CN102998389B - Gas chromatography detection method of corrosion removers in food - Google Patents
Gas chromatography detection method of corrosion removers in food Download PDFInfo
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- 235000013305 food Nutrition 0.000 title claims abstract description 29
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- 238000005260 corrosion Methods 0.000 title abstract 4
- 230000007797 corrosion Effects 0.000 title abstract 4
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- 239000000243 solution Substances 0.000 claims description 30
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- NVMFTNWVCRPAJR-UHFFFAOYSA-K calcium sodium propanoate Chemical compound [Na+].C(CC)(=O)[O-].[Ca+2].C(CC)(=O)[O-].C(CC)(=O)[O-] NVMFTNWVCRPAJR-UHFFFAOYSA-K 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a detection method for determining a plurality of corrosion removers in food by gas chromatography. The target is that the method has the characteristics of simple operation, matrix interference resistance, reliable result and the like, and the method is suitable for accurately determining the content of the plurality of corrosion removers in the food. The technical scheme is that the gas chromatography detection method of the plurality of corrosion removers in the food is processed according to the following steps: 1) preparing sample extracting solution; preparing liquid sample extracting solution, or preparing solid sample extracting solution; 2) concentrating; rotatably concentrating the sample extracting solution in a water bath at 40+/-2 DEG C until the volume is 0.3-0.5mL; drying by nitrogen, and determining the volume to 2.0-5.0mL by acetone, filtering the sample solution by 0.45 micron of filter membrane to test; and 3) detecting on a machine: inputting the solution to be tested into a gas chromatograph with a hydrogen flame detector to detect.
Description
Technical Field
The invention relates to a detection method, in particular to a detection method for detecting various preservatives in food by gas chromatography.
Background
Preservatives (preservative) are agents that inhibit the decay of substances, that is, agents that continuously inhibit the growth of microorganisms that use a decaying substance as a metabolic substrate, and are widely used in the fields of foods, daily chemicals, and the like.
There are many kinds of preservatives allowed to be added internationally, for example, about 50 kinds in the United states and 40 kinds in Japan. At present, only 32 food preservatives allowed to be used are approved in China, and the food preservatives are subjected to a large number of scientific experiments before being approved to be used, are low-toxicity and high-safety varieties and mainly comprise: benzoic acid and its sodium salt, sorbic acid and its potassium salt, sulfur dioxide, sodium (potassium) metabisulfite, sodium (calcium) propionate, parabens, dehydroacetic acid, etc.; sorbic acid, benzoic acid and salts thereof are more frequently used. In addition, there are some natural biological preservatives such as nisin, natamycin, chitosan, etc. and novel preservatives such as dimethyl fumarate, etc. As long as the food preservative used by food manufacturers is strictly controlled within the range specified by the national standard of food additive use health standard (GB2760-2011) in terms of variety, quantity and range, the food preservative cannot cause damage to human health, and the product can be eaten at ease. Unfortunately and with great concern, many food manufacturers have problems of illegal, abuse and overdose use of food preservatives due to the limitations of production cost, low quality of workers and no concept of damage to the preservatives, so that many foods become additives including the integrated food of the preservatives, and excessive ingestion has certain negative effects on physical health; the addition of preservatives can have a significant impact on society and consumers. Therefore, a set of rapid, accurate, simple and convenient and low-cost detection technical standard is established to be widely applied to beverages, cakes, condiments, preserved fruits and other foods, the detection efficiency of the preservative in the foods can be improved, the detection cost can be effectively controlled, the detection period is shortened, and the reasonable use of the preservative in the production process of enterprises and the rapid monitoring of the preservative adding condition by law enforcement departments in the market circulation process are facilitated; has important significance in ensuring food safety and has very obvious social benefit.
