CN115015410A - Method for auxiliary identification of oil stain smoke pollution source - Google Patents
Method for auxiliary identification of oil stain smoke pollution source Download PDFInfo
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- CN115015410A CN115015410A CN202210579245.9A CN202210579245A CN115015410A CN 115015410 A CN115015410 A CN 115015410A CN 202210579245 A CN202210579245 A CN 202210579245A CN 115015410 A CN115015410 A CN 115015410A
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000000779 smoke Substances 0.000 title claims abstract description 77
- 239000010687 lubricating oil Substances 0.000 claims abstract description 138
- 239000007789 gas Substances 0.000 claims abstract description 93
- 239000000523 sample Substances 0.000 claims abstract description 81
- 239000003921 oil Substances 0.000 claims abstract description 78
- -1 sulfur-phosphorus compound Chemical class 0.000 claims abstract description 67
- 238000001765 gas chromatography-flame photometric detection Methods 0.000 claims abstract description 25
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 238000004458 analytical method Methods 0.000 claims abstract description 24
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001228 spectrum Methods 0.000 claims abstract description 17
- 239000003517 fume Substances 0.000 claims abstract description 14
- 239000013074 reference sample Substances 0.000 claims abstract description 14
- 241000208125 Nicotiana Species 0.000 claims description 41
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010586 diagram Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000004071 soot Substances 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 49
- 235000019504 cigarettes Nutrition 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002199 base oil Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000013598 vector Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical class [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8686—Fingerprinting, e.g. without prior knowledge of the sample components
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Abstract
The invention relates to the technical field of identification of pollution sources of oil stain smoke, in particular to a method for assisting in identifying the pollution sources of the oil stain smoke. The method comprises the following steps: taking a similar lubricating oil as a reference sample; dispersing and dissolving each reference sample by using an organic solvent, performing GC/FPD analysis to obtain a gas chromatogram of the sulfur-phosphorus compound corresponding to the similar lubricating oil, and constructing a fingerprint spectrogram library of the sulfur-phosphorus compound of the similar lubricating oil; carrying out similarity comparison on the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oily fume and a fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil, and determining the pollution source of the oily fume according to the comparison result; the gas chromatogram of the sulfur-phosphorus compound comprises a sulfide gas chromatogram and a phosphide gas chromatogram. For the condition that the pollution source cannot be identified by adopting the existing GC/MS fingerprint spectrum method, the method provided by the invention can be adopted to carry out auxiliary judgment on the oil smoke pollution source, and the method has the characteristics of rapidness, accuracy and strong pertinence.
Description
Technical Field
The invention relates to the technical field of identification of pollution sources of oil stain smoke, in particular to a method for assisting in identifying the pollution sources of the oil stain smoke.
Background
The oil-spot cigarette refers to a finished cigarette with oil-spot spots of different areas and shapes on the cigarette paper. The existence of the oily spot smoke seriously affects the image of cigarette production enterprises and the acceptance of consumers on the cigarette quality, and meanwhile, the oily spot smoke can generate unknown harmful substances after burning and even seriously affects the cigarette sensory quality. The lubricating oil for the smoke machine comprises petroleum-produced lubricating oil, artificially synthesized lubricating oil, olive oil, glycerin and the like, and the lubricating oil forms oil stain cigarettes due to phenomena of running, leakage and the like of equipment in the using process.
At present, the tobacco industry mainly adopts infrared spectroscopy and gas chromatography-mass spectrometry to identify the oily mottle smoke. For most lubricating oil for cigarette machines, the basic components and additives of each lubricating oil have certain differences, most lubricating oils can be distinguished by adopting a gas chromatography-mass spectrometry (GC/MS) fingerprint spectrum method, and the source of oil spot smoke can be further identified. But sometimes two or more kinds of cigarette making machine lubricating oil gas chromatography mass spectrometry fingerprint characteristics are similar or basically similar, and the source of the oil stain smoke is difficult to identify only by adopting the gas chromatography mass spectrometry.
Disclosure of Invention
In order to solve or partially solve the problems in the related art, the invention provides a method for assisting in identifying the pollution source of the oil stain smoke.
