Method for identifying honey of Changbai mountain apis cerana in different producing areas
The volatile substances in honey were detected through GC-IMS technology, and the Changbai Mountain Chinese bee honey in different production areas were distinguished by specific indicators, which solved the problem of distinction, realized the origin of honey and the resource development, and provided effective identification and evaluation for the market. means.
Patent Information
- Application Number
- CN202411774846.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-05
- Publication Date
- 2025-01-03
AI Technical Summary
The existing technology has failed to effectively distinguish between Changbai Mountain Chinese bee honey in different production areas, making it difficult to achieve the traceability of honey production and the exploration and utilization of characteristic honey resources on the market.
Top air chromatography-ion migration spectrometry (GC-IMS) was used to detect volatile substances in honey in Chinese bees in Changbaishan in different production areas, and the three indicators of furfural, 3-methyl-1-butanol and ethyl acetate or furfural, The peak volumes of six indicators, 3-methyl-1-butanol, ethyl acetate, linalool oxidized, 2-methyl-1-propanol and acetic acid, distinguish honey from different production areas.
It has achieved effective distinction between the Chinese honey bees in Changbai Mountain in different production areas, provided a reference for the traceability of its origin, and provided a theoretical basis for the development and utilization of characteristic honey resources. It can also be used to identify the authenticity, quality and quality evaluation of honey.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of food detection, in particular to a method for identifying honey from Chinese honeybees in different production areas of Changbai Mountain. Background Art
[0002] Apis cerana cerana in Changbai Mountain (referred to as Changbai Mountain Chinese honey bee) is an excellent local bee species in the Chinese honey bee family, distributed in the Changbai Mountain area and its rest areas. The main production areas of the population are located in Tonghua City, Baishan City, Jilin City, Yanbian Korean Autonomous Prefecture in the eastern part of Jilin Province and the eastern mountainous area of Liaoning Province. The distribution area and number of Apis cerana cerana in Changbai Mountain in Jilin Province are much larger than those in Liaoning Province. It is the only oriental honey bee ecotype in the Changbai Mountain ecosystem and is listed in the "National Livestock and Poultry Variety Resource Protection List". It is currently in an "endangered-maintained" state. The honey fully brewed by the Changbai Mountain Chinese honey bee from wild mountain nectar is called Changbai Mountain Chinese honey (referred to as Changbai Mountain honey). It has the effects of nourishing the spleen and kidneys, moistening the lungs and intestines, calming the five internal organs, harmonizing hundreds of medicines and detoxifying. It was listed as a tribute of the best quality in ancient times and is known as "compound medicinal health honey" in modern times. It is a high-quality specialty honey with a small output.
[0003] The culture of Changbai Mountain Chinese honey has a long history. In ancient times, it was a tribute to the emperor, and in modern times it is a special product for export and foreign exchange. Since the Bohai Kingdom in the Tang Dynasty, it has been widely exchanged among officials and the public as tribute, gifts, and commodities with its excellent quality and unique flavor. When the Bohai Kingdom sent envoys to Japan, they often brought honey as gifts. This tradition continued until the Qing Dynasty. The Qing government established a special Dasheng Ula agency in Jilin City to collect and supply tribute honey for the royal family. In modern times, with the entry of live-frame Western honey bees into the Changbai Mountain area, the status of Changbai Mountain Chinese honey bees as the dominant bee species has gradually been replaced, causing a sharp drop in the production of Chinese honey. Therefore, the market price of Chinese honey is 10-20 times that of honey produced by Western honey bees. At present, bee colony breeding and wild beehive honey collection are still important sources of livelihood for residents in economically underdeveloped mountainous areas. There are many types of specialty honey in my country. Clarifying the characteristics of regional specialty honey is the basis for fully realizing its industrial value. However, a method that can effectively distinguish the honey of Changbai Mountain Chinese honey from different regions has not been found. Summary of the invention
[0004] The purpose of the present invention is to provide a method for identifying honey from different production areas of Changbai Mountain Chinese honey bees, so as to solve the problems existing in the above-mentioned prior art. The present invention provides a method for identifying honey from different production areas of Changbai Mountain Chinese honey bees, which can effectively distinguish the honey from different production areas of Changbai Mountain Chinese honey bees, provide corresponding references for its origin tracing and identification, and provide research ideas for the mining and utilization of other regional characteristic honey resources.
[0005] To achieve the above object, the present invention provides the following solutions:
[0006] The present invention uses headspace gas chromatography-ion mobility spectrometry (GC-IMS) to detect volatile substances in Changbai Mountain Chinese honey (Changbai Mountain honey) from different producing areas, and finally obtains a method that can effectively distinguish the producing areas of Changbai Mountain Chinese honey. The method can use furfural, 3-methyl-1-butanol and ethyl acetate as three indicators to distinguish the Changbai Mountain Chinese honey from Yanbian Korean Autonomous Prefecture (referred to as Yanbian Prefecture), the Changbai Mountain Chinese honey from Jilin Province, the Changbai Mountain Chinese honey from Tonghua City and the Changbai Mountain Chinese honey from Baishan City, as follows:
[0007] (1) The three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in the Changbai Mountain Chinese honey of Yanbian Korean Autonomous Region need to meet the following conditions at the same time: the peak volume of furfural is between 10757.20-10870.92, the peak volume of 3-methyl-1-butanol is between 1990.62-1999.04, and the peak volume of ethyl acetate is between 4790.11-4826.17;
[0008] (2) The three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in Changbai Mountain Chinese honey of Jilin Province need to meet the following conditions at the same time:
[0009] The peak volume of furfural was between 3294.67 and 3371.15, the peak volume of 3-methyl-1-butanol was between 2307.68 and 2331.04, and the peak volume of ethyl acetate was between 4827.84 and 4981.98;
[0010] (3) The three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in Changbai Mountain Chinese honey in Tonghua City need to meet the following conditions at the same time:
[0011] The peak volume of furfural was between 4319.55 and 4401.47, the peak volume of 3-methyl-1-butanol was between 4232.41 and 4274.57, and the peak volume of ethyl acetate was between 7876.64 and 7982.14;
[0012] (4) The three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in Changbai Mountain Chinese honey in Baishan City must meet the following conditions at the same time:
[0013] The peak volume of furfural is between 2288.06 and 2562.54, the peak volume of 3-methyl-1-butanol is between 2986.61 and 3056.83, and the peak volume of ethyl acetate is between 5090.68 and 5115.78.
