CN111855790A - Method for identifying specific aromatic compounds in complex environment sample - Google Patents
Method for identifying specific aromatic compounds in complex environment sample Download PDFInfo
- Publication number
- CN111855790A CN111855790A CN202010846186.8A CN202010846186A CN111855790A CN 111855790 A CN111855790 A CN 111855790A CN 202010846186 A CN202010846186 A CN 202010846186A CN 111855790 A CN111855790 A CN 111855790A
- Authority
- CN
- China
- Prior art keywords
- compounds
- aromatic
- mass
- compound
- aromatic hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
-
- 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
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
-
- 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
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention provides a method for identifying specific aromatic hydrocarbon compounds in a complex environment sample, which comprises the following steps: s1, separating aromatic components from the sample; s2, carrying out Fourier transform mass spectrometry on the aromatic components to obtain the structures of a first quantity of aromatic compounds; s3, performing full-two-dimensional gas chromatography-tandem time-of-flight mass spectrometry on the aromatic components to obtain the structure of a second quantity of aromatic compounds; s4, acquiring the intersection of the structure of the first quantity of aromatic compounds and the structure of the second quantity of aromatic compounds to obtain the structure of the third quantity of aromatic compounds; and S5, screening out the specific aromatic hydrocarbon compound matched with the standard product from the structures of the aromatic hydrocarbon compounds with the third quantity. The method provided by the invention can be used for more comprehensively analyzing the aromatic compounds in the complex environment sample.
Description
Technical Field
The invention relates to the technical field of environmental analytical chemistry, in particular to a method for identifying specific aromatic compounds in a complex environment sample.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) have attracted a high degree of human attention due to their broad range of pollution and severity of environmental and human health hazards. The current research on PAHs is mainly focused on 16 PAHs proposed by the us epa, however, besides these PAHs, there are some aromatic compounds that may have potential toxicity and large environmental load and need to be monitored routinely in order to evaluate risk more accurately. There are, of course, several studies that expand the list of analyses, including alkylation products of polycyclic aromatics as well as heteroatom polycyclic aromatics. However, the above studies are all targeted assays for PAHs in environmental media, which means that a large number of aromatic compounds are still overlooked in the assay. Furthermore, gas chromatography tandem mass spectrometry (GC-MS), a commonly used instrument for analyzing PAHs, cannot analyze PAHs with similar retention times or co-effluence. The existing analysis method cannot comprehensively analyze the aromatic compounds in the sample in the complex environment.
Disclosure of Invention
Technical problem to be solved
Aiming at the problems, the invention provides a method for identifying specific aromatic compounds in a complex environment sample, which is used for at least partially solving the technical problems that the traditional analysis method cannot comprehensively analyze the aromatic compounds in the complex environment sample and the like.
(II) technical scheme
The invention provides a method for identifying specific aromatic hydrocarbon compounds in a complex environment sample, which comprises the following steps: s1, separating aromatic components from the sample; s2, carrying out Fourier transform mass spectrometry on the aromatic components to obtain the structures of a first quantity of aromatic compounds; s3, performing full-two-dimensional gas chromatography-tandem time-of-flight mass spectrometry on the aromatic components to obtain the structure of a second quantity of aromatic compounds; s4, acquiring the intersection of the structure of the first quantity of aromatic compounds and the structure of the second quantity of aromatic compounds to obtain the structure of the third quantity of aromatic compounds; and S5, screening out the specific aromatic hydrocarbon compound matched with the standard product from the structures of the aromatic hydrocarbon compounds with the third quantity.
Further, S2 specifically includes: s201, carrying out Fourier transform mass spectrometry to obtain the molecular weight of the compound; s202, estimating a molecular formula according to the molecular weight of the compound; s203, screening the molecular formulas to obtain molecular formulas of a first amount of aromatic compounds; s204, presuming the structure of the first amount of aromatic compounds according to the molecular formula of the first amount of aromatic compounds;
further, screening the molecular formula in S203 includes screening out a molecular formula of the compound having an equivalent double bond value of more than 7 and an element composition of C, H.