The invention provides a method for assisting in identifying a pollution source of oil stain smoke, which comprises the following steps:
constructing a fingerprint spectrum library of sulfur and phosphorus compounds of similar lubricating oil:
step a), taking similar lubricating oil as a reference sample; the fingerprint characteristics of the GC/MS total ion flow diagram of the similar lubricating oil are similar;
step a2), dispersing and dissolving each reference sample by using an organic solvent to obtain a corresponding standard sample to be detected;
step a3), carrying out GC/FPD analysis on the standard sample to be detected to obtain a gas chromatogram of the sulfur-phosphorus compound corresponding to the similar lubricating oil, and constructing a fingerprint spectrogram library of the sulfur-phosphorus compound of the similar lubricating oil;
judging the pollution source of the oily spot smoke:
step b1), extracting the cut tobacco of the oily spot tobacco by using the organic solvent to obtain a sample to be detected of the oily spot tobacco;
step b2), adopting the method of the step a3) to carry out GC/FPD analysis on the sample to be detected of the oil stain smoke to obtain a gas chromatogram of a sulfur-phosphorus compound of the sample;
step b3), carrying out similarity comparison on the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oil spot smoke and the gas chromatogram of each sulfur-phosphorus compound of the lubricating oil in the fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil, and determining the pollution source of the oil spot smoke according to the comparison result;
the gas chromatogram of the sulfur-phosphorus compound comprises a sulfide gas chromatogram and a phosphide gas chromatogram.
Further, the organic solvent is a weak polar alkane organic solvent.
Further, the alkane organic solvent with weak polarity is n-hexane and cyclohexane.
Further, the step a2) is specifically as follows: and adding an organic solvent into each reference sample, oscillating, mixing, standing, taking supernatant, and filtering by using an organic phase filter membrane to obtain a corresponding standard sample to be detected.
Further, the step b1) is specifically: and adding the organic solvent into the tobacco shreds of the oil spot tobacco, oscillating, extracting, standing, taking supernatant, and filtering by using an organic phase filter membrane to obtain a sample to be detected of the oil spot tobacco.
Further, the analysis conditions of the GC/FPD analysis in the steps a3) and b2) are as follows:
a chromatographic column: HB-5 Quartz capillary chromatography column, 30m × 0.25mm × 0.25 μm;
carrier gas: helium gas;
column flow rate: 1.0 mL/min;
and (3) sample introduction mode: no flow diversion;
sample introduction amount: 1 mu L of the solution;
detector temperature: 300 ℃;
sample inlet temperature: 300 ℃;
temperature programming: maintaining at 100 deg.C for 1min, heating to 320 deg.C at 10 deg.C/min, and maintaining at 320 deg.C for 6 min;
H 2 flow rate: 60 mL/min;
air flow rate: 60 mL/min;
tail gas blowing flow: 60 mL/min.
Further, in the step b3), similarity comparison is performed by using a correlation coefficient method and/or an included angle cosine method.
Further, the step b3) is specifically as follows:
step b31), visually comparing the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oil stain smoke with the gas chromatogram of each lubricating oil in the fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil according to the characteristic peak position of the sulfur-phosphorus compound to obtain one or more primary selection targets of the lubricating oil;
step b31), calculating the similarity between the sulfur-phosphorus compound gas chromatogram of the sample to be detected of the oily fume and the primary selection target of the lubricating oil by adopting a correlation coefficient method and/or an included angle cosine method, and judging the pollution source of the oily fume according to the result of the similarity.
Further, the step b31) is: and simultaneously, calculating the similarity between the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oil stain smoke and the primary selection target of the lubricating oil by adopting a correlation coefficient method and an included angle cosine method, and judging that the two gas chromatograms have consistency if the similarity results reach more than 90 percent, namely judging the source of the oil stain smoke pollution source.
The method for assisting in identifying the oil stain smoke pollution source provided by the invention has the following beneficial effects:
1. the method takes the sulfur-phosphorus compound contained in most of the lubricating oil base oil or additives as a detection target, utilizes the characteristics of specificity and specificity of the flame photometric detector to the sulfur-phosphorus compound, establishes the fingerprint of the sulfur-phosphorus compound of the lubricating oil by adopting GC/FPD, and assists GC/MS to objectively and accurately identify the source of the cigarette with the cigarette oil spots. Therefore, under the condition that the pollution source cannot be identified by adopting the existing GC/MS fingerprint spectrum method, the method provided by the invention can be adopted to carry out auxiliary judgment on the oil stain smoke pollution source, so that the problem that part of oil stain smoke pollutants cannot be traced is solved, and the method has important significance for perfecting a system for quickly tracking the oil stain smoke pollution source and accurately identifying the source of the oil stain smoke pollution source.
