CN113686805A - Oil product characteristic fingerprint spectrum, establishing method and application in cigarette oil spot identification - Google Patents
Oil product characteristic fingerprint spectrum, establishing method and application in cigarette oil spot identification Download PDFInfo
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Abstract
The invention belongs to the field of cigarette product quality control, and discloses a method for establishing an oil product characteristic fingerprint spectrum and a method for identifying the source of cigarette oil spot pollutants based on the characteristic fingerprint spectrum, which comprises the following steps: collecting oil used in the production field, and preparing a standard sample on the cigarette paper; analyzing and detecting the standard sample by adopting infrared spectroscopy, gas chromatography and gas chromatography-mass spectrometry combined technology, and establishing a multi-spectral characteristic fingerprint spectrogram of each oil product; comparing the spectrogram of the oil spot to be identified with the characteristic fingerprint of the standard oil product, realizing the primary identification of the oil spot by infrared spectroscopy, and further identifying the pollution source of the oil spot by comprehensively comparing and simulating the consistency of information such as a distillation curve, the composition and the content of a characteristic marker and the like. The method provided by the invention combines multiple analysis means to obtain more comprehensive fingerprint information of the oil product, has the advantages of simple pretreatment and high sensitivity, and can provide a scientific, accurate and efficient identification method for judging the cigarette oil stain pollution source.
Description
Technical Field
The invention relates to an identification method of a cigarette oil stain pollution source, relates to an oil product characteristic fingerprint spectrum, an establishment method thereof and application in cigarette oil stain pollution source identification, and particularly relates to an oil product characteristic fingerprint spectrum established by adopting an infrared spectrum, gas chromatography and gas chromatography-mass spectrometry combined technical method, and rapid and accurate identification of the oil stain pollution source is carried out based on the characteristic fingerprint spectrum, belonging to the field of cigarette product quality control.
Background
The yellow spot cigarette refers to the finished cigarette with yellow brown spots on the surface. The national standard GB/T5606.3-2005 of cigarettes clearly states that the yellow spots on the surfaces of cigarettes belong to relatively serious quality defects, which not only directly affect the appearance quality of cigarette products, but also possibly cause the sensory quality of the products to change, so that the prevention and control of the yellow spot cigarettes are always one of the important points of attention in the tobacco industry.
The causes of cigarette yellow spots and oil stain defects are numerous, the cigarette yellow spots and oil stain defects can be derived from various links of cigarette production and are related to various factors in the processes of raw and auxiliary materials, a shredding process, a rolling process, a storage and transportation process and the like, and the leakage of oil for equipment is a potential cause of yellow spot cigarette generation. In the cigarette production process, oil products are used by cigarette making machine equipment in many links, the types of the oil products used in all the links are different, once oil stain spots appear, the production links need to be arranged, and the pollution source arrangement is time-consuming and labor-consuming.
In recent years, many researchers have conducted identification studies on the sources of oil contamination of cigarettes. Researchers use Fourier transform infrared spectroscopy (FTIR), attenuated total reflectance infrared spectroscopy (ATR-FTIR), Gas Chromatography (GC), gas chromatography-mass spectrometry (GC-MS), static headspace-gas mass spectrometry (HS-GC-MS) and the like to analyze pollution spots appearing in the production process, and compare the pollution spots with the spectrogram of a pollution source oil product through means of visual comparison, database retrieval or similarity calculation and the like to determine the oil product causing pollution.
However, the macular cigarette appearing in the actual production process has the characteristics of low detectable rate, small pollution area, difficulty in sampling and the like, so that the development of an analysis and detection method with simple pretreatment, high sensitivity, strong characteristics and high analysis speed is urgently needed. Although the existing oil spot analysis method adopts the infrared spectroscopy, the gas chromatography and the gas chromatography-mass spectrometry combined method, the uniqueness and the characteristic of the obtained oil chemical composition information are not strong because the targeted analysis is not adopted according to the chemical composition characteristics of the lubricating oil, so the existing analysis and detection method can not completely reflect the difference of different oils, and the accuracy of the identification result needs to be improved.
