CN111175368A - Method for identifying synthetic acetic acid added in brewed vinegar - Google Patents
Method for identifying synthetic acetic acid added in brewed vinegar Download PDFInfo
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- CN111175368A CN111175368A CN202010081607.2A CN202010081607A CN111175368A CN 111175368 A CN111175368 A CN 111175368A CN 202010081607 A CN202010081607 A CN 202010081607A CN 111175368 A CN111175368 A CN 111175368A
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 382
- 239000000052 vinegar Substances 0.000 title claims abstract description 126
- 235000021419 vinegar Nutrition 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000523 sample Substances 0.000 claims abstract description 94
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 63
- 239000001257 hydrogen Substances 0.000 claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 235000013305 food Nutrition 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 239000013068 control sample Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 38
- 235000013361 beverage Nutrition 0.000 claims description 31
- 239000003153 chemical reaction reagent Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 11
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012470 diluted sample Substances 0.000 claims description 6
- 238000000053 physical method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 238000012937 correction Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000013375 chromatographic separation Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims 21
- 150000001243 acetic acids Chemical class 0.000 claims 1
- 239000013074 reference sample Substances 0.000 claims 1
- 238000007689 inspection Methods 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 5
- 229960000583 acetic acid Drugs 0.000 description 109
- 241000220225 Malus Species 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000012362 glacial acetic acid Substances 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
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- 235000013339 cereals Nutrition 0.000 description 5
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 4
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- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 235000015197 apple juice Nutrition 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 244000298697 Actinidia deliciosa Species 0.000 description 1
- 235000009436 Actinidia deliciosa Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000241235 Citrullus lanatus Species 0.000 description 1
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 description 1
- 241001092040 Crataegus Species 0.000 description 1
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- 241000723267 Diospyros Species 0.000 description 1
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- 206010022998 Irritability Diseases 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
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- 235000021021 grapes Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a method for identifying illegally added synthetic acetic acid in brewed vinegar, belongs to the field of food adulteration detection, and can be used for food adulteration detection research and daily inspection. The method comprises the following steps: (1) eliminating the interference of acetic carboxyl site hydrogen and water in vinegar, and measuring the hydrogen isotope ratio of the acetic methyl site by using a stable isotope ratio mass spectrometer; (2) constructing a hydrogen isotope database of control samples; (3) and (5) determining the hydrogen isotope ratio of the acetic acid methyl site of the sample to be detected, and comparing with a control sample database to obtain a conclusion. The invention utilizes the stable isotope ratio mass spectrometer to measure the hydrogen isotope ratio, realizes the inspection of illegally added synthetic acetic acid in brewed vinegar, and solves the technical problem that the illegally added synthetic acetic acid in the brewed vinegar is difficult to detect.
Description
The technical field is as follows:
the invention relates to a method for identifying illegally added synthetic acetic acid in brewed vinegar, belongs to the field of food adulteration detection, and can be used for food adulteration detection research and daily inspection.
Background art:
the brewed vinegar includes fruit vinegar beverage, fruit vinegar, rice vinegar, edible vinegar, etc. The sour flavoring or beverage is brewed by using fruits including apples, hawthorns, grapes, persimmons, pears, apricots, oranges, kiwifruits, watermelons and the like or fruit processing leftovers, grains and the like as main raw materials and utilizing modern biotechnology.
In recent years, the industry of the fruit vinegar beverage in China is continuously expanded, the consumption in 2017 reaches 17.26 million tons, the market scale is about 16.76 hundred yuan, and large and small fruit vinegar beverage production enterprises are around thousand nationwide. But there are also some problems behind the rapid development of the industry: the real fruit vinegar beverage is prepared by fermenting fruit juice twice (obtained by alcoholic fermentation and acetic acid fermentation), and is added with other non-acetic acid materials, but the production period is long and the raw material cost is high. In order to shorten the time and reduce the cost, some enterprises fake fruit vinegar beverages by adding edible vinegar into fruit juice and producing fake and inferior products by adding edible glacial acetic acid, and even more, the fake and inferior products with low cost are mixed with industrial synthetic acetic acid for counterfeiting, so that the products of normal manufacturers can take steps, great troubles are caused to the healthy development of the fruit vinegar beverage industry, and the use of the synthetic acetic acid also brings great food safety risks to consumers.