2. The GC/FPD method is simple and convenient to operate, high in sensitivity and strong in specificity, and the method has the characteristics of rapidness, accuracy and strong pertinence in auxiliary identification of the oil stain smoke pollution source;
3. the method selects the tobacco shreds polluted by lubricating oil in the oil-spotted cigarette as the detection material, so as to prepare the liquid to be detected with higher concentration and suitable for detection, thereby being beneficial to accurately tracing the source of the oil-spotted cigarette pollution source.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
FIG. 1 is a gas chromatogram of a phosphorus-containing compound of lubricating oil sample # 1 in example 1 of the present invention
FIG. 2 is a gas chromatogram of a phosphorus-containing compound of lubricating oil sample # 2 of example 1 according to the present invention;
FIG. 3 is a gas chromatogram of a phosphorus-containing compound of a simulated sample A in example 1 of the present invention;
FIG. 4 is a gas chromatogram of sulfur-containing compounds of lubricating oil sample # 3 in example 2 of the present invention;
FIG. 5 is a gas chromatogram of sulfur-containing compounds of lubricating oil sample # 4 in example 2 of the present invention;
FIG. 6 is a gas chromatogram of a sulfur-containing compound of a simulated sample B in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this disclosure and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
It should be understood that although the terms "first", "second", "third", etc. may be used herein to describe various information, these information should not be limited to these terms. These terms are only used to distinguish one type of information from another. For example, first information can also be referred to as second information, and similarly, second information can also be referred to as first information, without departing from the scope of the present invention. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The invention provides a method for assisting in identifying a pollution source of oil stain smoke, which can be used for assisting in judging the pollution source of the oil stain smoke by adopting the method provided by the invention under the condition that the pollution source cannot be identified by adopting the existing gas chromatography-mass spectrometry fingerprint spectrum method, thereby solving the problem that part of oil stain smoke pollutants cannot be traced.
The method for assisting in identifying the oil stain smoke pollution source provided by the embodiment of the invention comprises the following steps:
constructing a fingerprint spectrum library of sulfur and phosphorus compounds of similar lubricating oil:
step a1), taking similar lubricating oil as a reference sample; the fingerprint characteristics of the GC/MS total ion flow diagram of the similar lubricating oil are similar;
step a2), dispersing and dissolving each reference sample by using an organic solvent to obtain a corresponding standard sample to be detected;
step a3), carrying out GC/FPD analysis on the standard sample to be detected to obtain a gas chromatogram of the sulfur-phosphorus compound corresponding to the similar lubricating oil, and constructing a fingerprint spectrogram library of the sulfur-phosphorus compound of the similar lubricating oil;
judging the pollution source of the oily spot smoke:
step b1), extracting the cut tobacco of the oily spot tobacco by using the organic solvent to obtain a sample to be detected of the oily spot tobacco;
step b2), adopting the method in the step a3) to carry out GC/FPD analysis on the sample to be detected of the oily fume to obtain a gas chromatogram of a sulfur-phosphorus compound of the sample;
step b3), carrying out similarity comparison on the sulfur-phosphorus compound gas chromatogram of the sample to be detected of the oily fume and the sulfur-phosphorus compound gas chromatogram of each lubricating oil in the sulfur-phosphorus compound fingerprint spectrogram library of similar lubricating oil, and determining the pollution source of the oily fume according to the comparison result;
the gas chromatogram of the sulfur-phosphorus compound comprises a sulfide gas chromatogram and a phosphide gas chromatogram.
Aiming at the lubricating oil of the cigarette machine with similar or approximately similar GC/MS fingerprint spectra, the inventor considers that most of the lubricating oil base oil or the additive contains various sulfur and phosphorus compounds, and establishes the sulfur and phosphorus compound fingerprint spectra of the lubricating oil by adopting a gas chromatography flame photometric detector (GC/FPD) method by utilizing the characteristics of the specificity and the specificity of the flame photometric detector to the sulfur and phosphorus compounds, thereby assisting the GC/MS to objectively and accurately identify the source of the cigarette oil spot smoke.
