CN115406974A - Method for rapidly detecting polycyclic aromatic hydrocarbon - Google Patents
Method for rapidly detecting polycyclic aromatic hydrocarbon Download PDFInfo
- Publication number
- CN115406974A CN115406974A CN202110578147.9A CN202110578147A CN115406974A CN 115406974 A CN115406974 A CN 115406974A CN 202110578147 A CN202110578147 A CN 202110578147A CN 115406974 A CN115406974 A CN 115406974A
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- polycyclic aromatic
- supercritical
- chromatography
- liquid chromatography
- phase liquid
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/89—Inverse chromatography
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
A method for rapidly detecting polycyclic aromatic hydrocarbons in a grease sample with high sensitivity comprises the following steps: performing component separation on the grease sample diluent by using supercritical chromatography, removing nonpolar interfering components in the grease sample, and keeping polycyclic aromatic hydrocarbons in the grease sample in a chromatographic column of the supercritical chromatography; introducing the polycyclic aromatic hydrocarbons retained in a chromatographic column of the supercritical chromatogram into a reversed-phase liquid chromatogram through an automatic valve switching technology so as to detect one or more polycyclic aromatic hydrocarbons, wherein a flowing phase in the supercritical chromatogram comprises a supercritical fluid and a modifier, and the modifier is a substance for adjusting the polarity of the supercritical fluid.
Description
Technical Field
The invention relates to the field of (qualitative/quantitative) detection of chemical substances, in particular to separation of fat-soluble components from a fat sample, and especially relates to a method and a device for separating fat-soluble polycyclic aromatic hydrocarbon(s) from the fat sample.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) are ubiquitous persistent environmental pollutants, some PAHs have carcinogenicity and genetic toxicity, and even PAHs without carcinogenicity can be used as a cancer promoter, thereby causing serious harm to human health.
Because PAHs are lipophilic, fats and oils such as edible oils are easily contaminated during production, processing and transportation. In the case of benzo (a) pyrene (B α P), which is a strong carcinogen, it is easily present in fats and oils due to its strong lipid solubility. Among them, edible vegetable oils are susceptible to the influence of processes, environments, or packaging materials, and the like, and thus are likely to contain such substances.
At present, certain exploration and standardization are carried out on the content of benzo (a) pyrene in the detection of oil products. Typically, for example, GB/2762-2017 (national food safety Standard-limit of contaminants in food) states that the limit of benzopyrene in fats and oils and their products is below 10 ug/kg. European Union EC Regulation 835/2011 specifies that the amount of benzo (a) pyrene in fats and oils other than cacao butter and coconut oil is limited to 2. Mu.g/kg, and 4 kinds of PAHs (benzo (a) anthracene, perylene, and perylene),
The sum of benzo (b) fluoranthene and benzo (a) pyrene)<10μg/kg。
At present, gas chromatography-mass spectrometry combined method and liquid chromatography fluorescence detection method have been tried in detection of PAHs in oil and fat. For example:
a standard for detecting polycyclic aromatic hydrocarbons, which specifies a method for liquid chromatography measurement of polycyclic aromatic hydrocarbons (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo [ a ] anthracene, benzo [ b ] fluoranthene, benzo [ k ] fluoranthene, anthracene, benzo [ a ] pyrene, indeno [1,2,3-c, d ] pyrene, dibenzo [ a, h ] anthracene and benzo [ g, h, i ] perylene in food and a method for gas chromatography-mass spectrometry measurement of aromatic hydrocarbons in food, is disclosed in cited document 1.
Citation 2 is a conventional detection method for benzo (a) pyrene in oil and fat, and mainly uses a gas chromatography-mass spectrometry combination method, a liquid chromatography-fluorescence detection method and a liquid chromatography tandem mass spectrometry method. Among them, the liquid chromatography-fluorescence detection method is a main detection method in the existing effective standard detection method due to its high sensitivity and good reproducibility.
However, in any method, complicated pre-treatment including liquid-liquid extraction, solid-phase extraction, gel permeation and the like is required for the oil sample, which is not only tedious and time-consuming, but also has high solvent toxicity, and has the problems of large error, unstable recovery rate and the like due to multiple operation steps. Therefore, many front-line inspectors perform various attempts and hope to establish a simpler and faster pretreatment method.
For example, the method of online solid-phase extraction disclosed in citation 3 simplifies the pretreatment process to some extent, improves the automation degree of grease sample analysis, but still uses a large amount of organic solvent, and the analysis time of each sample exceeds 80 minutes, so that rapid and environment-friendly detection cannot be really realized.
Citations 4 and 5 disclose methods of purifying a sample to be tested using a solid phase extraction cartridge (SPE) including a special packing; citation 6 discloses a method for purifying a sample to be tested using a gel chromatography column (GPC); further, cited document 7 discloses a method of directly dissolving a sample using tetrahydrofuran.
However, in the methods using SPE and GPC, the overall operation is still complicated, time-consuming and labor-consuming, and in fact, the optimization is not sufficient to simplify the pretreatment process of the sample to be tested. The method of directly dissolving and sampling by using tetrahydrofuran also has the problems of compatibility of the solubility of the grease sample and the mobile phase and short service life of the chromatographic column.
Therefore, from the conventional detection means, there is still room for further improvement in the convenience of pretreatment of the oil and fat sample and in the improvement of the rapidity and reliability of benzopyrene detection.
Citations
Citation 1: GB 5009.265-2016 determination of polycyclic aromatic hydrocarbons in national food Standard for food safety
Citation 2: GB/5009.27-2016 national food safety Standard determination of benzo (alpha) pyrene in food
Cited document 3: on-line solid phase extraction-high performance liquid chromatography for detecting 15+1 EU optimal control Polycyclic Aromatic Hydrocarbons (PAHs) in edible oil, rong Chun bud, and the like, "analytical chemistry", 2015, 43 (11), 1743-1748
Citation 4: CN106501411A
Citation 5: li Sheng pottery, etc., the HPLC-FLD method for the solid phase extraction pretreatment of the HiCapt Benzo is used for detecting Benzo (a) pyrene in the oil-tea camellia seed oil, and the science and technology of food industry, 2016, 37 (8), 7-80.
Citation 6: house aroma, and the like, and the quantitative analysis of benzopyrene in the vegetable oil by combining gel chromatography purification and ultra-high performance liquid chromatography, the journal of Chinese food and oil academy of sciences, 2018, 33 (9), 131-134.
Citation 7: jiangxuan and the like, "research on determination of benzopyrene in vegetable oil by reversed phase high performance liquid chromatography", journal of food science and technology, 2017, 35 (5), 91-94.
Disclosure of Invention
Problems to be solved by the invention
In view of the defects existing in the detection means in the field, the technical problem to be solved by the invention is to provide a proven and feasible method for simply detecting polycyclic aromatic hydrocarbons in grease. Particularly, the invention aims to provide a method for simultaneously detecting various polycyclic aromatic hydrocarbons contained in grease. Compared with the prior art, the method of the invention does not need to carry out complex pretreatment on the sample to be detected.