Further, S204 specifically includes: establishing a straight line formed by connecting the maximum equivalent double bond number corresponding to the given carbon number by using a graph of the equivalent double bond number and the carbon number, and estimating the superposition relationship among the compound structures according to the slope of the straight line to obtain the structures of the aromatic compounds with the first number.
Further, S2 is followed by: and S21, performing quality deviation verification on the structures of the first quantity of aromatic compounds.
Further, S21 specifically includes: the structure of the first amount of aromatic compounds in S2 was verified by plotting the Kendrick mass deviation over the integer Kendrick mass two-dimensionally, calculating the Kendrick mass value using different condensation patterns between the compounds.
Further, the Kendrick mass deviation calculation formula is as follows:
kendrick mass deviation-integer Kendrick mass-Kendrick mass;
the Kendrick mass calculation formula is as follows:
kendrick mass ═ theoretical relative molecular mass x (14/14.01565);
where the integer Kendrick mass is the closest integer mass value to the Kendrick mass.
Further, S3 specifically includes: and (3) obtaining a mass spectrum peak through comprehensive two-dimensional gas chromatography-tandem time-of-flight mass spectrometry, carrying out spectrum library retrieval, screening out a compound with the similarity of more than 600, the mass accuracy deviation of less than 5ppm and the equivalent double bond number of more than 7, and obtaining the structure of the second quantity of aromatic compounds.
Further, S5 further includes screening out compounds with high signal-to-noise ratio measured in fourier transform mass spectrometry and two-dimensional gas chromatography tandem time-of-flight mass spectrometry and compounds with similarity degree greater than 850 obtained by comparing mass spectra with a spectrum library.
Further, S1 specifically includes: and sequentially carrying out accelerated solvent extraction or Soxhlet extraction and column chromatography purification on the sample to separate out the aromatic components.
(III) advantageous effects
The method for identifying the specific aromatic compounds in the complex environment sample provided by the embodiment of the invention can identify and analyze the novel aromatic compounds in the complex environment sample in a non-targeted manner and more comprehensively by the ultrahigh resolution capability and high quality accuracy of Fourier transform mass spectrometry and the stronger gas chromatography separation capability of full-two-dimensional gas chromatography-tandem flight time mass spectrometry, screen out the novel aromatic compounds with larger environmental load and potential toxicity,
drawings
FIG. 1 schematically illustrates a flow diagram of a method for identifying specific aromatic compounds in a complex environmental sample, in accordance with an embodiment of the present invention;
FIG. 2 schematically illustrates a flow diagram of a method for obtaining a structure of a first quantity of an aromatic compound in accordance with an embodiment of the present invention;
FIG. 3 schematically shows a mass spectrum of an aromatic compound in a complex environment sample measured using FT-ICR MS according to an embodiment of the present invention;
FIG. 4 schematically shows a DBE-C diagram of aromatic compounds determined in an example according to the invention;
FIG. 5 schematically shows a KMD map of a sample according to an embodiment of the present invention;
FIG. 6 schematically shows a KMD chart of a linear addition benzene ring compound according to an embodiment of the present invention;
FIG. 7 schematically shows a KMD chart of a nonlinear adducted benzene ring compound according to an embodiment of the present invention;
FIG. 8 schematically illustrates a total ion flow graph for complex environmental sample determination using GC x GC-TOF MS according to an embodiment of the present invention;
FIG. 9 schematically shows a diagram of aromatic compounds DBE-C identified by FT-ICR MS together with GC x GC-TOF MS according to an embodiment of the present invention;
FIG. 10 schematically shows a two-dimensional time distribution plot of aromatic species identified by FT-ICR MS in conjunction with GC × GC-TOF MS according to an embodiment of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
Embodiments of the present invention provide a method for identifying specific aromatic compounds in a complex environmental sample, see fig. 1, comprising:
s1, separating aromatic components from the sample;
the complex environmental sample is purified by pretreatment methods such as extraction and the like, and aromatic components are selectively retained. The invention identifies that the specific aromatic hydrocarbon compounds are mainly semi-volatile non-polar aromatic hydrocarbon compounds, and does not include aromatic hydrocarbon compounds with middle polarity and strong polarity and difficult volatility.
