CN103344725B - Method for simultaneously and quantitatively detecting content of ethyl carbamate and phthalate in distilled white wine - Google Patents
Method for simultaneously and quantitatively detecting content of ethyl carbamate and phthalate in distilled white wine Download PDFInfo
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Abstract
The invention belongs to the field of white wine detection, particularly relates to a method for simultaneously and quantitatively detecting the content of ethyl carbamate and phthalate in the distilled white wine and aims to solve the problems the existing method for detecting is complex in operation and consumes long time. The method comprises the following steps of: (a) adding an internal standard substance I and an internal standard substance II into a white-wine sample, and (b) detecting by adopting a gas chromatograph mass spectrometer, monitoring and quantitating by using selected irons, and obtaining the content of the ethyl carbamate and the phthalate in the distilled white wine by adopting the internal standard method. The method provided by the invention has good reproducibility, is accurate and is low in detection cost, thereby being easy to popularize.
Description
Technical field
The invention belongs to liquor determination field, be specifically related to the method that simultaneous quantitative detects urethanes and phthalic acid ester content in distilled spirit.
Technical background
Urethanes (ethyl carbamate is called for short EC) has another name called urethane, is the accessory substance of fermented food natural formation in fermentation with storage process.After deliberation, the urethanes in distilled spirit is generated by carbamino compound and ethanol spontaneous reaction.1987, EC was classified as group2B by IARC (IARC): possible carcinogen; 2004, EC was listed in the list of " material having reason to expect to cause cancer " by NTP plan; IARC in 2007 reappraises EC, is listed in group2A with plumbous, mercury and acrylamide etc.At present, Chinese patent 201210441000.6 open the High Performance Liquid Chromatography/Mass Spectrometry detection method of urethanes " in the Spirit ", the method adopts decompression distillation to remove ethanol, use distilled water constant volume, directly enter LC-MS(liquid chromatography-mass spectrography), then calculate ethyl carbamate content by external standard method.The Chinese patent 201110339615.3 open method of ethyl carbamate content " in a kind of Fast Measurement Spirit ", the method adopts rotary evaporation removal of impurities, urethanes in Headspace-solid phase microextraction technology enrichment wine sample, GC-MS quantitatively detects, and then adopts external standard method to calculate the content of urethanes.
Phthalic ester is the widely used plastifier of a class, the flexibility of material can be increased or make materials liquefy, be widely used in hundreds of product such as toy, packaging material for food, Medical blood bag and sebific duct, vinyl flooring, detersive, lubricating oil, personal care articles (e.g., nail polish, shampoo).This compounds is confirmed to be environmental estrogens, has infringement to the reproductive system of people.Phthalic ester in white wine is mainly derived from plastic washer, plastic conduit etc. in the storage wine container of plastic products, wine bottle cover.Chinese patent 201210281033.9 open " a kind of colorimetric probe detects the method for phthalic ester "; Chinese patent 201210504503.3 open " a kind of mensuration reproduces the method for phthalate compound content in cigarette "; Chinese patent 201110076663.8 open " a kind of liquid chromatography-mass spectrography measures the method for phthalic acid ester content in Chinese medicine ".
At present, only have a few countries such as Canada, Czech, France to define the upper content limit of urethanes in Spirit, the content of most countries to urethanes there is no concrete regulation.Therefore, the method for the ethyl carbamate content in special detection Spirit is less.China's import-export commodity inspection industry standard: urethanes residual quantity method of inspection SN0285-1993 in outlet drinks, the method operation is comparatively loaded down with trivial details, the time long, it is comparatively large to affect by human users, is not too applicable to enterprise to the self-inspection in enormous quantities of producing product.
Detect the content Main Basis standard GB/T/T21911-2008 " mensuration of Phthalic Acid Esters in Food " of phthalic ester in distilled spirit, the method adopts liquid-liquid extraction, quantified by external standard method, after being applied to distilled spirit sample, testing result deviation is comparatively large, reappearance is poor.
Above two kinds of detection methods all need to carry out pre-treatment to sample, operation is comparatively loaded down with trivial details, the time is longer, and can not realize the content that single injected sampling detects urethanes and phthalic ester two class material simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is that existing detection method complex operation, time are longer.