In addition, the technical problem to be solved by the invention is to provide a method for rapidly (automatically) and simultaneously detecting multiple polycyclic aromatic hydrocarbons in grease, and compared with the prior art, the method can obviously save labor and time.
In addition, the technical problem to be solved by the present invention is to provide a reliable method for detecting multiple polycyclic aromatic hydrocarbons in oils and fats, which has excellent recovery rate for each polycyclic aromatic hydrocarbon, and has equivalent or improved detection accuracy and sensitivity compared with the prior art.
Meanwhile, the technical problem to be solved by the invention is to provide a method for rapidly detecting multiple polycyclic aromatic hydrocarbons in grease with small environmental burden.
In addition, the technical problem to be solved by the present invention is to provide a method for producing oil, especially vegetable oil, by using the polycyclic aromatic hydrocarbon detection method of the present invention on line in oil production, real-time content of various polycyclic aromatic hydrocarbons in oil production is monitored, so as to adjust production process and/or control parameters quickly and timely.
Means for solving the problems
According to the long-term research of the inventor of the present invention, the following technical scheme is implemented to solve the technical problems:
[1] the invention firstly provides a method for detecting polycyclic aromatic hydrocarbon in grease, which comprises the following steps:
performing component separation on a grease sample by using supercritical chromatography, removing non-polar components in the grease sample, and keeping one or more polycyclic aromatic hydrocarbons in the grease sample in a chromatographic column of the supercritical chromatography;
introducing the polycyclic aromatic hydrocarbon remaining in the chromatographic column of the supercritical chromatography into a reversed phase liquid chromatography to detect the polycyclic aromatic hydrocarbon,
the polycyclic aromatic hydrocarbon comprises a hydrocarbon compound having two or more aromatic rings in the molecular structure,
the fluid phase in the supercritical chromatography comprises a supercritical fluid and a modifier,
the modifier is a substance for adjusting the polarity of the supercritical fluid.
[2] The method according to [1], wherein the polycyclic aromatic hydrocarbon includes a hydrocarbon compound having 3 to 10 aromatic rings in a molecular structure.
[3] The method according to [1] or [2], wherein 4 or more kinds of polycyclic aromatic hydrocarbons are simultaneously detected in the detection of the polycyclic aromatic hydrocarbons.
[4]According to [1]]Or [2]]The method described above, wherein in the detection of the polycyclic aromatic hydrocarbon, the polycyclic aromatic hydrocarbon to be simultaneously detected at least comprises benzo (a) anthracene,
Benzo (b) fluoranthene and benzo (a) pyrene.
[5] The method according to [1] or [2], wherein the supercritical fluid comprises supercritical carbon dioxide; the modifier is selected from alcohols, nitriles or their water solution.
[6] The method according to [1] or [2], wherein the stationary phase in the supercritical chromatography is selected from silica gel modified with a polar group selected from a hydroxyl group, an amino group or a cyano group.
[7] The method according to [1] or [2], wherein the supercritical chromatography comprises a supercritical chromatography column; the reverse phase liquid chromatography comprises one or more reverse phase liquid chromatography columns.
[8] The method according to [1] or [2], wherein the reversed-phase liquid chromatography comprises a stationary phase and a mobile phase, the stationary phase is selected from silica gel modified by hydrophobic groups, the hydrophobic groups are selected from hydrocarbon groups, and the mobile phase is selected from polar organic solvents or aqueous solutions thereof.
[9] The method according to [1] or [2], wherein the supercritical chromatography and the reverse phase liquid chromatography are connected by a connecting means.
[10] The method according to [1] or [2], wherein the polycyclic aromatic hydrocarbon retained by the column of the supercritical chromatography is transferred to a reverse phase liquid chromatography by the modifier, and the supercritical fluid flowing out of the supercritical chromatography is removed in the reverse phase liquid chromatography.
[11] The method according to [1] or [2], wherein the reverse phase liquid chromatography includes a first reverse phase liquid chromatography column and a second reverse phase liquid chromatography column at a rear end of the first reverse phase liquid chromatography column, and the polycyclic aromatic hydrocarbon is detected after passing through the second reverse phase liquid chromatography column.
[12] The method according to [11], wherein the supply of the critical fluid in the supercritical chromatography is stopped, and the polycyclic aromatic hydrocarbon retained by the column of the supercritical chromatography is caused to be transferred into the first reverse phase liquid chromatography only by the modifier (the pressure of the pressure control unit is adjusted accordingly), and further, the polycyclic aromatic hydrocarbon is washed into the second reverse phase liquid chromatography by the mobile phase of the reverse phase liquid chromatography.
[13] The method according to [1] or [2], wherein before the component separation of the oil sample by the supercritical chromatography, a step of diluting the oil sample is further included.
[14] The method according to [1] or [2], wherein the polycyclic aromatic hydrocarbon is detected using a fluorescence detector.
[15] The invention further provides a method for producing a fat, which comprises the following steps:
a step of on-line monitoring of the content of one or more polycyclic aromatic hydrocarbons in oil production, which comprises the method according to any one of the above [1] to [14 ];
and determining to adjust or not to adjust the oil production process and/or control parameters according to the detected content of the polycyclic aromatic hydrocarbon.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention provides a novel detection method for detecting one or more polycyclic aromatic hydrocarbons in grease, and by implementing the technical scheme, the following technical effects can be obtained:
(1) The detection method provided by the invention can be used for simultaneously and rapidly detecting various polycyclic aromatic hydrocarbons, and the detection efficiency is greatly improved.
(2) According to the method disclosed by the invention, the detection results of the detection of various polycyclic aromatic hydrocarbon components in the grease have good linear correlation coefficients, good reproducibility and high recovery rate, and compared with the prior art, the method also has the same or improved detection precision and sensitivity, and provides effective reference for food safety detection.
(3) When polycyclic aromatic hydrocarbons in a grease sample are detected, a complex pretreatment means is not required for the sample, and the sample is not required to be purified by using a large amount of solvents or chromatographic columns in a pretreatment process like the conventional method, so that the convenience of detection can be effectively improved, manpower and material resources are saved, the discharge of waste is reduced, the environmental burden is reduced, and the analysis cost is also reduced;
(4) The invention can realize rapid and automatic detection by combining the supercritical chromatography and the reversed phase liquid chromatography, greatly improves the detection efficiency, and can obviously reduce the time required by the detection compared with the prior art (generally speaking, the total detection time including the sample preparation time in the invention can be controlled within the time of not more than 90min or 60min even if 10-20 polycyclic aromatic hydrocarbons are detected simultaneously);
(5) The detection method provided by the invention (when being used together with other detection devices) can be used for monitoring whether the oil product contains polycyclic aromatic hydrocarbon on line in the oil production and even monitoring the real-time content of the oil product, so that the production process can be adjusted in time, and the quality stability and reliability of the oil production can be ensured.