[0014] In summary, it can be seen that the method provided by the present invention only requires three indicators to distinguish the production areas of Changbai Mountain Chinese honey.
[0015] The present invention provides a method for identifying honey from Changbai Mountain Chinese honey in different producing areas, comprising the following steps:
[0016] Using headspace gas chromatography-ion mobility spectrometry to detect the Changbai Mountain Chinese honey bees honey from different production areas to obtain GC-IMS samples; constructing a fingerprint spectrum of volatile components of the Changbai Mountain Chinese honey bees honey, and screening the volatile components of the Changbai Mountain Chinese honey bees honey to obtain the common volatile components of the Changbai Mountain Chinese honey bees honey; using the peak volume of the common volatile components of the Changbai Mountain Chinese honey bees honey volatile components to distinguish the Changbai Mountain Chinese honey bees honey from different production areas;
[0017] The common volatile components include furfural, 3-methyl-1-butanol and ethyl acetate;
[0018] When the peak volume of furfural is between 10757.20-10870.92, the peak volume of 3-methyl-1-butanol is between 1990.62-1999.04, and the peak volume of ethyl acetate is between 4790.11-4826.17, it is judged that the Changbai Mountain Chinese honey production area is Yanbian Korean Autonomous Prefecture;
[0019] When the peak volume of furfural is between 3294.67-3371.15, the peak volume of 3-methyl-1-butanol is between 2307.68-2331.04, and the peak volume of ethyl acetate is between 4827.84-4981.98, it is judged that the Changbai Mountain Chinese honey production area is Jilin City;
[0020] When the peak volume of furfural is between 4319.55-4401.47, the peak volume of 3-methyl-1-butanol is between 4232.41-4274.57, and the peak volume of ethyl acetate is between 7876.64-7982.14, it is judged that the Changbai Mountain Chinese honey production area is Tonghua City;
[0021] When the peak volume of furfural is between 2288.06-2562.54, the peak volume of 3-methyl-1-butanol is between 2986.61-3056.83, and the peak volume of ethyl acetate is between 5090.68-5115.78, it is judged that the Changbai Mountain Chinese honey producing area is Baishan City.
[0022] Preferably, in the headspace gas chromatography-ion mobility spectrometry, the incubation temperature of the headspace injection is 80°C, the incubation time is 20 min, the injection volume is 500 µL, the incubation speed is 500 r / min, and the injection needle temperature is 85°C.
[0023] Preferably, in the headspace gas chromatography-ion mobility spectrometry, the chromatographic column used for gas chromatography detection is a MXT-WAX capillary chromatographic column, the column temperature is 60° C., the carrier gas is nitrogen, the temperature of the injection port is 80° C., and the running time is 60 min;
[0024] And / or, the pressure increase procedure for headspace gas chromatography detection is: an initial flow rate of 2.0 mL / min is maintained for 2 min; within 8 min, the flow rate is increased to 10.0 mL / min; within 10 min, the flow rate is increased to 100.0 mL / min and maintained for 40 min.
[0025] Preferably, in the headspace gas chromatography-ion mobility spectrometry, the ionization source for ion mobility spectrometry detection is a tritium source, the migration tube length is 53 mm, the electric field strength is 500 V / cm, the migration tube temperature is 45° C., the drift gas is nitrogen, the flow rate is 75.0 mL / min, and the mode is positive ion mode.
[0026] As an additional case, when the present invention detected the volatile substances of the Changbai Mountain Chinese honey from different production areas based on GC-IMS, it was also found that furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid six indicators can also be used to effectively distinguish the Changbai Mountain Chinese honey from Yanbian Korean Autonomous Region, the Changbai Mountain Chinese honey from Jilin Province, the Changbai Mountain Chinese honey from Tonghua City and the Changbai Mountain Chinese honey from Baishan City, as follows:
[0027] (1) The six indicators of furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid in the Changbai Mountain Chinese honey of Yanbian Korean Autonomous Region need to meet the following conditions at the same time: the peak volume of furfural is between 10757.20 and 10870.92, the peak volume of 3-methyl-1-butanol is between 1990.62 and 1999.04, the peak volume of ethyl acetate is between 4790.11 and 4826.17, the peak volume of linalool oxide is between 7129.62 and 7261.00, the peak volume of 2-methyl-1-propanol is between 3436.96 and 3440.20, and the peak volume of acetic acid is between 7438.95 and 7476.73;
[0028] (2) The six indicators of furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid in the honey of Chinese honeybees in Changbai Mountain, Jilin Province need to meet the following conditions at the same time:
[0029] The peak volume of furfural is between 3294.67-3371.15, the peak volume of 3-methyl-1-butanol is between 2307.68-2331.04, the peak volume of ethyl acetate is between 4827.84-4981.98, the peak volume of linalool oxide is between 6761.67-6999.11, the peak volume of 2-methyl-1-propanol is between 3426.79-3454.91, and the peak volume of acetic acid is between 9323.80-9626.98;
[0030] (3) The six indicators of furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid in Changbai Mountain Chinese honey in Tonghua City must meet the following conditions at the same time:
[0031] The peak volume of furfural is between 4319.55-4401.47, the peak volume of 3-methyl-1-butanol is between 4232.41-4274.57, the peak volume of ethyl acetate is between 7876.64-7982.14, the peak volume of linalool oxide is between 10278.09-10821.57, the peak volume of 2-methyl-1-propanol is between 5143.11-5156.31, and the peak volume of acetic acid is between 8178.21-8704.81;
[0032] (4) The six indicators of furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid in the honey of Chinese honey bees in Changbai Mountain, Baishan City must meet the following conditions at the same time:
[0033] The peak volume of furfural was between 2288.06-2562.54, the peak volume of 3-methyl-1-butanol was between 2986.61-3056.83, the peak volume of ethyl acetate was between 5090.68-5115.78, the peak volume of linalool oxide was between 7190.72-7259.70, the peak volume of 2-methyl-1-propanol was between 4249.73-4474.65, and the peak volume of acetic acid was between 9615.75-10159.73.
