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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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 52
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 title abstract description 25
- 235000020097 white wine Nutrition 0.000 title abstract 5
- 239000000126 substance Substances 0.000 claims abstract description 26
- 238000012544 monitoring process Methods 0.000 claims abstract description 24
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- 238000010813 internal standard method Methods 0.000 claims abstract description 8
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 30
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 30
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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 the field of liquor detection, and particularly relates to a method for simultaneously and quantitatively detecting the contents of ethyl carbamate and phthalic acid ester in distilled liquor.
Technical Field
Ethyl Carbamate (EC), also known as urethane, is a by-product naturally formed during fermentation and storage of fermented foods. The research shows that the ethyl carbamate in the distilled white spirit is generated by the spontaneous reaction of a carbamoyl compound and ethanol. In 1987, the international center for cancer research (IARC) listed ECs as group 2B: possibly carcinogenic substances; in 2004, NTP project listed ECs on "substances reasonably expected to cause cancer"; in 2007, IARC re-evaluated EC, in parallel with lead, mercury, and acrylamide, etc., in group 2A. At present, Chinese patent 201210441000.6 discloses a "high performance liquid chromatography-mass spectrometry detection method for ethyl carbamate in distilled liquor", which adopts reduced pressure distillation to remove ethanol, uses distilled water to fix volume, directly enters LC-MS (liquid chromatography-mass spectrometry), and then calculates the content of ethyl carbamate by an external standard method. Chinese patent 201110339615.3 discloses a method for rapidly determining ethyl carbamate content in distilled liquor, which adopts rotary evaporation to remove impurities, adopts headspace-solid phase microextraction technology to enrich ethyl carbamate in liquor sample, adopts GC-MS quantitative detection, and then adopts an external standard method to calculate the ethyl carbamate content.
Phthalates are a class of plasticizers that are widely used to increase the flexibility of materials or to liquefy materials, and are widely used in hundreds of products such as toys, food packaging materials, medical blood bags and tubing, vinyl flooring, cleaners, lubricants, personal care products (e.g., nail polish, shampoo), and the like. The compounds have been identified as environmental estrogens, which are harmful to the human reproductive system. The phthalate in the white spirit mainly comes from a wine storage container of a plastic product, a plastic gasket in a wine bottle cap, a plastic pipeline and the like. Chinese patent 201210281033.9 discloses a method for detecting phthalate by using a colorimetric probe; chinese patent 201210504503.3 discloses a method for measuring the content of phthalate compounds in reconstituted tobacco; chinese patent 201110076663.8 discloses a method for determining phthalate content in traditional Chinese medicine by liquid chromatography-mass spectrometry.
At present, only a few countries such as Canada, Czech and France stipulate the upper limit of the content of the ethyl carbamate in the distilled liquor, and most countries do not specifically stipulate the content of the ethyl carbamate. Therefore, there are few methods for specifically detecting the content of ethyl carbamate in distilled liquor. The inspection industry standard of import and export commodities in China is as follows: the method for testing the residual quantity of the ethyl carbamate in the export liquor is SN0285-1993, and the method is relatively complicated in operation, long in time and greatly influenced by personnel operation, and is not suitable for self-testing of enterprises on large batches of production products.
The content of phthalic acid ester in distilled liquor is detected mainly according to national standard GB/T21911-2008 'determination of phthalic acid ester in food', the method adopts liquid-liquid extraction and external standard method for quantification, and after the method is applied to distilled liquor samples, the detection result has large deviation and poor reproducibility.
The two detection methods need to carry out pretreatment on the sample, are relatively complex in operation and long in time, and cannot realize simultaneous detection of the contents of the two substances of the ethyl carbamate and the phthalic acid ester by one-time sample introduction.
Disclosure of Invention
The invention aims to solve the technical problems that the existing detection method is complicated to operate and long in time.
The technical scheme for solving the technical problems is to provide a method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, which comprises the following steps:
a. adding an internal standard substance I and an internal standard substance II into the wine sample;
b. detecting by using a gas chromatography-mass spectrometer, monitoring and quantifying by using selective ions, and obtaining the content of the ethyl carbamate and the phthalate by adopting an internal standard method.
