-2006, to rigid pack paper, with reference to printing impression, accurately cut master package face, 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 packing front middle section, accurately cut the sample of 22.0 cm * 5.5 cm.
The extraction of b, sample: sample is cut into the fragment of 5 mm* 5 mm left and right, mixes; Take 0.5 g sample (being accurate to 0.0001 g); Fragment is placed in to 50 mL tool plug triangular flasks, adds 15 mL to be preheated to the citrate buffer solution of 70 ± 2 ℃, fiercely shake, make liquid immersion sample, in 70 ± 2 ℃ of water-baths, place 30 min; Add hydrosulfurous acid sodium water solution 3 mL, keep 70 ± 2 ℃, reaction 30 min; Then will in the mobile cold water of conical flask, in 2min, be cooled to room temperature;
C, sample purification: toward the sodium hydroxide solution that adds respectively 1 mL 20% in triangular flask, mark (D9-4-aminobphenyl) solution, 10 mL t-butyl methyl ether and appropriate (8-10g) anhydrous sodium sulfate in 100 μ L, vibration 10 min, then standing 5 min.Get the upper strata stillness of night of 1 mL, the acetum that adds 2-3 to drip, nitrogen blows to dry to the greatest extent, with the methyl alcohol of 1 mL, redissolves, and enters LC-MS/MS and analyzes;
D, prepare standard operation solution: take respectively in the various aromatic amine standard items of 0.01g in 10 mL volumetric flasks, with methyl alcohol dilution and be finally mixed with the standard operation solution with concentration gradient;
E, liquid chromatography tandom mass spectrometry determination: draw the standard operation solution of the variable concentrations preparing, inject liquid chromatography-tandem mass spectrometer;
The calculating of f, aromatic amine measurement result
With internal standard method, carry out the quantitative test of residual quantity, with each aromatic amine and interior target quota ion, peak area is carried out to regretional analysis to its respective concentration, 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, substitution typical curve, tries to achieve the residual quantity of the aromatic amine in sample.
The manner of formulation of standard operation solution is as follows in the present invention: take 10 mg standard items in 10 mL volumetric flasks, be accurate to 0.0001g, with methyl alcohol, dilute 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, with methyl alcohol, dilute constant volume, obtain the hybrid working solution that concentration is about 10 μ g/mL; Pipette respectively the hybrid working solution of certain volume in 10 mL volumetric flasks, and add 100 μ L inner mark solutions.With methyl alcohol, dilute constant volume, be mixed with the standard operation 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 adopting is: chromatographic column: phenyl post (150 mm* 4.6 mm, 3 μ m); Mobile phase: methyl alcohol/5 m mol Ammoniom-Acetate aqueous solution, flow velocity: 200 μ L/min; Gradient elution program is in Table 1; Column temperature: 30 ℃; Sample size: 5 μ L; The mass spectrum condition adopting: scan mode: positive ion scanning; Electric spray ion source (ESI); Atomization gas flow is 50 psi; Gas curtain airshed 15 psi; Auxiliary heating airshed is 50 psi; 550 ℃ of ionization temperature; Collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 50 msec; Ionization voltage 5500 V, detection mode: positive ion polyion reaction monitoring (MRM), MRM parameter is in Table 2.
Method of the present invention has overcome the deficiency of prior art sample treatment, for cigarette tipping paper, internal lining paper and tobacco shred and box packaging paper sample, has optimized sample-pretreating method and instrument testing conditions.Compared with prior art the inventive method has following excellent results:
(1) the present invention takes the pretreatment mode that sample is shredded, and makes solvent better contact sample, and experimental result shows, processing can improve the extraction efficiency of reduction effect and aromatic amine like this.
(2) after the present invention's reduction, in extract, add NaOH, solution is adjusted into alkalescence, be conducive to the extraction of organic solvent to object.
(3) the present invention blows in journey and adds acetic acid at nitrogen, and aromatic amine is existed with ionic species, can avoid aromatic amine to blow to such an extent that lose in process at nitrogen, improves the recovery.
(4) the inventive method utilizes LC-MS/MS to measure the content of aromatic amine in paper, can carry out quantitatively and qualitative analysis simultaneously, without re-using other instruments, carries out qualitative analysis.