Therefore, in the embodiment, firstly, a step of constructing a fingerprint library of sulfur-phosphorus compounds of similar lubricating oil is performed, and firstly, the similar lubricating oil is sampled according to the step a1) to obtain a reference sample, the fingerprint characteristics of the GC/MS total ion flow graph of the similar lubricating oil are similar, and the similar lubricating oil is difficult to distinguish by adopting a conventional GC/MS analysis method.
Step a2) is a step of performing analytical pretreatment on the lubricating oil reference sample, because the lubricating oil is sticky and cannot be directly injected for analysis, the lubricating oil is dissolved and dispersed by using an organic solvent in the step. The organic solvent used in this step is preferably a weakly polar, alkane-based organic solvent. The selection of the alkane organic solvent with weak polarity is beneficial to improving the solubility of the sulfur-phosphorus compound. More preferably, n-hexane and cyclohexane are used. Most preferably, cyclohexane is selected to be slightly more polar.
Step a2) is particularly preferably: and adding an organic solvent into each reference sample, oscillating, mixing, standing, taking supernatant, and filtering by using an organic phase filter membrane to obtain a corresponding standard sample to be detected. Further, the mixing ratio of the reference sample to the organic solvent was 1g: (400 ml-600 ml), more preferably 1g: 500 ml. The step of shaking and mixing may specifically be: oscillating and mixing for 10-30 min at the rotating speed of 100-140 r/min.
Obtaining standard samples to be detected of all similar lubricating oil after the step a2), and then analyzing according to the step a3) to construct a sulfur-phosphorus compound fingerprint spectrum library. Sulfur and phosphorus compounds are not easy to detect on a gas chromatography mass spectrometer, and a Flame Photometric Detector (FPD) is a selective detector with strong specificity to sulfur and phosphorus compounds, and has the advantages of high sensitivity and strong specificity. Therefore, in the step, a gas chromatography flame photometric detector (GC/FPD) method is adopted to analyze the standard sample to be detected so as to obtain the gas chromatograms of the sulfur and phosphorus compounds corresponding to different lubricating oils. As can be understood by those skilled in the art, for each lubricating oil sample, the gas chromatogram of the sulfur compound and the gas chromatogram of the phosphorus compound can be obtained through GC/FPD analysis, and then a lubricating oil sulfide gas chromatography fingerprint spectrum library and a lubricating oil phosphide gas chromatography fingerprint spectrum library are established, which are collectively called a lubricating oil sulfur-phosphorus compound fingerprint spectrum library.
In step a3), the analysis conditions for the GC/FPD analysis are preferably as follows:
a chromatographic column: HB-5 Quartz capillary chromatography column, 30 m.times.0.25 mm.times.0.25 μm
Carrier gas: helium gas;
column flow rate: 1.0 mL/min;
and (3) sample introduction mode: no flow diversion;
sample introduction amount: 1 mu L of the solution;
detector temperature: 300 ℃;
sample inlet temperature: 300 ℃;
temperature programming: maintaining at 100 deg.C for 1min, heating to 320 deg.C at 10 deg.C/min, and maintaining at 320 deg.C for 6 min;
H 2 flow rate: 60 mL/min;
air flow rate: 60 mL/min;
tail gas blowing flow: 60 mL/min.
By setting the analysis conditions, the various sulfur-phosphorus compounds can achieve relatively good separation degree, and the lubricating oil can be conveniently distinguished.
After establishing a sulfur-phosphorus compound fingerprint spectrum library of similar lubricating oil, the step of judging the pollution source of the oil stain smoke can be carried out, and the pollutants are also required to be pretreated firstly so as to be convenient for subsequent analysis and sample injection. Considering that the lubricating oil usually pollutes the cigarette by the migration of cut tobacco to cigarette paper, and the oil content in the polluted cut tobacco is far higher than that in the oil spot of cigarette paper, the invention preferably selects the cut tobacco polluted by the lubricating oil in the oil spot cigarette as the analysis object. Step b1) is particularly preferably: adding the organic solvent used in the step a2) into the cut tobacco of the oily spot tobacco, oscillating, extracting, standing, taking supernatant, and filtering by using an organic phase filter membrane to obtain a sample to be detected of the oily spot tobacco. Further, the mixing ratio of the tobacco shreds to the organic solvent is 1g: (80 ml-120 ml), more preferably 1g:100 ml. The oscillating extraction steps can be specifically as follows: oscillating and extracting for 10min to 30min at the rotating speed of 100r/min to 140 r/min.