Drawings
FIG. 1: a schematic diagram of an analytical system in one embodiment of the present invention;
FIG. 2 is a schematic diagram: the invention is a first working channel schematic diagram (thick line) of the analysis system;
FIG. 3: the second working path of the analysis system of the invention is shown schematically (bold line);
FIG. 4 is a schematic view of: the third working path of the analysis system of the invention is schematically illustrated (bold line);
FIG. 5: assay results for standard samples (standard curve).
FIG. 6: detection map of embodiment 2 of the invention
Description of the reference numerals
11: supercritical fluids (CO) 2 ) Supply pump
12: liquid phase pump (methanol) 13: automatic sample injector
14: supercritical fluid chromatography column (diol group) 15: detector (diode array detector)
16: pressure control unit (backpressure control unit)
21: liquid phase pump (acetonitrile) 22: reversed phase liquid chromatography column (C18)
23: reversed phase liquid chromatography column (C18)
24: detector (FID)
41-46: six-way valve group V1
W: waste liquid/waste gas outlet
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, "benzopyrene", "benzo (a) pyrene" and "(B α P)" mean the same substance and have the same meaning.
In the present specification, the numerical range represented by "numerical value a-numerical value B" means a range including the end points of numerical values a and B.
The use of "%" means volume percent, i.e., "V%" unless otherwise specified.
The term "communicate" as used herein means that a plurality of devices or components are connected so as to form a passage for a mobile phase, a component to be measured, or waste/exhaust gas.
The term "switching" as used herein refers to, for example, switching of a multi-way valve block to cut off an originally communicating passage and to communicate between originally cut-off devices or components.
The supercritical fluid chromatography column, the one or more reverse phase liquid chromatography columns involved in the multi-dimensional chromatography system of the invention are in self-evident communication with a pump feeding the mobile phase during operation of the system to provide a corresponding mobile phase and/or modifier in the mobile phase in the respective chromatography apparatus.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the term "optional" or "optional" is used to indicate that certain substances, components, performance steps, application conditions, and the like are used or not used.
In the specification, the unit names used are all international standard unit names.
In the present specification, the term "plurality" means two or more than two unless otherwise specified.
Reference in the specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "embodiments," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< first aspect >
In a first aspect of the invention, there is provided a method for detecting one or more polycyclic aromatic hydrocarbons in a fat, comprising: and (3) performing component separation on the grease sample by using supercritical chromatography, so that the polycyclic aromatic hydrocarbon in the grease sample is retained in a chromatographic column of the supercritical chromatography, and simultaneously, the nonpolar component in the grease is removed. Here, the nonpolar component refers to a component in the oil and fat having a polarity less than that of the polycyclic aromatic hydrocarbon, particularly a component that may affect or interfere with the detection of the polycyclic aromatic hydrocarbon.
Grease
The fat or oil suitable for use in the present invention is not particularly limited, and may include a mixed fat or oil of one or more of vegetable oil and animal oil.
For the vegetable oils that can be detected, in some specific embodiments, one or more of rice oil, sunflower oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, linseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, hemp seed oil, jojoba oil, olive oil, cocoa butter, chinese tallow tree seed oil, almond oil, tung seed oil, rubber seed, corn germ oil, wheat germ oil, sesame seed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, linseed oil, glass chicory seed oil, sea buckthorn seed oil, tomato seed oil, macadamia nut oil, coconut oil are included. In some preferred embodiments, the vegetable oil of the present invention is preferably peanut oil, soybean oil, or olive oil.
For animal oils that can be detected, in some specific embodiments, one or more of tallow, lard, mutton fat, chicken bouillon, fish oil, seal oil, whale oil, dolphin's oil, oyster sauce, lanolin is included.
Further, the above-mentioned arbitrary kind of fat or oil mixture may be a freshly obtained fat or oil, for example, one obtained by chemical impregnation or one obtained by pressing; or used fats and oils such as heated and fried fats and oils; but also grease in use.
Due to the convenience of detection, the detection method is particularly suitable for detecting the polycyclic aromatic hydrocarbon in the vegetable oil or the blend oil formed by various vegetable oils.
The present invention is not particularly limited with respect to the pretreatment of the oil sample before detection, and for example, some pretreatment methods for removing interfering components that have been disclosed in the art may be employed. Of course, as mentioned above, the method provided by the present invention can provide a highly reliable detection result even without these pretreatments, and at the same time, improve the detection efficiency.
In other embodiments, the grease sample of the present invention may be subjected to a simple pretreatment, such as dilution of the grease sample to reduce the viscosity of the grease sample, to facilitate detection. The solvent that can be used for dilution is not particularly limited, and one or more of a hydrocarbon solvent, an ester solvent, an ether solvent, and a ketone solvent can be used. Preferably, a hydrocarbon solvent such as n-hexane is used. The amount of the diluent used is not particularly limited, and may be adjusted depending on the physical properties of the fat or oil. In some preferred embodiments of the present invention, the volume ratio of the grease sample to the diluent may be 1. For the diluted grease sample, the detection can be directly carried out according to the method of the invention.
Polycyclic aromatic hydrocarbons
Polycyclic Aromatic Hydrocarbons (PAHs) generally refer to aromatic compounds containing two or more aromatic rings.
In general, PAHs are volatile hydrocarbons generated when organic substances such as coal, petroleum, wood, tobacco, organic high molecular compounds and the like are incompletely combusted, and are important environmental and food pollutants. More than 200 PAHs have been discovered so far, and there still exist species which have not been recognized, and a considerable part of these compounds have carcinogenicity, such as benzo [ a ] pyrene, benzo [ α ] anthracene, etc.
In some specific embodiments of the present invention, the present invention is directed to aromatic hydrocarbon compounds having 2 or more basic aromatic rings (the ring having the least number of carbon atoms is the basic ring) in the molecular structure of the polycyclic aromatic hydrocarbon. These aromatic rings may be aromatic rings having 5 or more carbon atoms, and there may be mentioned, for example, aromatic rings having 5 carbon atoms or aromatic rings having 6 or more carbon atoms. The upper limit of the number of carbon atoms in the aromatic ring is not particularly limited in principle, and the upper limit of the number of carbon atoms in these basic aromatic rings may be 10 from the viewpoint of the possibility of existence.
In addition, they have a certain weak polarity to these polycyclic aromatic hydrocarbons. In some cases, some of the aromatic rings of these polycyclic aromatic hydrocarbons are linked by single bonds or by sharing two or more carbon atoms. In addition, these polycyclic aromatic hydrocarbon compounds may have non-aromatic carbocyclic rings of 5 or 6 carbon atoms between (as the basic rings) the aromatic rings. Further, these aromatic hydrocarbon compounds may have a substituent, and specific types of the substituent are not particularly limited, and may be, for example, an alkyl group having 1 to 6 carbon atoms.
In some preferred embodiments of the present invention, the polycyclic aromatic hydrocarbon molecule has a structure having 3 to 10 aromatic rings, more preferably 4 to 8 aromatic rings, and still more preferably 4 to 6 aromatic rings.