The characteristic fingerprint spectrum is a spectrum which can identify the chemical characteristics of a sample after the sample is properly processed and detected by adopting a certain analysis means and an instrument. Based on the characteristics of the chemical component information reflected by the characteristic fingerprint spectrum, different oil products can be effectively distinguished and identified. However, how to construct an oil product characteristic fingerprint spectrum to identify the source of the cigarette oil stain pollutants with high accuracy, high sensitivity and strong characteristics is not reported in the prior art.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for establishing an oil product characteristic fingerprint spectrum and a method for identifying a cigarette oil stain pollution source by using the oil product characteristic fingerprint spectrum. The method comprises the steps of analyzing and detecting all oil products used by cigarette equipment by adopting infrared spectroscopy, gas chromatography simulated distillation and gas chromatography-mass spectrometry, establishing a characteristic fingerprint of the oil products, comparing the spectrogram of the oil stain of the cigarette with the characteristic fingerprint, and determining the oil products causing the oil stain pollution by a method of visual comparison or similarity calculation of the spectrogram, so as to realize the identification of the pollution source of the cigarette. The method provided by the invention combines multiple analysis means to obtain the more comprehensive fingerprint information of the oil product, can accurately and efficiently identify the cigarette pollution source, has the characteristics of strong uniqueness and strong characteristics, is simple in pretreatment, is high in sensitivity, and can provide a scientific identification method for judging the cigarette oil stain pollution source.
The invention provides a method for establishing an oil product characteristic fingerprint spectrum, which comprises the following steps: collecting oil used in the production field, and preparing a standard sample on the cigarette paper; and (3) analyzing and detecting the standard sample by adopting infrared spectroscopy, gas chromatography and gas chromatography-mass spectrometry combined technology, and establishing a multi-spectral characteristic fingerprint spectrogram of each oil product.
Specifically, the method for establishing the oil product characteristic fingerprint spectrum comprises the following steps:
1) preparation of Standard samples
Collecting all oil products used in each production link of cigarette equipment, and coating the oil products on cigarette paper to prepare a standard sample, wherein the size of oil spots of the standard sample is similar to the size of actual spots of cigarettes to be detected.
2) Infrared spectroscopic analysis of standard samples
And acquiring a microscopic image of the standard sample, performing infrared spectrum scanning on the spot microscopic image, establishing a characteristic infrared spectrogram of each oil product, and determining a characteristic absorption peak of each oil product.
3) Gas chromatography simulated distillation analysis of standard samples
Cutting oil spots of a standard sample, placing the cut oil spots in a chromatographic bottle, adding an extracting agent for extraction, performing simulated distillation analysis on the standard sample by adopting a gas chromatograph, and establishing a characteristic gas chromatography characteristic simulated distillation curve of each oil product.
The simulated distillation refers to a gas chromatography method for measuring the distribution of different boiling ranges of oil products by adopting a temperature programming mode.
In the step 3), the extracting agent is one or more selected from n-hexane, toluene and carbon disulfide, and n-hexane is preferred.
4) Gas chromatography-mass spectrometry analysis of standard samples
Cutting a standard sample, placing the standard sample in a chromatographic bottle, adding an extracting agent for extraction, separating by using a gas chromatography-mass spectrometer, obtaining a characteristic gas chromatography-mass spectrogram of each oil product by adopting a full-scanning and selective ion detection (SIM) mode, wherein the characteristic gas chromatography-mass spectrogram comprises a gas chromatography-mass spectrometry total ion flow diagram and a mass chromatogram of three biomarkers of saturated paraffin, terpene hydrocarbons and sterane, and establishing a gas chromatography-mass spectrometry characteristic fingerprint spectrogram of each oil product based on an original spectrogram of the gas chromatography-mass spectrometry total ion flow diagram and distribution characteristics of the three markers.
Wherein, in the step 4), the three biomarkers of saturated alkane, terpene alkane and sterane specifically refer to: three biomarkers of saturated alkanes (m/z 85), terpenoids (m/z 191) and steroids (m/z 217).
In the step 4), the extracting agent is one or more selected from n-hexane, toluene and carbon disulfide, and n-hexane is preferred.
The invention also provides the oil product characteristic fingerprint spectrum established by the method. The oil product characteristic fingerprint contains comprehensive oil product fingerprint information, is used for detecting the source of the oil stain pollutants of the cigarettes, and can accurately and efficiently identify the source of the oil stain pollutants.
The invention also provides the application of the oil product characteristic fingerprint spectrum in the cigarette production process for identifying the cigarette oil stain pollution source. The oil characteristic fingerprint spectrum is established by analyzing and detecting a standard sample by adopting infrared spectroscopy, gas chromatography and gas chromatography-mass spectrometry combined technology. The method is used for detecting the source of the oil stain pollutants of the cigarettes, can accurately and efficiently identify the source of the oil stain pollutants, and has uniqueness and strong characteristics.
The invention also provides a method for identifying the oil stain pollution source by using the oil product characteristic fingerprint, which comprises the steps of determining the corresponding spectrogram of the oil stain to be detected according to the establishing method of the oil product characteristic fingerprint (standard sample), comparing the corresponding spectrogram with the oil product characteristic fingerprint, comprehensively comparing the infrared characteristic absorption peak, the simulated distillation curve and the consistency of the composition and the content of the characteristic marker, and identifying the pollution source of the oil stain to be detected.