[0034] In summary, it can be seen that using the method provided by the present invention, only six indicators are needed to distinguish the production areas of Changbai Mountain Chinese honey.
[0035] Further preferably, the common volatile components also include linalool oxide, 2-methyl-1-propanol and acetic acid.
[0036] Further preferably, when the common volatile components include furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid, the identification criteria are as follows:
[0037] The peak volume of furfural is between 10757.20-10870.92, the peak volume of 3-methyl-1-butanol is between 1990.62-1999.04, the peak volume of ethyl acetate is between 4790.11-4826.17, the peak volume of linalool oxide is between 7129.62-7261.00, the peak volume of 2-methyl-1-propanol is between 3436.96-3440.20, and the peak volume of acetic acid is between 7438.95-7476.73. It is judged that the Changbai Mountain Chinese honey production area is Yanbian Korean Autonomous Prefecture;
[0038] And / or, the peak volume of furfural is between 3294.67 and 3371.15, the peak volume of 3-methyl-1-butanol is between 2307.68 and 2331.04, the peak volume of ethyl acetate is between 4827.84 and 4981.98, the peak volume of linalool oxide is between 6761.67 and 6999.11, the peak volume of 2-methyl-1-propanol is between 3426.79 and 3454.91, and the peak volume of acetic acid is between 9323.80 and 9626.98, then it is judged that the Changbai Mountain Chinese honey producing area is Jilin City;
[0039] And / or, the peak volume of furfural is between 4319.55 and 4401.47, the peak volume of 3-methyl-1-butanol is between 4232.41 and 4274.57, the peak volume of ethyl acetate is between 7876.64 and 7982.14, the peak volume of linalool oxide is between 10278.09 and 10821.57, the peak volume of 2-methyl-1-propanol is between 5143.11 and 5156.31, and the peak volume of acetic acid is between 8178.21 and 8704.81, then it is judged that the Changbai Mountain Chinese honey producing area is Tonghua City;
[0040] And / or, the peak volume of furfural is between 2288.06-2562.54, the peak volume of 3-methyl-1-butanol is between 2986.61-3056.83, the peak volume of ethyl acetate is between 5090.68-5115.78, the peak volume of linalool oxide is between 7190.72-7259.70, the peak volume of 2-methyl-1-propanol is between 4249.73-4474.65, and the peak volume of acetic acid is between 9615.75-10159.73, then it is judged that the Changbai Mountain Chinese honey producing area is Baishan City.
[0041] The present invention provides application of the above identification method in identifying the authenticity of Changbai Mountain Chinese honey.
[0042] The present invention provides application of the above identification method in identifying the quality of honey from Apis cerana cerana in Changbai Mountain.
[0043] The invention provides application of the above identification method in evaluating the quality of honey from Changbai Mountain Apis cerana.
[0044] The present invention discloses the following technical effects:
[0045] In order to understand the quality characteristics of Changbai Mountain Chinese honey, the present invention measures and analyzes the volatile substances and other indicators of Changbai Mountain Chinese honey from different production areas, and finally obtains an identification method that can effectively distinguish the production areas of Changbai Mountain Chinese honey. The method can use furfural, 3-methyl-1-butanol and ethyl acetate three indicators or furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid six indicators to distinguish Changbai Mountain Chinese honey from Yanbian Korean Autonomous Region, Changbai Mountain Chinese honey from Jilin Province, Changbai Mountain Chinese honey from Tonghua City and Changbai Mountain Chinese honey from Baishan City. The results of the specific embodiments of the present invention show that the three indicators or six indicators can effectively distinguish the Changbai Mountain Chinese honey from different production areas. It can be seen that the present invention provides a theoretical basis for the development and utilization of the characteristic honey in Changbai Mountain area, provides a corresponding reference for its origin tracing identification, and provides a research idea for the excavation and utilization of other regional characteristic honey resources.
[0046] At the same time, the identification method provided by the present invention can also be used to identify the authenticity of Changbai Mountain Chinese honey, identify the quality of Changbai Mountain Chinese honey and evaluate the quality of Changbai Mountain Chinese honey. BRIEF DESCRIPTION OF THE DRAWINGS
[0047] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0048] Figure 1 This is the GC-IMS three-dimensional spectrum of volatile components in the honey sample of the Chinese honey bee from Changbai Mountain;
[0049] Figure 2 This is the GC-IMS two-dimensional spectrum of volatile components in the honey sample of the Chinese honey bee from Changbai Mountain;
[0050] Figure 3 This is the GC-IMS difference spectrum of volatile components in the honey samples of Apis cerana cerana from Changbai Mountain;
[0051] Figure 4 This is the fingerprint of volatile components in the honey samples of Apis cerana cerana from Changbai Mountain;
[0052] Figure 5The PCA score diagram of volatile components in the Changbai Mountain Chinese honey samples; the squares enclosed by triangles are the Changbai Mountain Chinese honey of Yanbian Korean Autonomous Region (YB), the squares enclosed by rectangles are the Changbai Mountain Chinese honey of Jilin Province (JL), the squares enclosed by diamonds are the Changbai Mountain Chinese honey of Baishan City (BS), and the squares enclosed by ellipses are the Changbai Mountain Chinese honey of Tonghua City (TH);
[0053] Figure 6 This is the qualitative analysis spectrum of the volatile components of Chinese honey (TH) from Changbai Mountain in Tonghua City;
[0054] Figure 7 This is the qualitative analysis spectrum of the volatile components of Chinese honey (JL) from Changbai Mountain, Jilin Province;
[0055] Figure 8 This is the qualitative analysis spectrum of the volatile components of Chinese honey (YB) from Changbai Mountain in Yanbian Korean Autonomous Region;
[0056] Fig. 9 This is the qualitative analysis spectrum of the volatile components of Chinese honey (BS) from Changbai Mountain in Baishan City. DETAILED DESCRIPTION
[0057] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0058] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.
[0059] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.
[0060] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.
[0061] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.
[0062] The principle of GC-IMS is as follows: the sample enters the instrument with the carrier gas, first undergoes primary separation in the gas chromatography column, and then enters the ion migration tube. After the molecules to be tested are ionized in the ionization zone, they migrate to the Faraday disk detection under the action of the electric field and the reverse drift gas to achieve secondary separation. It combines the advantages of high separation of gas chromatography and high sensitivity of ion mobility spectrometry, and can quickly detect trace volatile organic compounds without any special sample pretreatment.