In order to standardize the vinegar brewing industry, national standards GB2719-2018 national food safety standards edible vinegar, GB/T30884-2014 apple vinegar beverage and ministry of agriculture standards NY/T2987-2016 green food fruit vinegar beverage are established in China, and production raw materials and processes of brewed vinegar and related beverages are specified. The establishment of the standards is beneficial to ensuring and improving the quality of brewed vinegar products in the market, but the effective implementation of the related product standards is difficult to ensure by the self-discipline of industrial enterprises, and particularly, a technical means for detecting counterfeit and shoddy products illegally added with glacial acetic acid (especially synthetic acetic acid) in brewed vinegar is effectively lacked at present.
Meanwhile, glacial acetic acid (also known as glacial acetic acid) and glacial acetic acid (low-pressure carbonylation method) cannot be used for vinegar in GB2719, and the total acid (counted by acetic acid) content is regulated to be more than or equal to 3.5g/100mL (sweet vinegar is more than or equal to 2.5g/100 mL). In order to improve the acetic acid concentration of the product or to gain more profits, illegal vendors may increase the acetic acid content of brewed vinegar by adding glacial acetic acid from an external source and blend rice vinegar, wherein the glacial acetic acid is generated by fermenting edible raw materials and has no safety risk, but if the glacial acetic acid is industrial-grade synthetic acetic acid, more food safety hazards are introduced. The existing method GB/T5009.41 can only determine the content of acetic acid, cannot detect the source of the acetic acid, and is difficult to indicate whether the acetic acid in the product is from edible raw materials such as grains and grains or industrial acetic acid.
At the present stage, the method for identifying and synthesizing acetic acid in China is based on GB/T22099-2008 and is based on radioactive isotopes in acetic acid14C, detecting the synthetic glacial acetic acid according to the nature characteristic, however, due to the special properties and the use requirements of the radioactive isotope, a food quality supervision department cannot detect nature indexes, only the radiology research institute of Shanghai Fudan university can carry out related detection nationwide, the technology is only limited to the detection of glacial acetic acid and is not suitable for the analysis of brewed vinegar and related products, and the reason is that the acetic acid in the vinegar needs to be purified when vinegar samples such as fruit vinegar, fruit vinegar beverages and the like are brewed, and the difficulty of technical popularization is increased.
Foreign research shows that acetic acid can be distinguished and synthesized according to the hydrogen isotope ratio characteristic of the acetic acid [ Remaud, G.; guillou, c.; vallet, C.; martin, g.j.a coupled NMR and MS isopatic method for the authentication of natural vitamins, fresenius j.anal.chem.1992,342,457. however, since brewed vinegar contains a large amount of moisture, the effect of moisture needs to be removed before measurement, and hydrogen atoms on the carboxyl groups of acetic acid are easily exchanged with hydrogen isotopes of water in the environment, the significance and the application effect of measuring the hydrogen isotope ratio of the whole acetic acid molecule are limited. Hermann et al developed a method for analyzing the stable hydrogen isotope ratio of the methyl acetate sites in vinegar using the point-specific fractionation-nuclear magnetic resonance technique (SNIF-NMR) after distilling and purifying acetic acid, [ Hermann, A. (2001) Determination of D/H isotope ratios in acetic acid from vitamins and packed products by H-2-NMR spectroscopy, Eur Food Res Techn, 212683-686; fauhl, C., Wittkowski, R. (1996) On-line 1H-NMR to factite tube prediction in SNIF-NMR analysis. Z LebensmUnters Forsch (1996), 541-545; HsiehC W, Li P H, Cheng J Y, et al. using SNIF-NMRmethod to identify the addition of a matrix of synthetic acid in a matrix of genes [ J ]. Industrial crops and products,2013,50: 904-908; perini M, Paolini M, Simoni M, et al, Stable isotope ratio analysis for verifyingthe analysis of balsamic and wire, J. Journal of agricutural and food chemistry,2014,62(32):8197-8203], but because deuterium is low in abundance in nature (natural abundance of about 150 x 10-6), and deuterium nuclei have low resonance frequency and low dispersion of spectral lines, SNIF-NMR method has low sensitivity, a single sample needs a long analysis time (> 8h) to obtain satisfactory signal-to-noise ratio signal and measurement accuracy, and acetic acid in vinegar sample needs special equipment for separation and purification, and analysis efficiency is low and cost is high.