The different preservatives have different structural properties, and the existing sample matrixes are complex and diverse, so that the detection means for different preservatives and different food types are different in the current standard. At present, the existing preservative detection standards are various in types, the related experimental conditions are different, the types of the targeted preservatives are single, and the various common preservatives cannot be rapidly detected at one time, so that the inspection period is prolonged, and the inspection efficiency is reduced. The preservative is generally detected by a method such as liquid chromatography, liquid chromatography-mass spectrometry, gas chromatography, and gas chromatography-mass spectrometry. Although the liquid chromatography and the liquid chromatography-mass spectrometry combined method can simultaneously detect a plurality of preservatives, the matrix impurities of the food samples can cause interference due to various types of matrixes, false positive or false negative results are easily caused, and accurate quantification is influenced. The gas chromatography-mass spectrometry combined method has higher requirements on instruments and is not suitable for popularization and use.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a detection method capable of simultaneously detecting a plurality of common preservatives in food, and the method has the characteristics of simple and convenient operation, matrix interference resistance, reliable result and the like and is suitable for accurately detecting the content of the plurality of preservatives in the food.
In order to achieve the above object, the inventors have conducted extensive and intensive studies and determined the following technical solutions:
a gas chromatography detection method for various preservatives in food is carried out according to the following steps:
1) preparing a sample extracting solution:
preparing liquid sample extracting solution: weighing 5-10g of liquid sample in a 125mL separating funnel, adding 10mL of saturated NaCl aqueous solution and 1.0mL of hydrochloric acid solution for acidification, uniformly mixing, adding 1.0mL of internal standard solution, extracting with diethyl ether for three times, combining ether layers, washing with saturated NaCl aqueous solution to be neutral, and dehydrating the ether layer with anhydrous sodium sulfate for later use; or,
preparing a solid sample extracting solution: weighing 5-10g of solid sample in a 100mL volumetric flask, adding water, soaking and extracting in water bath at 80 +/-2 ℃ for 30-60min, taking out, cooling to room temperature, and adding water to a constant volume of 100 mL; filtering again, and putting 10.0-25.0mL of filtrate in a 125mL separating funnel; adding 10mL of saturated NaCl aqueous solution and 1.0mL of hydrochloric acid solution, mixing uniformly, adding 1.0mL of internal standard solution, extracting with ethyl ether for three times, combining ether layers, washing with saturated NaCl aqueous solution to be neutral, and dehydrating the ether layers by using anhydrous sodium sulfate for later use;
2) and concentrating: rotationally concentrating the above sample extractive solution in 40 + -2 deg.C water bath to 0.3-0.5mL, blow-drying with nitrogen, diluting with acetone to 2.0-5.0mL, and filtering with 0.45 μm filter membrane to be measured;
3) and computer detection: and (3) inputting the liquid to be detected into a gas chromatograph equipped with a hydrogen flame detector for detection.
The various preservatives are propionic acid, sorbic acid, benzoic acid, dehydroacetic acid, methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, heptyl paraben, and dimethyl fumarate.
The hydrochloric acid used for acidification in the step 1) is mixed solution prepared by equal volume of concentrated hydrochloric acid with the concentration of 12moL/L and water.
The components of the internal standard solution in the step 1) are undecanoic acid and acetone, and the content of the undecanoic acid is 1-2 mg/mL.
In the step 1), diethyl ether is adopted for extraction for 3 times, and the diethyl ether adopted in sequence is 50mL, 30mL and 30 mL.
The invention has the beneficial effects that:
1) the sample is acidified by hydrochloric acid and extracted by ether, so that the interference of a sample matrix on a color spectrum output peak is avoided;
2) the internal standard (undecanoic acid) method is adopted to carry out quantitative determination on various preservatives in the food, so that the influence of the extraction efficiency on the result in the sample preparation process can be effectively reduced;
3) the detection of the standard working solution proves that: the detection method established by the invention has the characteristics of multiple types of preservatives, good linearity of detection results, high detection sensitivity (the detection limit is 0.84-5.01 mg/kg), good anti-specificity (the precision is 1.9-4.3%, the recovery rate is 88.9-101.6%), simplicity and convenience in operation, matrix interference resistance and reliable results, is suitable for accurately measuring the content of multiple preservatives in food, and provides powerful technical support for quality supervision of the food.
Drawings
FIG. 1 is a schematic gas chromatograph showing a mixture of preservatives; 1-12 in the figures refer to: 1-propionic acid, dimethyl 2-fumarate, 3-sorbic acid, 4-dehydroacetic acid, 5-internal standard undecanoic acid, 6-benzoic acid, methyl 7-paraben, isopropyl 8-paraben, ethyl 9-paraben, propyl 10-paraben, butyl 11-paraben and isobutyl paraben, heptyl 12-paraben.