[0063] Example 1
[0064] 1. Sample collection
[0065] Honey from the Changbai Mountain Chinese honeybees was collected from bee farms in four regions of Jilin Province, including Yanbian Korean Autonomous Prefecture, Jilin City, Tonghua City, and Baishan City in 2020. The honey samples were provided by local beekeepers, and the bee species collected were all pure Changbai Mountain Chinese honeybees. The bee colonies were raised and managed in the Changbai Mountain Chinese honeybee Nature Reserve in the traditional drum breeding mode. The samples were simply filtered and bottled and stored at 4°C for later use. Three batches of honey samples were taken from each sampling site. The sample information is detailed in Table 1.
[0066] Table 1 Sample collection information
[0067]
[0068] 2. Reagents and Materials
[0069] n-Ketones (2-butanone, 2-pentanone, 2-hexanone, 2-heptanone, 2-octanone, and 2-nonanone (all analytically pure)) were purchased from Aladdin;
[0070] 99.999% nitrogen, 20 mL headspace bottle, purchased from Shandong Haineng Scientific Instrument Co., Ltd.;
[0071] MXT-WAX capillary chromatographic column (30 m×0.53 mm, 1.0 μm) was purchased from Restek Company, USA.
[0072] 3. Instruments and equipment
[0073] FlavourSpec® gas phase ion mobility spectrometer, purchased from GAS (Dortmund, Germany);
[0074] CTC-PAL 3 static headspace autosampler, purchased from CTC Analytics AG (Zwingen, Switzerland);
[0075] VOCal data processing software (0.4.03) was from GAS (Dortmund, Germany).
[0076] 4. Test methods
[0077] 4.1 Sample processing
[0078] Weigh 2 g of sample and place it in a 20 mL headspace bottle. Incubate at 80 °C for 20 min before injecting. Each sample was measured in triplicate.
[0079] 4.2 Headspace injection conditions
[0080] Incubation temperature: 80℃; incubation time: 20min; injection volume: 500µL; splitless injection; incubation speed: 500r / min; injection needle temperature: 85℃.
[0081] 4.3 GC conditions
[0082] Gas chromatography column: MXT-WAX capillary column;
[0083] Chromatographic column temperature: 60°C; carrier gas: high-purity nitrogen (purity ≥ 99.999%);
[0084] Program pressure increase: initial flow rate 2.0 mL / min, maintained for 2 min, linearly increased to 10.0 mL / min within 8 min, linearly increased to 100.0 mL / min within 10 min, maintained for 40 min;
[0085] Gas chromatography running time: 60 min; injection port temperature: 80 °C.
[0086] The gas chromatography conditions are shown in Table 2.
[0087] Table 2 Gas chromatography conditions
[0088]
[0089] 4.4 IMS conditions
[0090] Ionization source: tritium source (3H); migration tube length: 53mm; electric field strength: 500V / cm; migration tube temperature: 45℃; drift gas: high-purity nitrogen (purity ≥99.999%); flow rate: 75.0mL / min; positive ion mode.
[0091] 5. Data processing and analysis
[0092] A mixed standard of 6 n-ketones (2-butanone, 2-pentanone, 2-hexanone, 2-heptanone, 2-octanone and 2-nonanone (all analytically pure), purchased from Aladdin) was detected. The concentrations of the 6 n-ketones in the mixed standard were 0.1 μL / mL, 0.25 μL / mL, 0.5 μL / mL, 0.75 μL / mL, 1 μL / mL and 2 μL / mL, respectively. A calibration curve of retention time and retention index was established, and then the retention index of the substance was calculated according to the retention time of the target substance. The built-in GC retention index (NIST 2020) database and IMS migration time database of the VOCal software were used for retrieval and comparison, and the target was qualitatively analyzed.
[0093] The Reporter, Gallery Plot and Dynamic PCA plug-ins in the VOCal data processing software were used to generate three-dimensional spectra, two-dimensional spectra, difference spectra, fingerprint spectra and PCA graphs of volatile components for comparison of volatile organic compounds between samples.
[0094] 6. Results
[0095] (1) Comparative analysis of volatile component spectra of honey from four sampling sites in Changbai Mountain area:
[0096] According to the three-dimensional spectrum results of GC-IMS, the differences in volatile organic compounds in honey samples from different production areas in Changbai Mountain area can be intuitively seen (see Figure 1 ), the three coordinate axes represent migration time (X-axis), retention time (Y-axis) and signal peak intensity (Z-axis).
[0097] For easy observation, take the top view for comparison. Figure 2 As shown. Figure 2 It can be seen that there are certain differences in the volatile organic compounds in different samples.
[0098] In order to further compare the differences in volatile components in the samples, the spectrum of the Tonghua area sample (TH) was selected as a reference, and the reference was deducted from the spectra of other samples to obtain the difference comparison diagram of different samples, as shown in the figure. Figure 3 If the volatile organic compound content in the target sample and the reference is the same, the subtracted background is white, while red represents that the concentration of the substance in the target sample is higher than that in the reference, and blue represents that the concentration of the substance in the target sample is lower than that in the reference.