The stable isotope ratio mass spectrometer has the advantages of rapidness and convenience in the aspect of measuring the stable hydrogen isotope composition characteristics of substances, and a plurality of quality supervision departments in China have equipped the instrument, but in the field of brewed vinegar analysis, how to eliminate interference factors of hydrogen isotope analysis in acetic acid and accurately measure the hydrogen isotope ratio, and the determination of the isotope characteristic difference between the brewed vinegar and the synthetic acetic acid is the premise and key of relevant research and application.
The invention content is as follows:
in order to solve the problem that a method for simply, quickly and cheaply detecting synthetic acetic acid is lacked in brewed vinegar, the invention adopts a stable isotope technology to accurately measure the hydrogen isotope characteristics of acetic acid methyl sites in the brewed vinegar, provides a method for constructing a hydrogen isotope database of the brewed vinegar, and detects whether the product contains the synthetic acetic acid on the basis of the method.
The scheme adopted by the invention is as follows: analyzing the characteristic difference of the hydrogen isotopes of the methyl acetate sites of the sample to be detected for judgment by establishing a real acetic acid methyl site hydrogen isotope ratio database in brewed vinegar;
the brewed vinegar comprises fruit vinegar beverage, fruit vinegar, edible vinegar (including sorghum vinegar, rice vinegar, etc.), etc.;
further, the method of the present invention comprises the steps of:
(1) control sample: obtaining a real sample of brewed vinegar produced from fruit or grain as a raw material from a brewed vinegar manufacturing enterprise;
furthermore, the brewed vinegar is fruit vinegar beverage or fruit vinegar, and meets the definition requirements of national standard GB/T30884-2014 apple vinegar beverage and agricultural ministry standard NY/T2987-2016 green food fruit vinegar beverage;
furthermore, the brewed vinegar is vinegar, and meets the definition requirements of GB2719 national standard vinegar for food safety;
(2) a sample to be detected: a brewed vinegar sample requiring detection of whether the labeled production raw material containing synthetic acetic acid is fruit or grain;
(3) respectively detecting the hydrogen isotope ratio (delta D) of the acetic acid methyl site in the control sample and the sample to be detected;
further, the control samples were collected over 20 batches of the same year nationwide;
(4) and (3) constructing a hydrogen isotope ratio database of the acetic acid methyl sites in the control sample: arranging the data of the hydrogen isotope ratio of the methyl acetate sites of the control samples determined in the step (3) in sequence, and determining the numerical range of the hydrogen isotope ratio of the methyl acetate sites according to the maximum value and the minimum value;
(5) judging the synthetic acetic acid in the sample to be detected: comparing the hydrogen isotope ratio of the methyl acetate site in the sample to be detected determined in the step (3) with the numerical range of the control sample obtained in the step (4), wherein if the numerical value of the sample to be detected exceeds the numerical range of the step (4), the sample to be detected contains synthetic acetic acid;
further, the method for detecting the hydrogen isotope ratio (δ D) of the methyl acetate site in the sample in the step (3) is as follows:
removing hydrogen at a carboxyl site of acetic acid by using a chemical reagent to convert the acetic acid into acetate;
secondly, removing water in the sample by a physical method to obtain a solid sample;
dissolving the solid sample in the last step by using a dilute acid solution to obtain an acidified sample;
fourthly, properly diluting the acidified sample by using an organic reagent to obtain a diluted sample;
separating acetic acid, other organic reagents, a small amount of water and other hydrogen-containing compound components in the diluted sample by using a capillary chromatographic column;
⑥, the acetic acid component is converted into hydrogen (H) by high-temperature pyrolysis at 1420 DEG C2) Measuring the hydrogen isotope ratio D/H of the hydrogen by using a stable Isotope Ratio Mass Spectrometer (IRMS);
and seventhly, correcting data by using an acetic acid standard substance with a known delta D value as a reference to obtain a sample delta D.
Further, the chemical agent includes but is not limited to at least one of alkaline materials such as sodium hydroxide, calcium hydroxide, potassium hydroxide and the like or carbonates such as calcium carbonate, sodium carbonate, potassium carbonate and the like;
further, the chemical agent is added in an amount to convert all of the acetic acid in the sample to acetate; preferably calcium hydroxide;
further, the physical method includes but is not limited to at least one of drying method, chromatographic separation method, and freeze drying method;
preferably, the physical method is a freeze-drying method;
further, the dilute acid solution includes, but is not limited to, at least one of dilute sulfuric acid, dilute hydrochloric acid, dilute phosphoric acid, and dilute nitric acid.