In some other preferred embodiments of the present invention, the aromatic ring is an aromatic ring having 5 and/or 6 carbon atoms, and more preferably the aromatic ring is a benzene ring.
As the polycyclic aromatic hydrocarbon suitable for the detection method of the present invention, typical examples of the polycyclic aromatic hydrocarbon include: naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, benzo (c) fluorene, pyrene, benzo (a) anthracene, anthracene,
5-methyl radical
Benzo (J) fluoranthene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, dibenzo (a, h) anthracene, dibenzo (a, l) pyrene, benzo (g, h, i) perylene, indeno (1, 2,3-c, d) pyrene, dibenzo (a, e) pyrene, dibenzo (a, h) pyrene, dibenzo (a, i) pyrene, and the like.
With respect to the polycyclic aromatic hydrocarbon of the present invention, by using the method of the present invention which will be described later, one or more compounds can be detected at one time of detection. In some preferred embodiments, the detection method of the present invention can detect 4 or more than 4 polycyclic aromatic hydrocarbon compounds. The upper limit of the number of polycyclic aromatic hydrocarbon compounds that can be simultaneously detected is not particularly limited, and in some specific embodiments, the upper limit of the number of polycyclic aromatic hydrocarbons that can be simultaneously detected may be 25, and from the viewpoint of detection efficiency and reliability, the upper limit of the number of polycyclic aromatic hydrocarbons that can be simultaneously detected may be preferably 20, and more preferably 18.
In other preferred embodiments, the detection method of the present invention can be used for detecting 4 to 16 polycyclic aromatic hydrocarbons; in a further preferred embodiment, the detectable polycyclic aromatic hydrocarbon of the invention comprises at least benzo (a) anthracene,
Benzo (b) fluoranthene andbenzo (a) pyrene. Furthermore, in some embodiments, polycyclic aromatic hydrocarbon content in the sample tested can be assessed by benzo (a) pyrene content. In other embodiments, the detection of the benzo (a) anthracene,
The total content of the four species, benzo (b) fluoranthene and benzo (a) pyrene, was evaluated for the polycyclic aromatic content in the samples tested. Of course, it is understood that the polycyclic aromatic hydrocarbon content of the samples tested can be more fully and accurately assessed by simultaneously detecting more polycyclic aromatic hydrocarbons.
In some embodiments of the invention, for peaks in a spectrum obtained from a single test sample, the compounds corresponding to those peaks can be determined by comparison with standard retention times for the compounds (e.g., retention times tested for standard solutions). And the channels of the detector described below or the time control program of the frequency conversion of the detector (excitation and detection) can be adjusted/calibrated according to the retention properties of these compounds.
Of course, in some cases, peaks at positions not recorded in the standard list may also appear upon detection, and for these substances, if desired, may be determined by using other devices in combination, such as mass spectrometers and the like.
Analysis system
The analysis system used for the detection method of the present invention includes a supercritical chromatography device and a reverse phase chromatography device and a detector, and they are connected by using a connecting device.
(supercritical chromatography)
Supercritical Fluid Chromatography (SFC) uses a fluid including a supercritical fluid as a mobile phase, which is a chromatographic process for separation and analysis depending on the solvating power of the mobile phase.
Supercritical fluid chromatography has the characteristics of both gas chromatography and liquid chromatography. It can analyze the sample with high boiling point and low volatility which is not suitable for gas chromatography, and has faster analysis speed and better condition than high performance liquid chromatography. In the invention, a supercritical chromatographic column is used for pre-cleaning a sample solution, i.e. the nonpolar components of the grease sample to be detected are removed.
The supercritical chromatography column of the present invention may be a packed column, and in some embodiments, a packed column supercritical fluid chromatography system (pcscfc) is preferred.
The stationary phase in the supercritical chromatographic column is selected from polar group modified silica gel, and for the polar group, one or more of hydroxyl, amino or cyano can be selected. In some preferred embodiments, hydroxyl groups are preferred as the modifying groups, in view of the retention time required to allow for suitable polycyclic aromatic hydrocarbons when the sample solution is pre-washed using a supercritical chromatography column. More specifically, the stationary phase in the supercritical chromatography column in the present invention may preferably use a diol-based silica gel. Which is bonded using an organosilane containing a 1, 2-dihydroxypropyl functional group. In addition, the stationary phase is a spherical silica gel which may be porous.
The mobile phase in the supercritical chromatography column in the present invention comprises a supercritical fluid, which is a state of a substance at a critical temperature and a critical pressure or higher, which is between a gas and a liquid. Suitable supercritical fluids may be supercritical carbon dioxide or supercritical ethane, etc.
In some preferred embodiments of the invention, the supercritical fluid is selected from supercritical carbon dioxide. The operating temperature and pressure are largely determined by the supercritical fluid selected. In the present invention, when supercritical carbon dioxide is used as the supercritical fluid, the operating temperature is 31 ℃ or higher, preferably 35 ℃ or higher, and the operating pressure is 7.3MPa or higher, preferably 7.5MPa or higher. The operating temperature is preferably 40 to 60 ℃ and the operating pressure is preferably 7.5 to 15MPa from the viewpoint of the degree of solvation of the polycyclic aromatic hydrocarbon by the supercritical fluid, the retention time, and the operability.
In the present invention, a modifier is used as a substance for adjusting the polarity of the supercritical fluid. The modifier may be selected from alcohols or nitriles. As the alcohol substance, various aliphatic alcohols such as methanol and isopropyl alcohol; for nitriles, acetonitrile or the like can be used as a modifier. The amount (relative flow rate) of the modifier used may be usually 10% or less of the supercritical fluid. In the present invention, the amount of the modifier used is preferably 6% or less, more preferably 3% or less, specifically, 0%,1%,2%, 2.5% or the like of the supercritical fluid, from the viewpoint of controlling the retention time of the polycyclic aromatic hydrocarbon. From the viewpoint of controlling the retention time, a modifier (aqueous) solution having a modifier content of 80% or more, preferably 90% or more, and more preferably 100% can be used as the modifier.
The supercritical fluid and modifier of the invention may be fed to the chromatography column by a pump, preferably as separate CO 2 Supplying supercritical fluid by a pump; for the supply of the modifier, in some embodiments of the invention, the supply may be by a liquid phase pump with a flow regulating valve or by separate liquid phase component supply pumps. Additionally, in some specific embodiments, the supercritical chromatography column of the present invention may be placed in a column incubator.
Furthermore, in performing some modes of operation, the supercritical chromatography may also be connected or in communication with the auxiliary detector and the pressure control unit by means of connecting means. In some embodiments, a pressure control unit is disposed at the end of the supercritical chromatography section for removing supercritical fluid and waste/off-gas; the auxiliary detector is not particularly limited, and is disposed before the pressure control unit, and can detect various components eluted from the column, and in particular, can detect an outflow signal of any polycyclic aromatic hydrocarbon, thereby determining the minimum retention time of various polycyclic aromatic hydrocarbons in the sample solution. The secondary detector may be a diode array detector or a Mass Spectrometry (MS) detector, preferably a diode array detector.
