CN108680691B - Method for determining phthalate in tobacco flavor and fragrance - Google Patents

Method for determining phthalate in tobacco flavor and fragrance Download PDF

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CN108680691B
CN108680691B CN201810459475.5A CN201810459475A CN108680691B CN 108680691 B CN108680691 B CN 108680691B CN 201810459475 A CN201810459475 A CN 201810459475A CN 108680691 B CN108680691 B CN 108680691B
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王颖
杨飞
邓惠敏
刘珊珊
唐纲岭
边照阳
张威
柯玮
范子彦
李中皓
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National Tobacco Quality Supervision and Inspection Center
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Abstract

A method for measuring Phthalate (PAEs) in tobacco flavor and fragrance is characterized by comprising the following steps: dispersing and primarily extracting a sample by adopting an ethanol water solution with certain concentration, performing liquid-liquid extraction on the primary extraction solution by adopting a mixed solvent of n-hexane, ethyl acetate and isopropanol with certain proportion, and taking supernatant for direct sample injection analysis after layering of the liquid-liquid extraction. The method can realize good dispersion of most essence and spice samples in the primary extraction step, and adopts the mixed solvent of normal hexane, ethyl acetate and isopropanol to carry out liquid-liquid extraction on the primary extraction liquid, thereby not only realizing purification of the primary extraction liquid, but also ensuring that the recovery rates of 18 PAEs are more than 90 percent. The method uses fewer glass instruments, and uses an internal standard method, so that the solution transfer step is further simplified, the probability of pollution introduction in the pretreatment is greatly reduced, and the method is suitable for measuring mass samples.

Description

Method for determining phthalate in tobacco flavor and fragrance
Technical Field
The invention belongs to the field of physical and chemical analysis of harmful components of tobacco additives, and is suitable for measuring phthalate in tobacco essence flavors (liquid, paste and emulsion).
Background
The tobacco essence is one of edible essences. The essence is added in the cigarette blending process, so that the taste and the mouthfeel of the tobacco can be neutralized and corrected or changed to a certain extent, and a pleasant effect is achieved. However, the tobacco essence is not only used for perfuming cut tobacco, but also used on cigarette packaging materials (such as cigarette paper, filter sticks and the like) and used for meeting the olfactory demands of consumers. It can be said that, when the consumer consumes the cigarette product, there is a very large chance that the consumer directly contacts the essence for cigarette. The safety and health requirements of the tobacco essence are mainly related to edible essence at present.
Phthalate (PAEs) is one of the controlled indexes of the safety and sanitation standards of the flavor and fragrance for cigarettes. However, the standard only stipulates specific migration amount of PAEs, and the total amount still refers to the limit of edible essence and flavor (less than 60 mg/kg) of the national standard. PAEs in the tobacco essence are derived from raw materials to a great extent, because some PAEs can reduce the volatilization of fragrant substances; and secondly, the essence is transferred from other materials during storage and transportation. PAEs are currently recognized as environmental hormones, and long-term accumulation of PAEs in the body can seriously affect normal physiological functions of the human body and has the hazards of teratogenesis, carcinogenesis, mutagenesis and the like.
There is no national standard method recommended for the determination of phthalates in fragrances. The tobacco industry relates to a recommended method for determination in tobacco essence, but the method adopts ethanol to directly dilute a sample, adopts GC-MS to perform determination, and has no impurity removal step, so that a plurality of problems exist in use. On one hand, a plurality of essences or spices are not dissolved in ethanol (such as some extractum), on the other hand, the essence components are complex, direct sample injection can pollute an analytical column and an ion source, and the matrix effect is obvious. The invention improves the pretreatment and analysis of the prior method and is suitable for the determination of PAEs in most of tobacco flavors and fragrances at present.
Disclosure of Invention
The invention aims to provide a method for measuring phthalate in tobacco flavor and fragrance based on the prior art, which mixes ethanol water solution with a flavor and fragrance sample to be measured, and performs preliminary extraction on components to be measured in the sample while well dispersing the sample; then, liquid-liquid extraction is carried out on the primary extraction solution by adopting a normal hexane/ethyl acetate/isopropanol solution with a certain proportion, and PAEs in the primary extraction solution are measured by adopting a gas chromatography-mass spectrometer (GC-MS).