The technical scheme that the present invention solves the problems of the technologies described above there is provided a kind of method that simultaneous quantitative detects urethanes and phthalic ester in distilled spirit, comprises the following steps:
A, in wine sample, add internal standard compound I and internal standard compound II;
B, use gas chromatograph-mass spectrometer (GCMS) detect, and use Salbutamol Selected Ion Monitoring with quantitative, adopt internal standard method to obtain the content of urethanes and phthalic ester.
Wherein, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, and the internal standard compound I described in step a is deuterated urethanes.Purity >=98% of described deuterated urethanes.
Further, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, and internal standard compound I is 3 ︰ 5000 with the volume ratio of wine sample.
Wherein, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, and the internal standard compound II described in step a is di-iso-amyl phthalate.Purity >=98% of described di-iso-amyl phthalate.
Further, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, and internal standard compound II is 3 ︰ 5000 with the volume ratio of wine sample.
Wherein, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, internal standard method described in step b comprises: in sample, add internal standard compound, then obtain peak area through instrumental analysis, then according to the typical curve result of calculation of having drawn.
Further, the condition of gas chromatography described in step b is: adopt ZB-WAXplus capillary chromatographic column to be separated, injector temperature 250 DEG C, sample size 0.5 μ L, Splitless injecting samples, post flow 1mL/min; Heating schedule: 40 DEG C keep 2min, rise to 160 DEG C, then rise to 230 DEG C with 30 DEG C/min with 10 DEG C/min, keep 15.6min.
Further, the length of described ZB-WAXplus capillary chromatographic column is 30m, and internal diameter is 0.25mm, and thickness is 0.25 μm.
Further, described in step b, mass spectrographic condition is: electron ionization sources, ionization voltage 70eV; Scan mode is Salbutamol Selected Ion Monitoring, ion source temperature 230 DEG C, level Four bar temperature 150 DEG C, GC-MS auxiliary heating temperature 240 DEG C.
Further, described Salbutamol Selected Ion Monitoring is: the monitoring ion m/z62 of urethanes, the monitoring ion m/z64 of deuterated urethanes, the monitoring ion m/z163 of repefral, the monitoring ion of diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-ethyl) own ester and di-iso-amyl phthalate is m/z149.
The inventive method adopts internal standard method to detect the content of phthalic ester first, and can detect the content of urethanes simultaneously, and testing result reappearance is better, error is low.This method is easy and simple to handle, does not need to carry out pre-treatment to sample, and testing cost is low, and analysis time is short, only needs the content that just can obtain urethanes and phthalic ester for more than 30 minute, saves instrument, is applicable to enterprises and carries out batch samples self-inspection.The instrument that the present invention uses is laboratory conventional analytical instruments, and inventive method is easy to promote, and testing cost is low.
Accompanying drawing explanation
The chromatogram of Fig. 1 urethanes standard solution (containing internal standard compound I).
The chromatogram of Fig. 2 phthalic ester standard solution (containing internal standard compound II).
The chromatogram of urethanes and phthalic ester (containing internal standard compound I, II) in Fig. 3 wine sample.
Embodiment
Simultaneous quantitative detects the method for urethanes and phthalic ester in distilled spirit, comprises the following steps:
A, in wine sample, add internal standard compound I and internal standard compound II;
B, use gas chromatograph-mass spectrometer (GCMS) detect, and use Salbutamol Selected Ion Monitoring with quantitative, adopt internal standard method to obtain the content of urethanes and phthalic ester.
Wherein, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, and the internal standard compound I described in step a is deuterated urethanes.Purity >=98% of described deuterated urethanes.
Further, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, adds 30 μ L internal standard compounds I in every 50mL wine sample.
Wherein, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, and the internal standard compound II described in step a is di-iso-amyl phthalate.Purity >=98% of described di-iso-amyl phthalate.
Further, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, adds 30 μ L internal standard compounds II in every 50mL wine sample.
Wherein, above-mentioned simultaneous quantitative detects in the method for urethanes and phthalic ester in distilled spirit, internal standard method described in step b comprises: in sample, add internal standard compound, then obtain peak area through instrumental analysis, then according to the typical curve result of calculation of having drawn.
Further, the condition of gas chromatography described in step b is: adopt ZB-WAXplus capillary chromatographic column to be separated, injector temperature 250 DEG C, sample size 0.5 μ L, Splitless injecting samples, post flow 1mL/min; Heating schedule: 40 DEG C keep 2min, rise to 160 DEG C, then rise to 230 DEG C with 30 DEG C/min with 10 DEG C/min, keep 15.6min.
