CN106918487B - Preparation method of dibutyl phthalate standard sample - Google Patents
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Abstract
The invention discloses a preparation method of a dibutyl phthalate standard sample, which relates to the preparation of a standard sample, and aims to solve the problem that the standard sample is not easy to prepare in phthalate detection, and the method comprises the following steps: the dibutyl phthalate is added into a matrix, wherein the content of the dibutyl phthalate is 1-5 mg/kg, and the matrix is milk powder. The method provided by the invention is beneficial to improving the accuracy and reliability of the detection data of the phthalate in the laboratory food, and lays a foundation for unifying the detection standard of the phthalate in the food. The invention is applied to the field of phthalate detection.
Description
Technical Field
The invention relates to the field of preparation of standard samples, in particular to a preparation method of a standard sample for measuring dibutyl phthalate in milk powder.
Background
The phthalate is mainly used for improving the processing performance and the strength of plastics and is widely applied to plastic and rubber material products. The phthalate ester and the plastic molecules are connected by hydrogen bonds and Van der Waals force, and are easy to migrate from the plastic and the products thereof to the environment. Because the phthalate esters widely exist in nature, migrate through physical and chemical actions such as contact, friction, dissolution and the like of food packaging materials, or are introduced into food as illegal food additives, the phthalate esters can interfere the endocrine system of a human body after being ingested, harm the immune function, the digestive system and the reproductive system of the human body, and have potential 'three-cause' effects. The European Union, the United states, Japan and the like successively restrict the use of the substances in the fields of food contact materials, children toys and the like, and China sets limit standards of dibutyl phthalate (DBP), di (2-ethyl) hexyl phthalate (DEHP) and diisononyl phthalate (DINP) in foods in 2011.
Phthalate esters are most commonly left in food products with strong fat solubility and food products with a certain solubility in them. In the national laboratory program, the risk monitoring of DBP, DEHP, DINP in dairy products, infant food, wines, fats and oils and other foods has been carried out for several years. At present, the detection standards and methods for phthalate substances in related food at home and abroad are more, and the comparison result of a laboratory for detecting dibutyl phthalate in milk powder in Heilongjiang province in 2016, which is born by the applicant of the invention, shows that the whole detection data is in a large discrete degree, which indicates that the detection of the item has certain difficulty, and the detection capability of each laboratory for the item is not uniform, so that the detection is yet to be enhanced. In addition, the ability verification or comparison projects developed in the field of domestic milk powder detection mostly focus on the analysis of protein, fat and other nutrient components, and a standard sample for measuring phthalate esters is not available. Therefore, the standard sample for phthalate determination is developed as soon as possible by taking the milk powder as a matrix, and the method has very important significance for objectively evaluating the accuracy and reliability of the phthalate detection result in a laboratory.
While the standard sample generally requires high enough uniformity and stability, the specificity of phthalate detection is not only that it is present in trace amount in the milk powder, but also that a relatively high and difficult-to-control laboratory blank is easily introduced during the laboratory treatment process, and therefore, it is difficult to prepare a uniform sample at this content level.
Disclosure of Invention
The invention aims to overcome the defects and provide a standard sample for measuring phthalate in milk powder, the content of the standard sample is close to the actual residual quantity, the standard sample can be transported at normal temperature, and the uniformity and the stability of the standard sample can meet the standard requirements. In addition, the preparation method can uniformly distribute a trace amount of phthalate substances into the substance to be detected, and has high success rate of sample preparation, wherein the preparation rate is 82%.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the invention relates to a preparation method of a dibutyl phthalate standard sample, which is carried out according to the following steps:
firstly, matrix pretreatment: mixing the milk powder, sieving, and collecting the milk powder without dibutyl phthalate;
secondly, preparing a sample: by adopting a uniform distribution method, firstly, quantitatively dissolving dibutyl phthalate in a solvent, and uniformly mixing to obtain a dibutyl phthalate solution; uniformly distributing the prepared dibutyl phthalate solution into a matrix, uniformly stirring, freeze-drying after the solvent is volatilized, crushing, uniformly stirring again, sieving to obtain a small sample with the concentration of 10-20 mg/kg, uniformly stirring the matrix and the small sample, and sieving to obtain a dibutyl phthalate standard sample;
wherein the mass volume ratio of the dibutyl phthalate to the solvent is as follows: 0.1 g: 100 mL; the mass-volume ratio of the dibutyl phthalate solution to the matrix is as follows: 0.5-0.8 mL: 1g of a compound; the mass ratio of the sample to the matrix is as follows: 0.3-0.5 g: 1g of the total weight of the composition.