Further, the dilute acid solution is added in an amount to ensure that the excess chemical reagent in the first step neutralizes the excess chemical reagent in the previous step, and the acetate is re-acidified to form acetic acid; preferably a dilute sulfuric acid solution;
further, the organic reagent includes but is not limited to at least one of ethanol, methanol, acetone, propanol, and diethyl ether; preferably, the organic agent is acetone;
further, the addition amount of the organic reagent is to dilute the acetic acid content to 1 g/L-10 g/L; preferably 4-8 g/L;
further, the diluted sample is left standing at a low temperature for a certain period of time, and then the precipitate is removed and used for chromatographic column separation;
further, the capillary chromatography column includes, but is not limited to, a polar chromatography column, a molecular sieve chromatography column, a carbon-based bonded chromatography column, a polystyrene-divinylbenzene chromatography column, a bonded divinylbenzene/ethylene glycol dimethacrylate chromatography column; preferably a bonded divinylbenzene/ethylene glycol dimethacrylate chromatographic column;
preferably, the sample injection volume is 1 mu L, the gas chromatography sample injection port temperature is 270 ℃, the gas chromatography flow rate is constant flow 1.2mL/min, the split flow ratio of the gas chromatography sample injection port is 20:1, and the temperature raising program of the gas chromatography is constant at 180 ℃;
further, the temperature of the cracking module is ensured to be constant at 1420 ℃;
further, an acetic acid standard substance with a known delta D value of a methyl site is selected, processed and measured according to a pretreatment step of the sample, and finally corrected to obtain the delta D value of the methyl site of the acetic acid in the sample.
Has the advantages that:
the invention adopts the stable isotope technology to measure the hydrogen isotope ratio of the acetic acid methyl site in the brewed vinegar, overcomes the defect that the integral hydrogen isotope characteristic of the acetic acid in the brewed vinegar is lack of application value, solves the technical problem that the hydrogen isotope ratio of the acetic acid methyl site in the brewed vinegar is difficult to measure, utilizes the characteristic of the hydrogen isotope characteristic difference of the brewed acetic acid and the synthetic acetic acid caused by stable isotope fractionation, realizes the detection of the synthetic acetic acid in the brewed vinegar by comparing real samples, and provides a new method for the authenticity identification of the traditional brewed vinegar products.
The specific implementation mode is as follows:
the invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
In the following examples of the present invention, the method for determining the hydrogen isotope ratio of the methyl acetate sites in the vinegar product comprises the following steps:
(1) removing hydrogen at the acetic acid carboxyl sites by using a chemical reagent to convert acetic acid into acetate which is difficult to volatilize, so that the subsequent acetic acid purification step is simple;
(2) the moisture in the sample is removed by a physical method instead of independently extracting the acetic acid component, so that the sample can be processed in a large scale, and the sample processing efficiency is improved;
(3) treating acetate with dilute acid solution to make it redissolved and have volatile property, so as to obtain acidified sample;
(4) the acidified sample is suitably diluted with an organic reagent to allow the hydrogen (H) produced by the cleavage of acetic acid2) The measurement requirement of IRMS can be met;
(5) the separation of organic reagent, acetic acid, small amount of moisture and other hydrogen-containing compounds is realized by using a capillary chromatographic column;
(6) the acetic acid component is converted into hydrogen (H) by pyrolysis2) Then, the hydrogen isotope ratio (delta D) of the methyl acetate site in the sample is obtained by measuring with a stable isotope ratio mass spectrometer and correcting with a standard substance.