Further, the length of described ZB-WAXplus capillary chromatographic column is 30m, and internal diameter is 0.25mm, and thickness is 0.25 μm.
Further, described in step b, mass spectrographic condition is: electron ionization sources, ionization voltage 70eV; Scan mode is Salbutamol Selected Ion Monitoring, ion source temperature 230 DEG C, level Four bar temperature 150 DEG C, GC-MS auxiliary heating temperature 240 DEG C.
Further, described Salbutamol Selected Ion Monitoring is: the monitoring ion m/z62 of urethanes, the monitoring ion m/z64 of deuterated urethanes, the monitoring ion m/z163 of repefral, the monitoring ion of diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-ethyl) own ester and di-iso-amyl phthalate is m/z149.
In experimentation, inventor once attempted using external standard method to carry out quantitative test, but found that quantitative result reappearance is poor, and error is comparatively large, the especially assay of phthalic ester, and its result error is also larger.So, select internal standard method to carry out quantitative test.For the selection of internal standard compound, there is following ask for something: can not contain this internal standard compound in sample, do not react with sample, similar to test substance character, retention time and response factor are close as far as possible.Before the selection carrying out internal standard compound, inventor is first to the distilled spirit of various odor type, as, Luzhou-flavor, delicate fragrance type, Maotai-flavor, carry out full scan detection, find in distilled spirit main containing five kinds of phthalate compounds: repefral, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and phthalic acid two (2-ethyl) own ester.According to the selection requirement of internal standard compound, need to select a kind of phthalate material do not contained in distilled spirit as interior mark.In the process selecting internal standard compound II, inventor once used dioctyl phthalate as interior mark II, the data obtained show: the quantitative result error of this interior mark to phthalic acid two (2-ethyl) own ester is low, reappearance better, but the quantitative result error of its dimethyl terephthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate is comparatively large, reappearance is on the low side.So it is suitable that inventor again must find in numerous phthalate compounds.Through a large amount of contrast experiments, inventor finally have selected di-iso-amyl phthalate as interior mark II.Experimental result shows: when using di-iso-amyl phthalate as interior mark II, and the quantitative result of five kinds of phthalic esters is all accurate, error is low, favorable reproducibility.Five kinds of phthalic esters can not only be quantitatively detected well using di-iso-amyl phthalate as interior mark II, and itself and internal standard compound I are with the use of producing interference each other, urethanes and several phthalic ester can be detected by simultaneous quantitative well.
Inventor not only to need through a large amount of screening experiments, to determine internal standard compound II, also to need to select applicable chromatographic column by a large amount of experiments.In the process selecting chromatographic column, inventor once used Agilent DB-5MS capillary chromatographic column to carry out the separation of composition in wine sample, although this chromatographic column can be good at isolating several phthalic ester, effectively can not isolate urethanes.After experienced by failure many times, inventor attempted using Phenomenex ZB-WAXplus capillary chromatographic column afterwards, was surprised to find that, this chromatographic column can isolate urethanes and several phthalic ester simultaneously well, and peak type is better.
Further, drawing standard curve is needed.Wherein, sample is y-axis with the ratio of interior target peak area, and sample is x-axis with the ratio of interior target concentration.The step of drawing standard curve is:
1, urethanes typical curve is drawn
The preparation of urethanes storing solution: accurately take the urethanes of 22.8mg in 50mL beaker, adding after about 20mL ethanol dissolves completely is transferred in 100mL volumetric flask, with a small amount of alcohol flushing beaker 2-3 time, washing fluid is transferred in volumetric flask, is finally settled to scale with ethanol.
The preparation of internal standard compound I solution: accurately take the deuterated urethanes of 41.6mg in 50mL beaker, adding after about 20mL ethanol dissolves completely is transferred in 50mL volumetric flask, with a small amount of alcohol flushing beaker 2-3 time, washing fluid is transferred in volumetric flask, is finally settled to scale with ethanol.
The preparation of series urethanes standard working solution: pipette 50 μ L, 250 μ L, the urethanes storing solution of 500 μ L and 60 μ L internal standard compound I solution respectively in 100mL volumetric flask, with 50%(v/v) ethanol be settled to scale.
Adopt gas chromatography-mass spectrum to be measured by serial urethanes standard working solution successively, drawing standard curve, obtains linear equation: y=ax, R
2=0.9999, wherein a=1.058; The ratio of x=urethanes and the concentration of internal standard compound I; The ratio of y=urethanes and the peak area of internal standard compound I.