In the method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, the internal standard substance I in the step a is deuterated ethyl carbamate. The purity of the deuterated ethyl carbamate is more than or equal to 98 percent.
Further, in the method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, the volume ratio of the internal standard substance I to the liquor sample is 3: 5000.
In the method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, the internal standard substance II in the step a is diisoamyl phthalate. The purity of the diisoamyl phthalate is more than or equal to 98 percent.
Further, in the method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, the volume ratio of the internal standard substance II to the liquor sample is 3: 5000.
Wherein, in the method for simultaneously and quantitatively detecting the ethyl carbamate and the phthalic acid ester in the distilled white spirit, the internal standard method in the step b comprises the following steps: adding an internal standard substance into the sample, analyzing by an instrument to obtain a peak area, and calculating a result according to a drawn standard curve.
Further, the gas chromatography conditions in step b are as follows: separating with ZB-WAXplus capillary chromatographic column at 250 deg.C with sample inlet temperature of 0.5 μ L, flow rate of column of 1 mL/min; temperature rising procedure: maintaining at 40 deg.C for 2min, heating to 160 deg.C at 10 deg.C/min, heating to 230 deg.C at 30 deg.C/min, and maintaining for 15.6 min.
Further, the ZB-WAXplus capillary column had a length of 30m, an inner diameter of 0.25mm and a film thickness of 0.25. mu.m.
Further, the mass spectrum conditions in step b are as follows: an electron ionization source with an ionization voltage of 70 eV; the scanning mode is selected from ion monitoring, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, and the GC-MS auxiliary heating temperature is 240 ℃.
Further, the selective ion monitoring is: monitoring ion m/z62 for ethyl carbamate, monitoring ion m/z64 for deuterated ethyl carbamate, monitoring ion m/z163 for dimethyl phthalate, and monitoring ions for diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-ethyl) hexyl phthalate, and diisopentyl phthalate, all were m/z 149.
The method provided by the invention adopts an internal standard method to detect the content of the phthalic acid ester for the first time, can detect the content of the ethyl carbamate at the same time, and has the advantages of good detection result reproducibility and low error. The method is simple and convenient to operate, does not need to carry out pretreatment on the sample, has low detection cost and short analysis time, can obtain the contents of the ethyl carbamate and the phthalic acid ester in thirty or more minutes, saves instruments, and is suitable for carrying out self-detection on a large number of samples in an enterprise. The instruments used by the method are conventional laboratory analytical instruments, and the method is easy to popularize and low in detection cost.
Drawings
FIG. 1 chromatogram of a standard solution of urethane (containing an internal standard I).
FIG. 2 chromatogram of phthalate standard solution (containing internal standard II).
FIG. 3 is a chromatogram of ethyl carbamate and phthalic acid ester (containing internal standards I and II) in a wine sample.
Detailed Description
The method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor comprises the following steps:
a. adding an internal standard substance I and an internal standard substance II into the wine sample;
b. detecting by using a gas chromatography-mass spectrometer, monitoring and quantifying by using selective ions, and obtaining the content of the ethyl carbamate and the phthalate by adopting an internal standard method.
In the method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, the internal standard substance I in the step a is deuterated ethyl carbamate. The purity of the deuterated ethyl carbamate is more than or equal to 98 percent.
Furthermore, in the method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, 30 mu L of the internal standard substance I is added into every 50mL of liquor sample.
In the method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, the internal standard substance II in the step a is diisoamyl phthalate. The purity of the diisoamyl phthalate is more than or equal to 98 percent.
Furthermore, in the method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor, 30 mu L of the internal standard substance II is added into every 50mL of liquor sample.
Wherein, in the method for simultaneously and quantitatively detecting the ethyl carbamate and the phthalic acid ester in the distilled white spirit, the internal standard method in the step b comprises the following steps: adding an internal standard substance into the sample, analyzing by an instrument to obtain a peak area, and calculating a result according to a drawn standard curve.