In the embodiment of the invention, the method for determining the hydrogen isotope ratio of the acetic acid methyl site in the vinegar product comprises the following steps:
(1) adding an alkaline reagent into the sample, centrifuging to remove the excessive alkaline reagent, and taking the supernatant for later use;
(2) putting the supernatant into a drying oven or a freeze dryer, removing original water in the sample, and taking the solid for later use;
(3) acidifying the solid component with a dilute acid solution to react to form acetic acid;
(4) diluting the dilute acid solution containing acetic acid with an organic reagent until the acetic acid content is 1 g/L-10 g/L, standing for a period of time, removing precipitates, taking supernate for analysis, and preferably, the acetic acid dilution concentration is 4-8 g/L;
(5) setting parameters of a gas chromatography-cracking-stable isotope ratio mass spectrometer, preferably, the sample introduction volume is 1 mu L, the gas chromatography sample introduction port temperature is 270 ℃, the gas chromatography flow rate is constant current 1.2mL/min, the gas chromatography sample introduction port split ratio is 20:1, the gas chromatography temperature rise program is constant temperature of 180 ℃, and the temperature of a cracking module is constant temperature of 1420 ℃;
in the process, the capillary chromatographic column separates acetic acid and other organic reagents, a small amount of moisture and other hydrogen-containing compound components in the diluted sample; the acetic acid component is converted into hydrogen (H) by pyrolysis2) And further measuring hydrogen content of the hydrogen gas by stable Isotope Ratio Mass Spectrometer (IRMS)The bit element ratio D/H;
specifically, the working environment, the air tightness and the vacuum degree of an ion chamber of the stable isotope ratio mass spectrometer are confirmed to meet the analysis requirements, and then an inspection instrument is used for measuring H2Precision and linearity of the middle delta D, and adjusting ion source parameter values when necessary;
setting mass spectrum parameters: preparing a measuring program, allowing hydrogen-containing compounds (such as water and acetone) except acetic acid to flow out of the chromatographic column and discharge into the air, and introducing only acetic acid into the cracking device for cracking to generate hydrogen (H)2)；
And (3) determining a sample: in a hydrogen isotope determination mode, selecting a two-point standard drift correction mode to place a sample to be detected on a sample tray, and determining a delta D value of acetic acid in the sample under the control of a computer;
(6) selecting an acetic acid standard substance with a known delta D value of a methyl site, treating and measuring according to a pretreatment step of a sample, and correcting the sample by using the measured value to obtain the delta D value of the methyl site of the acetic acid in the sample.
The invention will be further explained below by means of specific examples.
Example 1: determination of hydrogen isotope ratio of acetic acid methyl site in apple vinegar beverage
a) Measuring 100mL of apple vinegar beverage sample, adding 1g of calcium hydroxide, performing vortex oscillation for 2h, centrifuging at 8000rpm for 30min, and taking supernatant for storage;
b) freeze-drying the supernatant in a freeze dryer, and reserving the powder for later use;
c) adding 15mL of sulfuric acid solution (1moL/L) into the sample powder, and performing vortex oscillation for 1 h;
d) adding anhydrous acetone into the sample treated by dilute sulfuric acid according to the concentration of acetic acid in the original sample until the concentration of the acetic acid is about 4g/L, standing, and taking the supernatant for analysis;
e) setting the temperature of a gas chromatography sample inlet to 270 ℃, setting the flow rate of the gas chromatography to be constant flow of 1.2mL/min, setting the split ratio of the gas chromatography sample inlet to be 20:1, setting the temperature raising program of the gas chromatography to be constant at 180 ℃, and setting the temperature of a cracking module to ensure that the temperature is constant at 1420 ℃;
f) confirming stable parityThe working environment, the air tightness and the vacuum degree of the ion chamber of the elemental ratio mass spectrometer meet the requirements, and then an inspection instrument is used for measuring H2Precision and stability of middle delta D, and adjusting ion source parameter values when necessary;
g) pure acetic acid, water and acetone are taken as experimental materials, and the retention time of each substance is determined by respective sample injection measurement;
h) injecting 1 μ L of the treated sample, separating acetic acid with chromatographic column, and converting into hydrogen (H) in high temperature cracking device2) The hydrogen isotope ratio (D/H, recorded as delta D) is then determinedMeasuring) The results are shown in Table 1;
i) acetic acid with a known hydrogen isotope ratio at the methyl site was chosen as the standard (here the laboratory working standard WSD, δ D, was used)CH3-223.93 ‰), the hydrogen isotope ratio was determined after treatment according to the above treatment method, and the results are shown in table 2;
j) and (3) data correction: the difference between the measured value and the given value of the acetic acid working standard WSD is 27.66 per thousand, so that the delta D value of the fruit vinegar beverage sample is known to be the measured value delta DMeasuringResults obtained after subtracting 27.66% o are shown in table 3;
TABLE 1 determination of acetic acid in fruit Vinegar beverage samples delta DMeasuring(‰)
| Repetition of-1 | Repetition of-2 | Mean value of | Standard deviation of | |
| Apple vinegar beverage | -278.82 | -275.69 | -277.26 | 2.21 |
Table 2 measurement results of acetic acid working standard WSD
| Number of measurements | Repetition of-1 | Repetition of-2 | Mean value of |
| δDMeasuring(‰) | -195.48 | -197.06 | -196.27 |
TABLE 3 hydrogen isotope ratio of methyl acetate sites δ D in fruit vinegar beverage samplesCH3(‰)
| Repetition of-1 | Repetition of-2 | Mean value of | Standard deviation of | |
| Apple vinegar beverage | -306.48 | -303.35 | -304.92 | 2.21 |
Example 2: detection example of synthetic acetic acid in to-be-detected apple vinegar beverage sample
a) Collecting real fruit vinegar beverage samples with raw materials of apple (juice) or concentrated apple juice from regular apple vinegar beverage production enterprises in different places in China, wherein the number of the samples is 22;
b) 3 samples of apple vinegar beverage are purchased from the market and provided with label information;
c) the hydrogen isotope ratio of the methyl site of acetic acid in each sample was measured by the method of example 1;
d) through statistics, the delta D of 22 real fruit vinegar beverage samplesCH3The distribution range of ‰ 275.14 ‰ -321.50 ‰
e) Delta D of fruit vinegar sample to be detected in marketCH3Results are shown in table 2.