FIG. 2 is a gas chromatography schematic of soy sauce.
Figure 3 is a gas chromatography schematic of an orange juice beverage.
FIG. 4 is a schematic gas chromatography of vinegar.
Fig. 5 is a gas chromatography schematic of egg yolk crisps.
Detailed Description
Weighing a certain amount of liquid sample or solid sample filtrate soaked in water bath into a container, adding hydrochloric acid for acidification, a saturated sodium chloride aqueous solution and a fixed amount of internal standard solution, uniformly mixing, respectively extracting for 3 times by using ether, combining ether layers, washing to be neutral by using the saturated sodium chloride aqueous solution, removing a water layer, and dehydrating the ether layer for later use; carrying out rotary evaporation on the extracting solution until the extracting solution is nearly dry, blow-drying the extracting solution by nitrogen, then fixing the volume by acetone, and passing a sample solution through a membrane to be detected; and (3) inputting the liquid to be detected into a gas chromatograph equipped with a hydrogen flame detector for detection.
1) The first point in the method is to detect a plurality of preservatives simultaneously (a plurality of preservatives include propionic acid, sorbic acid, benzoic acid, dehydroacetic acid, methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, heptyl paraben, dimethyl fumarate); the detection is carried out rapidly while 12 preservatives are covered, so that the detection efficiency is improved;
2) the second point in the method is that the sample adopts 1: 1, acidifying with hydrochloric acid, and extracting with diethyl ether for 3 times, so that interference of a sample matrix on a color spectrum emergence peak is avoided;
3) the third main point in the method is that an internal standard (undecanoic acid) method is adopted to carry out quantitative determination on various preservatives in the food, and the influence of the extraction efficiency in the sample preparation process on the result can be effectively reduced.
The following details are described with respect to the present invention:
1 reagents and materials
All reagents were analytically pure and water was tertiary water as specified in GB/T6682 unless otherwise stated.
1: 1 hydrochloric acid solution: mixing concentrated hydrochloric acid with the concentration of 12moL/L and water in equal volume;
diethyl ether;
saturated aqueous sodium chloride solution: adding sodium chloride into distilled water, stirring and dissolving until saturation;
anhydrous sodium sulfate;
acetone;
undecanoic acid: weighing 0.1000g of the solution, dissolving and diluting the solution by using acetone to fix the volume to 100mL, and preparing an internal standard solution for later use, wherein the content of the undecanoic acid in the internal standard solution is 1 mg/mL;
12 preservative standards (propionic acid, sorbic acid, benzoic acid, dehydroacetic acid, methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, heptyl paraben, dimethyl fumarate);
preservative standard stock solutions: respectively weighing 0.2000g of preservative standard substance, dissolving with acetone and diluting to 100mL, so that the concentration of each preservative is 2 mg/mL;
mixing standard working solution: transferring 0.1mL, 0.2mL, 0.5mL, 1.0mL, 2.0mL and 5.0mL of preservative standard stock solution into 6 5.0mL volumetric flasks respectively, transferring 1.0mL of undecanoic acid internal standard solution into the volumetric flasks respectively, diluting to 5.0mL with acetone to prepare a mixed standard working solution series so that the final concentration of each preservative is 0.04mg/mL, 0.08mg/mL, 0.2mg/mL, 0.4mg/mL, 1.0mg/mL and 2.5mg/mL respectively;
0.45 μm filter.
2 instruments and apparatus
Gas chromatograph: is provided with an FID detector;
analytical balance: the sensory amounts are 0.0001g and 0.01 g;
a water bath kettle;
a rotary evaporator.
3 sample treatment
3.1 liquid sample (e.g. beverage, soy sauce, etc.)