Further, the gas chromatography conditions in step b are as follows: separating with ZB-WAXplus capillary chromatographic column at 250 deg.C with sample inlet temperature of 0.5 μ L, flow rate of column of 1 mL/min; temperature rising procedure: maintaining at 40 deg.C for 2min, heating to 160 deg.C at 10 deg.C/min, heating to 230 deg.C at 30 deg.C/min, and maintaining for 15.6 min.
Further, the ZB-WAXplus capillary column had a length of 30m, an inner diameter of 0.25mm and a film thickness of 0.25. mu.m.
Further, the mass spectrum conditions in step b are as follows: an electron ionization source with an ionization voltage of 70 eV; the scanning mode is selected from ion monitoring, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, and the GC-MS auxiliary heating temperature is 240 ℃.
Further, the selective ion monitoring is: monitoring ion m/z62 for ethyl carbamate, monitoring ion m/z64 for deuterated ethyl carbamate, monitoring ion m/z163 for dimethyl phthalate, and monitoring ions for diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-ethyl) hexyl phthalate, and diisopentyl phthalate, all were m/z 149.
During the experiment, the inventor tries to perform quantitative analysis by using an external standard method, but the quantitative result is found to be poor in reproducibility and large in error, and particularly the result of the content measurement of the phthalate ester is still larger in deviation. Thus, an internal standard method was selected for quantitative analysis. For the selection of the internal standard, there are some requirements: the sample cannot contain the internal standard substance, does not react with the sample, has similar properties with the substance to be detected, and has retention time and response factor as close as possible. Before the selection of the internal standard substance, the inventor firstly carries out full-scan detection on distilled liquor with various flavors, such as strong flavor type, faint scent type and Maotai flavor type, and finds that the distilled liquor mainly contains five phthalate compounds: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and di (2-ethyl) hexyl phthalate. According to the selection requirement of the internal standard substance, a phthalate ester substance which is not contained in the distilled liquor is required to be selected as the internal standard substance. In selecting internal standard II, the inventors used dioctyl phthalate as internal standard II, and the data obtained show that: the internal standard has low error in quantitative results of di (2-ethyl) hexyl phthalate and good reproducibility, but has large error in quantitative results of dimethyl phthalate, diethyl phthalate, diisobutyl phthalate and dibutyl phthalate and low reproducibility. Thus, the inventors had to search for a suitable compound among the phthalate esters. After a large number of comparative experiments, the inventors finally selected diisoamyl phthalate as internal standard II. The experimental results show that: when the diisoamyl phthalate is used as an internal standard II, the quantitative results of the five phthalates are accurate, the error is low, and the reproducibility is good. The diisoamyl phthalate serving as the internal standard II can be used for well quantitatively detecting five phthalic acid esters, and the diisoamyl phthalate and the internal standard I can be used in a matched manner without interference, so that the ethyl carbamate and several phthalic acid esters can be well and quantitatively detected at the same time.
The inventors not only need to go through a large number of screening experiments to determine the internal standard II, but also need to select a suitable chromatographic column through a large number of experiments. In the process of selecting the column, the inventor used an Agilent DB-5MS capillary column to separate the components of the wine sample, and although the column was able to separate a few phthalates well, it was not able to separate the urethanes efficiently. After a number of failures, the inventors have subsequently tried to use a Phenomenex ZB-WAXplus capillary chromatography column, which surprisingly found good separation of both urethane and several phthalates with good peak patterns.
Further, a standard curve needs to be drawn. Wherein the ratio of the peak areas of the sample and the internal standard is the y-axis, and the ratio of the concentration of the sample and the internal standard is the x-axis. The steps of drawing the standard curve are as follows:
1. drawing a standard curve of the ethyl carbamate
Preparing a stock solution of the ethyl carbamate: accurately weighing 22.8mg of ethyl carbamate in a 50mL beaker, adding about 20mL of ethanol to completely dissolve the ethyl carbamate, transferring the ethyl carbamate to a 100mL volumetric flask, washing the beaker with a small amount of ethanol for 2-3 times, transferring the washing liquid to the volumetric flask, and finally fixing the volume to the scale with ethanol.