After the sample to be detected of the oily fume is obtained in the step b2), the GC/FPD is carried out on the oily fume according to the method in the step a3) to obtain a sulfide gas chromatogram and a phosphide gas chromatogram of the oily fume. It will be appreciated by those skilled in the art that the conditions for analysis of the GC/FPD in this step should be the same as in step a 3). And (3) obtaining a gas chromatogram of a sulfur-containing compound and a gas chromatogram of a phosphorus-containing compound of each sample to be detected of the oil soot.
The gas chromatogram of the sulfur-phosphorus compound of the oily spot smoke can be obtained through the step b2), then the similarity comparison is carried out on the gas chromatogram of the sulfur-phosphorus compound of the oily spot smoke and the fingerprint spectrogram library of the sulfur-phosphorus compound of the lubricating oil according to the step b3), and the pollution source of the oily spot smoke can be determined according to the comparison result. Similar lubricating oils which are not easily distinguished on GC/MS may have differences on sulfide gas chromatograms, may also have differences on phosphide gas chromatograms or have certain differences between the two, and similar lubricating oils can be effectively distinguished by comparing the different sulfide gas chromatograms or phosphide gas chromatograms. The step b3) may specifically be: comparing the similarity of the sulfide gas chromatogram of the sample to be detected of the oil stain smoke with the sulfide gas chromatograms of all lubricating oils in the fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil; or comparing the similarity of the phosphide gas chromatogram of the sample to be detected of the oil stain smoke with the phosphide gas chromatogram of each lubricating oil in the fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil; or comparing the similarity of the sulfide gas chromatogram and the phosphide gas chromatogram of the sample to be detected of the oil stain smoke with the similarity of the sulfide gas chromatogram and the phosphide gas chromatogram of each lubricating oil in the fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil; determining a pollution source of the oily spot smoke according to the comparison result;
preferably, the step adopts a correlation coefficient method and/or an included angle cosine method to carry out similarity comparison.
Further, b3) may be specifically:
step b31), visually comparing the sulfur-phosphorus compound gas chromatogram of the sample to be detected of the oil stain smoke with the sulfur-phosphorus compound gas chromatograms of all lubricating oils in a sulfur-phosphorus compound fingerprint spectrogram library of similar lubricating oils according to the characteristic peak position of the sulfur-phosphorus compound to obtain one or more lubricating oil primary selection targets;
step b32), calculating the similarity between the sulfur-phosphorus compound gas chromatogram of the sample to be detected of the oily fume and the primary selection target of the lubricating oil by adopting a correlation coefficient method and/or an included angle cosine method, and judging the pollution source of the oily fume according to the result of the similarity.
In the step b31), the visually comparing the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oil smoke with the gas chromatogram of the sulfur-phosphorus compound of each lubricating oil in the fingerprint spectrogram library of the sulfur-phosphorus compound of the similar lubricating oil can specifically be:
visually comparing the sulfide gas chromatogram of the sample to be detected of the oil stain smoke with the sulfide gas chromatograms of all lubricating oils in the fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil; or visually comparing the phosphide gas chromatogram of the sample to be detected of the oil stain smoke with phosphide gas chromatograms of various lubricating oils in a sulfur-phosphorus compound fingerprint spectrogram library of similar lubricating oils; or visually comparing the sulfide gas chromatogram and phosphide gas chromatogram of the sample to be detected of the oil stain smoke with the sulfide gas chromatogram and phosphide gas chromatogram of each lubricating oil in a sulfur-phosphorus compound fingerprint spectrogram library of similar lubricating oil;
the correlation coefficient method and the included angle cosine method belong to different similarity calculation methods and can reflect the similar situation of spectrograms from different angles, and are common methods for evaluating the similarity between two spectrograms. The correlation coefficient method compares whether the two vectors are on the same straight line, namely the correlation coefficient (r) among 2 vectors is used for reflecting the similarity degree among samples, and the calculation method is shown in a formula (1); the cosine of the included angle (cos theta) method reflects the similarity of the samples by comparing cosine values of the included angle between vectors, and the calculation method is shown in a formula (2).