The supercritical chromatography system used in the present invention is commercially available, and may be, for example, a "Nexera UC" supercritical chromatography system manufactured by shimadzu corporation.
After a to-be-detected grease sample is added into the supercritical chromatographic device through the automatic sampling device, the supercritical chromatographic device is started, and through adjustment of the composition and the flow rate of a mobile phase, nonpolar components in the grease which possibly interfere with polycyclic aromatic hydrocarbon detection are quickly eluted from the chromatographic column, so that various polycyclic aromatic hydrocarbons, especially target polycyclic aromatic hydrocarbons are kept on the chromatographic column. As previously mentioned, these non-polar components are less polar than the polycyclic aromatic hydrocarbon to be detected.
In the step, the rapid pre-cleaning of the grease sample is completed by using the supercritical chromatography, so that the nonpolar interference components can be simply and conveniently removed.
(connecting device)
In the present invention, different operation modes or operation paths can be formed by connecting the supercritical chromatography and the reverse phase chromatography, the detector, and the like by using a connecting device and providing a communication manner by the connecting device.
In the present invention, the preferred connection means may be a manifold block. After treatment by supercritical chromatography, after removal of the apolar oily components and before the (earliest) retention time of the polycyclic aromatic hydrocarbon has been reached, the analytical system is switched to reverse phase liquid chromatography operation.
The manifold is not particularly limited, and various types of manifold for sample introduction which are conventional in liquid chromatography can be used. Preferably, a six-way or ten-way valve block is used in the present invention, and more preferably a six-way valve block may be used. Different channels or working paths can be realized by different switching operations of the multi-way valve group, and the multi-way valve group is particularly suitable for communication and control among various devices.
(reverse phase liquid chromatography)
In the present invention, the reversed phase liquid chromatography section includes one or more reversed phase liquid chromatography columns. In some embodiments, these reverse phase liquid chromatography columns are placed in a column oven at the time of use. In addition, in some preferred embodiments of the present invention, the reversed phase liquid chromatography column of the present invention has a length of 30 to 300mm and an inner diameter of 1.5 to 5mm in view of improving a linear range of detection (limit of quantitation LOQ) and a limit of detection (LOD). In addition, if a plurality of reverse phase liquid chromatography columns are used, the length of the reverse phase liquid chromatography column for performing the final separation of various polycyclic aromatic hydrocarbons is preferably 120 to 180mm, and the inner diameter is preferably 1.5 to 2.5mm.
The stationary phase in the reversed phase liquid chromatography column of the present invention may be silica gel modified with hydrophobic groups, which may be various hydrocarbon groups such as C8 group, C18 group, phenyl group, or the like. In some embodiments of the invention, a C18-modified silica gel is used as the stationary phase. As the mobile phase, a polar organic solvent or an aqueous solution thereof, such as alcohols or nitriles, may be used. As the alcohol, various aliphatic alcohols such as methanol and isopropyl alcohol; for nitriles, acetonitrile and the like may be used, and in some embodiments, the mobile phase may be used in the form of an aqueous solution, for example, methanol or acetonitrile.
In the case of using as an aqueous solution, the content of the polar organic solvent in the mobile phase should be 60% or more, preferably 80% or more, more preferably 90% or more, from the viewpoint of shortening the retention time. In some preferred embodiments of the present invention, the mobile phase in reverse phase liquid chromatography contains 70% to 100% acetonitrile for the purpose of improving the linear range of detection (limit of quantitation LOQ) and limit of detection (LOD). Also, in some embodiments of the invention, a gradient elution may be used for the use of the mobile phase in one or more of the reverse phase liquid chromatographs described above. For example, the gradient rinsing mode is set according to actual detection or adjustment, and the liquid is supplied by a liquid pump with a flow control valve or a plurality of individual liquid component supply pumps.
In some embodiments of the invention, the reverse phase liquid chromatography portion may comprise only one chromatography column. As described above, after the supercritical chromatography is processed, the supercritical chromatography is connected in series with the reversed-phase liquid chromatography by switching the multiway valve bank (after the supercritical chromatography is processed, the liquid outlet of the supercritical chromatography column is disconnected from the auxiliary detector and the pressure control unit, and the liquid outlet of the supercritical chromatography column is connected with the liquid inlet of the reversed-phase liquid chromatography through the multiway valve bank). At this time, the reverse phase liquid chromatography end may also be switched or connected to the above mentioned pressure control unit connection.
After the switching of the chromatographic column, the various polycyclic aromatic hydrocarbons originally retained in the supercritical chromatographic column are continuously washed by the modifier, and in some preferred embodiments, from the viewpoint of improving elution efficiency, the flow rate of the modifier can be increased at this time, so that the polycyclic aromatic hydrocarbons with low polarity can be more quickly eluted from the supercritical chromatographic column. For example, the flow rate of the modifier may be increased to 0.6 to 1.3mL/min. At this time, the polycyclic aromatic hydrocarbon remaining in the supercritical chromatography column can be eluted (only) by the flow of the modifier so as to be introduced into the reverse phase liquid chromatography section through the multi-port valve block together with the supercritical fluid remaining in the system.
At this time, since the end of the reverse phase liquid chromatography column is already connected to the pressure control unit, the supercritical fluid can be separated out in a supercritical state using the pressure control unit. In such a process, the state of other mobile phases or components is not affected, i.e., in the reverse phase liquid chromatography, the mobile phase flowing out from the supercritical chromatography is removed.
And (3) introducing a mobile phase into the reversed-phase liquid chromatographic column by using a liquid phase pump while or after removing the supercritical fluid. In the invention, because the supercritical fluid phase from the supercritical chromatography is removed, and only the weakly polar component to be separated and the modifier with polarity are reserved in the reversed phase liquid chromatography, the polar mobile phase can be directly introduced into the reversed phase liquid chromatography column, thereby solving the problem of unmatched mobile phases when different types of chromatographic columns are switched.
When the polar mobile phase is introduced into the reversed phase liquid chromatographic column system again, the polycyclic aromatic hydrocarbon with weak polarity can be separated and detected. That is, in the above-mentioned reversed phase liquid chromatography, a mobile phase is further introduced to separate substances present in the reversed phase liquid chromatography, and the separated polycyclic aromatic hydrocarbon component or components are obtained.
In addition, when the above-described processing is executed, particularly after the supercritical mobile phase derived from the supercritical chromatogram is completely removed by the pressure control means, the reverse phase liquid chromatogram may be disconnected from the pressure control means, and the reverse phase liquid chromatogram may be connected to the detector by switching the multi-port valve block. At this time, the polycyclic aromatic hydrocarbon component separated as described above may be detected and analyzed using a detector.