S2, carrying out Fourier transform mass spectrometry on the aromatic components to obtain the structures of a first quantity of aromatic compounds;
establishing a method for analyzing aromatic compounds in a complex environment medium by a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS); the determined instrument parameters include: the type of the ion source, the sample introduction speed, the flow rate of the drying gas, the temperature of the drying gas, the ion accumulation time and the like; the set data processing parameters include: mass-to-charge ratio range, elemental composition, elemental ratio range, signal-to-noise ratio, and the like; the structure of the first quantity of aromatic compounds is obtained by analysis.
S3, performing full-two-dimensional gas chromatography-tandem time-of-flight mass spectrometry on the aromatic components to obtain the structure of a second quantity of aromatic compounds;
establishing an analysis method for analyzing various aromatic compounds in a complex environment medium by using a full two-dimensional gas chromatography-tandem time-of-flight mass spectrum (GC multiplied by GC-TOF MS); and establishing an analysis method for simultaneously and rapidly separating multiple aromatic compounds in a complex medium by optimizing instrument parameters such as chromatographic column combination, a temperature rise program, a modulation period and the like, and analyzing to obtain the structure of a second quantity of aromatic compounds.
S4, acquiring the intersection of the structure of the first quantity of aromatic compounds and the structure of the second quantity of aromatic compounds to obtain the structure of the third quantity of aromatic compounds;
the compounds detected by FT-ICR MS and GC XGC-TOF MS are screened out, the structure of the compound estimated by FT-ICR MS is verified by GC XGC-TOF MS, non-targeted analysis can be performed on the aromatic compounds in a complex environment medium, and hundreds of aromatic compounds can be identified.
And S5, screening out the specific aromatic hydrocarbon compound matched with the standard product from the structures of the aromatic hydrocarbon compounds with the third quantity.
And screening the specific aromatic compounds which have potential toxicity, higher environmental load and can be matched with the standard products from the structures of the third amount of aromatic compounds. The compounds were qualitatively and quantitatively studied using standard substances, and the structure of the final specific aromatic hydrocarbon compound was confirmed using GC x GC-TOF MS.
On the basis of the foregoing embodiment, S2 specifically includes: referring to fig. 2, S201, performing fourier transform mass spectrometry to obtain the molecular weight of the compound; s202, estimating a molecular formula according to the molecular weight of the compound; s203, screening the molecular formulas to obtain molecular formulas of a first amount of aromatic compounds; and S204, presuming the structure of the first amount of aromatic compounds according to the molecular formula of the first amount of aromatic compounds.
Because FT-ICR MS has ultrahigh resolution capability, a plurality of mass ions can be distinguished in less than one mass unit, and a plurality of aromatic compounds can be matched. Determining the molecular formula of a series of polycyclic aromatic hydrocarbon compounds obtained by matching mass spectrum peaks with higher abundance in a mass spectrogram, screening out possible target aromatic hydrocarbon compounds according to the molecular formula, and obtaining the structures of the aromatic hydrocarbon compounds with the first quantity through structure speculation.
Based on the above examples, screening the molecular formula in S203 includes screening out the molecular formula of the compound having an equivalent double bond value greater than 7 and an element composition of C, H.
And screening the matched molecular formula by using a Double Bond Equivalent (DBE) to obtain a possible molecular formula of the aromatic compound, wherein most of the specific aromatic compound to be screened is polycyclic aromatic hydrocarbon with condensed rings, the equivalent double bond value is more than 7, the element composition is C, H, no heteroatom such as O, N is contained, and a part of non-target aromatic compound is screened out by using the condition.
On the basis of the foregoing embodiment, S204 specifically includes: establishing a straight line formed by connecting the maximum equivalent double bond number corresponding to the given carbon number by using a graph of the equivalent double bond number and the carbon number, and estimating the superposition relationship among the compound structures according to the slope of the straight line to obtain the structures of the aromatic compounds with the first number.
And (3) utilizing an abundance graph of DBE-C, taking the C number as an abscissa and DBE (unsaturation) as an ordinate, and plotting the detected molecular formula into a bubble graph, wherein the radius of the bubble graph is in direct proportion to the intensity of the molecular formula in an FT-ICR MS mass spectrum. The compound structure was deduced from the slope of the plane limit reflected in the DBE-C plot. Meanwhile, aromatic compounds with high relative abundance are found for key analysis, and the distribution characteristics of the compounds are used for deducing the possible sources of the compounds. The compounds with the same DBE number and different C numbers can be homologues, and further, the possible structural formulas of a series of compounds can be deduced. Judging whether the aromatic compounds in the sample have linear addition of benzene rings or nonlinear addition according to the slope of plane restriction.