TABLE 2 Delta D values (‰) of fruit vinegar samples commercially available for testing
| Sample numbering | Sample No. 1 to be tested | 2# sample to be tested | 3# sample to be tested |
| δDCH3 | -287.51 | -292.11 | -321.01 |
As shown in Table 2, no synthetic acetic acid was contained in any of the 3 commercially available fruit vinegar beverage samples.
Example 3: detection example of synthetic acetic acid in to-be-detected apple vinegar sample
a) Collecting real fruit vinegar samples with apple (juice) or concentrated apple juice as raw materials from regular apple vinegar production enterprises in different places in China, wherein the total number of the real fruit vinegar samples is 22;
b) 3 samples of apple vinegar are purchased from the market with label information remarks;
c) the hydrogen isotope ratio of the methyl site of acetic acid in each sample was measured by the method of example 1;
d) through statistics, the delta D of 22 real fruit vinegar samplesCH3The distribution range of (‰) is-275.14 ‰ -322.6 ‰;
e) delta D of commercially available fruit vinegar sample to be detectedCH3Results are shown in table 3.
TABLE 3 Delta D values (‰) of commercially available fruit vinegar samples to be tested
| Sample numbering | Sample No. 1 to be tested | 2# sample to be tested | 3# sample to be tested |
| δDCH3 | -277.36 | -295.58 | -321.00 |
As can be seen from Table 3, 3 of the commercially available fruit vinegar samples contained no synthetic acetic acid.
Example 4: detection example of synthetic acetic acid in vinegar sample to be detected
a) Vinegar samples with real raw material information are collected from vinegar production enterprises in Zhejiang, Beijing, Guangdong, Jiangsu, Shanxi and the like respectively, and 21 samples are counted;
b) 3 samples of vinegar with label information remarked are purchased from the market;
c) the hydrogen isotope ratio of the methyl site of acetic acid in each sample was measured by the method of example 1;
d) through statistics, the delta D of 21 real vinegar samplesCH3The distribution range of (‰) is-310.31 ‰ -346.87 ‰;
e) delta D of commercial vinegar sample to be testedCH3Results are shown in table 4.
TABLE 4 Delta D values (‰) of commercially available test edible vinegar samples
| Sample numbering | Sample No. 1 to be tested | 2# sample to be tested | 3# sample to be tested |
| δDCH3 | -342.15 | -312.59 | -339.37 |
As is clear from Table 4, synthetic acetic acid was not contained in 3 commercially available vinegar samples.
Example 5: example of detection of synthetic acetic acid in simulated sample
Examples 2 to 4 show the acetic acid δ D of each sample to be examinedCH3The values were all in accordance with the range of values for the corresponding control samples, indicating no synthetic acetic acid was added, probably because all samples tested were from a certified brand from a regular manufacturer. To verify the feasibility of the present invention in testing synthetic acetic acid in brewed vinegar, a sample of synthetic acetic acid (delta D) was purchased from the marketCH3A value of 78.08 ‰), 20%, 40%, 60% and 80% of synthetic acetic acid was added to a sample of apple vinegar and vinegar, respectively, in terms of acetic acid content, and delta D was measured using the method of the preceding exampleCH3The results are shown in Table 5.