The purpose of the invention is realized by the following technical scheme:
a method for measuring Phthalic Acid Esters (PAEs) in tobacco essence and flavor comprises the steps of firstly pretreating a sample to be measured, and then measuring by a gas chromatography-mass spectrometry (GC-MS) technology, wherein the specific process comprises the following steps:
(1) pretreatment
Weighing 0.3-0.6g of essence and spice sample into a 25mL triangular flask with a plug, accurately obtaining 0.0001g, adding 7-15mL of ethanol water solution, adding 250 mu L of internal standard solution, performing ultrasonic extraction for 30min, taking 2mL of primary extraction solution into a 15mL glass centrifuge tube, adding 5mL of n-hexane/ethyl acetate/isopropanol solution, performing vortex oscillation for 5min at 2000rpm, centrifuging for 5min at 4000 rpm, taking supernatant, and determining.
(2) Blank experiment
And (3) repeating the step (1) without adding a sample. Because phthalate generally exists in the environment, blank determination is needed in all pretreatment for determining PAEs, if the blank contains a certain amount of PAEs, the blank cannot be simply deducted, the reason needs to be strictly searched, and the introduction of PAEs in the blank is avoided.
(3) Instrumental analysis
The measurement conditions by GC-MS were as follows.
Gas chromatography conditions:
stationary phase of chromatographic column: 5% phenyl/95% methylpolysiloxane; specification: [30 m (length). times.0.25 mm (inner diameter). times.0.25 μm (film thickness) ].
Sample inlet temperature: 280 ℃; sample introduction amount: 1 mu L, split-flow sample injection (split-flow ratio: 10: 1); carrier gas: helium (purity is more than or equal to 99.999%), constant-current mode, flow rate: 1.0 mL/min; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C/min at a rate of 20 deg.C/min, and is maintained for 1min, and then increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15 min.
Mass spectrum conditions:
an ionization mode: an electron impact source (EI); ionization energy: 70 eV; transmission line temperature: 280 ℃; ion source temperature: 280 ℃ and above; temperature of the quadrupole rods: 150 ℃; the measurement method comprises the following steps: selecting an ion monitoring mode (SIM) scan; solvent retardation: and 6 min. The SIM conditions for each compound are shown in Table 1
Figure DEST_PATH_IMAGE002
(4) In the invention, deuterated Dibutyl phthalate (Dibutyl phthalate-3,4,5,6-D4, CAS number: 93952-11-5) is used as an internal standard substance, the purity is more than or equal to 99 percent, and the internal standard substance is diluted by ethanol when in use, and the concentration is 0.1 mg/mL.
(5) The concentration of the ethanol water solution is 50 percent by volume; the volume ratio of n-hexane/ethyl acetate/isopropanol solution was 3:1: 1.
(6) The glassware is used for the experiment, washed, rinsed with primary water for three times, soaked in acetone for 1 h, dried at room temperature, baked at 200 ℃ for 2 h, and cooled to room temperature for later use.
(7) Preparation of standard solution and internal standard solution:
mixing a standard solution I: 0.02 g (to the nearest 0.1 mg) of each PAEs standard was weighed into the same 10mL volumetric flask and mixed with n-hexane/ethyl acetate/isopropanol (3: 1:1,V:V:V) Dissolving and fixing the volume to prepare a mixed standard solution I with the concentration of 2 mg/mL. Storing in 0-4 deg.c refrigerator in dark place for 6 months.
Mixing a standard solution II: accurately transferring 0.5 mL of the mixed standard solution I, placing the mixed standard solution I in a 10mL volumetric flask, and adding n-hexane/ethyl acetate/isopropanol (3: 1:1,V:V:V) And (5) fixing the volume, and preparing a mixed standard solution II with the concentration of 0.1 mg/mL. Storing in 0-4 deg.c refrigerator in dark place for 6 months.