In formula (1) and formula (2): r is a correlation coefficient; cos theta is the cosine of the included angle; x is the number of i The peak area is the peak area of the characteristic peak of the standard sample to be detected; y is i The peak area of the characteristic peak of the sample to be detected for the oil smoke; let the number of characteristic peaks i equal to 1, 2, …, n.
The judgment rule may specifically be: and if the similarity result reaches more than 90%, the two gas chromatograms are consistent, and the source of the oil stain smoke pollution source can be judged.
Because the characteristic peaks in the gas chromatogram of the sulfur-phosphorus compound of part of the lubricating oil samples are more and concentrated, in order to improve the accuracy of similarity judgment, the similarity between the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oil smoke and the primary selection target of the lubricating oil is preferably calculated by simultaneously adopting a correlation coefficient method and an included angle cosine method, and the similarity results reach more than 90 percent, and then the two gas chromatograms are considered to have consistency, so that the source of the oil smoke pollution source can be judged.
From the above, the method for assisting in identifying the pollution source of the oil smoke provided by the embodiment of the invention has the following advantages:
1. the method takes the sulfur-phosphorus compound contained in most of the lubricating oil base oil or additives as a detection target, utilizes the characteristics of the specificity and specificity of the flame photometric detector to the sulfur-phosphorus compound, establishes a sulfur-phosphorus compound fingerprint spectrum library of the lubricating oil by adopting a GC/FPD method, and assists GC/MS to objectively and accurately identify the source of the cigarette with the oil spots. Therefore, under the condition that the pollution source cannot be identified by adopting the existing GC/MS fingerprint spectrum method, the method provided by the invention can be adopted to carry out auxiliary judgment on the oil stain smoke pollution source, so that the problem that part of oil stain smoke pollutants cannot be traced is solved, and the method has important significance for perfecting a system for quickly tracking the oil stain smoke pollution source and accurately identifying the source of the oil stain smoke pollution source.
2. The GC/FPD method is simple and convenient to operate, high in sensitivity and strong in specificity, and the method has the characteristics of rapidness, accuracy and strong pertinence in auxiliary identification of the oil stain smoke pollution source;
3. the method selects the tobacco shreds polluted by the lubricating oil in the oil-spotted cigarette as the detection material to prepare the liquid to be detected with higher concentration and suitable for detection, thereby being beneficial to accurately tracing the source of the oil-spotted cigarette pollution source.
4. Furthermore, the similarity between the oil stain smoke and the lubricating oil fingerprint spectrum is calculated by simultaneously utilizing a correlation coefficient method and an included angle cosine method, so that mutual verification of similarity results is facilitated, and the accuracy of identifying the oil stain smoke source is improved.
The technical scheme of the invention is further explained by combining specific examples as follows:
example 1
2 cigarette machine lubricating oil samples of 1# and 2# are selected from a cigarette production workshop, GC/MS analysis is carried out on the 2 lubricating oil samples, and from a GC/MS total ion flow diagram, the GC/MS fingerprint characteristics of the two lubricating oil samples are very similar, namely, the 1# lubricating oil and the 2# lubricating oil are the similar lubricating oil, and cannot be distinguished.
Weighing 0.1g of each of the 2 similar lubricating oil samples, adding 50.0mL of cyclohexane into a 100mL triangular flask with a plug, oscillating and extracting for 20min at the rotating speed of 120r/min, standing, filtering supernatant liquid by an organic phase filter membrane, and performing GC/FPD analysis on filtrate to obtain sulfide gas chromatography fingerprints and phosphide gas chromatography fingerprints of the lubricating oil samples. FIG. 1 is a gas chromatogram of a phosphorus-containing compound of a No. 1 lubricating oil sample, FIG. 2 is a gas chromatogram of a phosphorus-containing compound of a No. 2 lubricating oil sample, and it is obvious from FIGS. 1 and 2 that gas chromatogram fingerprint characteristics of the phosphorus-containing compounds of the No. 1 and No. 2 lubricating oil samples are obviously different and can be used for rapidly and accurately identifying the source of oil speckle.