The solvent of the invention is selected to meet the following three conditions at the same time: a, the solubility of dibutyl phthalate in a solvent is good; b dibutyl phthalate does not change therein; c, good volatility of the solvent; the milk powder does not cake in the milk powder and is easy to disperse.
Compared with the prior art, the invention has the following advantages and beneficial effects: the standard sample for measuring dibutyl phthalate, which is obtained by the preparation method, is beneficial to improving the accuracy and reliability of phthalate detection data in laboratory food, and lays a foundation for unifying phthalate detection standards in food. The matrix is selected from the types which are common in laboratories and have high processing difficulty, the preparation method is simple and has strong operability, trace dibutyl phthalate can be uniformly distributed in the matrix, the standard sample can be transported and transferred at normal temperature, and the content of the dibutyl phthalate is close to that of the actual sample and is sufficiently uniform and stable. The sample preparation rate of the invention is 82%, the F value of the sample is less than the F critical value (F0.05(9, 10) ═ 3.02) by F test, there is no significant difference between samples, i.e. the sample is uniform and can be kept stable for 6 months.
Detailed Description
The first embodiment is as follows: the scheme of the embodiment is as follows: a preparation method of a dibutyl phthalate standard sample is carried out according to the following steps:
firstly, matrix pretreatment: mixing the milk powder, sieving, and collecting the milk powder without dibutyl phthalate;
secondly, preparing a sample: by adopting a uniform distribution method, firstly, quantitatively dissolving dibutyl phthalate in a solvent, and uniformly mixing to obtain a dibutyl phthalate solution; uniformly distributing the prepared dibutyl phthalate solution into a matrix, uniformly stirring, freeze-drying after the solvent is volatilized, crushing, uniformly stirring again, sieving to obtain a small sample with the concentration of 10-20 mg/kg, uniformly stirring the matrix and the small sample, and sieving to obtain a dibutyl phthalate standard sample;
wherein the mass volume ratio of the dibutyl phthalate to the solvent is as follows: 0.1 g: 100 mL; the mass-volume ratio of the dibutyl phthalate solution to the matrix is as follows: 0.5-0.8 mL: 1g of a compound; the mass ratio of the sample to the matrix is as follows: 0.3-0.5 g: 1g of the total weight of the composition.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the solvent is acetonitrile, methanol or absolute ethyl alcohol. The rest is the same as the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the mass ratio of the sample to the matrix is as follows: 0.3-0.4 g: 1g of the total weight of the composition. The rest is the same as the first embodiment.
The fourth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the mass ratio of the sample to the matrix is as follows: 0.4-0.5 g: 1g of the total weight of the composition. The rest is the same as the first embodiment.
The fifth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the mass-volume ratio of the matrix to the dibutyl phthalate solution is as follows: 1 g: 0.7-1.0 mL. The rest is the same as the first embodiment.
The sixth specific implementation mode: the first difference between the present embodiment and the specific embodiment is: the mass-volume ratio of the matrix to the dibutyl phthalate solution is as follows: 1 g: 0.7-0.8 mL. The rest is the same as the first embodiment.
The seventh embodiment: the first difference between the present embodiment and the specific embodiment is: the mass-volume ratio of the matrix to the dibutyl phthalate solution is as follows: 1 g: 0.5-0.7 mL. The rest is the same as the first embodiment.
The specific implementation mode is eight: the first difference between the present embodiment and the specific embodiment is: the mass-volume ratio of the matrix to the dibutyl phthalate solution is as follows: 1 g: 0.5-0.6 mL. The rest is the same as the first embodiment.
The specific implementation method nine: the first difference between the present embodiment and the specific embodiment is: and the solvent volatilization in the step two is carried out by adopting water bath at 80 ℃, and is continuously stirred in the solvent volatilization process, and is transferred into a freeze dryer when the solvent is nearly dry. The rest is the same as the first embodiment.
The detailed implementation mode is ten: the first difference between the present embodiment and the specific embodiment is: the freeze-drying conditions of the second step are as follows: performing pre-freeze-drying under the condition of 20pa of vacuum degree (pressure), wherein the pre-freeze-drying condition is as follows: keeping the temperature at 5 ℃ for 1h, and cooling to-5 ℃ for 1 h; performing main freeze-drying after pre-freeze-drying, wherein the main freeze-drying conditions are as follows: holding at-25 deg.C for 3 h; desorbing: the temperature is kept at 30 ℃ for 3 h. The rest is the same as the first embodiment.