Standard working solution: accurate movement25, 50, 100, 250, 500 and 750. mu.L of the mixed standard solution II are taken and placed in respective 25mL volumetric flasks, then 250. mu.L of the internal standard solution is accurately added, and the mixture is dissolved in a solvent such as n-hexane/ethyl acetate/isopropanol (3: 1:1,V:V:V) And (5) fixing the volume to a scale to obtain a series of standard working solutions. The concentration of the prepared series of standard solutions is as follows: 1. 2, 4, 10, 20 and 50 mg/kg.
And (3) carrying out GC/MS analysis on the standard working solution, wherein the ordinate is the ratio of the quantitative ion peak area of each analyte to the quantitative ion peak area of the internal standard substance, the abscissa is the concentration of each analyte, and at least 5 points are taken to prepare a standard working curve of each analyte. The 18 PAEs have good linearity in the concentration range of 1-50 mg/kg, and the correlation coefficient is from 0.9978-0.9999.
Selecting positive samples for test, carrying out a standard addition recovery rate test, wherein the standard addition amount is 2, 10 and 40 mg/kg, the standard addition amount is measured in parallel for 5 times on each standard addition level, taking an average value, and calculating the relative average standard deviation (RSD) of the 5 parallel measurements, so as to obtain the average recovery rate and the RSD of the 18 PAEs on different standard addition levels, wherein the specific result is shown in Table 2.
Figure DEST_PATH_IMAGE004
As can be seen from Table 2, the recovery rate of 18 PAEs under the low, medium and high standard adding conditions of 3 is in the range of 90.2-105.8%, and the recovery rate is good; the average RSD is less than 8 percent, and the determination precision is good.
The positive samples for test were selected, spiked with the lowest cup concentration of the standard curve, the assay was repeated 10 times, the SD of the assay results was calculated, 3SD and 10SD were used as the detection Limit (LOD) and quantification Limit (LOQ) of the method, respectively, and the results are shown in table 3.
Figure DEST_PATH_IMAGE006
(8) Advantages and explanations of the invention:
Figure 195172DEST_PATH_IMAGE007
the sample to be tested is dispersed and primarily extracted by using 50 percent (volume percentage) of ethanol solution, and most of the sample is better dispersed compared with the sample extracted by using ethanol in the existing standard. The reason is that some flavors and fragrances are soluble in water and insoluble in ethanol, some are only soluble in ethanol, and a few samples are insoluble in both ethanol and water, and a 50% ethanol solution (the ratio of ethanol to water is 1: 1) is adopted to disperse and dissolve the samples, so that good dissolution of most flavor and fragrance samples can be realized in practice, a better dispersing effect is achieved, namely, the matrix is more thoroughly damaged, and the components to be measured can be better dissolved.
Figure DEST_PATH_IMAGE008
The mixed solvent of n-hexane, ethyl acetate and isopropanol in a specific proportion is adopted to carry out liquid-liquid extraction on the ethanol water solution, and compared with the existing standard in which ethanol is directly adopted to extract and sample, the method has the double effects of removing impurities and protecting an analytical instrument. The reason is that liquid-liquid extraction layering is performed, the ethanol water solution is at the lower layer, and n-hexane/ethyl acetate/isopropanol with a specific proportion is at the upper layer, the step is equivalent to a purification step, and a plurality of interferents in the essence are not extracted into the final sample injection solution, so that a certain purification effect is achieved (see fig. 3-5 in particular); on the other hand, the n-hexane/ethyl acetate/isopropanol solution has weaker polarity than ethanol, so the method is more suitable for the sampling requirement of a nonpolar analytical column. The sample injection solution is cleaner and has weaker polarity, so that the pollution to the analytical column and the ion source can be avoided to a greater extent.