Preparing an internal standard substance I solution: accurately weighing 41.6mg of deuterated ethyl carbamate in a 50mL beaker, adding about 20mL of ethanol to completely dissolve the deuterated ethyl carbamate, transferring the deuterated ethyl carbamate into a 50mL volumetric flask, washing the beaker with a small amount of ethanol for 2-3 times, transferring the washing liquid into the volumetric flask, and finally fixing the volume to the scale with ethanol.
Preparing a series of ethyl carbamate standard working solutions: 50. mu.L, 250. mu.L, 500. mu.L of the urethane stock solution and 60. mu.L of the internal standard I solution were transferred into a 100mL volumetric flask and the volume was adjusted to the mark with 50% (v/v) ethanol.
Sequentially measuring the series of ethyl carbamate standard working solutions by adopting gas chromatography-mass spectrometry, drawing a standard curve, and obtaining a linear equation: y = ax, R2=0.9999, wherein a = 1.058; x = ratio of the concentration of ethyl carbamate to internal standard i; y = ratio of peak areas of the urethane to the internal standard i.
2. Drawing a phthalate standard curve
Preparing phthalate stock solution: 20mg of DMP (dimethyl phthalate), 50mg of DEP (diethyl phthalate), 35mg of DIBP (diisobutyl phthalate), 45mg of DBP (dibutyl phthalate) and 65mg of DEHP (di (2-ethyl) hexyl phthalate) are accurately weighed into a 50mL beaker, about 30mL of ethanol is added, the mixture is completely dissolved and then transferred into a 100mL volumetric flask, the beaker is washed with a small amount of ethanol for 3-5 times, the beaker is transferred into the volumetric flask, and finally the volume of the washing solution is fixed to a scale by using ethanol.
Preparing an internal standard substance II solution: accurately weighing 100mg of diisoamyl phthalate in a 50mL beaker, adding about 30mL of ethanol to completely dissolve the diisoamyl phthalate, transferring the diisoamyl phthalate into a 100mL volumetric flask, washing the beaker with a small amount of ethanol for 3-5 times, transferring the washing liquid into the volumetric flask, and finally fixing the volume to the scale with ethanol.
Preparation of a series of phthalate standard working solutions: 50. mu.L, 75. mu.L, 150. mu.L of phthalate stock solution and 60. mu.L of internal standard II solution were transferred to a 100mL volumetric flask and the volume was made up to the mark with 50% (v/v) ethanol.
Sequentially measuring the series phthalate standard working solutions by adopting gas chromatography-mass spectrometry, drawing a standard curve, and obtaining a linear equation of each phthalate as follows: y = ax2+ bx; wherein,
the linear equation for dimethyl phthalate is: y =0.2044x2+0.6239x，R2=0.9999, x = the ratio of the concentration of dimethyl phthalate to the concentration of the internal standard ii; y = the ratio of the peak areas of the dimethyl phthalate and the internal standard substance II;
the linear equation for diethyl phthalate is: y =0.07384x2+0.5726x，R2=0.9999, x = the ratio of the concentration of diethyl phthalate to the concentration of the internal standard ii; y = the ratio of the peak areas of diethyl phthalate and the internal standard substance II;
the linear equation for diisobutylphthalate is: y =0.1350x2+0.8949x，R2=0.9999, x = the ratio of the concentration of diisobutylphthalate to the internal standard ii; y = ratio of peak areas of diisobutylphthalate and internal standard II;
the linear equation for dibutyl phthalate is: y =0.1284x2+1.118x，R2=0.9999, x = ratio of concentration of dibutyl phthalate to internal standard ii; y = peak area ratio of dibutyl phthalate to internal standard substance II;
the linear equation for di (2-ethyl) hexyl phthalate is: y =0.06119x2+0.8346x，R2=0.9998, x = the ratio of the concentration of di (2-ethyl) hexyl phthalate to the internal standard ii; y = ratio of peak areas of di (2-ethyl) hexyl phthalate to internal standard II.