2, phthalic ester typical curve is drawn
The preparation of phthalic ester storing solution: the DMP(repefral accurately taking 20mg), the DEP(diethyl phthalate of 50mg), the DIBP(diisobutyl phthalate of 35mg), the DBP(dibutyl phthalate of 45mg) and DEHP(phthalic acid two (2-ethyl) the own ester of 65mg) in 50mL beaker, adding after about 30mL ethanol dissolves completely is transferred in 100mL volumetric flask, with a small amount of alcohol flushing beaker 3-5 time, washing fluid is transferred in volumetric flask, is finally settled to scale with ethanol.
The preparation of internal standard compound II solution: accurately take the di-iso-amyl phthalate of 100mg in 50mL beaker, adding after about 30mL ethanol dissolves completely is transferred in 100mL volumetric flask, with a small amount of alcohol flushing beaker 3-5 time, washing fluid is transferred in volumetric flask, is finally settled to scale with ethanol.
The preparation of series phthalic ester standard working solution: pipette 50 μ L, 75 μ L, the phthalic ester storing solution of 150 μ L and 60 μ L internal standard compound II solution in 100mL volumetric flask, with 50%(v/v) ethanol be settled to scale.
Adopt gas chromatography-mass spectrum to be measured by serial phthalic ester standard working solution successively, drawing standard curve, the linear equation obtaining often kind of phthalic ester is: y=ax
2+ bx; Wherein,
The linear equation of repefral is: y=0.2044x
2+ 0.6239x, R
2the ratio of=0.9999, x=repefral and the concentration of internal standard compound II; The ratio of y=repefral and the peak area of internal standard compound II;
The linear equation of diethyl phthalate is: y=0.07384x
2+ 0.5726x, R
2the ratio of=0.9999, x=diethyl phthalate and the concentration of internal standard compound II; The ratio of y=diethyl phthalate and the peak area of internal standard compound II;
The linear equation of diisobutyl phthalate is: y=0.1350x
2+ 0.8949x, R
2the ratio of=0.9999, x=diisobutyl phthalate and the concentration of internal standard compound II; The ratio of y=diisobutyl phthalate and the peak area of internal standard compound II;
The linear equation of dibutyl phthalate is: y=0.1284x
2+ 1.118x, R
2the ratio of=0.9999, x=dibutyl phthalate and the concentration of internal standard compound II; The ratio of y=dibutyl phthalate and the peak area of internal standard compound II;
The linear equation of phthalic acid two (2-ethyl) own ester is: y=0.06119x
2+ 0.8346x, R
2the ratio of=0.9998, x=phthalic acid two (2-ethyl) own ester and the concentration of internal standard compound II; The ratio of y=phthalic acid two (2-ethyl) own ester and the peak area of internal standard compound II.
Further, the content of urethanes in wine sample is calculated by following formula:
m=A/A
S×m
s/a
Wherein, the content of urethanes in m-wine sample, unit is mg/litre (mg/L);
The peak area of A-urethanes;
A
sthe peak area of-deuterated urethanes;
M
smark content in-wine sample solution, unit is mg/litre (mg/L);
A-drawn by equation of linear regression.
Further, the content of phthalic ester in wine sample is calculated by following formula:
m=[-b+(4a×A/A
s+b
2)
1/2]×m
s/2a
Wherein, the content of often kind of phthalic ester in m-wine sample, unit is mg/litre (mg/L);
B-drawn by equation of linear regression;
A-drawn by equation of linear regression;
The peak area of A-often kind phthalic ester;
A
sthe peak area of-di-iso-amyl phthalate;
M
smark content in-wine sample solution, unit is mg/litre (mg/L).
The instrument that the embodiment of the present invention uses and reagent:
Agilent Technologies of U.S. Agilent7890A gas chromatograph, Agilent Technologies of U.S. Agilent5975C mass spectrometer, the ZB-WAXplus capillary chromatographic column that Phenomenex company produces.
Ethanol is that top grade is pure; Purity >=98% of urethanes standard items, deuterated urethanes standard items and phthalic ester standard items, is AccuStandard company of the U.S. and produces.