Figure 909050DEST_PATH_IMAGE009
The n-hexane/ethyl acetate/isopropanol solution with the volume ratio of 3:1:1 is adopted to carry out liquid-liquid extraction on the primary extraction solution, so that the determination recovery rates of the 18 PAEs to be detected are all higher than 90%. This is because there have been reports in the literature that PAEs in paper for cigarettes were measured by soaking in water, preliminarily extracting with ethanol, and then subjecting to liquid-liquid extraction with n-hexane (tanggang mountain, shin-yang, yangfei, etc., tipping paper for cigarettes, paper,Determination of 18 phthalates in inner liner paper and cigarette carton and carton packaging paper [ J]Tobacco technology, 2012 (9): 36-40.), because the DMP and DEP carbon chains in the PAEs are very short, have certain polarity and have certain solubility in water, the solubility in normal hexane is poor, and the extraction efficiency is very low (Zhang Yang Ming, Zhang hong Hai, Lijianlong, and the like, solid phase microextraction-gas chromatography-mass spectrometry are used for measuring phthalate pollutants [ J ] in seawater and sediments]Analytical chemistry, 2017, 45 (3): 348-; for the compounds with weaker polarity, such as DEHP, DNP and the like, the best solubility is realized only in n-hexane, the better extraction of 18 components can be realized by adopting n-hexane/ethyl acetate/isopropanol solution with the volume ratio of 3:1:1, and the recovery rate of all the components of the added standard sample can reach 90 percent (see table 2).
Figure DEST_PATH_IMAGE010
In the determination, the temperature of the ion source is set to be 280 ℃ or above, so that the pollution of impurities to the ion source can be effectively avoided. Many of the current methods operate according to the conventional temperature setting of the ion source, such as the conventional setting of the ion source temperature of an agilent instrument as 230 ℃, and the ion source temperature is not emphasized in many standard methods for measuring PAEs, and in fact, PAEs compounds easily pollute the ion source, especially under the condition of incomplete sample purification. The temperature of the ion source is increased, so that the sample can be ionized more completely, and the cleaning frequency of the ion source is reduced.
Drawings
FIG. 1 is a chromatogram of a standard solution according to the present invention;
in the figure: 1-DMP 2-DEP 3-DAP 4-DIBP 5-DBP 6-DMEP 7-BMPP 8-DEEP 9-DPP 10-DHXP 11-BBP 12-DBEP 13-DCHP 14-DEHP 15-diphenyl phthalate 16-DNOP17-DINP 18-DNP IS-internal standard.
FIG. 2 is a chromatogram of a standard sample assay according to the present invention,
in the figure: 1-DEP 2-DAP 3-DBP IS-internal standard.
FIG. 3 shows the selective ion spectrum of DIBP in the same sample measured by the industry recommendation method and the method of the present invention,
wherein A is an industry recommendation method, and B is the method of the invention.
FIG. 4 shows that the selective ion spectrum of DBP of the same sample is determined by the industry recommendation method and the method of the invention,
wherein A is an industry recommendation method, and B is the method of the invention.
FIG. 5 shows the selective ion spectrum of deuterated DBP (internal standard) of the same sample measured by the method recommended by the industry and the method of the invention,
wherein A is an industry recommendation method, and B is the method of the invention.
Detailed Description
The invention is further described below with reference to the following examples:
example (b): and (3) measuring phthalate in the tobacco flavor and fragrance sample.
(1) Pretreatment
Weighing 0.3-0.6g of essence and spice sample into a 25mL triangular flask with a plug, accurately obtaining 0.0001g, adding 7-15mL of ethanol water solution (volume ratio is 1: 1), adding 250 muL of internal standard solution (solvent is ethanol, concentration is 0.1 mg/mL), performing ultrasonic extraction for 30min, taking 2mL of primary extraction solution into a 15mL glass centrifuge tube, adding 5mL of n-hexane/ethyl acetate/isopropanol solution (volume ratio is 3:1: 1), performing vortex oscillation for 5min at 2000rpm, centrifuging for 5min at 4000 rpm, taking supernatant, and testing.
(2) Blank experiment
And (3) repeating the step (1) without adding a sample.
(3) Instrumental analysis
The measurement conditions by GC-MS were as follows.
Gas chromatography conditions:
stationary phase of chromatographic column: 5% phenyl/95% methylpolysiloxane; specification: [30 m (length). times.0.25 mm (inner diameter). times.0.25 μm (film thickness) ].