Weighing 5-10g (accurate to 0.01 g) of sample in a 125mL separating funnel, adding 10mL of saturated NaCl aqueous solution and 1mL of hydrochloric acid solution, mixing uniformly, adding 1mL of internal standard solution, extracting with 50mL of diethyl ether, 30mL of diethyl ether and 30mL of diethyl ether for three times respectively, combining ether layers, washing with 30mL of saturated NaCl aqueous solution to be neutral, dehydrating by anhydrous sodium sulfate, carrying out rotary concentration in water bath at 40 +/-2 ℃ until the solution is nearly dry, carrying out nitrogen blow-drying, and carrying out volume fixing by using acetone to 2.0-5.0 mL; the sample solution is measured after passing through a 0.45 mu m filter membrane.
3.2 solid sample (e.g. cake, preserve, etc.)
Weighing 5-10g (accurate to 0.01 g) of sample in a 100mL volumetric flask, adding water, soaking and extracting in water bath at 80 +/-2 ℃ for 30-60min, taking out, cooling to room temperature, adding water to a constant volume of 100mL, filtering, and taking 10.0-25.0mL of filtrate in a 125mL separating funnel; adding 10mL of saturated NaCl aqueous solution and 1.0mL of hydrochloric acid solution, uniformly mixing, adding 1.0mL of internal standard solution, extracting with 50mL of ether, 30mL of ether and 30mL of ether for three times respectively, combining ether layers, washing with 30mL of saturated NaCl aqueous solution to be neutral, dehydrating by anhydrous sodium sulfate, carrying out rotary concentration in a water bath at 40 +/-2 ℃ until the solution is nearly dry, carrying out nitrogen blow-drying, and carrying out volume fixing to 2.0-5.0mL by using acetone; the sample solution is measured after passing through a 0.45 mu m filter membrane.
4 gas chromatography assay
4.1GC reference conditions
A chromatographic column: HP-innowax, 30 m.times.320 μm.times.0.25 μm;
column temperature: the initial temperature is 130 ℃, the temperature is increased to 170 ℃ at the speed of 10 ℃/min, the temperature is kept for 3min, the temperature is increased to 260 ℃ at the speed of 20 ℃/min, and the temperature is kept for 21.5 min;
sample inlet temperature: 250 ℃;
detector temperature: 260 ℃;
carrier gas: high purity N2, flow rate 0.8 mL/min;
sample introduction amount: 1 mu L of the solution; the split ratio is as follows: 10: 1;
4.2 drawing of Standard Curve
And (3) carrying out sample injection detection on the diluted standard working solution according to the concentration from low to high, and drawing by peak area-concentration to obtain a standard curve regression equation, wherein a standard map is shown in a figure 1.
5 Linear relationship and detection Limit
Taking the ratio of the mass concentration of each preservative to the internal standard substance (undecanoic acid) as an abscissa and the corresponding peak area as an ordinate, and performing linear regression, wherein the linear concentration range is 0.04-2.50 mg/mL. According to the signal-to-noise ratio of 3 times, 5.00g of a sample (liquid) is actually weighed, the final volume is 5.0mL, and the correlation coefficient R of the linear regression equation of various preservatives2In the range of 0.99860-0.99980, the lowest detection limit is 0.84-5.01mg/kg, and the detection limit meets the daily monitoring requirement of the preservative in the food.
6 precision and recovery
According to the operation of the method, the mixed standard working solution is added into the sample and the sample is subjected to parallel determination for 6 times respectively, the determination repeatability of the content of the preservative in the sample is good, the RSD values of the preservative are all less than 5.0%, the recovery rate is between 90.6% and 98.8%, the extraction rate of the ethyl ether is influenced due to the fact that propionic acid is high in water solubility, and the influence of the extraction rate on the propionic acid quantification can be partially eliminated by adding the internal standard (undecanoic acid).
7 determination of the actual sample
The detection technology of the invention is adopted to measure the content of the preservative in several types of foods sold on the market.