On the basis of the above embodiment, S2 is followed by: and S21, performing quality deviation verification on the structures of the first quantity of aromatic compounds.
The mass deviation is used to verify whether the structures of the first quantity of aromatic compounds in S2 have linear superposition and non-linear superposition of aromatic ring structures.
On the basis of the foregoing embodiment, S21 specifically includes: the structure of the first amount of aromatic compounds in S2 was verified by plotting the Kendrick mass deviation over the integer Kendrick mass two-dimensionally, calculating the Kendrick mass value using different condensation patterns between the compounds.
Aromatic structures were screened using Kendrick Mass Defect (KMD). Compounds with the same number of DBEs and the same number of heteroatom types belong to the family of homologs.
On the basis of the above embodiment, the Kendrick mass deviation calculation formula is as follows:
kendrick mass deviation-integer Kendrick mass-Kendrick mass; (1)
the Kendrick mass calculation formula is as follows:
kendrick mass ═ theoretical relative molecular mass x (14/14.01565); (2)
where the integer Kendrick mass is the closest integer mass value to the Kendrick mass.
Kendrick converts the theoretical relative molecular Mass (IUPAC Mass) to Kendrick Mass, see equation (2). Using this equation (2), the relative molecular masses between homologues differ by integer multiples of 14, but their relative molecular mass fractions are partially identical, and the deviation between the transformed mass value and the nearest integer mass value is defined as the Kendrick Mass Deviation (KMD), equation (1). According to the size of the KMD, the compound type can be rapidly and accurately distinguished, the KMD is used for drawing a two-dimensional graph of the integral Kendrick quality, and the compound type and the carbon number distribution range can be visually seen. The KMD values calculated by different condensation modes (peri-ring combination or attomo-position condensation) possibly existing among the compounds are simultaneously used for drawing a graph to verify the structural relationship of the compounds presumed by plane limitation.
On the basis of the foregoing embodiment, S3 specifically includes: and (3) obtaining a mass spectrum peak through comprehensive two-dimensional gas chromatography-tandem time-of-flight mass spectrometry, carrying out spectrum library retrieval, screening out a compound with the similarity of more than 600, the mass accuracy deviation of less than 5ppm and the equivalent double bond number of more than 7, and obtaining the structure of the second quantity of aromatic compounds.
The full two-dimensional gas chromatography has better separation capability on aromatic compounds in a complex medium, GC-TOFMS data are searched through searching mass spectrum peaks and a spectrum library, and then matched compounds are screened according to similarity (similarity is more than 600) and mass accuracy deviation (less than 5ppm) and DBE (Break detection index) is more than 7.
On the basis of the above embodiment, S5 further includes screening out compounds with high signal-to-noise ratio measured in fourier transform mass spectrometry and two-dimensional gas chromatography tandem time-of-flight mass spectrometry and compounds with similarity degree greater than 850 obtained by comparing mass spectra with a spectrum library.
The signal-to-noise ratio is high, namely the intensity of the compound on an FT-ICR MS mass spectrum and the signal-to-noise ratio measured by GC-TOF MS are high (specific numerical values are not specified, and the intensity and the signal-to-noise ratio of the compound are usually higher than 50 percent); the higher matching degree means that the similarity obtained by comparing a compound mass spectrogram with a spectral library is more than 850 when the spectral library is searched.
Based on the above embodiment, S1 specifically includes sequentially performing accelerated solvent extraction or soxhlet extraction, column chromatography purification, and separation of aromatic components on the sample.
After the complex environmental sample is extracted by accelerated solvent extraction or Soxhlet extraction, the sample is purified by column chromatography and other pretreatment methods, and aromatic components are selectively retained.