In other embodiments of the invention, more than one column may be included in the reverse phase liquid chromatography portion. In typical embodiments, the reverse phase liquid chromatography portion may comprise two chromatography columns which may be formed in series.
When two reversed-phase chromatographic columns which can form series connection are used for separating components of a sample to be detected by using supercritical chromatography, after nonpolar oily substances are removed, the supply of a supercritical fluid phase is stopped, and a modifier is continuously introduced, so that the chromatographic columns can be switched by means of the multi-way valve bank in a mode of increasing the flow velocity of the introduced modifier, and the polycyclic aromatic hydrocarbon with weak polarity remained in the supercritical chromatographic columns is conveyed to the first reversed-phase liquid chromatographic column.
Further, the first reverse phase liquid chromatography column end is connected to a pressure control unit, and the supercritical mobile phase fed into the column is removed.
And then, switching is carried out again through the multi-way valve group, and the first reversed-phase liquid chromatography column is disconnected from the pressure control unit and is communicated with the second reversed-phase liquid chromatography column.
When the steps are carried out, a liquid phase pump is started at the same time of or after the supercritical fluid phase is removed, a polar mobile phase is conveyed into the first reversed-phase liquid chromatographic column, after the first reversed-phase liquid chromatographic column and the second reversed-phase liquid chromatographic column are communicated, the polycyclic aromatic hydrocarbon with weak polarity retained in the first reversed-phase liquid chromatographic column is further washed into the second reversed-phase liquid chromatographic column, and one or more polycyclic aromatic hydrocarbons are separated and detected in the second reversed-phase liquid chromatographic column.
For each polycyclic aromatic hydrocarbon separated in the second reversed-phase liquid chromatography, analysis and detection can be performed using a detector connected in series with the column.
The first and second reversed-phase liquid chromatography columns above may be the same or different. In a preferred embodiment of the invention, the two are different, for example the second reverse phase liquid chromatography column is longer than the first reverse phase liquid chromatography column. Such a design makes it easier to wash the less polar substances in the first reversed phase liquid chromatography column and improves the accuracy of the separation in the second reversed phase liquid chromatography column. Therefore, the first reversed-phase liquid chromatographic column can be regarded as a pretreatment column of the second reversed-phase liquid chromatographic column, and the main effects of the first reversed-phase liquid chromatographic column include polycyclic aromatic hydrocarbon enrichment and supercritical mobile phase removal, and the stability and the accuracy of detection of the latter chromatographic column are improved.
(Detector)
In the present invention, one or more polycyclic aromatic hydrocarbons separated from the reverse phase liquid chromatography are detected by a detector for qualitative or quantitative analysis. The present invention uses a fluorescence detector (FID) from the viewpoint of improving the accuracy of detection and the detection limit.
In some specific embodiments of the invention, the fluorescence detector can provide excitation wavelengths in different wavelength ranges and correspondingly detection wavelengths (compound emission wavelengths) in different wavelength ranges in order to address the detection of multiple polycyclic aromatic hydrocarbons. The excitation wavelength may be, for example, in the range of 200 to 350nm, preferably 230 to 320nm; the detection wavelength may be, for example, in the range of 330 to 520nm, preferably 350 to 510nm.
In addition, in some preferred embodiments of the present invention, the detector can perform multi-channel detection, each channel can have different emission/detection wavelengths, and the detector detection can operate at a preset time level, so that different substances can be detected in a targeted manner at different times.
(other auxiliary devices)
In the present invention, any other auxiliary equipment required in the art other than the above-described devices can be used without limitation.
Typically, the ancillary equipment will be containers for supercritical fluids, modifiers, polar solvents and power equipment (typically pumps) to supply these reagents to other detection means, and sample loading means, typically an autosampler or the like. Regarding the capacity of the auto-sampler, the capacity of the auto-sampler is more than 10 μ L, preferably 15 μ L or more, in view of improving the linear range (limit of quantitation LOQ) and the limit of detection (LOD) of the detection of the present invention.
In addition, as described above, in the supercritical chromatography, an auxiliary detector and a pressure control unit are optionally used. The auxiliary detector that can be used may be a diode array detector, a mass spectrometer detector, or the like, but a diode array detector is more preferable from the viewpoint of improving the detection efficiency. The pressure control unit is not particularly limited, and is mainly used for assisting the condition control of the supercritical fluid, and in some preferred embodiments, the pressure control unit may be selected from a back pressure control unit BPR.
In addition, the polycyclic aromatic hydrocarbon detection method can be carried out manually, or can be carried out in a semi-automatic or full-automatic mode.
In a semi-automatic or full-automatic mode, a method file of workstation software can be used for automatic control, and after a sample is loaded, a working channel or a combination of the working channel and the working channel is automatically controlled according to the property of the sample, so that an automatic, simple and convenient automatic (on-line) detection method is realized. The automatic control software applicable to the system of the present invention is not particularly limited, and a control program commonly used in the art or a program written in situ according to the actual condition of the device may be used.
Mode of operation
Hereinafter, typical operation modes and operation paths occurring in the detection method of the present invention will be described in detail with reference to the drawings. In particular, the mode of operation when using two reverse phase liquid chromatography columns is illustrated by figures 1-4 of the accompanying drawings.
In particular, FIG. 1 shows the overall detection system of the present invention. According to the invention, different working passages (the passage conditions are shown by thick lines in figures 2-4) are formed in an analysis system by switching the multi-way valve bank, so that the analysis and detection of polycyclic aromatic hydrocarbon in a grease sample are simply and conveniently realized. In some specific embodiments of the invention, the set of valves is designated as a multi-way valve set V1.
(first working channel)
In the invention, the first working channel can be used for preprocessing a sample by switching the multi-way valve group V1. Specifically, under the working channel, the automatic sample introduction device is communicated with the supercritical fluid chromatographic column, and the supercritical fluid chromatographic column is communicated with the auxiliary detector, the pressure control unit and the waste liquid/waste gas outlet through the multi-way valve group V1.
As shown in fig. 2, the first working path of the present invention may include communicating the auto-sampler 13, the supercritical fluid chromatographic column 14, the multi-port valve block V1 (41 and 46 ports), the auxiliary detector 15, the pressure control unit 16, and the waste/exhaust gas outlet W, and the liquid phase pumps 11 and 12 supply carbon dioxide and the modifier methanol, respectively; wherein the liquid phase pump 12 is provided with a flow regulating valve to adjust the composition of the modifying agent, although two liquid phase pumps providing water and modifying agent respectively may be used instead of the liquid phase pump 12 in some embodiments.
The first working channel is used for eluting nonpolar components in the grease sample to be detected so as to prevent the components from interfering the detection of polycyclic aromatic hydrocarbon. In addition, the polycyclic aromatic hydrocarbon retention time (shortest retention time) can be determined by an auxiliary detector, and before the retention time of the polycyclic aromatic hydrocarbon is reached, the first working channel is ended, and the second working channel is entered by switching the multi-way valve bank.