When the method is used for identifying the cigarette oil stain pollution source, the invention provides a method for identifying the cigarette oil stain pollution source by using the oil product characteristic fingerprint spectrum, which comprises the following steps: collecting oil used in the production field, and preparing a standard sample on the cigarette paper; analyzing and detecting the standard sample by adopting infrared spectroscopy, gas chromatography and gas chromatography-mass spectrometry combined technology, and establishing a multi-spectral characteristic fingerprint spectrogram of each oil product; the spectrogram of the oil stain to be identified is compared with the characteristic fingerprint of the standard oil product, and the identification of the oil stain pollution source is realized by comprehensively comparing the consistency of information such as infrared characteristic absorption peaks, simulated distillation curves, the composition and the content of characteristic markers and the like.
Specifically, the method for identifying the cigarette oil stain pollution source by using the oil product characteristic fingerprint spectrum comprises the following steps:
a) infrared spectroscopic analysis of a sample to be examined
Collecting a microscopic image of a sample to be detected, carrying out infrared spectrum scanning on the spot microscopic image, establishing a characteristic infrared spectrogram of the sample to be detected (oil product to be detected), and determining a characteristic absorption peak of the sample to be detected.
b) Gas chromatography simulated distillation analysis of a sample to be tested
Cutting oil spots of a sample to be detected, placing the oil spots in a chromatographic bottle, adding n-hexane for extraction, performing simulated distillation analysis on the sample to be detected by adopting a gas chromatograph, and establishing a gas chromatography characteristic simulated distillation curve of the sample to be detected.
c) Gas chromatography-mass spectrometry of a sample to be tested
Cutting a sample to be detected, placing the sample in a chromatographic bottle, adding n-hexane for extraction, separating by using a gas chromatography-mass spectrometer, obtaining a characteristic gas chromatography-mass spectrogram of the sample to be detected by using a full-scanning and selective ion detection (SIM) mode, wherein the characteristic gas chromatography-mass spectrogram comprises a gas chromatography-mass spectrometer total ion flow diagram and a mass chromatogram of three biomarkers of saturated paraffin, terpenes and steranes, and establishing the gas chromatography-mass spectrometer characteristic fingerprint spectrogram of the sample to be detected based on an original spectrogram and distribution characteristics of the three markers.
Wherein, the three biomarkers of saturated alkane, terpenoid and sterane specifically refer to: three biomarkers of saturated alkanes (m/z 85), terpenoids (m/z 191) and steroids (m/z 217).
d) Identification of samples to be examined (cigarette contaminants)
d-1) comparing the infrared spectrogram of the sample to be detected with the characteristic infrared spectrogram of a standard oil product, primarily screening a pollution source according to the characteristic infrared absorption peak of each oil product to be detected, and continuing to perform gas chromatography and gas chromatography-mass spectrometry if the oil spot characteristics are met and the type of the polluted oil product cannot be determined; if the yellow spots do not accord with the oil spot characteristics, the yellow spots to be detected are not caused by oil product pollution.
d-2) comparing the gas chromatography characteristic simulation distillation curve of the sample to be detected with the characteristic simulation distillation curve of each standard oil product, and further judging the type of the polluted oil product by means of visual comparison or similarity calculation of the characteristics such as the position of the bulge, the profile shape, the burr peak and the like.
d-3) comparing the original spectrogram of the total ion flow of the gas chromatography-mass spectrometry of the sample to be detected and the quality chromatograms of the three markers with the characteristic spectrums of each standard oil product respectively, and further confirming the type of the polluted oil product through visual comparison of the distribution and the content of the characteristic markers.
In a specific embodiment, the method for identifying the cigarette oil stain pollution source by using the characteristic fingerprint spectrum comprises the following steps:
i) preparation of Standard samples
Collecting all oil products used in each production link of cigarette equipment, coating the oil products on cigarette paper to prepare standard samples, wherein the size of oil spot is similar to the size of actual spot of cigarette, the diameter is about 1-5mm, and the number of the standard samples prepared from each oil product is not less than 10.
ii) Infrared spectroscopic analysis of the Standard sample
Collecting microscopic image of standard sample, and performing infrared spectrum scanning (scan range is 4000 cm) on spot region in the collected microscopic image by using attenuated total reflection infrared spectrum (ATR)-1～700cm-1) Establishing a characteristic infrared spectrogram of each oil product, and determining a characteristic absorption peak of each oil product.