The present invention is described in detail below with reference to a specific embodiment. Selecting an atmospheric particulate matter sample in the Beijing area under heavy haze weather, and identifying a novel aromatic compound in the complex environment sample, wherein the method comprises the following steps:
(1) and (3) carrying out ASE extraction on the atmospheric particulate sample, and purifying the extracting solution by using an activated silica gel column to separate out the aromatic compounds.
(2) As shown in figure 3, the APPI (+) -FT-ICR MS is used for analyzing the aromatic compounds in the atmospheric particulates, the accurate molecular formula of each mass spectrum peak is determined according to the accurate molecular weight of each mass spectrum peak, and then the corresponding possible molecular formula of the aromatic compounds is screened according to the conditions such as DBE value and the like. It can be seen from fig. 3 that due to the ultra-high resolving power of FT-ICR MS, multiple mass ions can be resolved in less than one mass unit,matching with a plurality of aromatic compounds. And a series of polycyclic aromatic hydrocarbon compounds obtained by matching mass spectrum peaks with higher abundance in the mass spectrogram can be observed. Molecular formulas C with molecular weights of 228, 252, 276, 302, 350 and 376 which can be matched respectively18H12，C20H12，C22H12，C24H14，C28H14，C30H16. Therefore, the APPI-FT-ICR MS method established by the inventor has higher sensitivity to aromatic compounds in atmospheric particulates.
(3) The structure of the compound was predicted by using the DBE-C diagram, as shown in FIG. 4, in combination with the molecular formula. Judging whether the aromatic compounds in the sample have linear addition of benzene rings or nonlinear addition according to the slope of plane restriction. Molecular formula C20H12The DBE number is 15, which is inferred to be benzo a pyrene (or benzo e pyrene, etc.) according to the search results of Pubchem database. As can be seen from fig. 4, the more abundant molecular formulas match to obtain polycyclic aromatic hydrocarbons with mostly condensed rings. We generally consider compounds with the same DBE number but different C numbers as homologues, with the alkyl side chain distribution narrowing and the number of homologues decreasing as the DBE number increases.
The plane limit is a straight line connecting the maximum DBE number corresponding to a given C number. Research shows that when the slope of the plane limit equation is 0.75, the structure of linearly superposed aromatic rings exists; when the slope is 1, a non-linear superimposed structure exists. The slope of the planar limit in the figure is 0.81, which infers that there may be both linear and non-linear stacking of aromatic ring structures.
(4) The KMD is used for further identifying the structure of the aromatic compound, as shown in figure 5, and the KMD is used for further verifying the relation that the aromatic compound in the sample has linear and nonlinear benzene ring addition, as shown in figures 6 and 7. The KMD graph has the abscissa of integer value of Kendrick Mass and the ordinate of KMD, as shown in FIG. 5, and compounds of the same class have the same KMD, while KMD of compounds of different classes and groups are different. If one of the compounds is deduced, the compound can be deduced to haveStructure of homologues of the same KMD values. We conclude that the compound anthracene (C) is present as combined with data from a full two-dimensional gas chromatograph14H10) With a Kendrick Mass of 178, a KMD value of 0.121154 and coordinates on the KMD map of (178, 0.121154), a compound lying on the same horizontal line as the point would be inferred to be a series of homologs that are likely to be parent anthracenes, such as 1-methylanthracene (C)15H12) 1, 3-dimethylanthracene (C)16H14)。
In linear addition, the molecular formula of the aromatic compound is removed by adding two H and one C4H4The Kendrick mass (H) was calculated from the increase in molecular weight by 50Da2/C4H4) The formula of (1) is:
calculating the KMD (H) of the CH compounds by using the formula2/C4H4) This gives the result shown in FIG. 6. According to the principle of KMD, the molecular formulas of compounds in the same line have a difference of n C4H2The compound is a series of compounds for linear addition of benzene rings. As shown in the figure, the integer Kendrick mass is 202, KMD (H)2/C4H4) 0.014454, assuming that the compound structure is pyrene, the structure of the compound in line with it is shown in FIG. 6.