(second working channel)
In the present invention, at the end of the first working path, the weakly polar polycyclic aromatic hydrocarbon or hydrocarbons are retained on the supercritical fluid chromatography column. In some cases, these less polar substances include not only the fat-soluble component to be measured but also other less polar components. When the second working channel is switched, the weak polar substance is only conveyed to the reversed phase chromatographic column through the modifier in the supercritical fluid chromatography.
In the case of the above-mentioned less polar substances including polycyclic aromatic hydrocarbons, to the reversed phaseAfter liquid chromatography, preferably, supercritical CO derived from supercritical fluid chromatography in the system can be separated in a second working path 2 Removed (from the waste/exhaust outlet via the pressure control unit).
Thus, in some preferred embodiments of the present invention, typically, as shown in fig. 3, the second working channel may communicate the auto-sampler 13, the supercritical fluid chromatography column 14, the multi-port block V1 (41 and 42 interfaces), the reverse phase liquid chromatography column 22, the multi-port block V1 (45 and 46 interfaces), the auxiliary detector 15, the pressure control unit 16, and the waste/exhaust gas outlet W.
(third operation path)
The third working channel in the present invention can be formed by changing the above-described second working channel (see fig. 4), i.e., shutting off the communication of 41 and 42 in the multi-port block V1, while shutting off the communication of 45 and 46 in the multi-port block V1. Meanwhile, the reversed phase liquid chromatography column 22, the multi-way valve group V1 (interfaces 45 and 44), the reversed phase liquid chromatography column 23 and the detector 24 are communicated to form a passage. The mobile phase delivered by the liquid phase pump 21 can be supplied to the third working passage through the multi-port valve group V1 (43 and 42).
The polycyclic aromatic hydrocarbon is transferred from the reversed phase liquid chromatographic column 22 to the reversed phase liquid chromatographic column 23 through the third working path, and then is separated and detected under the action of the mobile phase. Preferably, the mobile phase at this time may be a polar solvent such as methanol, acetonitrile or an aqueous solution thereof. From the viewpoint of increasing the limit of quantitation and the limit of detection, the mobile phase is preferably acetonitrile or an aqueous solution containing acetonitrile in an amount of 70% to 80%. Wherein, for the liquid phase pump providing the mobile phase, the liquid phase pump 21 is provided with a flow regulating valve to adjust the composition of the mobile phase, and of course, two liquid phase pumps providing water and polar solvent respectively may be used instead of the above liquid phase pump 21 in some specific embodiments. The feed rate of the mobile phase may be 0.6 to 1.5mL/min, preferably 0.8 to 1.2mL/min, in view of the compatibility between the supercritical chromatography and the reversed-phase liquid chromatography.
The invention has surprisingly found that the detection method of the invention not only has excellent detection convenience and reliability for single polycyclic aromatic hydrocarbon, such as benzopyrene, but also can carry out qualitative detection rapidly and reliably even if a plurality of polycyclic aromatic hydrocarbons are detected simultaneously, which is really beyond the prior detection method.
Furthermore, the method for detecting polycyclic aromatic hydrocarbons in the grease provided by the invention can be used together with any other detection instrument, such as a mass spectrum detector, and feasibility is provided for rapid quantitative detection of conventional harmful polycyclic aromatic hydrocarbon substances in the grease.
< second aspect >
In a second aspect of the present invention, a method for producing oil, especially an on-line monitoring method for detecting whether polycyclic aromatic hydrocarbons are contained or their contents in the oil production process, is provided.
The method can quickly and accurately detect the polycyclic aromatic hydrocarbon content in the grease sample. Therefore, the oil production process can realize real-time online monitoring of the oil in any process step.
The production process itself of the oil or fat is not particularly limited, and there are some methods for producing vegetable oils, such as chemical immersion, squeezing, and enzymatic hydrolysis. Of course, the production process of the grease also includes a regeneration process of the grease.
The monitoring means is not particularly limited. In some embodiments of the invention, the monitoring location may be located at any suitable location in the grease production process. And meanwhile, corresponding sampling devices are arranged at the positions, and automatic sampling is carried out at certain intervals. Such sampling may be performed continuously, and the required interval time is not particularly limited and may be determined according to the conditions of the actual production process. And detecting the automatically sampled sample by using the method disclosed by the invention, so as to obtain the real-time polycyclic aromatic hydrocarbon containing condition of the grease in the sampling position.
And comparing with the preset value of product quality management to determine whether the grease at the positions meets the standard requirement. If the standard requirements are not met, the corresponding process can be adjusted to ensure that process control can obtain qualified grease.
Examples
The embodiment verifies the effectiveness and the analysis accuracy of the detection method, and the method is used for carrying out quantitative analysis on the grease containing some current commercial products.
< chemicals and reagents >
Methanol (LC-MS grade) and n-hexane (HPLC grade) (HPLC grade from Thermo Fisher Scientific).
Carbon dioxide (CO) 2 The purity is more than or equal to 99.99 percent, china Beijing).
Acetonitrile, LC-MS grade, commercially available (HPLC grade, from Thermo Fisher).
< Instrument >
The experiment was performed using a Nexera UC system, shimadzu corporation (Kyoto house, japan);
a fluorescence detector: RF-20A XS, shimadzu Corp, kyoto, japan;
LC-30AD SF CO 2 pump, LC-30AD pump, SIL-30AC autosampler (20 μ L), CTO-20AC column oven, SPD M20A diode array detector (with high voltage detection cell), and an SFC-30A Back Pressure Regulator (BPR).
In addition, a high-pressure six-way valve is arranged in the column incubator and used for switching chromatographic columns.
SFC mode inspection of SFC columns (4.6 mm. Times.250 mm; 5 μm) for pre-separation, the material was UC-X Diol (Diol based). Short C18 column (VP-ODS, 4.6 mm. Times.50 mm; 5 μm). A long C18 column (2.1 mm. Times.150 mm; 5 μm) was used to separate the polycyclic aromatic hydrocarbons.
All columns were purchased from Shimadzu (Shanghai) laboratory instruments, inc.
Example 1
The detection of benzopyrene in the test sample was evaluated according to the following method.
< preparation of Standard sample >
A mother liquor containing a known benzopyrene content was used, and diluted by adding n-hexane to obtain standard samples having concentrations of 0.05ppb, 0.1ppb, 0.5ppb, 1ppb, 5ppb, 10ppb, 20ppb, 50ppb, 100ppb, and 200ppb, respectively, for detection.
< test results >
The standard sample was tested using the system shown in fig. 1 (sequentially passing through the first, second and third working paths described above), and processed to obtain a standard curve as shown in fig. 5, and the linear range, limit of quantitation (LOQ) and limit of detection (LOD) are shown in table 1 below.