Randomly selecting a lubricating oil from the No. 1 and No. 2 samples, adding the lubricating oil into cut tobacco of a cigarette according to a certain amount to prepare a simulated sample A, placing the cut tobacco added with the lubricating oil for 24 hours, manually rolling the cut tobacco into a cigarette, balancing the cut tobacco in a constant temperature and humidity box for 48 hours, peeling the cigarette, taking cut tobacco polluted by the lubricating oil (namely soft parts in the cut tobacco) after air drying, treating the cut tobacco polluted by the lubricating oil according to the pretreatment method, and obtaining a chromatogram of the simulated sample A of the oil spot cigarette after GC/FPD analysis. And simultaneously, GC/FPD analysis is carried out on blank cut tobacco, and no interference exists in the peak retention time of the target compound. FIG. 3 is a gas chromatogram of a phosphorus-containing compound in a simulated sample A, and the simulated sample is visually and preliminarily judged to contain 1# lubricating oil by comparing FIG. 1 with FIG. 2.
Similarity of the simulated sample A and the No. 1 lubricating oil map is calculated by adopting a correlation coefficient method and an included angle cosine method, the correlation coefficient and the included angle cosine of the simulated sample A and the No. 1 lubricating oil map are respectively 96.1% and 97.6%, and the fact that the simulated sample A really contains the No. 1 lubricating oil and oil stain smoke is polluted by the No. 1 lubricating oil is verified.
Example 2
2 cigarette machine lubricating oil samples of 3# and 4# are selected from a cigarette production workshop, the 2 lubricating oil samples are subjected to GC/MS analysis, and from a GC/MS total ion flow diagram, the GC/MS fingerprint characteristics of the two lubricating oil samples are very similar, namely 3# lubricating oil and 4# lubricating oil are similar lubricating oil, and cannot be distinguished.
Weighing 2 similar lubricating oil samples 0.1g in each of 100mL triangular flasks with stoppers, adding 50.0mL cyclohexane, performing oscillation extraction at a rotation speed of 120r/min for 20min, standing, filtering supernatant with an organic phase filter membrane, and performing GC/FPD analysis on the filtrate to obtain sulfide gas chromatography fingerprints and phosphide gas chromatography fingerprints of the lubricating oil samples. Fig. 4 is a gas chromatogram of sulfur-containing compounds of # 3 lubricating oil sample, and fig. 5 is a gas chromatogram of sulfur-containing compounds of # 4 lubricating oil sample. From fig. 4 and fig. 5, it is obvious that the gas chromatography fingerprints of the sulfur-containing compounds of the samples # 3 and # 4 are obviously different, and can be used for quickly and accurately identifying the source of the oily fume.
Randomly selecting one lubricating oil from the No. 3 and No. 4 lubricating oil samples, adding the lubricating oil into cut tobacco of a cigarette according to a certain amount to prepare a simulated sample B, placing the cut tobacco added with the lubricating oil for 24 hours, manually rolling the cut tobacco into a cigarette, balancing the cut tobacco in a constant temperature and humidity box for 48 hours, peeling off the cigarette, taking cut tobacco (namely soft parts in the cut tobacco) polluted by the lubricating oil after air drying, treating the cut tobacco polluted by the lubricating oil according to the pretreatment method, and analyzing by GC/FPD to obtain a chromatogram map of the oily spot cigarette simulated sample B. And simultaneously, GC/FPD analysis is carried out on blank cut tobacco, and no interference exists in the peak retention time of the target compound. FIG. 6 is a gas chromatogram of a sulfur-containing compound of a simulated sample B, and the simulated sample is visually and preliminarily judged to contain # 3 lubricating oil by comparing FIG. 4 with FIG. 5.