The concrete implementation mode eleven: the first difference between the present embodiment and the specific embodiment is: the prepared dibutyl phthalate standard sample needs to be diluted and then used, and specifically, the dibutyl phthalate standard sample is diluted step by step into 1-5 mg/kg of dibutyl phthalate standard sample by adopting a blank matrix in an equivalent incremental manner. The rest is the same as the first embodiment.
The specific implementation mode twelve: the first difference between the present embodiment and the specific embodiment is: the prepared dibutyl phthalate standard sample needs to be diluted and then used, and specifically, the dibutyl phthalate standard sample is diluted step by step into 1-4 mg/kg of dibutyl phthalate standard sample by adopting a blank matrix in an equivalent incremental manner. The rest is the same as the first embodiment.
The specific implementation mode is thirteen: the first difference between the present embodiment and the specific embodiment is: the prepared dibutyl phthalate standard sample needs to be diluted and then used, and specifically, the dibutyl phthalate standard sample is diluted step by step into 1-3 mg/kg of dibutyl phthalate standard sample by adopting a blank matrix in an equivalent incremental manner. The rest is the same as the first embodiment.
The specific implementation mode is fourteen: the first difference between the present embodiment and the specific embodiment is: the prepared dibutyl phthalate standard sample needs to be diluted and then used, and specifically, the dibutyl phthalate standard sample is diluted step by step into 1-2 mg/kg of dibutyl phthalate standard sample by adopting a blank matrix in an equivalent incremental manner. The rest is the same as the first embodiment.
The following examples demonstrate the beneficial effects of the present invention:
example 1
In the standard sample for measuring dibutyl phthalate in this example, dibutyl phthalate was added to a base material so that the content was: 2mg/kg, and the matrix is milk powder.
The preparation method of the dibutyl phthalate standard sample comprises the following steps:
1. matrix pretreatment: fully and uniformly mixing the milk powder, sieving by a 80-mesh sieve, and detecting that the milk powder does not contain a substance to be detected (namely dibutyl phthalate);
2. sample preparation: the method comprises the steps of firstly, quantitatively dissolving dibutyl phthalate in a solvent by adopting an even distribution method, uniformly mixing, then, uniformly distributing a prepared dibutyl phthalate solution into a small amount of milk powder, fully stirring and mixing, freeze-drying after the solvent is volatilized to be nearly dry, crushing, uniformly stirring, sieving, preparing a high-concentration small sample, and then, gradually diluting the sample to a standard sample with the required concentration by using a blank matrix.
Wherein:
(1) selecting a solvent which meets the following three conditions simultaneously: a, the solubility of dibutyl phthalate in a solvent is good; b dibutyl phthalate does not change therein; c, good volatility of the solvent; d, the milk powder does not cake in the milk powder and is easy to disperse;
(2) preferred solvents are ethanol, acetonitrile;
(3) in the preparation process of the high-concentration small sample, the dosage of the solvent is 70 ml per 100 g of the milk powder matrix solvent;
(4) in the preparation process of the high-concentration small sample, volatilizing the solvent by adopting water bath at 80 ℃, continuously stirring, and transferring into a freeze dryer when the solvent is nearly dry;
(5) the lyophilization conditions were: pre-freeze-drying under the condition of vacuum degree (pressure) of 20 pa: keeping the temperature at 5 ℃ for 1 hour, and cooling to-5 ℃ for 1 hour; main freeze-drying: hold at-25 ℃ for 3 hours; desorbing: the temperature was maintained at 30 ℃ for 3 hours.
(6) After the preparation of the high-concentration small sample is finished, the small sample and the blank milk powder are diluted step by step in an equivalent increasing mode.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The present invention is further described in detail with reference to specific examples below:
reagents and standards used:
ethanol: chromatographic grade, acetonitrile: a chromatographic grade;
dibutyl phthalate, dr.e, purity 99.4%, CAS: 84-76-9.
1. Matrix pretreatment: and (3) opening the package of commercially available milk powder, fully and uniformly mixing the milk powder, sieving the milk powder with a 80-mesh sieve, detecting that the milk powder does not contain the substance to be detected, and uniformly mixing to prepare a blank matrix.