[0099] (2) Comparative analysis of fingerprint spectra of volatile components of honey from four sampling sites in Changbai Mountain area:
[0100] The volatile substances in the samples were further compared and fingerprint analysis was performed on all volatile substances. Figure 4 As shown. Figure 4 The following information can be obtained:
[0101] 1) Butyric acid, α-terpineol, 4-terpineol, 3-furanmethanol, Z-2-penten-1-ol, 3-methyl-1-pentanol, 2-heptanol, 3-methyl-3-butenol, 3-methyl-1-butanol, 1-butanol, 2-pentanol, 3-pentanol, 2-methyl-1-propanol, ethanol, methyl salicylate, ethyl lactate, hexyl acetate, ethyl hexanoate, ethyl 3-methylbutyrate, ethyl 2-methylbutyrate, ethyl butyrate, ethyl propionate, ethyl isobutyrate, ethyl acetate, acetophenone, 2-nonanone, 6-methyl-5-hepten-2-one, 1-hydroxy-2-propanone, 3-hydroxy-2-butanone, 2-heptanone, 4-heptenone The contents of substances such as ketone, 4-methyl-3-penten-2-one, 3-penten-2-one, 2-hexanone, 4-methyl-2-pentanone, 2-pentanone, 2-butanone, acetone, (E,E)-2,4-nonadienal, (E,E)-2,4-heptadienal, E-2-hexenal, 3-methyl-2-butenal, 2-methyl-2-pentenal, benzaldehyde, hexanal, valeraldehyde, 3-methylbutanal, 2-methylpropanal, propanal, 2-acetylfuran, 2-ethylfuran, linalool oxide, 2-ethyl-3-methylpyrazine, 3-ethylpyridine, p-cymene, 1,8-cineole, dimethyl trisulfide, and dimethyl sulfide are relatively high;
[0102] 2) The contents of acetic acid, phenylacetaldehyde, and 2-pentylfuran in JL were relatively high;
[0103] 3) YB contains high levels of 2-methylpropionic acid, propionic acid, γ-butyrolactone, 5-methyl-2-furfural, furfural, 2,4-hexadienal, cyclopentanone, and p-xylene;
[0104] 4) BS contains relatively high contents of nonanal, heptaldehyde, acetaldehyde, 2-propenal, linalool, Z-3-hexenol, 1-hexanol, 1-pentanol, 1-penten-3-ol, 1-propanol, 2-butanol, 2-propanol, leaf propionate, methyl caproate, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, and α-terpinene.
[0105] Volatile substances are an important component of honey's special aroma. Honey from different regions has different volatile components, which gives honey a unique flavor. Figure 4It can be seen that 3-furanmethanol, 3-methyl-1-butanol, ethanol, 2-methyl-1-propanol, ethyl lactate, 1-hydroxy-2-propanone, 3-hydroxy-2-butanone, acetone, hexanal, dimethyl sulfide, acetic acid, furfural, cyclopentanone, nonanal, heptanal, acetaldehyde, 2-propenal, 1-propanol, 2-propanol, etc. are volatile components with high concentrations in honey samples from the four origins. Further screening and analysis showed that furfural, nonanal, 1-hydroxy-2-propanone, 3-hydroxy-2-butanone, 3-methyl-1-butanol, linalool oxide, heptanal, cyclopentanone, 2-methyl-1-propanol, hexanal, etc. have sweet, banana, rose, citrus and other floral and fruity aromas and pleasant fresh and refreshing smells, which have important contributions to the formation of the characteristic odor of Changbai Mountain Chinese honey. Changbai Mountain Chinese Bee Honey from different origins has its own unique volatile components and content characteristics. Overall, the smell of Changbai Mountain Chinese Bee Honey is mainly floral, supplemented by sweet and fresh fruity aroma.
[0106] (3) Qualitative analysis of the spectra of volatile components of honey from four sampling sites in Changbai Mountain area:
[0107] The volatile components in the samples were determined using GC-IMS technology. A total of 80 volatile components and 105 peaks were identified in the four samples (although there are 134 components in Tables 3 to 9, 29 components have no identified signal peaks, so there are a total of 105 peaks). The detailed list of volatile components is shown in Tables 3 to 9.
[0108] Table 3 List of volatile components in samples
[0109]
[0110] Note: Dt represents migration time, RIPrel represents RIP normalization, and numbers represent unidentified signal peaks, the same below.
[0111] Table 4 Detailed list of volatile components in samples
[0112]
[0113] Note: The numbers are the same as above and below.
[0114] Table 5 List of volatile components in samples
[0115]
[0116] Table 6 List of volatile components in samples
[0117]
[0118] Table 7 List of volatile components in samples
[0119]
[0120] Table 8 List of volatile components in samples
[0121]
[0122] Table 9 Detailed list of volatile components in samples
[0123]
[0124] The peak volume (peak intensity) of all identified volatile components was calculated. The larger the peak volume, the higher its content. The top 10 volatile components in terms of peak volume of honey samples from different origins were statistically compiled. The statistical results of the common volatile substances in the honey of Chinese honey bees from Changbai Mountain in four regions are shown in Table 10.
[0125] Table 10 Peak volumes of characteristic volatile compounds in honey from the Changbai Mountain Apis cerana cerana from four different sampling sites
[0126]
[0127] As recorded in Table 10, linalool oxide, furfural, 2-methyl-1-propanol, 3-methyl-1-butanol, acetic acid and ethyl acetate are the common volatile substances of the Changbai Mountain Chinese honey from the four regions, indicating that they are the characteristic volatile components of the Changbai Mountain Chinese honey; and the production area of the Changbai Mountain Chinese honey can be determined by the peak volume of each component.
[0128] When the three indicators of furfural, 3-methyl-1-butanol and ethyl acetate are used for identification, the details are as follows:
[0129] The three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in TH need to meet the following conditions at the same time:
[0130] The peak volume of furfural was between 4319.55 and 4401.47, the peak volume of 3-methyl-1-butanol was between 4232.41 and 4274.57, and the peak volume of ethyl acetate was between 7876.64 and 7982.14;
[0131] The three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in JL need to meet the following conditions at the same time:
[0132] The peak volume of furfural was between 3294.67 and 3371.15, the peak volume of 3-methyl-1-butanol was between 2307.68 and 2331.04, and the peak volume of ethyl acetate was between 4827.84 and 4981.98;
[0133] The three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in YB need to meet the following conditions at the same time:
[0134] The peak volume of furfural was between 10757.20 and 10870.92, the peak volume of 3-methyl-1-butanol was between 1990.62 and 1999.04, and the peak volume of ethyl acetate was between 4790.11 and 4826.17;
[0135] The three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in BS need to meet the following conditions at the same time:
[0136] The peak volume of furfural is between 2288.06 and 2562.54, the peak volume of 3-methyl-1-butanol is between 2986.61 and 3056.83, and the peak volume of ethyl acetate is between 5090.68 and 5115.78.