Table 1:
table 2 below shows the results of the test of the present invention compared to the prior art test:
table 2:
| Method | detection limit,. Mu.g/kg |
| GB/T 22509-2008 | 0.1 |
| GB 5009.27-2016 | 0.2 |
| Prior document 1 | 0.04 |
| Prior document 2 | 0.2 |
| The SFC-LC-FID of the invention | 0.1 |
Note:
prior art document 1: determination of benzopyrene in vegetable oil by liquid extraction-reversed phase high performance liquid chromatography, pentagon et al, CHINA OILS AND FATS, 2018 Vol.43 No.10.
Prior art document 2: "high performance liquid chromatography for determining benzopyrene content in wild camellia oil", haoyuan Yuan, physical and chemical examination-chemistry Manual, 2018, volume 54.
The detection method provided by the invention not only obviously simplifies the pretreatment means, reduces the detection time to be within 30min, but also has a wide linear range, and the detection limit can reach or exceed the existing detection method.
In addition, as shown in table 3 below, the process of the present invention has a good recovery rate.
Table 3:
application example 1
Further, using the method of the present invention, various commercially available oils were tested and the results are shown in table 4 below:
table 4:
example 2：
The detection system of the invention is used for analyzing 16 PAHs standard mixed solutions:
the system leaching conditions are as follows in table 5:
TABLE 5
The detection was performed under the above-mentioned elution conditions, and the chromatogram of the detection result is shown in FIG. 6, and the peak appearance is shown in Table 6.
Table 6:
the following test samples were prepared by diluting an oil sample (olive oil as a base oil) containing polycyclic aromatic hydrocarbons with 10-fold n-hexane, and the results are shown in table 7:
table 7:
the above examples 1 and 2 show that the invention can rapidly detect one or more polycyclic aromatic hydrocarbons simultaneously, and the detection result has good precision and reliability.
Industrial applicability
The method for detecting benzopyrene can be used for industrially detecting the grease sample.
Claims (15)
1. A method for detecting polycyclic aromatic hydrocarbons in grease is characterized by comprising the following steps:
performing component separation on a grease sample by using supercritical chromatography, removing non-polar components in the grease sample, and keeping one or more polycyclic aromatic hydrocarbons in the grease sample in a chromatographic column of the supercritical chromatography;
introducing the polycyclic aromatic hydrocarbon remaining in the chromatographic column of the supercritical chromatography into a reversed phase liquid chromatography to detect the polycyclic aromatic hydrocarbon,
the polycyclic aromatic hydrocarbon comprises a hydrocarbon compound having two or more aromatic rings in the molecular structure,
the fluid phase in the supercritical chromatography comprises a supercritical fluid and a modifier,
the modifier is a substance for adjusting the polarity of the supercritical fluid.
2. The method of claim 1, wherein the polycyclic aromatic hydrocarbon comprises a hydrocarbon compound having from 3 to 10 aromatic rings in the molecular structure.
3. The method according to claim 1 or 2, wherein 4 or more polycyclic aromatic hydrocarbons are detected simultaneously in the detection of the polycyclic aromatic hydrocarbon.
4. The method according to claim 1 or 2, wherein in the detection of the polycyclic aromatic hydrocarbon, the polycyclic aromatic hydrocarbon detected simultaneously at least comprises benzo (a) anthracene,
Benzo (b) fluoranthene and benzo (a) pyrene.
5. The method of claim 1 or 2, wherein the supercritical fluid comprises supercritical carbon dioxide; the modifier is selected from alcohols, nitriles or their water solution.
6. The method according to claim 1 or 2, wherein the stationary phase in the supercritical chromatography is selected from silica gel modified by polar groups selected from hydroxyl, amino or cyano.
7. The method according to claim 1 or 2, wherein the supercritical chromatography comprises a supercritical chromatography column; the reverse phase liquid chromatography comprises one or more reverse phase liquid chromatography columns.
8. The method according to claim 1 or 2, wherein the reversed phase liquid chromatography comprises a stationary phase and a mobile phase, the stationary phase is selected from silica gel modified by hydrophobic groups, the hydrophobic groups are selected from hydrocarbon groups, and the mobile phase is selected from polar organic solvents or aqueous solutions thereof.
9. The method according to claim 1 or 2, characterized in that the supercritical chromatography is connected to the reverse phase liquid chromatography by a connection means.
10. The method according to claim 1 or 2, wherein polycyclic aromatic hydrocarbons retained by the column of the supercritical chromatography are transferred to the reversed-phase liquid chromatography by the modifier, and the supercritical fluid flowing out of the supercritical chromatography is removed in the reversed-phase liquid chromatography.
11. The method of claim 1 or 2, wherein the reverse phase liquid chromatography comprises a first reverse phase liquid chromatography column and a second reverse phase liquid chromatography column at a rear end of the first reverse phase liquid chromatography column, and wherein the polycyclic aromatic hydrocarbon is detected after passing through the second reverse phase liquid chromatography column.
12. The method according to claim 11, characterized in that the supply of the supercritical fluid in the supercritical chromatography is stopped and the polycyclic aromatic hydrocarbons retained by the column of the supercritical chromatography are transferred into the first reversed-phase liquid chromatography column only under the influence of the modifier, and in turn the polycyclic aromatic hydrocarbons are washed into the second reversed-phase liquid chromatography column under the influence of the mobile phase of the reversed-phase liquid chromatography.
13. The method according to claim 1 or 2, further comprising the step of diluting the fat sample prior to the step of performing the separation of components of the fat sample using supercritical chromatography.
14. The method of claim 1 or 2, wherein the polycyclic aromatic hydrocarbon is detected using a fluorescence detector.
15. A method for producing a fat, comprising:
a step of on-line monitoring of the content of one or more polycyclic aromatic hydrocarbons in the production of fats and oils, comprising the method according to any one of claims 1 to 14;
and determining to adjust or not to adjust the oil production process and/or control parameters according to the detected content of the polycyclic aromatic hydrocarbon.
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| CN1936572A (en) * | 2005-09-23 | 2007-03-28 | 中国科学院大连化学物理研究所 | Super-critical flow extraction-efficient liquid-phase colour spectrum combined system |
| WO2019207871A1 (en) * | 2018-04-27 | 2019-10-31 | 株式会社島津製作所 | Rapid detection method for vitamin d in oil/fat or biological sample |
| CN110824053A (en) * | 2019-11-20 | 2020-02-21 | 徐州健一家健康管理有限公司 | Vegetable food multipoint detection method based on supercritical fluid extraction |
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| CN1936572A (en) * | 2005-09-23 | 2007-03-28 | 中国科学院大连化学物理研究所 | Super-critical flow extraction-efficient liquid-phase colour spectrum combined system |
| WO2019207871A1 (en) * | 2018-04-27 | 2019-10-31 | 株式会社島津製作所 | Rapid detection method for vitamin d in oil/fat or biological sample |
| CN110412189A (en) * | 2018-04-27 | 2019-11-05 | 株式会社岛津制作所 | A kind of method of quick detection grease or the vitamin D in biological sample |
| CN110824053A (en) * | 2019-11-20 | 2020-02-21 | 徐州健一家健康管理有限公司 | Vegetable food multipoint detection method based on supercritical fluid extraction |
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