2. Sample preparation: the total sample size was determined to be 1600g based on demand and statistical design usage.
Firstly, precisely weighing 0.1610g of dibutyl phthalate (DBP) (with the purity of 99.4%) standard substance, dissolving the standard substance in 100mL of acetonitrile to prepare a dibutyl phthalate (DBP) standard solution with the concentration of 1.6mg/mL, sucking 2mL of the dibutyl phthalate (DBP) standard solution (1.6mg/mL) from the DBP standard solution, placing the DBP standard solution in a 100mL volumetric flask, and adding ethanol to fix the volume to a scale;
secondly, weighing 200g of milk powder, adding the milk powder into a clean iron tray, adding the dibutyl phthalate (DBP) ethanol solution obtained in the first step, uniformly stirring, placing on a water bath at 80 ℃, and freeze-drying after the solvent is volatilized to be nearly dry, wherein the freeze-drying conditions are as follows: pre-freeze-drying under the condition of vacuum degree (pressure) of 20 pa: keeping the temperature at 5 ℃ for 1 hour, and cooling to-5 ℃ for 1 hour; main freeze-drying: hold at-25 ℃ for 3 hours; desorbing: the temperature was maintained at 30 ℃ for 3 hours. Taking out, standing to room temperature, repeatedly pulverizing in a stirrer for three times, stirring, sieving with 80 mesh sieve, and making into high concentration small sample (16 mg/kg).
And thirdly, weighing 200g of milk powder matrix, mixing the milk powder matrix with the 200g of high-concentration standard sample obtained in the second step, fully and uniformly mixing the milk powder matrix for three times by using a sample mixer, weighing 400g of milk powder matrix, adding the milk powder matrix into the sample, fully and uniformly mixing the milk powder matrix for three times by using the sample mixer, weighing 800g of milk powder matrix, adding the milk powder matrix into the sample, fully and uniformly mixing the milk powder matrix for three times by using the sample mixer, and sieving the milk powder matrix with a 80-mesh sieve to obtain the standard sample (the concentration is about 2mg/kg) for measuring the dibutyl phthalate in the.
About 20g of the prepared sample is weighed into a 25mL glass sample bottle, the outer layer is a sealed aluminum foil bag, and the sample is randomly numbered and recorded.
The prepared samples were tested for properties:
1. and (3) testing the uniformity of the sample:
homogeneity testing was carried out according to the method of CNAS: GL03-2006, and from the prepared standard samples, 10 homogeneity test samples were randomly extracted, and the measurement was repeated 2 times for each sample. The same testing personnel uses the same testing method (SN/T3147-α(f1, f2) shows that the prepared sample is uniform. The test results are shown in tables 1 and 2:
TABLE 1 sample uniformity test results
TABLE 2 analysis of sample homogeneity variance results
Critical value of F0.05(9, 10) ═ 3.02. The calculated F value was 1.794, which is < F cutoff, indicating that the standard sample for dibutyl phthalate (DBP) determination was homogeneous at a significance level of 0.05.
2. And (3) testing the stability of the sample:
the sample is stored under the environment condition which can be experienced after being sent out, so as to research whether the object to be tested has significant change in the transportation and transmission process of the sample. The method is used for ensuring that the standard sample can be detected within the valid period without stability problems. The standard sample is basically placed under the condition of normal temperature (18-25 ℃), the total span of stability test is 180 days, and the stability test is carried out according to the method of CNAS: GL 03-2006.
Samples were randomly extracted in 5 portions every 30 days, the assay was repeated 2 times for each portion, and the assay, testing personnel, instruments, laboratory conditions and homogeneity tests were identical and tested by standard methods (SN/T3147 + 2012 "assay of phthalate in export foods"). Evaluating the stability of the sample by adopting a t value test method, and if the t value is less than tα(n1+n2And 2), no significant difference exists among the 2 average values, namely the prepared sample is stable. The test results are shown in tables 3 and 4:
table 3 sample stability test results
Table 4 sample stability test results
Claims (9)
1. The preparation method of the dibutyl phthalate standard sample is characterized by comprising the following specific operations:
firstly, matrix pretreatment: mixing the milk powder, sieving, and collecting the milk powder without dibutyl phthalate;
secondly, preparing a sample: by adopting a uniform distribution method, firstly, quantitatively dissolving dibutyl phthalate in a solvent, and uniformly mixing to obtain a dibutyl phthalate solution; uniformly distributing the prepared dibutyl phthalate solution into a matrix, uniformly stirring, freeze-drying after the solvent is volatilized, crushing, uniformly stirring again, sieving to obtain a small sample with the concentration of 10-20 mg/kg, uniformly stirring the matrix and the small sample, and sieving to obtain a dibutyl phthalate standard sample;
wherein the mass volume ratio of the dibutyl phthalate to the solvent is as follows: 0.1 g: 100 mL; the mass-volume ratio of the dibutyl phthalate solution to the matrix is as follows: 0.5-0.8 mL: 1g of a compound; the mass ratio of the sample to the matrix is as follows: 0.3-0.5 g: 1g of a compound; and the solvent volatilization in the step two is carried out by adopting water bath at 80 ℃, and is continuously stirred in the solvent volatilization process, and is transferred into a freeze dryer when the solvent is nearly dry.