(5) the inventive method is owing to not needing solid-phase extraction column, without the loaded down with trivial details purifications such as rotary evaporation and concentrated step, make the method have operation accurately, the advantage such as the recovery is high, fast and convenient and sensitivity is high.
1. the detectability of the inventive method:
The aromatic amine standard operation solution of variable concentrations is injected to LC-MS/MS, with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), calculate detectability (LOD), detectability is in Table 3.
2. the repeatability of the inventive method and recovery of standard addition:
The standard solution that adds aromatic amine in blank sample, then carries out pre-treatment by method of the present invention and LC-MS/MS analyzes, and calculates 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 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 spectrometers; Water-bath constant temperature oscillator; Switzerland Mettler AE 163 electronic balance (sensibility reciprocals: 0.0001g).
2. sample preparation:
First sample is carried out to cutting: the cutting method of cigarette tipping paper carries out according to the regulation of YC 171-2008, accurately cut long 200 mm, the tipping paper sample of wide 40 mm (should comprise monolateral); The cutting method of tobacco lining paper carries out according to the regulation of YC 264-2008, i.e. cutting area approximately 170 cm
2(being equivalent to the internal lining paper area that the soft box packing of regular-size cigarette adopts); The cutting method of tobacco shred and box packaging paper carries out according to the regulation of YC/T 207-2006; to rigid pack paper; with reference to printing impression, accurately cut master package face; 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 packing front middle section, accurately cut the sample of 22.0 cm* 5.5 cm;
The fragment that sample is cut into 5 mm* 5 mm left and right, mixes; Take 0.5 g sample (being accurate to 0.01 g); Fragment is placed in to 50 mL tool plug triangular flasks, adds 17 mL to be preheated to the citrate buffer solution of 70 ± 2 ℃, fiercely shake, make liquid immersion sample, in 70 ± 2 ℃ of water-baths, place 30 min; Add hydrosulfurous acid sodium water solution 3 mL, keep 70 ± 2 ℃, reaction 30 min; Then conical flask is cooled in 2min to room temperature;
In triangular flask, add respectively the sodium hydroxide solution of 1 mL20%, the anhydrous sodium sulfate of 100 μ L inner mark solutions, 10 mL t-butyl methyl ether and 8-10 g, vibration 10 min, then standing 5 min.Get the upper strata stillness of night of 1 mL, the acetum that adds 2-3 to drip, nitrogen blows to dry to the greatest extent.With the methyl alcohol of 1 mL, redissolve, enter LC-MS/MS and analyze;
3. prepare standard operation solution: take the various aromatic amine standard items of 10 mg to 10 mL volumetric flasks in, be accurate to 0.0001g, with methyl alcohol, dilute 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, with methyl alcohol, dilute constant volume, obtain the hybrid working solution that concentration is about 10 μ g/mL; Pipette respectively the hybrid working solution of certain volume in 10 mL volumetric flasks, and add 100 μ L inner mark solutions.With methyl alcohol, dilute constant volume, be 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: carry out the quantitative test of residual quantity with internal standard method, with each aromatic amine and interior target quota ion, peak area is carried out to regretional analysis to its respective concentration, 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, substitution 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 respectively 2.08 μ g/g, 1.01 μ g/g and 0.85 μ g/g.