TABLE 5 simulation of acetic acid delta D in samplesCH3Value (‰)
| Proportion of synthetic acetic acid addition (%) | 100 | 80 | 60 | 40 | 20 | 0 |
| Apple vinegarSimulation sample | 78.08 | -25.11 | -115.17 | -187.39 | -257.28 | -321.00 |
| Vinegar simulation sample | 78.08 | -3.76 | -88.49 | -165.33 | -239.08 | -312.59 |
The results in the table show that the incorporation of 20% in apple vinegar is beyond the database of apple vinegar in example 3, and therefore synthetic acetic acid incorporation in each of the simulated samples was detectable; the 20% of the vinegar was out of the range of the vinegar in example 4, and it was judged that synthetic acetic acid was added to all of the above products.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. A method for identifying synthetic acetic acid added in brewed vinegar is characterized by comprising the following steps:
(1) control sample: obtaining a real sample of brewed vinegar produced from fruit or grain as a raw material from a brewed vinegar manufacturing enterprise;
(2) a sample to be detected: a brewed vinegar sample requiring detection of whether the labeled production raw material containing synthetic acetic acid is fruit or grain;
(3) respectively detecting the hydrogen isotope ratio delta D of the acetic acid methyl site in the reference sample and the sample to be detected;
(4) constructing a hydrogen isotope ratio database of the acetic acid methyl sites in the control sample;
(5) judging the synthetic acetic acid in the sample to be detected: and (4) comparing the hydrogen isotope ratio of the methyl acetate site in the sample to be detected determined in the step (3) with the delta D of the control sample obtained in the step (4), wherein if the difference is obvious, the sample to be detected contains synthetic acetic acid.
2. The method for identifying the addition of synthetic acetic acid in brewed vinegar according to claim 1, wherein the brewed vinegar is a fruit vinegar beverage or fruit vinegar, and meets the definition requirements of national standard GB/T30884-2014 apple vinegar beverage and agricultural ministry standard NY/T2987-2016 green food fruit vinegar beverage.
3. The method for identifying the addition of synthetic acetic acid in brewed vinegar according to claim 1, wherein the brewed vinegar is vinegar, and meets the definition requirements of GB2719 national Standard Vinegar for food safety.
4. The method for discriminating the addition of synthetic acetic acid to brewed vinegar according to claim 1, wherein the control sample is collected over 20 batches nationwide in the same year.
5. The method for identifying the amount of synthetic acetic acid added to brewed vinegar according to claim 1, wherein the hydrogen isotope ratio δ D of the methyl acetate site is determined by the following method:
removing hydrogen at a carboxyl site of acetic acid by using a chemical reagent to convert the acetic acid into acetate;
secondly, removing water in the sample by a physical method to obtain a solid sample;
dissolving the solid sample in the last step by using a dilute acid solution to obtain an acidified sample;
fourthly, properly diluting the acidified sample by using an organic reagent to obtain a diluted sample;
separating acetic acid, other organic reagents, a small amount of water and other hydrogen-containing compound components in the diluted sample by using a capillary chromatographic column;
⑥, the acetic acid component is converted into hydrogen (H) by high-temperature pyrolysis at 1420 DEG C2) Measuring the hydrogen isotope ratio D/H of the hydrogen by using a stable Isotope Ratio Mass Spectrometer (IRMS);
and seventhly, correcting data by using an acetic acid standard substance with a known delta D value as a reference to obtain a sample delta D.
6. The method of claim 5, wherein the method comprises the steps of adding synthetic acetic acid to brewed vinegar,
the chemical reagent is at least one of sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium carbonate, sodium carbonate and potassium carbonate;
the physical method comprises at least one of drying method, chromatographic separation method and freeze drying method;
the dilute acid solution comprises at least one of dilute sulfuric acid, dilute hydrochloric acid, dilute phosphoric acid and dilute nitric acid;
the organic reagent comprises at least one of ethanol, methanol, acetone, propanol and diethyl ether.
7. The method for identifying the addition of synthetic acetic acid in brewed vinegar according to claim 6, wherein the organic reagent is added in an amount to dilute the acetic acid to 1g/L to 10 g/L.
8. The method for discriminating between synthetic acetic acids added to brewed vinegar according to claim 5, wherein the data correction is a selection of an acetic acid standard substance having a known δ D value of the methyl site, which is processed and measured according to the pretreatment step of the sample, and the final correction is a δ D value of the methyl site of acetic acid in the sample.
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