2. The method according to claim 1, wherein the solvent is acetonitrile.
3. The method for preparing the dibutyl phthalate standard sample according to claim 1, wherein the mass ratio of the small sample to the matrix is as follows: 0.3-0.4 g: 1g of the total weight of the composition.
4. The method for preparing the dibutyl phthalate standard sample according to claim 1, wherein the mass-to-volume ratio of the matrix to the dibutyl phthalate solution is as follows: 1 g: 0.5-0.7 mL.
5. The method for preparing the dibutyl phthalate standard sample according to claim 1, wherein the mass-to-volume ratio of the matrix to the dibutyl phthalate solution is as follows: 1 g: 0.7-0.8 mL.
6. The method for preparing the dibutyl phthalate standard sample according to claim 1, wherein the mass-to-volume ratio of the matrix to the dibutyl phthalate solution is as follows: 1 g: 0.5-0.6 mL.
7. The method for preparing a dibutyl phthalate standard sample according to claim 1, characterized in that the freeze-drying conditions of step two are as follows: performing pre-freeze-drying under the condition of vacuum degree of 20pa, wherein the pre-freeze-drying condition is as follows: keeping the temperature at 5 ℃ for 1h, and cooling to-5 ℃ for 1 h; performing main freeze-drying after pre-freeze-drying, wherein the main freeze-drying conditions are as follows: holding at-25 deg.C for 3 h; desorbing: the temperature is kept at 30 ℃ for 3 h.
8. The method for preparing the dibutyl phthalate standard sample according to claim 1, wherein the prepared dibutyl phthalate standard sample is diluted and used, specifically, the dibutyl phthalate standard sample is diluted step by step into 1-5 mg/kg of dibutyl phthalate standard sample by adopting a blank matrix in an equivalent incremental manner.
9. The method for preparing the dibutyl phthalate standard sample according to claim 1, wherein the prepared dibutyl phthalate standard sample is diluted and used, specifically, the dibutyl phthalate standard sample is diluted step by step into 1-3 mg/kg of dibutyl phthalate standard sample by adopting a blank matrix in an equivalent incremental manner.
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| CN102565235A (en) * | 2012-02-13 | 2012-07-11 | 河北中烟工业有限责任公司 | Method for detecting phthalic ester in white emulsion for cigarette use |
| CN103645079A (en) * | 2013-12-05 | 2014-03-19 | 山东出入境检验检疫局检验检疫技术中心 | Preparation method and application of standard sample for detecting pesticide residue by taking paprika as matrix |
| CN104075926A (en) * | 2014-07-24 | 2014-10-01 | 云南健牛生物科技有限公司 | Preparation method and application of standard sample for detecting benzoapyrene taking soil as matrix |
| CN104764835A (en) * | 2015-04-28 | 2015-07-08 | 中华人民共和国福清出入境检验检疫局 | Potato powder matrix standard sample containing flumorph residue and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102565235A (en) * | 2012-02-13 | 2012-07-11 | 河北中烟工业有限责任公司 | Method for detecting phthalic ester in white emulsion for cigarette use |
| CN103645079A (en) * | 2013-12-05 | 2014-03-19 | 山东出入境检验检疫局检验检疫技术中心 | Preparation method and application of standard sample for detecting pesticide residue by taking paprika as matrix |
| CN104075926A (en) * | 2014-07-24 | 2014-10-01 | 云南健牛生物科技有限公司 | Preparation method and application of standard sample for detecting benzoapyrene taking soil as matrix |
| CN104764835A (en) * | 2015-04-28 | 2015-07-08 | 中华人民共和国福清出入境检验检疫局 | Potato powder matrix standard sample containing flumorph residue and preparation method thereof |
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