Sample inlet temperature: 280 ℃; sample introduction amount: 1 mu L, split-flow sample injection (split-flow ratio: 10: 1); carrier gas: helium (purity is more than or equal to 99.999%), constant-current mode, flow rate: 1.0 mL/min; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C/min at a rate of 20 deg.C/min, and is maintained for 1min, and then increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15 min.
Mass spectrum conditions:
an ionization mode: an electron impact source (EI); ionization energy: 70 eV; transmission line temperature: 280 ℃; ion source temperature: 280 ℃ and above; temperature of the quadrupole rods: 150 ℃; the measurement method comprises the following steps: selecting an ion monitoring mode (SIM) scan; solvent retardation: and 6 min. The SIM conditions for each compound are shown in table 1.
4) Preparation of Standard solutions
Mixing a standard solution I: 0.02 g (to the nearest 0.1 mg) of each PAEs standard was weighed into the same 10mL volumetric flask and mixed with n-hexane/ethyl acetate/isopropanol (3: 1:1,V:V:V) Dissolving and fixing the volume to prepare a mixed standard solution I with the concentration of 2 mg/mL. Storing in 0-4 deg.c refrigerator in dark place for 6 months.
Mixing a standard solution II: accurately transferring 0.5 mL of the mixed standard solution I, placing the mixed standard solution I in a 10mL volumetric flask, and adding n-hexane/ethyl acetate/isopropanol (3: 1:1,V:V:V) And (5) fixing the volume, and preparing a mixed standard solution II with the concentration of 0.1 mg/mL. Storing in 0-4 deg.c refrigerator in dark place for 6 months.
Standard working solution: accurately transferring 25, 50, 100, 250, 500 and 750 mu L of the mixed standard solution II into respective 25mL volumetric flasks, then accurately adding 250 mu L of the internal standard solution, adding n-hexane/ethyl acetate/isopropanol (3: 1:1,V:V:V) And (5) fixing the volume to a scale to obtain a series of standard working solutions. The concentration of the prepared series of standard solutions is as follows: 1. 2, 4, 10, 20 and 50 mg/kg.
5) And (3) carrying out GC/MS analysis on the standard working solution, wherein the ordinate is the ratio of the quantitative ion peak area of each analyte to the quantitative ion peak area of the internal standard substance, the abscissa is the concentration of each analyte, and at least 5 points are taken to prepare a standard working curve of each analyte. And obtaining the content of the component to be detected in the tobacco flavor and fragrance according to the standard curve. The final measurement result is the average value of two parallel measurements, and the accuracy is 1 mg/kg.
The specific results in this example are shown in Table 4 and the chromatogram is shown in FIG. 2.
TABLE 4 sample content
Figure DEST_PATH_IMAGE011

Claims (4)

1. A method for measuring Phthalic Acid Esters (PAEs) in tobacco flavor and fragrance comprises the steps of pretreating a sample to be measured, and measuring by a gas chromatography-mass spectrometry (GC-MS) technology, and is characterized in that: the pretreatment process comprises the following steps: firstly, carrying out dispersed primary extraction on a sample by adopting an ethanol aqueous solution, and then carrying out liquid-liquid extraction on a primary extraction solution by adopting a mixed solvent, wherein the specific process is as follows:
weighing 0.3-0.6g of essence and spice sample into a 25mL triangular flask with a stopper, accurately weighing to 0.0001g, adding 7-15mL of ethanol water solution, adding 250 mu L of internal standard solution, carrying out ultrasonic extraction for 30min, taking 2mL of primary extraction solution into a 15mL glass centrifuge tube, adding 5mL of n-hexane/ethyl acetate/isopropanol solution, carrying out vortex oscillation for 5min under the condition of 2000rpm, centrifuging for 5min under the condition of 4000 rpm, taking supernatant, and carrying out GC-MS (gas chromatography-mass spectrometry) determination; performing blank tests on each batch, namely adding no sample, and repeating the steps;
the volume percentage of the ethanol water solution is 50%; the volume ratio of n-hexane/ethyl acetate/isopropanol solution was 3:1: 1.