Further, the content of ethyl carbamate in the wine sample is calculated by the following formula:
m=A/AS×ms/a
wherein m is the content of the ethyl carbamate in the wine sample, and the unit is milligram per liter (mg/L);
a-peak area of ethyl carbamate;
ASpeak area of deuterated urethane;
ms-the content of internal standard in the wine-like solution in milligrams per liter (mg/L);
a-is derived from a linear regression equation.
Further, the content of phthalate in the wine sample is calculated by the following formula:
m=[-b+(4a×A/As+b2)1/2]×ms/2a
wherein m is the content of each phthalate in the wine sample in milligrams per liter (mg/L);
b-is obtained from a linear regression equation;
a-is obtained from a linear regression equation;
a-peak area for each phthalate;
ASpeak area of diisoamyl phthalate;
ms-the content of internal standard in the wine-like solution in milligrams per liter (mg/L).
The instruments and reagents used in the examples of the invention:
agilent7890A gas chromatograph, Agilent5975C mass spectrometer, ZB-WAXplus capillary chromatography column from Phenomenex.
Ethanol is superior pure; the purities of the urethane standard, the deuterated urethane standard and the phthalate standard are more than or equal to 98 percent and are all produced by AccuStandard company of America.
Example 1
Cleaning a 50mL volumetric flask for 2-3 times by using a wine sample to be detected, adding about 10mL of the wine sample to be detected into the volumetric flask after the cleaning is finished, then respectively adding 30 mu L of the internal standard substance I and 30 mu L of the internal standard substance II into the volumetric flask by using a liquid transfer gun, finally fixing the volume to the scale by using the wine sample to be detected, shaking gently, and mixing uniformly. And pouring the well-mixed liquor sample to be detected with the internal standard substance into an Agilent sample bottle for gas chromatography-mass spectrometry detection.
The conditions of the gas chromatography were: separating with ZB-WAXplus capillary chromatographic column with length of 30m, inner diameter of 0.25mm, and film thickness of 0.25 μm; the sample inlet temperature is 250 ℃, the sample injection amount is 0.5 mu L, the split-flow sample injection is not carried out, and the column flow is 1 mL/min; temperature rising procedure: maintaining at 40 deg.C for 2min, heating to 160 deg.C at 10 deg.C/min, heating to 230 deg.C at 30 deg.C/min, and maintaining for 15.6 min.
The conditions of mass spectrum are: an electron ionization source with an ionization voltage of 70 eV; the scanning mode is selected from ion monitoring, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, and the GC-MS auxiliary heating temperature is 240 ℃. The selective ion monitoring was: monitoring ion m/z62 for ethyl carbamate, monitoring ion m/z64 for deuterated ethyl carbamate, monitoring ion m/z163 for dimethyl phthalate, and monitoring ions for diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-ethyl) hexyl phthalate, and diisopentyl phthalate, all were m/z 149.
And calculating the content of the ethyl carbamate and the phthalic acid ester according to the peak areas of the obtained internal standard substance and the component to be detected. Substituting the obtained peak area, the concentration of the internal standard substance and a and b in the linear equation into a formula:
the ethyl carbamate content in the wine sample is calculated by the following formula:
m=A/AS×ms/a
wherein: m-ethyl carbamate content in wine samples in milligrams per liter (mg/L);
a-peak area of ethyl carbamate;
ASpeak area of deuterated urethane;
ms-the content of internal standard in the wine-like solution in milligrams per liter (mg/L);
a-is derived from a linear regression equation.
The linear equation: y = ax, R2=0.9999, wherein a = 1.058;
the content of the phthalic acid ester in the wine sample is calculated by the following formula:
m=[-b+(4a×A/As+b2)1/2]×ms/2a
wherein: m-the content of each phthalate in the wine sample in milligrams per liter (mg/L);
b-is obtained from a linear regression equation;
a-is obtained from a linear regression equation;
a-peak area for each phthalate;
ASpeak area of diisoamyl phthalate;
ms-the content of internal standard in the wine-like solution in milligrams per liter (mg/L).