iii) gas chromatography simulated distillation analysis of standard samples
Cutting a standard sample, placing the standard sample in a chromatographic bottle, adding about 50 mu L of n-hexane for extraction, performing simulated distillation analysis on the standard sample by adopting a gas chromatograph, and establishing a gas chromatogram characteristic simulated distillation curve of each oil product.
iv) gas chromatography-mass spectrometry analysis of standard samples
Cutting a standard sample, placing the standard sample in a chromatographic bottle, adding about 50 mu L of n-hexane for extraction, separating by using a gas chromatography-mass spectrometer, obtaining a total ion flow graph of characteristic gas chromatography-mass spectrometry of each oil product and mass chromatograms of biomarkers of saturated paraffin (m/z 85), terpenes (m/z 191) and steroids (m/z 217) by using a full-sweep and selective ion detection (SIM) mode, and establishing a gas chromatography-mass spectrometry characteristic spectrogram of each oil product based on an original spectrogram and distribution characteristics of the three markers.
v) identification of cigarette contaminants
And (3) analyzing and detecting the oil stain sample to be identified in the step ii) to obtain an infrared spectrogram of the sample, comparing the infrared spectrogram of the sample to be detected with the characteristic infrared spectrogram of the oil product, and primarily screening the pollution source according to the characteristic infrared absorption peak of each oil product.
And if the infrared spectrogram accords with the characteristics of the oil product and cannot determine the type of the polluted oil product, analyzing and detecting in the steps iii) and iv) to respectively obtain a gas chromatogram and a gas chromatogram-mass spectrogram of the sample. And comparing the gas chromatography simulated distillation curve of the sample to be detected with the characteristic simulated distillation curve of each oil product, and further judging the type of the polluted oil product by means of visual comparison or similarity calculation of the characteristics such as the position of the bulge, the profile shape, the burr peak and the like. And comparing the original spectrogram of the total ion flow of the gas chromatography-mass spectrometry of the sample to be detected and the extracted ion flow graph of the three markers with the characteristic maps of the oil products respectively, and confirming the types of the polluted oil products through visual comparison of the distribution and the content of the characteristic markers.
Compared with the prior art, the invention has the following advantages:
(1) combines a plurality of detection and analysis methods, establishes a more comprehensive multispectral characteristic fingerprint spectrum library of the oil product, and improves the accuracy and reliability of identification.
(2) The microscopic infrared analysis adopted by the invention combines an optical microscope and an infrared spectrum, and the yellow spots can be directly placed on the surface of the crystal for analysis without sample preparation, and the method has high sensitivity and high analysis speed, and can perform nondestructive analysis on the spots in a micron region compared with the traditional attenuated total reflection infrared method. The method can quickly reduce the range of pollution sources, and if the oil spot characteristics are met and the types of the polluted oil products cannot be determined, the subsequent analysis is carried out, so that the detection efficiency is effectively improved.
(3) The invention adopts a gas chromatography simulated distillation method to obtain a simulated distillation curve of the oil product, adopts a gas chromatography-mass spectrometry combined method to obtain the composition and the content of various characteristic markers in the oil product, obtains a more comprehensive oil product characteristic map, and identifies the polluted oil product based on the characteristic fingerprint map. The analysis method has high sensitivity and the pretreatment method is simple.
(4) A comprehensive identification system of the cigarette oil stain pollution source is established based on the characteristic fingerprint spectrum, and compared with manual investigation, the comprehensive identification system is more objective, accurate and efficient, and compared with a single detection analysis method, the comprehensive identification system is more accurate and reliable in identification result.
Drawings
FIG. 1 is an infrared characteristic fingerprint spectrum of oil products of 7 standard samples (the numbers are 1#, 2#, 3#, 4#, 5#, 6#, and 7#, respectively).
FIG. 2 is a gas chromatography characteristic simulated distillation curve of oil products of 7 standard samples (numbered 1#, 2#, 3#, 4#, 5#, 6#, and 7#, respectively); wherein, the abscissa is retention time (min) and is 4, 6, 8, 10, 12, 14, 16, 18 and 20 from left to right; the ordinate is response (pA) and is from bottom to top in the order 50, 100, 150, 200, 250, 300, 350.
FIG. 3 is a gas chromatography-mass spectrometry characteristic fingerprint of oil products of 7 standard samples (numbered 1#, 2#, 3#, 4#, 5#, 6#, and 7#, respectively); wherein, the abscissa of each graph is time (min).
FIG. 4 is an infrared spectrum of a sample of oil spots to be identified according to an embodiment of the present invention.