When the compound is subjected to nonlinear benzene ring superposition, the molecular formula of the compound is removed by two H and one C2H2Molecular weight increase 24Da, Kendrick mass (H) calculated2/C2H2) The formula of (1) is:
calculating the KMD (H) of the CH compounds by using the formula2/C2H2) As shown in FIG. 7, the molecular formulas of compounds in the same line have a difference of n C according to the principle of KMD2Is a series of non-linear addition benzeneA cyclic compound. As shown, the integer Kendrick mass is 228, KMD (H)2/C2H2) To 0.09352, the structure of the compound is presumed to be
The structure of the compound in line therewith is shown in fig. 7.
(5) The aromatic compounds in the same sample are separated and analyzed by using GC x GC-TOF MS, as shown in figure 8, it can be seen that the full two-dimensional gas chromatography has better separation capability on the aromatic compounds in the complex medium; GC × GC-TOFMS data were obtained by finding mass peaks, searching spectral libraries, and screening matched compounds according to similarity (similarity > 600) and mass accuracy deviation (< 5ppm), DBE > 7. As can be seen from the figure, the established GC x GC-TOF MS analysis method can separate and analyze a plurality of aromatic compounds in a complex medium. Various isomers can also be well separated.
(6) The compounds detected by GC × GC-TOF MS and FT-ICR MS together (see FIG. 9) were screened, and the two-dimensional retention times of these compounds are shown in FIG. 10. 386 aromatic compounds are screened in total, and the structures of 26 aromatic hydrocarbon compounds are identified in total by carrying out structure verification on purchased standard products of the compounds which have higher response, higher matching degree and stronger toxicity. The 26 compounds included 16 compounds specified in the EPA standard, and 10 compounds screened. Compounds with a similarity of greater than 850 of 82 were first screened from 386 compounds, from which compounds with higher response and potential toxicity were selected. In addition, the compound with the highest degree of unsaturation and the compound with the highest relative molecular mass among all the compounds were selected. These compounds were counted in 10 and then purchased as standards for standard substance validation using GC x GC-TOF MS. The two-dimensional retention time of the standard substance is similar to the two-dimensional retention time and mass spectrum of the mass spectrum and the compound in the sample, so that the structure can be determined.
PAHs detected by GC × GC-TOF MS can be mostly detected by FT-ICR MS, and PAHs detected in a whole two-dimensional mode are concentrated in compounds with low C number, low DBE number and short alkyl side chain, which is related to the properties of gas chromatography. High ring number PAHs with high C number and DBE number have high boiling points, which make them undetectable on chromatography due to temperature limitations of the column. And FT-ICR MS has no gas chromatography limitation, and can preliminarily identify PAHs with high ring number by utilizing the great sensitivity of an APPI source to aromatic substances. The two instruments can be complementary, as shown in fig. 9. We screened the compounds detected by both instruments and separated them into PAHs and alkylated PAHs (apahs) by the results of library search, the time distribution on the two-dimensional chromatogram being shown in fig. 10.
In summary, the aromatic compounds identified in the above embodiments indicate that the existing polycyclic aromatic hydrocarbon monitoring list needs to be updated urgently, so that the aromatic compounds in the complex environment sample can be analyzed as comprehensively as possible, and novel aromatic compounds with large environmental load and potential toxicity are screened out, thereby providing certain data support for pollution prevention and control, environmental risk evaluation and human health risk evaluation; meanwhile, the invention provides a feasible solution for separating and analyzing a plurality of compounds in complex media (environment, biology and the like).
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of identifying a specific aromatic compound in a complex environmental sample, comprising:
s1, separating aromatic components from the sample;
s2, carrying out Fourier transform mass spectrometry on the aromatic components to obtain structures of a first number of aromatic compounds;
s3, performing comprehensive two-dimensional gas chromatography-tandem time-of-flight mass spectrometry on the aromatic components to obtain the structures of a second quantity of aromatic compounds;
s4, acquiring the intersection of the structure of the first quantity of aromatic hydrocarbon compounds and the structure of the second quantity of aromatic hydrocarbon compounds to obtain the structure of a third quantity of aromatic hydrocarbon compounds;
and S5, screening out the specific aromatic hydrocarbon compound matched with the standard product from the structures of the third amount of aromatic hydrocarbon compounds.