Linear equation for dimethyl phthalate: y = ax2+ bx, wherein a =0.2044, b = 0.6239;
linear equation for diethyl phthalate: y = ax2+ bx, wherein a =0.07384, b = 0.5726;
linear equation for diisobutylphthalate: y = ax2+ bx, wherein a =0.1350, b = 0.8949;
linear equation for dibutyl phthalate: y = ax2+ bx, wherein a =0.1284, b = 1.118;
linear equation for di (2-ethyl) hexyl phthalate: y = ax2+ bx, where a =0.06119, b = 0.8346.
The contents of ethyl carbamate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate and di (2-ethyl) hexyl phthalate in the wine sample are obtained by calculation and are 0.3295mg/L, 0.1044mg/L, 0.2946mg/L, 0.2906mg/L, 0.2926mg/L and 0.3476mg/L respectively.
Example 2 precision and sensitivity of the method of the invention
An alcohol sample was tested in parallel 5 times according to the method of example 1, and the results of the precision of the samples are shown in Table 1:
TABLE 1 precision of the process of the invention
| 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 |
The results in table 1 show that RSD (relative standard deviation) is less than 10%, indicating that the content of urethane and phthalate in the wine sample can be accurately determined.
The quantitative limit and the detection limit are the sensitivity of the detection method, and can be used for determination only when the detection limit is obviously lower than the maximum residual limit. Taking the content when the signal-to-noise ratio S/N =3 as a detection limit; the content when the signal-to-noise ratio S/N =10 is taken as a quantitative limit. The results in table 2 show that the sensitivity of the method is higher.
TABLE 2 sensitivity of the method of the invention
| EC | DMP | DEP | DIBP | DBP | DEHP | |
| Detection limit (mg/L) | 0.0005 | 0.00005 | 0.00006 | 0.00002 | 0.00005 | 0.00002 |
| Limit of quantitation (mg/L) | 0.023 | 0.0024 | 0.0025 | 0.0014 | 0.0021 | 0.0017 |
The experimental results show that the method provided by the invention is simple to operate, high in sensitivity, high in accuracy and good in reproducibility.
Claims (5)
1. The method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled liquor comprises the following steps:
a. adding an internal standard substance I and an internal standard substance II into the wine sample; the internal standard substance I is deuterated ethyl carbamate; the internal standard substance II is diisoamyl phthalate;
b. detecting by using a gas chromatography-mass spectrometer, monitoring and quantifying by using selective ions, and obtaining the content of the ethyl carbamate and the content of the phthalic acid ester by adopting an internal standard method; the conditions of the gas chromatography are as follows: separating with ZB-WAXplus capillary chromatographic column at 250 deg.C with sample inlet temperature of 0.5 μ L, flow rate of column of 1 mL/min; temperature rising procedure: maintaining at 40 deg.C for 2min, heating to 160 deg.C at 10 deg.C/min, heating to 230 deg.C at 30 deg.C/min, and maintaining for 15.6 min; an electron ionization source with an ionization voltage of 70 eV; the scanning mode is selected from ion monitoring, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, and the GC-MS auxiliary heating temperature is 240 ℃.
2. The method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled spirit according to claim 1, wherein the method comprises the following steps: the volume ratio of the internal standard substance I to the wine sample in the step a is 3: 1000.
3. The method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled spirit according to claim 1, wherein the method comprises the following steps: the volume ratio of the internal standard substance II to the wine sample in the step a is 3: 1000.
4. The method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled spirit according to claim 1, wherein the method comprises the following steps: the ZB-WAXplus capillary chromatography column of step b had a length of 30m, an internal diameter of 0.25mm and a membrane thickness of 0.25. mu.m.
5. The method for simultaneously and quantitatively detecting ethyl carbamate and phthalic acid ester in distilled spirit according to claim 1, wherein the method comprises the following steps: the selective ion monitoring in the step b is as follows: monitoring ion m/z62 for ethyl carbamate, monitoring ion m/z64 for deuterated ethyl carbamate, monitoring ion m/z163 for dimethyl phthalate, and monitoring ions for diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-ethyl) hexyl phthalate, and diisopentyl phthalate, all were m/z 149.
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