[0137] When furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid are used for identification, the details are as follows:
[0138] The peak volume of linalool oxide in TH is between 10278.09-10821.57, the peak volume of 2-methyl-1-propanol is between 5143.11-5156.31, the peak volume of ethyl acetate is between 7876.64-7982.14, the peak volume of acetic acid is between 8178.21-8704.81, the peak volume of furfural is between 4319.55-4401.47, and the peak volume of 3-methyl-1-butanol is between 4232.41-4274.57;
[0139] The peak volume of linalool oxide in JL was between 6761.67 and 6999.11, the peak volume of 2-methyl-1-propanol was between 3426.79 and 3454.91, the peak volume of ethyl acetate was between 4827.84 and 4981.98, the peak volume of acetic acid was between 9323.80 and 9626.98, the peak volume of furfural was between 3294.67 and 3371.15, and the peak volume of 3-methyl-1-butanol was between 2307.68 and 2331.04;
[0140] The peak volume of linalool oxide in YB was between 7129.62-7261.00, the peak volume of 2-methyl-1-propanol was between 3436.96-3440.20, the peak volume of ethyl acetate was between 4790.11-4826.17, the peak volume of acetic acid was between 7438.95-7476.73, the peak volume of furfural was between 10757.20-10870.92, and the peak volume of 3-methyl-1-butanol was between 1990.62-1999.04;
[0141] The peak volume of linalool oxide in BS was between 7190.72-7259.70, the peak volume of 2-methyl-1-propanol was between 4249.73-4474.65, the peak volume of ethyl acetate was between 5090.68-5115.78, the peak volume of acetic acid was between 9615.75-10159.73, the peak volume of furfural was between 2288.06-2562.54, and the peak volume of 3-methyl-1-butanol was between 2986.61-3056.83.
[0142] According to the above data, it can be known that the production area can be determined by determining the peak volumes of furfural, 3-methyl-1-butanol and ethyl acetate in the Changbai Mountain Chinese honey or the peak volumes of furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid.
[0143] Example 2 Classification and Identification of Honey from Changbai Mountain of Chinese Honeybees from Different Origins
[0144] 1. Sample collection
[0145] The sample information is the same as Table 1 in Example 1. Three batches of honey samples were taken from each sampling site, and each batch was repeated three times. The collection time was 2021.
[0146] 2. Reagents and Materials
[0147] Same as Example 1.
[0148] 3. Instruments and equipment
[0149] Same as Example 1.
[0150] 4. Test methods
[0151] Same as Example 1.
[0152] 5. Data processing and analysis
[0153] A mixed standard of 6 ketones was detected, and a calibration curve of retention time and retention index was established. The retention index of the substance was then calculated according to the retention time of the target substance. The GC retention index (NIST 2020) database and IMS migration time database built into the VOCal software were used for retrieval and comparison, and a qualitative analysis of the target substance was performed.
[0154] The plug-in in the VOCal data processing software was used to generate qualitative volatile component maps and PCA plots for the comparison of volatile organic compounds between samples.
[0155] 6. Results
[0156] (1) Cluster analysis of volatile components:
[0157] Principal component analysis is a statistical method that recombine the original variables into a group of new independent comprehensive variables. At the same time, according to actual needs, several fewer comprehensive variables can be extracted to reflect as much information as possible from the original variables. It is also a method used for dimensionality reduction in mathematics.
[0158] In order to further analyze the differences in volatile components in honey from Changbai Mountain of different origins, principal component analysis (PCA) was performed on the volatile component content data of three batches of honey samples from each sampling site. Honey samples from Jilin (JL), Yanbian (YB), Tonghua (TH) and Baishan (BS) were effectively classified. The results are shown in Figure 2. Figure 5 As shown. Through PCA analysis, Figure 5 It can be seen that the variance contributions of principal component 1 and principal component 2 are 58% and 29% respectively, all sample points are within the 95% confidence interval and show good clustering, and there are significant differences in the volatile components of Changbai Mountain Chinese honey from the four regions.
[0159] (2) Qualitative analysis of the spectrum of volatile components of honey from Changbai Mountain Chinese honeybees:
[0160] The volatile components of honey samples from Changbai Mountain Chinese honeybees from different origins were determined. The qualitative spectra are detailed in Figure 6-Figure 9 and Table 11.
[0161] Table 11 Peak volumes of characteristic volatile compounds in honey from the four sampling sites of the Changbai Mountain Apis cerana
[0162]
[0163] Note: Data are the average of three replicates.
[0164] Depend on Figure 6-Figure 9As shown in Table 11, the peak volume of linalool oxide in TH is between 10278.09 and 10821.57, the peak volume of 2-methyl-1-propanol is between 5143.11 and 5156.31, the peak volume of ethyl acetate is between 7876.64 and 7982.14, the peak volume of acetic acid is between 8178.21 and 8704.81, the peak volume of furfural is between 4319.55 and 4401.47, and the peak volume of 3-methyl-1-butanol is between 4232.41 and 4274. .57; the peak volume of linalool oxide in JL is between 6761.67-6999.11, the peak volume of 2-methyl-1-propanol is between 3426.79-3454.91, the peak volume of ethyl acetate is between 4827.84-4981.98, the peak volume of acetic acid is between 9323.80-9626.98, the peak volume of furfural is between 3294.67-3371.15, and the peak volume of 3-methyl-1-butanol is between 2307.68-2331.04 The peak volume of linalool oxide in YB is between 7129.62-7261.00, the peak volume of 2-methyl-1-propanol is between 3436.96-3440.20, the peak volume of ethyl acetate is between 4790.11-4826.17, the peak volume of acetic acid is between 7438.95-7476.73, the peak volume of furfural is between 10757.20-10870.92, and the peak volume of 3-methyl-1-butanol is between 1990.62-1999.04 The peak volume of linalool oxide in BS is between 7190.72-7259.70, the peak volume of 2-methyl-1-propanol is between 4249.73-4474.65, the peak volume of ethyl acetate is between 5090.68-5115.78, the peak volume of acetic acid is between 9615.75-10159.73, the peak volume of furfural is between 2288.06-2562.54, and the peak volume of 3-methyl-1-butanol is between 2986.61-3056.83. And by comparison, it can be seen that it is only necessary to determine the peak volumes of furfural, 3-methyl-1-butanol and ethyl acetate in the Changbai Mountain Chinese honey or the peak volumes of furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid to determine the production area.
[0165] Example 3 Classification and Identification of Honey from Changbai Mountain of Chinese Honeybees from Different Origins
[0166] 1. Sample collection
[0167] The sample information is the same as Table 1 in Example 1. Fifteen batches of honey samples were taken from each sampling site, and each batch was repeated three times. The collection time was 2022.