FIG. 5 is a gas chromatograph simulated distillation curve (A) of an oil stain sample to be identified and a calculation result (B) of the similarity thereof according to an embodiment of the present invention; in fig. 5A, the abscissa is retention time (min) and is 4, 6, 8, 10, 12, 14, 16, 18, and 20 in sequence from left to right; the ordinate is response (pA), and is 0, 500, 1000, 1500, 2000, and 2500 from bottom to top.
FIG. 6 is a GC-MS spectrum of an oil spot sample to be identified according to an embodiment of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The reagents and equipment used in the following examples are as follows:
1. reagent: n-hexane, toluene and chromatographic grade reagent. Polywax 655, available from Agilent Inc. (5188-. C12-C20 n-alkanes from AccuStandard, Inc.
2. The instrument comprises the following steps: the infrared analysis adopts a Nicolet iN10 Fourier transform micro infrared spectrometer of Thermo company; the gas chromatography column was an Agilent DB-HT (5 m.times.0.53 mm,0.1 μm) simulated distillation column and a DB-5MS (30 m.times.0.25 mm0.25 μm) capillary column.
The method specifically comprises the following steps:
1. standard sample preparation
Collecting all oil products used in each production link of cigarette equipment, coating the oil products on cigarette paper to prepare a standard sample, wherein the size of oil stain spots is similar to the actual spot size of a cigarette, the diameter is about 1-5mm, and the number of the oil stain standard samples prepared from each oil product is not less than 10.
2. Infrared spectroscopic analysis of standard samples
Collecting microscopic images of the standard samples, carrying out infrared spectrum scanning on the areas where the spots are located in the collected microscopic images by using attenuated total reflectance infrared (ATR) spectra, establishing characteristic infrared spectrograms of the oil products, and determining characteristic absorption peaks of the oil products of the standard samples.
Wherein, the scanning range of the attenuated total reflection infrared spectrum is 4000cm-1～700cm-1The number of scanning times is 32, and the scanning interval is 2cm-1。
3. Gas chromatography simulated distillation (SIMDIS) analysis of standard samples
Cutting a standard sample, placing the standard sample in a chromatographic bottle, adding about 50 mu L of n-hexane for extraction, performing simulated distillation analysis on the standard sample by using a gas chromatograph (GC-FID), and establishing a characteristic gas chromatogram, namely a characteristic simulated distillation curve, of each oil product.
Wherein n-hexane can be replaced by toluene and carbon disulfide.
Correction of retention time: polywax 655 was dissolved in toluene, and then C12-C20 n-alkane was added as a calibration sample to correct the retention time of the gas chromatogram.
PTV injection port: increasing the temperature from 60 ℃ to 400 ℃ at 400 ℃/min, keeping the temperature for 10min, and reducing the temperature to 60 ℃ at 100 ℃/min.
Gas chromatography working conditions: column, DB-HT simulated distillation column (5m × 0.53mm,0.1 μm); heating at 60 deg.C for 1min, heating to 400 deg.C at 20 deg.C/min, and maintaining for 10 min; carrying gas He, wherein the column flow rate is 16 mL/min; no split-flow injection was performed and the solvent was delayed for 5 min. FID detector, temperature 400 deg.C, hydrogen flow rate 40mL/min, air flow rate 450mL/min, tail gas blowing flow rate 45 mL/min.
4. Gas chromatography-mass spectrometry (GC-MS) analysis of standard samples
Cutting a standard sample, placing the standard sample in a chromatographic bottle, adding about 50 mu L of n-hexane for extraction, separating by using a gas chromatography-mass spectrometry (GC-MS) combined instrument, obtaining a characteristic gas chromatography-mass spectrometry total ion flow graph and mass chromatograms of biomarkers of saturated paraffin (m/z 85), terpene (m/z 191) and sterane (m/z 217) by using a full-scanning and selective ion detection (SIM) mode, and establishing a gas chromatography-mass spectrometry characteristic spectrogram of each oil product based on the original spectrogram and the distribution characteristics of the three biomarkers.
Wherein n-hexane can be replaced by toluene and carbon disulfide.
Gas chromatography working conditions: chromatography column, DB-5MS (30m × 0.25mm,0.25 μm) capillary column; heating, maintaining the initial temperature at 60 deg.C for 2min, heating to 320 deg.C at 10 deg.C/min, and maintaining for 20 min; the temperature of a sample inlet is 300 ℃; carrier gas He, the flow rate is 1.5 mL/min; no split-flow injection was performed and the solvent was delayed for 5 min.
Mass spectrum conditions: EI ion source, wherein the electron energy is 70eV, the scanning range is 45-800 m/z, the ion source temperature is 280 ℃, and the transmission line temperature is 320 ℃; the scanning mode is a full scan and a selective ion Scanning (SIM) mode, and the SIM mode selects m/ z 85, 191 and 217 respectively to carry out the determination of saturated alkane, terpenoid and sterane markers.