2. The method for identifying a specific aromatic hydrocarbon compound in a complex environment sample according to claim 1, wherein the S2 specifically comprises:
s201, carrying out Fourier transform mass spectrometry to obtain the molecular weight of the compound;
s202, estimating a molecular formula according to the molecular weight of the compound;
s203, screening the molecular formulas to obtain the molecular formulas of the aromatic compounds with the first quantity;
and S204, presuming to obtain the structure of the first amount of aromatic hydrocarbon compounds according to the molecular formula of the first amount of aromatic hydrocarbon compounds.
3. The method of claim 2, wherein said screening said molecular formula in S203 comprises screening said molecular formula for a compound having an equivalent double bond value greater than 7 and an elemental composition of C, H.
4. The method for identifying a specific aromatic hydrocarbon compound in a complex environment sample according to claim 2, wherein the step S204 specifically comprises: establishing a straight line formed by connecting the maximum equivalent double bond number corresponding to the given carbon number by using a graph of the equivalent double bond number and the carbon number, and estimating the superposition relationship among the compound structures according to the slope of the straight line to obtain the structures of the aromatic compounds with the first number.
5. The method for identifying specific aromatic hydrocarbon compounds in a complex environment sample according to claim 2, further comprising after the step of S2: and S21, performing quality deviation verification on the structures of the first quantity of aromatic compounds.
6. The method for identifying specific aromatic hydrocarbon compounds in a complex environment sample according to claim 5, wherein the S21 specifically comprises: and (3) performing a two-dimensional graph of Kendrick mass deviation on the integral Kendrick mass, calculating the Kendrick mass value by using different condensation modes between the compounds, and verifying the structure of the first quantity of aromatic compounds in the S2.
7. The method of identifying specific aromatic compounds in a complex environmental sample according to claim 6, wherein the Kendrick mass deviation calculation formula is as follows:
kendrick mass deviation-integer Kendrick mass-Kendrick mass;
wherein the Kendrick mass calculation formula is as follows:
kendrick mass ═ theoretical relative molecular mass x (14/14.01565);
wherein the integer Kendrick mass is the closest integer mass value to Kendrick mass.
8. The method for identifying a specific aromatic hydrocarbon compound in a complex environment sample according to claim 1, wherein the S3 specifically comprises: and (3) obtaining a mass spectrum peak through the full-two-dimensional gas chromatography-tandem time-of-flight mass spectrometry, carrying out spectrum library retrieval, screening out a compound with the similarity of more than 600, the mass accuracy deviation of less than 5ppm and the equivalent double bond number of more than 7, and obtaining the structure of the second quantity of aromatic compounds.
9. The method of claim 1, wherein said step S5 further comprises screening compounds with high signal-to-noise ratio determined by fourier transform mass spectrometry and two-dimensional gas chromatography tandem time-of-flight mass spectrometry and compounds with similarity degree greater than 850 obtained by comparing mass spectrum with spectrum library.
10. The method for identifying a specific aromatic hydrocarbon compound in a complex environment sample according to claim 1, wherein the S1 specifically comprises: and sequentially carrying out accelerated solvent extraction or Soxhlet extraction and column chromatography purification on the sample to separate out the aromatic components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010846186.8A CN111855790A (en) | 2020-08-20 | 2020-08-20 | Method for identifying specific aromatic compounds in complex environment sample |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010846186.8A CN111855790A (en) | 2020-08-20 | 2020-08-20 | Method for identifying specific aromatic compounds in complex environment sample |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111855790A true CN111855790A (en) | 2020-10-30 |