[0168] 2. Reagents and Materials
[0169] Same as Example 1.
[0170] 3. Instruments and equipment
[0171] Same as Example 1.
[0172] 4. Test methods
[0173] Same as Example 1.
[0174] 5. Data processing and analysis
[0175] A mixed standard of 6 ketones was detected, and a calibration curve of retention time and retention index was established. The retention index of the substance was then calculated according to the retention time of the target substance. The GC retention index (NIST 2020) database and IMS migration time database built into the VOCal software were used for retrieval and comparison, and a qualitative analysis of the target substance was performed.
[0176] The plug-in in the VOCal data processing software was used to generate qualitative volatile component maps and PCA plots for the comparison of volatile organic compounds between samples.
[0177] 6. Results
[0178] The volatile components of honey samples from Changbai Mountain Chinese honey bees from different origins were measured, and the test results are shown in Tables 12 to 14.
[0179] Table 12 Peak volumes of characteristic volatile compounds in honey from the four sampling sites of Changbai Mountain Apis cerana
[0180]
[0181] Note: Data are the average of three replicates, the same below.
[0182] Table 13 Peak volumes of characteristic volatile compounds in honey from the four sampling sites of the Changbai Mountain Apis cerana
[0183]
[0184] Table 14 Peak volumes of characteristic volatile compounds in honey from the four sampling sites of Changbai Mountain Apis cerana
[0185]
[0186] As shown in Tables 12 to 14, the peak volume of linalool oxide in TH is between 10278.09 and 10821.57, the peak volume of 2-methyl-1-propanol is between 5143.11 and 5156.31, the peak volume of ethyl acetate is between 7876.64 and 7982.14, the peak volume of acetic acid is between 8178.21 and 8704.81, the peak volume of furfural is between 4319.55 and 4401.47, and the peak volume of 3-methyl-1-butanol is between 4232.41 and 4332.31. 274.57; the peak volume of linalool oxide in JL is between 6761.67-6999.11, the peak volume of 2-methyl-1-propanol is between 3426.79-3454.91, the peak volume of ethyl acetate is between 4827.84-4981.98, the peak volume of acetic acid is between 9323.80-9626.98, the peak volume of furfural is between 3294.67-3371.15, and the peak volume of 3-methyl-1-butanol is between 2307.68-2331. 04; the peak volume of linalool oxide in YB is between 7129.62-7261.00, the peak volume of 2-methyl-1-propanol is between 3436.96-3440.20, the peak volume of ethyl acetate is between 4790.11-4826.17, the peak volume of acetic acid is between 7438.95-7476.73, the peak volume of furfural is between 10757.20-10870.92, and the peak volume of 3-methyl-1-butanol is between 1990.62-1999.04 The peak volume of linalool oxide in BS is between 7190.72-7259.70, the peak volume of 2-methyl-1-propanol is between 4249.73-4474.65, the peak volume of ethyl acetate is between 5090.68-5115.78, the peak volume of acetic acid is between 9615.75-10159.73, the peak volume of furfural is between 2288.06-2562.54, and the peak volume of 3-methyl-1-butanol is between 2986.61-3056.83. And through comparison, it can be seen that it is only necessary to determine the peak volumes of the three indicators of furfural, 3-methyl-1-butanol and ethyl acetate in the Changbai Mountain Chinese honey or to determine the peak volumes of the six indicators of furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid to determine the production area.
[0187] Example 4 Classification and Identification of Honey from Changbai Mountain of Chinese Honeybees from Different Origins
[0188] 1. Sample collection
[0189] The sample information is shown in Table 15. Three batches of honey samples were taken from each sampling site, and each batch was repeated three times.
[0190] Table 15 Sample collection information
[0191]
[0192] 2. Reagents and Materials
[0193] Same as Example 1.
[0194] 3. Instruments and equipment
[0195] Same as Example 1.
[0196] 4. Test methods
[0197] Same as Example 1.
[0198] 5. Data processing and analysis
[0199] A mixed standard of 6 ketones was detected, and a calibration curve of retention time and retention index was established. The retention index of the substance was then calculated according to the retention time of the target substance. The GC retention index (NIST 2020) database and IMS migration time database built into the VOCal software were used for retrieval and comparison, and a qualitative analysis of the target substance was performed.
[0200] The plug-in in the VOCal data processing software was used to generate qualitative volatile component maps and PCA plots for the comparison of volatile organic compounds between samples.
[0201] 6. Results
[0202] The volatile components of honey samples from Changbai Mountain Chinese honey bees from different origins were measured, and the test results are shown in Tables 16 to 27.
[0203] Table 16 Test results of volatile components of the first batch of Changbai Mountain Chinese honey samples from the YB production area
[0204]
[0205] Note: Data are the average of three replicates, the same below.