5. Analysis and identification of cigarette contaminants
And (3) analyzing and detecting the oil stain sample to be identified in the step (2) to obtain an infrared spectrogram of the sample, comparing the infrared spectrogram of the oil stain sample to be identified with the characteristic infrared spectrogram of each oil product, and primarily screening the pollution source according to the characteristic infrared absorption peak of each oil product. If the characteristics of the oil product are met and the type of the polluted oil product cannot be determined, continuing to perform the analysis and detection of the step 3 and the step 4; if the infrared characteristic absorption peak of the oil product is not consistent, the yellow spots are not caused by oil product pollution.
And (3) respectively carrying out analysis detection in the steps (3) and (4) on the oil stain sample to be identified to obtain a gas chromatography simulated distillation curve and a gas chromatography-mass spectrogram of the sample. Comparing the gas chromatography simulated distillation curve of the sample to be identified with the characteristic simulated distillation curve of each oil product, and judging the type of the polluted oil product by means of visual comparison or similarity calculation of the characteristics such as the position of the bulge, the profile shape, the burr peak and the like; comparing the original spectrogram of the total ion flow of the gas chromatography-mass spectrometry of the oil spot sample to be identified and the quality chromatograms of the three markers with the characteristic spectrums of each oil product respectively, and further confirming the type of the polluted oil product through visual comparison of the distribution characteristics and the content of the characteristic markers.
And identifying the oil product causing oil stain pollution by comprehensively comparing the information consistence of infrared characteristic absorption peaks, simulated distillation curves, distribution characteristics and contents of characteristic markers and the like of the sample to be detected and the standard sample.
The method identifies the oil spots on the surface of the cigarette through the construction and analysis of the oil characteristic fingerprint spectrum, and can quickly and accurately judge the oil source causing the oil spot pollution, so that the using equipment and the application position of the polluted oil are mainly checked, and the support is practically provided for guaranteeing the quality of the cigarette product.
The specific embodiment is as follows:
1. collection of standard oil
According to the actual situation of the production site of a certain brand of cigarettes in a certain cigarette factory, 7 types of lubricating oil products in use are collected, and a standard oil product list is established according to the source and the application position.
2. Preparation of Standard samples
Respectively coating the collected oil products on cigarette paper to prepare standard samples (standard oil products), wherein the size of oil spots is similar to the actual spot size of a sample to be detected, the diameter is about 1-5mm, and the number of the standard samples prepared from each oil product is not less than 10.
3. Establishment of standard sample characteristic map
Performing infrared spectrum scanning (scan range is 4000 cm) on the prepared standard sample by using attenuated total reflection infrared spectrum (ATR)-1～700cm-1) And establishing a characteristic infrared spectrogram of each standard sample oil product. After cutting and extraction, respectively carrying out gas chromatography and gas chromatography-mass spectrometry analysis to obtain a gas chromatogram (characteristic simulation distillation curve) and a gas chromatography-mass spectrogram (including a total ion flow graph and mass chromatograms of three characteristic markers) of each standard sample oil product.
FIG. 1 is an infrared characteristic fingerprint spectrum of oil products of 7 standard samples (the serial numbers are 1#, 2#, 3#, 4#, 5#, 6#, and 7#), and cigarette paper is 3100-4000 cm-1、700～1500cm-1The infrared spectra of 7 standard sample oil products are basically similar after eliminating the interference of the cigarette paper and are 2925cm-1、2855cm-1、2960cm-1And 2870cm-1Has characteristic absorption peaks. Wherein, 2925cm-1And 2855cm-1The two strong absorption peaks of (2) are C-H stretching vibration peaks of methylene, 2960cm-1And 2870cm-1The two absorption peaks are C-H stretching vibration peaks of methyl, which shows that each standard sample oil product contains a large amount of alkane substances with long carbon chains.
Fig. 2 is a gas chromatography characteristic simulated distillation curve of oil products of 7 standard samples (the numbers are 1#, 2#, 3#, 4#, 5#, 6#, and 7#, respectively), the simulated distillation curve difference is large due to the difference of the distribution of different oil product fractions, and the bulge position, the contour shape and the burr peak have remarkable characteristics.
Fig. 3 is a gas chromatography-mass spectrometry characteristic fingerprint of oil products of 7 standard samples (numbered 1#, 2#, 3#, 4#, 5#, 6#, and 7#, respectively), which includes a total ion flow graph and a mass chromatogram of three characteristic markers of saturated paraffin, terpenoid and sterane. The n-alkanes, terpenoids and stanols are different in content and composition in different oils.