Example 1
Determination of preservatives in Soy sauce
Weighing 5.00g (accurate to 0.01 g) of soy sauce in a 125mL separating funnel, adding 10mL of saturated NaCl aqueous solution and 1.0mL of hydrochloric acid solution, mixing uniformly, adding 1.0mL of undecanoic acid internal standard solution, extracting with 50mL, 30mL and 30mL of diethyl ether for three times, combining ether layers, washing with 30mL of saturated NaCl aqueous solution to be neutral, dehydrating with anhydrous sodium sulfate, carrying out rotary concentration in water bath at 40 +/-2 ℃ to 0.3-0.5mL, carrying out nitrogen blow-drying, and metering to 5.0mL with acetone. The sample solution was passed through a 0.45 μm filter and then measured by gas chromatography, and the chromatogram was shown in FIG. 2, and the soy sauce contained 0.034g/kg propionic acid, 0.010g/kg dimethyl fumarate, 0.082g/kg dehydroacetic acid, 0.67g/kg sorbic acid, and 0.40g/kg benzoic acid.
Example 2
Determination of preservatives in orange juice beverages
Weighing 10.00g (accurate to 0.01 g) of orange juice beverage in a 125mL separating funnel, adding 10mL of saturated NaCl aqueous solution and 1.0mL of hydrochloric acid solution, mixing uniformly, adding 1.0mL of undecanoic acid internal standard solution, extracting with 50mL, 30mL and 30mL of diethyl ether for three times, combining ether layers, washing with 30mL of saturated NaCl aqueous solution to be neutral, dehydrating by anhydrous sodium sulfate, carrying out rotary concentration in 40 +/-2 ℃ water bath to be 0.3-0.5mL, drying by nitrogen, and metering to 5.0mL by using acetone. The sample solution is filtered through a 0.45 μm filter membrane and then enters a gas chromatograph for measurement, a spectrogram is shown in figure 3, and the beverage is measured to contain 0.10g/kg of benzoic acid.
Example 3
Determination of preservative in Vinegar
Weighing 7.00g of vinegar (accurate to 0.01 g) in a 125mL separating funnel, adding 10mL of saturated NaCl aqueous solution and 1.0mL of hydrochloric acid solution, mixing uniformly, adding 1.0mL of undecanoic acid internal standard solution, extracting with 50mL, 30mL and 30mL of diethyl ether for three times, combining ether layers, washing with 30mL of saturated NaCl aqueous solution to be neutral, dehydrating by anhydrous sodium sulfate, carrying out rotary concentration in 40 +/-2 ℃ water bath to be 0.3-0.5mL, drying by nitrogen, and metering the volume to 5.0mL by using acetone. The sample solution passes through a 0.45-micron filter membrane and then enters a gas chromatograph for measurement, a spectrogram is shown in figure 4, and the vinegar contains 0.42g/kg of propionic acid and 0.075g/kg of dimethyl fumarate.
Example 4
Determination of preservative in egg yolk crisp
Weighing 10.00g of crisp egg yolk (accurate to 0.01 g) in a 100mL volumetric flask, adding water to soak and extract in a water bath at 80 +/-2 ℃ for 30min, taking out and cooling to room temperature, adding water to a constant volume, filtering, taking 20.0mL of filtrate in a 125mL separating funnel, adding 10mL of saturated NaCl aqueous solution and 1.0mL of hydrochloric acid solution to mix uniformly, adding 1.0mL of internal standard solution, extracting with 50mL, 30mL and 30mL of diethyl ether for three times respectively, combining ether layers, washing with 30mL of saturated NaCl aqueous solution to be neutral, dehydrating by anhydrous sodium sulfate, carrying out rotary concentration in a water bath at 40 +/-2 ℃ until the solution is nearly dry, carrying out nitrogen blow-drying, and fixing the volume to 5.0mL by using acetone. The sample solution is filtered through a 0.45 μm filter membrane and then enters a gas chromatograph for measurement, the spectrogram is shown in figure 5, and the egg yolk crisp contains 0.12g/kg of sorbic acid and 0.065g/kg of benzoic acid.
8 small knot
The detection method established by the invention has the characteristics of multiple types of preservatives, good linearity, high detection sensitivity (detection limit is 0.84-5.01 mg/kg), good anti-specificity (precision is 1.9-4.3%, recovery rate is 88.9-101.6%), simple and convenient operation, matrix interference resistance and reliable result, is suitable for accurately measuring the content of multiple preservatives in food, and provides powerful technical support for quality supervision of food.