And (3) calculating the similarity of the maps of the simulated sample B and the 3# lubricating oil by adopting a correlation coefficient method and an included angle cosine method to obtain that the correlation coefficient and the included angle cosine of the simulated sample B are respectively 91.7 and 97.4 percent, and confirming that the simulated sample B really contains the 3# lubricating oil and the oil stain smoke is polluted by the 3# lubricating oil.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (9)
1. A method for assisting in identifying a source of oil smoke pollution, comprising:
constructing a fingerprint spectrum library of sulfur and phosphorus compounds of similar lubricating oil:
step a), taking similar lubricating oil as a reference sample; the fingerprint characteristics of GC/MS total ion flow diagrams of the similar lubricating oil are similar;
step a2), dispersing and dissolving each reference sample by using an organic solvent to obtain a corresponding standard sample to be detected;
step a3), carrying out GC/FPD analysis on the standard sample to be detected to obtain a gas chromatogram of the sulfur-phosphorus compound corresponding to the similar lubricating oil, and constructing a fingerprint spectrogram library of the sulfur-phosphorus compound of the similar lubricating oil;
judging the pollution source of the oily spot smoke:
step b1), extracting the cut tobacco of the oily spot tobacco by adopting the organic solvent to obtain a sample to be detected of the oily spot tobacco;
step b2), adopting the method in the step a3) to carry out GC/FPD analysis on the sample to be detected of the oily fume to obtain a gas chromatogram of a sulfur-phosphorus compound of the sample;
step b3), carrying out similarity comparison on the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oil spot smoke and the gas chromatogram of each sulfur-phosphorus compound of the lubricating oil in the fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil, and determining the pollution source of the oil spot smoke according to the comparison result;
the gas chromatogram of the sulfur-phosphorus compound comprises a sulfide gas chromatogram and a phosphide gas chromatogram.
2. The method for assisting in identifying the pollution source of the oil smoke according to claim 1, wherein the organic solvent is a low-polarity alkane organic solvent.
3. The method for assisting in identifying the pollution source of the oil smoke according to claim 2, wherein the alkane organic solvent with weak polarity is n-hexane and cyclohexane.
4. The method for assisting in identifying the pollution source of the oil smoke according to claim 1, wherein the step a2) is specifically as follows: and adding an organic solvent into each reference sample, oscillating, mixing, standing, taking supernatant, and filtering by using an organic phase filter membrane to obtain a corresponding standard sample to be detected.
5. The method for assisting in identifying the pollution source of the oil smoke according to claim 1, wherein the step b1) is specifically as follows: and adding the organic solvent into the tobacco shreds of the oil spot tobacco, oscillating, extracting, standing, taking supernatant, and filtering by using an organic phase filter membrane to obtain a sample to be detected of the oil spot tobacco.
6. The method for assisting in identifying the pollution source of the oil smoke according to claim 1, wherein the analysis conditions of the GC/FPD analysis in the steps a3) and b2) are as follows:
a chromatographic column: HB-5 Quartz capillary chromatography column, 30m × 0.25mm × 0.25 μm;
carrier gas: helium gas;
column flow rate: 1.0 mL/min;
and (3) sample introduction mode: no flow diversion;
sample injection amount: 1 mu L of the solution;
detector temperature: 300 ℃;
sample inlet temperature: 300 ℃;
temperature programming: maintaining at 100 deg.C for 1min, heating to 320 deg.C at 10 deg.C/min, and maintaining at 320 deg.C for 6 min;
H 2 flow rate: 60 mL/min;
air flow rate: 60 mL/min;
tail gas blowing flow: 60 mL/min.
7. The method for assisting in identifying the pollution source of the oil smoke according to claim 1, wherein in the step b3), a correlation coefficient method and/or an included angle cosine method are used for similarity comparison.
8. The method for assisting in identifying the pollution source of the oil smoke according to claim 7, wherein the step b3) is specifically as follows:
step b31), visually comparing the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oil stain smoke with the gas chromatogram of each lubricating oil in the fingerprint spectrogram library of the sulfur-phosphorus compound of similar lubricating oil according to the characteristic peak position of the sulfur-phosphorus compound to obtain one or more primary selection targets of the lubricating oil;
and b31), calculating the similarity between the sulfur-phosphorus compound gas chromatogram of the sample to be detected of the oil stain smoke and the primary selection target of the lubricating oil by adopting a correlation coefficient method and/or an included angle cosine method, and judging the pollution source of the oil stain smoke according to the similarity result.
9. The method for assisting in identifying the source of soot contamination according to claim 8, wherein the step b31) is: and simultaneously, calculating the similarity between the gas chromatogram of the sulfur-phosphorus compound of the sample to be detected of the oil stain smoke and the primary selection target of the lubricating oil by adopting a correlation coefficient method and an included angle cosine method, and judging that the two gas chromatograms have consistency if the similarity results reach more than 90 percent, namely judging the source of the oil stain smoke pollution source.
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