Overall, these 7 oils contain predominantly terpenoids and stanols markers, with a relatively low content of saturated paraffins; in the paraffin quality chromatograms of 7 oils, an indistinguishable mixture (UCM) has a great advantage, and the content of saturated paraffin is very low except oil 2# and 5 #; the distribution and content of the terpene alkane and sterane markers of 7 oil products are greatly different and mainly reflected in that: the terpene alkane and sterane markers in oil products 2#, 4#, 5# and 6# are widely distributed and have higher compound content, while the compounds in oil products 1#, 3# and 7# are less distributed and have lower content.
4. Analysis and identification of cigarette pollutants
And (3) cutting a certain batch of finished cigarettes with the oil stain quality defect, and then carrying out attenuated total reflection infrared spectroscopy analysis.
FIG. 4 is an infrared spectrum of 2925cm in the spectrum of the oil spot to be identified-1、2855cm-1、2960cm-1And 2870cm-1Has a characteristic absorption peak, especially 2925cm-1And 2855cm-1The strong absorption peak of C-H stretching vibration of two methylene groups is positioned, which shows that the yellow spots to be detected contain a large amount of organic matters with long carbon chains, which accords with the characteristics of oil spots, but can not determine which kind of oil products.
After the yellow spots are extracted, gas chromatography and gas chromatography-mass spectrometry are adopted for analysis, and the obtained spectrograms are respectively compared with the characteristic spectrogram of a standard sample.
FIG. 5(A) is a gas chromatography simulated distillation curve of oil spots to be identified, which is most similar to oil products No. 2 and No. 6 through visual comparison of the shapes of the simulated distillation curves and similarity calculation of the oil products. The similarity calculation result is shown in figure 5(B), and the similarity of the feature simulation distillation curve of the macular samples to be identified relative to each oil product is calculated by adopting a cosine included angle method.
The similarity calculation method comprises the following steps: introducing gas chromatogram data acquired by GC-FID into Excel, and calculating the similarity of the unknown oil spots to each oil standard map by using XLSSTAT software in Excel through a cosine included angle method.
FIG. 6 is a gas chromatography-mass spectrum of the oil spot to be identified, and according to the total ion flow diagram and the mass chromatogram of the three biomarkers, it can be seen that the overall profile of the oil spot to be identified and the oil product No. 2, and the composition and content of each marker are basically consistent.
And (4) integrating the comparison results to judge that the cigarette oil spots in the batch are pollution caused by the oil product No. 2.
The above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; variations and advantages that may occur to those skilled in the art may be made without departing from the spirit and scope of the inventive concept, which is intended to be covered by the claims.
Claims (10)
1. A method for establishing a characteristic fingerprint spectrum for identifying a cigarette oil stain pollution source in the cigarette production process is characterized by comprising the following steps:
1) preparation of Standard samples
Collecting oil products in the cigarette production process, and respectively coating the oil products on cigarette paper to prepare standard samples; wherein the spot size of the oil spot of the standard sample is similar to that of the oil spot of the sample to be detected;
2) infrared spectroscopic analysis of standard samples
Collecting a microscopic image of the oil stain of the standard sample, carrying out infrared spectrum scanning on the microscopic image of the oil stain of the standard sample, establishing a characteristic infrared spectrogram of the standard sample, and determining a characteristic absorption peak of the standard sample;
3) gas chromatography simulated distillation analysis of standard samples
Cutting standard sample oil spots, placing the standard sample oil spots in a chromatographic bottle, adding an extracting agent for extraction, performing simulated distillation analysis on the standard sample oil spots by adopting a gas chromatograph, and establishing a characteristic gas chromatography characteristic simulated distillation curve of a standard sample;
4) gas chromatography-mass spectrometry analysis of standard samples
Cutting standard sample oil spots, placing the standard sample oil spots in a chromatographic bottle, adding an extracting agent for extraction, separating by using a gas chromatography-mass spectrometer, obtaining a characteristic gas chromatography-mass spectrogram of the standard sample by adopting a full-scanning and ion detection selection mode, wherein the characteristic gas chromatography-mass spectrogram comprises a gas chromatography-mass spectrometry total ion flow diagram and mass chromatograms of three biomarkers of saturated paraffin, terpenes and steranes, and establishing a gas chromatography-mass spectrometry characteristic fingerprint spectrogram of the standard sample, namely the characteristic fingerprint for identifying the cigarette oil spot pollution source in the cigarette production process based on the gas chromatography-mass spectrometry total ion flow diagram and the distribution characteristics of the three markers.