2. The method for determining phthalate esters (PAEs) in tobacco flavor and fragrance according to claim 1, wherein the method comprises the following steps: the internal standard adopts deuterated dibutyl phthalate, the concentration is 0.1mg/mL, and the solvent is ethanol.
3. The method for determining phthalate esters (PAEs) in tobacco flavor and fragrance according to claim 1, wherein the method comprises the following steps: the GC-MS instrument analysis conditions were as follows:
gas chromatography conditions:
stationary phase of chromatographic column: 5% phenyl/95% methylpolysiloxane; specification: 30 m.times.0.25 mm.times.0.25 μm,
sample inlet temperature: 280 ℃; sample introduction amount: 1 μ L, split injection, split ratio: 10: 1; carrier gas: helium, constant flow mode, flow rate: 1.0 mL/min; temperature rising procedure: the initial temperature is 60 ℃, the temperature is kept for 1min, the speed is 20 ℃/min to 220 ℃, the temperature is kept for 1min, and then the speed is 5 ℃/min to 280 ℃, and the temperature is kept for 15 min;
mass spectrum conditions:
an ionization mode: an electron impact source (EI); ionization energy: 70 eV; transmission line temperature: 280 ℃; ion source temperature: 280 ℃ and above; temperature of the quadrupole rods: 150 ℃; the measurement method comprises the following steps: selecting an ion monitoring mode (SIM) scan; solvent retardation: 6 min; the SIM conditions for each compound were as follows:
serial number Compound (I) English abbreviation Retention time Selection of ions 1 Phthalic acid dimethyl ester DMP 7.79 163、77、135、194 2 Phthalic acid diethyl ester DEP 8.66 149、177、121、222 3 Diallyl phthalate DAP 9.59 149、189、132、104 4 Phthalic acid diisobutyl ester DIBP 10.42 149、223、205、167 5 Dibutyl phthalate DBP 11.17 149、223、205、121 6 Phthalic acid di (2-methoxy) ethyl ester DMEP 11.53 59、149、104、207 7 Phthalic acid di (4-methyl-2-pentyl) ester BMPP 12.21 149、251、167、121 8 Phthalic acid di (2-ethoxy) ethyl ester DEEP 12.60 149、45、72、176 9 Diamyl phthalate DPP 13.01 149、237、219、167 10 Dihexyl phthalate DHXP 15.20 149、251、104、26 11 Butylbenzyl phthalate BBP 15.35 149、91、206、238 12 Bis (2-butoxy) ethyl phthalate DBEP 16.78 149、176、193、249 13 Phthalic anhydrideAcid dicyclohexyl ester DCHP 17.47 149、167、83、249 14 Di (2-ethyl) hexyl phthalate DEHP 17.62 149、167、279、113 15 Phthalic acid diphenyl ester － 17.82 225、77、153、104 16 Di-n-octyl phthalate DNOP 20.19 149、279、167、261 17 Diisononyl phthalate DINP 20.40-22.20 149、293、127、167 18 Dinonyl phthalate DNP 22.79 149、293、127、167 IS Deuterated dibutyl phthalate D4-DBP 11.18 153、227
4. The method for determining phthalate esters (PAEs) in tobacco flavor and fragrance according to claim 1, wherein the method comprises the following steps: in the GC-MS measurement, firstly, a phthalate standard solution is prepared, wherein the phthalate standard solution is prepared by using n-hexane/ethyl acetate/isopropanol in a volume ratio of 3:1:1, and the concentrations of the phthalate standard solution are 1, 2, 4, 10, 20 and 50mg/kg respectively.
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应用气相色谱/质谱联用法对液态食用香精中3种邻苯二甲酸酯类化合物的测定;刘然等;《食品工程》;20170331(第1期);第48～51页 *
茉莉净油、桂花净油等10种天然香料中15种邻苯二甲酸酯的检测研究;林葵等;《香料香精化妆品》;20150831(第4期);第25～29页 *

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