[0206] Table 17 Volatile component test results of the second batch of Changbai Mountain Chinese honey samples from the YB production area
[0207]
[0208] Table 18 Volatile component test results of the third batch of Changbai Mountain Chinese honey samples from YB production area
[0209]
[0210] Table 19 Volatile component test results of the first batch of Changbai Mountain Chinese honey samples from JL production area
[0211]
[0212] Table 20 Volatile component test results of the second batch of Changbai Mountain Chinese honey samples from JL production area
[0213]
[0214] Table 21 Volatile component test results of the third batch of Changbai Mountain Chinese honey samples from JL production area
[0215]
[0216] Table 22 Volatile component test results of the first batch of honey samples from Changbai Mountain, TH production area
[0217]
[0218] Table 23 Volatile component test results of the second batch of Changbai Mountain Chinese honey samples from TH production area
[0219]
[0220] Table 24 Volatile component test results of the third batch of Changbai Mountain Chinese honey samples from TH production area
[0221]
[0222] Table 25 Volatile component test results of the first batch of Changbai Mountain Chinese honey samples from BS production area
[0223]
[0224] Table 26 Volatile component test results of the second batch of Changbai Mountain Chinese honey samples from BS production area
[0225]
[0226] Table 27 Volatile component test results of the third batch of Changbai Mountain Chinese honey samples from BS production area
[0227]
[0228] As shown in Tables 16 to 27, the peak volumes of linalool oxide in the honey samples from three different altitudes in TH were all between 10278.09 and 10821.57, the peak volumes of 2-methyl-1-propanol were all between 5143.11 and 5156.31, the peak volumes of ethyl acetate were all between 7876.64 and 7982.14, the peak volumes of acetic acid were all between 8178.21 and 8704.81, the peak volumes of furfural were all between 4319.55 and 4401.47, and the peak volumes of 3-methyl-1-butanol were all between 4232.4 and 4332.33. The peak volumes of linalool oxide in honey samples from three different altitudes in JL were all between 6761.67 and 6999.11, the peak volumes of 2-methyl-1-propanol were all between 3426.79 and 3454.91, the peak volumes of ethyl acetate were all between 4827.84 and 4981.98, the peak volumes of acetic acid were all between 9323.80 and 9626.98, the peak volumes of furfural were all between 3294.67 and 3371.15, and the peak volumes of 3-methyl-1-butanol were all between 2307.68 and 233 1.04; the peak volumes of linalool oxide in the honey samples from four different altitudes in YB were all between 7129.62-7261.00, the peak volumes of 2-methyl-1-propanol were all between 3436.96-3440.20, the peak volumes of ethyl acetate were all between 4790.11-4826.17, the peak volumes of acetic acid were all between 7438.95-7476.73, the peak volumes of furfural were all between 10757.20-10870.92, and the peak volumes of 3-methyl-1-butanol were all between 1990.62-1999.0 4; the peak volumes of linalool oxide in honey samples from 6 locations at different altitudes in BS were all between 7190.72-7259.70, the peak volumes of 2-methyl-1-propanol were all between 4249.73-4474.65, the peak volumes of ethyl acetate were all between 5090.68-5115.78, the peak volumes of acetic acid were all between 9615.75-10159.73, the peak volumes of furfural were all between 2288.06-2562.54, and the peak volumes of 3-methyl-1-butanol were all between 2986.61-3056.83. It can be seen from this that the production area can be determined by only determining the peak volumes of three indicators, furfural, 3-methyl-1-butanol and ethyl acetate, or determining the peak volumes of six indicators, furfural, 3-methyl-1-butanol, ethyl acetate, linalool oxide, 2-methyl-1-propanol and acetic acid in the Changbai Mountain Chinese honey bee honey. This identification method is reproducible and is not affected by external conditions (such as altitude factors).
[0229] In summary, it can be seen that the Changbai Mountain Chinese honey from different production areas can be distinguished by the identification indexes given in Example 1. The method provided by the present invention can effectively distinguish the Changbai Mountain Chinese honey from different production areas, and can also be used for the detection of the quality of Changbai Mountain Chinese honey.
[0230] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.
Claims
1. A method for identifying honey from different production areas of Changbai Mountain Chinese honey, characterized in that: The following steps are involved: Using headspace gas chromatography-ion mobility spectrometry to detect the Changbai Mountain Chinese honey bees honey from different production areas to obtain GC-IMS samples; constructing a fingerprint spectrum of volatile components of the Changbai Mountain Chinese honey bees honey, and screening the volatile components of the Changbai Mountain Chinese honey bees honey to obtain the common volatile components of the Changbai Mountain Chinese honey bees honey; using the peak volume of the common volatile components of the Changbai Mountain Chinese honey bees honey volatile components to distinguish the Changbai Mountain Chinese honey bees honey from different production areas; The common volatile components include furfural, 3-methyl-1-butanol and ethyl acetate; When the peak volume of furfural is between 10757.20-10870.92, the peak volume of 3-methyl-1-butanol is between 1990.62-1999.04, and the peak volume of ethyl acetate is between 4790.11-4826.17, it is judged that the Changbai Mountain Chinese honey production area is Yanbian Korean Autonomous Prefecture; When the peak volume of furfural is between 3294.67-3371.15, the peak volume of 3-methyl-1-butanol is between 2307.68-2331.04, and the peak volume of ethyl acetate is between 4827.84-4981.98, it is judged that the Changbai Mountain Chinese honey production area is Jilin City; When the peak volume of furfural is between 4319.55-4401.47, the peak volume of 3-methyl-1-butanol is between 4232.41-4274.57, and the peak volume of ethyl acetate is between 7876.64-7982.14, it is judged that the Changbai Mountain Chinese honey production area is Tonghua City; When the peak volume of furfural is between 2288.06-2562.54, the peak volume of 3-methyl-1-butanol is between 2986.61-3056.83, and the peak volume of ethyl acetate is between 5090.68-5115.78, it is judged that the Changbai Mountain Chinese honey producing area is Baishan City.
2. The identification method according to claim 1, characterized in that: In the headspace gas chromatography-ion mobility spectrometry, the incubation temperature of the headspace injection is 80°C, the incubation time is 20min, the injection volume is 500µL, the incubation speed is 500r / min, and the injection needle temperature is 85°C.
3. The identification method according to claim 1, characterized in that: In the headspace gas chromatography-ion mobility spectrometry, the chromatographic column used for gas chromatography detection is a MXT-WAX capillary chromatographic column, the column temperature is 60°C, the carrier gas is nitrogen, the temperature of the injection port is 80°C, and the running time is 60min; And / or, the pressure increase procedure for headspace gas chromatography detection is: an initial flow rate of 2.0 mL / min is maintained for 2 min; within 8 min, the flow rate is increased to 10.0 mL / min; within 10 min, the flow rate is increased to 100.0 mL / min and maintained for 40 min.
4. The identification method according to claim 1, characterized in that: In the headspace gas chromatography-ion mobility spectrometry, the ionization source for ion mobility spectrometry detection is a tritium source, the migration tube length is 53 mm, the electric field strength is 500 V / cm, the migration tube temperature is 45° C., the drift gas is nitrogen, the flow rate is 75.0 mL / min, and the mode is a positive ion mode.
5. Application of the identification method according to any one of claims 1 to 4 in identifying the authenticity of Changbai Mountain Chinese honey.
6. Application of the identification method according to any one of claims 1 to 4 in identifying the quality of honey from Apis cerana cerana in Changbai Mountain.
7. Application of the identification method according to any one of claims 1 to 4 in evaluating the quality of honey from Apis cerana cerana in Changbai Mountain.
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