2. The method of claim 1, wherein in step 2), the infrared spectrum is scanned over a range of 4000cm-1～700cm-1The number of scanning times is 32, and the scanning interval is 2cm-1。
3. The establishing method according to claim 1, wherein in step 3) or step 4), the extracting agent is independently selected from one or more of n-hexane, toluene and carbon disulfide.
4. The method for establishing according to claim 1, wherein in the step 3), the conditions of the gas chromatography simulated distillation analysis comprise:
correction of retention time: dissolving Polywax 655 in toluene, adding C12-C20 normal alkane as a calibration sample, and correcting the retention time of the gas chromatogram;
PTV injection port: raising the temperature from 60 ℃ to 400 ℃ at a speed of 400 ℃/min, keeping the temperature for 10min, and lowering the temperature to 60 ℃ at a speed of 100 ℃/min;
gas chromatography working conditions: chromatographic column, DB-HT simulated distillation column; heating at 60 deg.C for 1min, heating to 400 deg.C at 20 deg.C/min, and maintaining for 10 min; carrying gas He, wherein the column flow rate is 16 mL/min; injecting sample without shunting, and delaying solvent for 5 min; FID detector, temperature 400 deg.C, hydrogen flow rate 40mL/min, air flow rate 450mL/min, tail gas blowing flow rate 45 mL/min.
5. The method for establishing, according to claim 1, wherein in step 4), the conditions for gas chromatography-mass spectrometry include:
gas chromatography working conditions: chromatographic column, DB-5MS capillary column; heating, maintaining the initial temperature at 60 deg.C for 2min, heating to 320 deg.C at 10 deg.C/min, and maintaining for 20 min; the temperature of a sample inlet is 300 ℃; carrier gas He, the flow rate is 1.5 mL/min; injecting sample without shunting, and delaying solvent for 5 min;
mass spectrum conditions: EI ion source, wherein the electron energy is 70eV, the scanning range is 45-800 m/z, the ion source temperature is 280 ℃, and the transmission line temperature is 320 ℃; the scanning mode is a full scanning mode and a selective ion scanning mode, and the SIM mode selects m/z 85, 191 and 217 respectively to carry out the determination of saturated alkane, terpene alkane and sterane markers.
6. The method for establishing according to claim 1, wherein in step 4), the three biomarkers of saturated alkane, terpenoid and stanol are specifically: saturated paraffins m/z 85, terpenes m/z 191 and stanols m/z 217.
7. The characteristic fingerprint spectrum for identifying the cigarette oil stain pollution source in the cigarette production process, which is obtained by the establishing method according to any one of claims 1 to 6.
8. Use of a fingerprint according to claim 7 for the identification of a source of oil stain contamination of a cigarette during the manufacture of a cigarette.
9. A method for identifying the source of oil stain contamination using the signature fingerprint of claim 7 comprising the steps of: the method for establishing the standard oil product characteristic fingerprint spectrum according to claim 7, wherein a corresponding spectrum of the oil stain to be detected is determined, and the pollution source of the oil stain to be detected is identified by comparing the corresponding spectrum with the standard oil product characteristic fingerprint spectrum, comprehensively comparing the infrared characteristic absorption peak, the simulated distillation curve and the consistency of the composition and the content of the characteristic marker.
10. The method according to claim 9, characterized in that it comprises in particular the steps of:
i) obtaining an infrared spectrogram of a sample
Comparing the infrared spectrogram of the oil stain sample to be detected with the characteristic infrared spectrogram of each standard oil product, and carrying out primary screening on a pollution source according to the characteristic infrared absorption peak of each standard oil product;
if the infrared characteristic absorption peaks of the oil spots to be detected do not meet the requirement, the yellow spots are not caused by oil product pollution;
if the oil spots to be detected accord with the characteristics of the oil product and the types of the polluted oil product cannot be determined, continuing to perform step ii) gas chromatography simulated distillation analysis and gas chromatography-mass spectrometry analysis;
ii) obtaining a gas chromatography simulated distillation curve and a gas chromatography-mass spectrogram of the oil spot to be detected
Comparing the gas chromatography simulated distillation curve of the oil stain to be detected with the characteristic simulated distillation curve of each standard oil product, and judging the type of the polluted oil product by a method of bump position, profile shape and burr peak comparison or similarity calculation;
further comparing the original spectrogram of the total ion current of the gas chromatography-mass spectrometry of the oil spot sample to be identified and the mass chromatograms of the three markers with the characteristic spectrums of each standard oil product, and further confirming the type of the polluted oil product by comparing the distribution characteristics and the contents of the characteristic markers; wherein, the three markers are: saturated paraffins m/z 85, terpenes m/z 191 and stanols m/z 217.
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