Embodiment 1
50mL volumetric flask is cleaned 2-3 time with wine sample to be measured, in volumetric flask, add the wine sample to be measured of about 10mL after cleaning, then add respectively in 30 μ L internal standard compounds I and 30 μ L internal standard compound II to volumetric flasks with liquid-transfering gun, be finally settled to scale with wine sample to be measured, jog, mixing.The wine sample to be measured being added with internal standard compound mixed is poured in Agilent sample bottle, carries out gas chromatography-mass spectrometry analysis detection.
The condition of gas chromatography is: adopt ZB-WAXplus capillary chromatographic column to be separated, the length of chromatographic column is 30m, and internal diameter is 0.25mm, and thickness is 0.25 μm; Injector temperature 250 DEG C, sample size 0.5 μ L, Splitless injecting samples, post flow 1mL/min; Heating schedule: 40 DEG C keep 2min, rise to 160 DEG C, then rise to 230 DEG C with 30 DEG C/min with 10 DEG C/min, keep 15.6min.
Mass spectrographic condition is: electron ionization sources, ionization voltage 70eV; Scan mode is Salbutamol Selected Ion Monitoring, ion source temperature 230 DEG C, level Four bar temperature 150 DEG C, GC-MS auxiliary heating temperature 240 DEG C.Salbutamol Selected Ion Monitoring is: the monitoring ion m/z62 of urethanes, the monitoring ion m/z64 of deuterated urethanes, the monitoring ion m/z163 of repefral, the monitoring ion of diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-ethyl) own ester and di-iso-amyl phthalate is m/z149.
By the internal standard compound that obtains and the calculated by peak area urethanes of component to be measured and the content of phthalic ester.A and b in the concentration of the peak area obtained, internal standard compound and linear equation is substituted into formula:
The content of urethanes in wine sample is calculated by following formula:
m=A/A
S×m
s/a
Wherein: the content of urethanes in m-wine sample, unit is mg/litre (mg/L);
The peak area of A-urethanes;
A
sthe peak area of-deuterated urethanes;
M
smark content in-wine sample solution, unit is mg/litre (mg/L);
A-drawn by equation of linear regression.
Linear equation: y=ax, R
2=0.9999, wherein a=1.058;
The content of phthalic ester in wine sample is calculated by following formula:
m=[-b+(4a×A/A
s+b
2)
1/2]×m
s/2a
Wherein: the content of often kind of phthalic ester in m-wine sample, unit is mg/litre (mg/L);
B-drawn by equation of linear regression;
A-drawn by equation of linear regression;
The peak area of A-often kind phthalic ester;
A
sthe peak area of-di-iso-amyl phthalate;
M
smark content in-wine sample solution, unit is mg/litre (mg/L).
The linear equation of repefral: y=ax
2+ bx, wherein a=0.2044, b=0.6239;
The linear equation of diethyl phthalate: y=ax
2+ bx, wherein a=0.07384, b=0.5726;
The linear equation of diisobutyl phthalate: y=ax
2+ bx, wherein a=0.1350, b=0.8949;
The linear equation of dibutyl phthalate: y=ax
2+ bx, wherein a=0.1284, b=1.118;
The linear equation of phthalic acid two (2-ethyl) own ester: y=ax
2+ bx, wherein a=0.06119, b=0.8346.
0.3295mg/L, 0.1044mg/L, 0.2946mg/L, 0.2906mg/L, 0.2926mg/L, 0.3476mg/L is respectively by the content calculating urethanes, repefral, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and phthalic acid two (2-ethyl) own ester in this wine sample.
The precision of embodiment 2 the inventive method and sensitivity
According to the method for embodiment 1 to certain wine sample replicate determination 5 times, the precision result obtaining sample is as shown in table 1:
The precision of table 1 the inventive method
| ? | 1# | 2# | 3# | 4# | 5# | RSD(%) |
| EC(mg/L) | 0.3322 | 0.3291 | 0.3312 | 0.3254 | 0.3260 | 0.925 |
| DMP(mg/L) | 0.0126 | 0.0126 | 0.0124 | 0.0124 | 0.0125 | 0.799 |
| DEP(mg/L) | 0.0360 | 0.0364 | 0.0360 | 0.0361 | 0.0361 | 0.482 |
| DIBP(mg/L) | 0.1209 | 0.1223 | 0.1222 | 0.1221 | 0.1222 | 0.468 |
| DBP(mg/L) | 0.0738 | 0.0736 | 0.0738 | 0.0738 | 0.0740 | 0.180 |
| DEHP(mg/L) | 0.0128 | 0.0125 | 0.0121 | 0.0120 | 0.0123 | 2.728 |
Result display in table 1, RSD(relative standard deviation) be less than 10%, showing can the content of urethanes and phthalic ester in Accurate Measurement wine sample.