Accuracy for determination methods, in this sample, add the biphenylamine of 1.0 μ g, 4, 4-diaminodiphenylmethane and 2, 4-diaminotoluene standard mixed solution, carry out the same sample pre-treatments, with LC-MS/MS, record the selection quasi-molecular ions area of various aromatic amines, substitution typical curve, try to achieve the biphenylamine in sample now, 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, be 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 (5)
1. in a Cigarette paper, forbid the assay method of azo dyes, it is characterized in that: be to add reducing solution after Cigarette paper sample is shredded, make azo material by sodium hydrosulfite, be reduced into aromatic amine in citric acid solution, then by the method for liquid-liquid extraction, extract the aromatic amine in solution, after concentrated, with methyl alcohol, redissolve, with Liquid Chromatography-Tandem Mass Spectrometry combined instrument, measure, inner mark method ration, concrete steps are as follows:
A, Cigarette paper sample is carried out to cutting;
The extraction of b, sample: sample is cut into the fragment of 5 mm*5 mm left and right, mixes; Take 0.5 g sample; Fragment is placed in to 50 mL tool plug triangular flasks, adds 15 mL to be preheated to the citrate buffer solution of 70 ± 2 ℃, fiercely shake, make liquid immersion sample, in 70 ± 2 ℃ of water-baths, place 30 min; Add hydrosulfurous acid sodium water solution 3 mL, keep 70 ± 2 ℃, reaction 30 min; Then will in the mobile cold water of conical flask, in 2min, be cooled to room temperature;
C, sample purification: toward the sodium hydroxide solution that adds respectively 1 mL 20% in triangular flask, the anhydrous sodium sulfate of mark (D9-4-aminobphenyl) solution, 10 mL t-butyl methyl ether and 8-10g in 100 μ L, 10 min vibrate, then standing 5 min, get the upper strata stillness of night of 1 mL, the acetum that adds 2-3 to drip, nitrogen blows to dry to the greatest extent, with the methyl alcohol of 1 mL, redissolve, enter LC-MS/MS and analyze;
D, preparation standard operation solution: take respectively the various aromatic amine standard items of 0.01g in 10 mL volumetric flasks, with methyl alcohol dilution, be also finally mixed with the standard operation solution with concentration gradient;
E, liquid chromatography tandom mass spectrometry determination: draw the standard operation solution of the variable concentrations preparing, inject liquid chromatography-tandem mass spectrometer;
The calculating of f, aromatic amine measurement result
With internal standard method, carry out the quantitative test of residual quantity, with each aromatic amine and interior target quota ion, peak area is carried out to regretional analysis to its respective concentration, 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, substitution typical curve, tries to achieve the residual quantity of the aromatic amine in sample.
2. in Cigarette paper according to claim 1, forbid the assay method of azo dyes, 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, accurately cut long 200 mm, the tipping paper sample of wide 40 mm (should comprise monolateral); The cutting method of tobacco lining paper carries out according to the regulation of YC 264-2008, i.e. cutting area approximately 170 cm
2(being equivalent to the internal lining paper area that the soft box packing of regular-size cigarette adopts); The cutting method of tobacco shred and box packaging paper carries out according to the regulation of YC/T 207-2006, to rigid pack paper, with reference to printing impression, accurately cut master package face, 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 packing front middle section, accurately cut the sample of 22.0 cm* 5.5 cm.
3. in Cigarette paper according to claim 1, forbid the assay method of azo dyes, it is characterized in that: the manner of formulation of standard operation solution is as follows: take the various aromatic amine standard items of 10 mg in 10 mL volumetric flasks, with methyl alcohol, dilute 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, with methyl alcohol, dilute constant volume, obtain the hybrid working solution that concentration is about 10 μ g/mL; Pipette respectively the hybrid working solution of certain volume in 10 mL volumetric flasks, and add 100 μ L inner mark solutions; With methyl alcohol, dilute constant volume, be mixed with the standard operation 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. in Cigarette paper according to claim 1, forbid the assay method of azo dyes, it is characterized in that: the liquid phase chromatogram condition of employing is: chromatographic column: phenyl post (150 mm* 4.6 mm, 3 μ m); Mobile phase: methyl alcohol/5 m mol Ammoniom-Acetate aqueous solution, flow velocity: 200 μ L/min; Gradient elution; Column temperature: 30 ℃; Sample size: 5 μ L; The mass spectrum condition adopting: scan mode: positive ion scanning; Electric spray ion source (ESI); Atomization gas flow is 50 psi; Gas curtain airshed 15 psi; Auxiliary heating airshed is 50 psi; 550 ℃ of ionization temperature; Collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 50 msec; Ionization voltage 5500 V, detection mode: positive ion polyion reaction monitoring (MRM).
5. in Cigarette paper according to claim 1, forbid the assay method of azo dyes, it is characterized in that: gradient elution program sees the following form:
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| CN114594182A (en) * | 2022-03-09 | 2022-06-07 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | Method for detecting 5 forbidden components in cosmetics |
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