Claims (2)
1. A gas chromatography detection method for various preservatives in food is carried out according to the following steps:
1) preparing a sample extracting solution:
preparing liquid sample extracting solution: weighing 5-10g of a liquid sample in a 125mL separating funnel, adding 10mL of saturated NaCl aqueous solution and 1.0 part of hydrochloric acid solution for acidification, uniformly mixing, adding 1.0mL of internal standard solution, extracting with diethyl ether for three times, combining ether layers, washing with saturated NaCl aqueous solution to be neutral, and dehydrating the ether layer with anhydrous sodium sulfate for later use; or,
preparing a solid sample extracting solution: weighing 5-10g of solid sample in a 100mL volumetric flask, adding water, soaking and extracting in water bath at 80 +/-2 ℃ for 30-60min, taking out, cooling to room temperature, adding water to a constant volume of 100mL, filtering, and taking 10.0-25.0mL of filtrate in a 125mL separating funnel; adding 10mL of saturated NaCl aqueous solution and 1.0mL of hydrochloric acid solution, mixing uniformly, adding 1.0mL of internal standard solution, extracting with ethyl ether for three times, combining ether layers, washing with saturated NaCl aqueous solution to be neutral, and dehydrating the ether layers by using anhydrous sodium sulfate for later use;
2) and concentrating: rotationally concentrating the above sample extractive solution in 40 + -2 deg.C water bath to 0.3-0.5mL, blow-drying with nitrogen, diluting with acetone to 2.0-5.0mL, and filtering with 0.45 μm filter membrane to be measured;
3) and computer detection: inputting the liquid to be detected into a gas chromatograph equipped with a hydrogen flame detector for detection; the chromatographic conditions are as follows:
column temperature: the initial temperature is 130 ℃, the temperature is increased to 170 ℃ at the speed of 10 ℃/min, the temperature is kept for 3min, the temperature is increased to 260 ℃ at the speed of 20 ℃/min, and the temperature is kept for 21.5 min;
the various preservatives are propionic acid, sorbic acid, benzoic acid, dehydroacetic acid, methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, heptyl paraben, and dimethyl fumarate;
the hydrochloric acid used for acidification in the step 1) is mixed solution prepared by equal volume of concentrated hydrochloric acid with the concentration of 12moL/L and water;
the components of the internal standard solution in the step 1) are undecanoic acid and acetone, and the content of the undecanoic acid is 1-2 mg/mL.
2. The gas chromatography detection method for preservatives in food according to claim 1, characterized in that the ether is used for extraction 3 times in step 1), and the volumes of the ether used in sequence are 50mL, 30mL and 30 mL.
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| CN103743835A (en) * | 2013-12-23 | 2014-04-23 | 广西科技大学 | Detection method for butoben in food corrosion remover |
| CN103760248A (en) * | 2013-12-23 | 2014-04-30 | 广西科技大学 | Method for detecting hydroxybenzene methyl formate in food preservative |
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| CN103743833A (en) * | 2013-12-23 | 2014-04-23 | 广西科技大学 | Detection method of hydroxybenzoic acid propyl ester serving as food preservative |
| CN103760247A (en) * | 2013-12-23 | 2014-04-30 | 广西科技大学 | Method for detecting hydroxybenzene ethyl formate in food preservative |
| CN104807912B (en) * | 2015-05-13 | 2016-05-18 | 梧州市产品质量检验所 | Detect the method for sorbic acid in food |
| CN105911171A (en) * | 2016-04-14 | 2016-08-31 | 梧州市产品质量检验所 | Determination method for preservative in food |
| CN107192769A (en) * | 2017-04-11 | 2017-09-22 | 河南省粮油饲料产品质量监督检验中心 | Propionic acid, sorbic acid, benzoic acid, the method for dehydroactic acid content in a kind of Rapid Simultaneous Determination food |
| CN107367420B (en) * | 2017-07-13 | 2020-10-30 | 广州品悦生物科技有限公司 | Method for rapidly and quantitatively measuring propionic acid and ammonium propionate in combined manner |
| CN108107121B (en) * | 2017-12-12 | 2020-08-04 | 中华人民共和国台州出入境检验检疫局 | Method for detecting specific migration amounts of 4 parabens by gas chromatography-mass spectrometry |
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