Quantitative limit and detectability are the sensitivity embodying detection method, when being only starkly lower than maximum residue limit, can be used for measuring.With content during signal to noise ratio (S/N ratio) S/N=3 for detectability; With content during signal to noise ratio (S/N ratio) S/N=10 for quantitative limit.Result display in table 2, the sensitivity of the method is higher.
The sensitivity of table 2 the inventive method
| ? | EC | DMP | DEP | DIBP | DBP | DEHP |
| Detectability (mg/L) | 0.0005 | 0.00005 | 0.00006 | 0.00002 | 0.00005 | 0.00002 |
| Quantitative limit (mg/L) | 0.023 | 0.0024 | 0.0025 | 0.0014 | 0.0021 | 0.0017 |
As can be seen from above-mentioned experimental result, method provided by the invention is simple to operate, and sensitivity is higher, and accuracy is high, favorable reproducibility.
Claims (5)
1. simultaneous quantitative detects the method for urethanes and phthalic ester in distilled spirit, comprises the following steps:
A, in wine sample, add internal standard compound I and internal standard compound II; Described internal standard compound I is deuterated urethanes; Described internal standard compound II is di-iso-amyl phthalate;
B, use gas chromatograph-mass spectrometer (GCMS) detect, and use Salbutamol Selected Ion Monitoring with quantitative, adopt internal standard method to obtain the content of urethanes and phthalic ester; The condition of described gas chromatography is: adopt ZB-WAXplus capillary chromatographic column to be separated, injector temperature 250 DEG C, sample size 0.5 μ L, Splitless injecting samples, post flow 1mL/min; Heating schedule: 40 DEG C keep 2min, rise to 160 DEG C, then rise to 230 DEG C with 30 DEG C/min with 10 DEG C/min, keep 15.6min; Electron ionization sources, ionization voltage 70eV; Scan mode is Salbutamol Selected Ion Monitoring, ion source temperature 230 DEG C, level Four bar temperature 150 DEG C, GC-MS auxiliary heating temperature 240 DEG C.
2. simultaneous quantitative according to claim 1 detects the method for urethanes and phthalic ester in distilled spirit, it is characterized in that: described in step a, internal standard compound I is 3 ︰ 1000 with the volume ratio of wine sample.
3. simultaneous quantitative according to claim 1 detects the method for urethanes and phthalic ester in distilled spirit, it is characterized in that: described in step a, internal standard compound II is 3 ︰ 1000 with the volume ratio of wine sample.
4. simultaneous quantitative according to claim 1 detects the method for urethanes and phthalic ester in distilled spirit, and it is characterized in that: described in step b, the length of ZB-WAXplus capillary chromatographic column is 30m, internal diameter is 0.25mm, and thickness is 0.25 μm.
5. simultaneous quantitative according to claim 1 detects the method for urethanes and phthalic ester in distilled spirit, it is characterized in that: the Salbutamol Selected Ion Monitoring described in step b is: the monitoring ion m/z62 of urethanes, the monitoring ion m/z64 of deuterated urethanes, the monitoring ion m/z163 of repefral, the monitoring ion of diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-ethyl) own ester and di-iso-amyl phthalate is m/z149.
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| CN103913525B (en) * | 2014-04-01 | 2015-04-22 | 山东省分析测试中心 | Method for detecting 17 plasticizers in white spirit by high performance liquid chromatography-tandem mass spectrometry |
| CN103954568A (en) * | 2014-04-22 | 2014-07-30 | 华南理工大学 | Chemical detection method for rapidly detecting content of ethyl carbamate |
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| CN106468688B (en) * | 2015-08-21 | 2018-08-24 | 菏泽天鸿果蔬有限公司 | A kind of detection method of urethanes residual quantity |
| CN110007039A (en) * | 2019-05-13 | 2019-07-12 | 四川轻化工大学 | Qualitative determination method and content determination method for formic acid in edible wine |
| CN110591965B (en) * | 2019-09-29 | 2021-05-04 | 北京工商大学 | Burkholderia polyphylla culture method and application thereof in catalytic synthesis of white spirit flavor ester and degradation of white spirit harmful ester |
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