Family
ID=72969949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010846186.8A Pending CN111855790A (en) | 2020-08-20 | 2020-08-20 | Method for identifying specific aromatic compounds in complex environment sample |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111855790A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116297794A (en) * | 2023-05-11 | 2023-06-23 | 深圳大学 | Organic matter determining method and terminal equipment based on ultra-high resolution mass spectrometer |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135549A (en) * | 1991-01-30 | 1992-08-04 | The Board Of Trustees Of Southern Illinois University | Chromatographic technique and apparatus |
| US20050063864A1 (en) * | 2003-08-13 | 2005-03-24 | Akihiro Sano | Mass spectrometer system |
| CN101726558A (en) * | 2009-12-10 | 2010-06-09 | 清华大学 | Method for detecting polycyclic aromatic hydrocarbon component in coking wastewater processing system |
| CN102749405A (en) * | 2012-07-23 | 2012-10-24 | 中国石油天然气股份有限公司 | Quantitative analysis method for pentacyclic triterpane compound in petroleum sample |
| CN103269776A (en) * | 2010-12-16 | 2013-08-28 | 埃克森美孚研究工程公司 | Generation of model-of-composition of petroleum by high resolution mass spectrometry and associated analytics |
| CN103792275A (en) * | 2013-09-24 | 2014-05-14 | 中国科学院成都生物研究所 | High-resolution mass spectrum accurate molecular formula forecasting method |
| CN105319262A (en) * | 2015-12-07 | 2016-02-10 | 中国石油天然气集团公司 | Analysis method of molecular composition of aromatic compound and application thereof |
| CN105987946A (en) * | 2015-03-03 | 2016-10-05 | 中国石油化工股份有限公司 | Oil migration direction tracing method |
| CN107884493A (en) * | 2017-11-08 | 2018-04-06 | 国家地质实验测试中心 | The method of short chain chlorinated paraffin in comprehensive two dimensional gas chromatography flying time mass spectrum analysis environmental sample |
| CN109696506A (en) * | 2017-10-23 | 2019-04-30 | 中国石油化工股份有限公司 | A method of for carrying out molecular recognition to sample |
| CN110646556A (en) * | 2019-09-26 | 2020-01-03 | 中国神华煤制油化工有限公司 | Method for analyzing components of organic sample |
-
2020
- 2020-08-20 CN CN202010846186.8A patent/CN111855790A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135549A (en) * | 1991-01-30 | 1992-08-04 | The Board Of Trustees Of Southern Illinois University | Chromatographic technique and apparatus |
| US20050063864A1 (en) * | 2003-08-13 | 2005-03-24 | Akihiro Sano | Mass spectrometer system |
| CN101726558A (en) * | 2009-12-10 | 2010-06-09 | 清华大学 | Method for detecting polycyclic aromatic hydrocarbon component in coking wastewater processing system |
| CN103269776A (en) * | 2010-12-16 | 2013-08-28 | 埃克森美孚研究工程公司 | Generation of model-of-composition of petroleum by high resolution mass spectrometry and associated analytics |
| CN102749405A (en) * | 2012-07-23 | 2012-10-24 | 中国石油天然气股份有限公司 | Quantitative analysis method for pentacyclic triterpane compound in petroleum sample |
| CN103792275A (en) * | 2013-09-24 | 2014-05-14 | 中国科学院成都生物研究所 | High-resolution mass spectrum accurate molecular formula forecasting method |
| CN105987946A (en) * | 2015-03-03 | 2016-10-05 | 中国石油化工股份有限公司 | Oil migration direction tracing method |
| CN105319262A (en) * | 2015-12-07 | 2016-02-10 | 中国石油天然气集团公司 | Analysis method of molecular composition of aromatic compound and application thereof |
| CN109696506A (en) * | 2017-10-23 | 2019-04-30 | 中国石油化工股份有限公司 | A method of for carrying out molecular recognition to sample |
| CN107884493A (en) * | 2017-11-08 | 2018-04-06 | 国家地质实验测试中心 | The method of short chain chlorinated paraffin in comprehensive two dimensional gas chromatography flying time mass spectrum analysis environmental sample |
| CN110646556A (en) * | 2019-09-26 | 2020-01-03 | 中国神华煤制油化工有限公司 | Method for analyzing components of organic sample |
Non-Patent Citations (2)
| Title |
|---|
| 乔林: "大气中新型有机污染物的筛查研究", 《持久性有机污染物论坛2018暨化学品环境安全大会论文集》 * |
| 乔林等: ""利用全二维气相色谱-飞行时间质谱和傅立叶变换离子回旋共振质谱联合开展环境样品中有机污染物非靶标筛查研究"", 《第三届全国质谱分析学术报告会摘要集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116297794A (en) * | 2023-05-11 | 2023-06-23 | 深圳大学 | Organic matter determining method and terminal equipment based on ultra-high resolution mass spectrometer |
| CN116297794B (en) * | 2023-05-11 | 2023-10-31 | 深圳大学 | Organic matter determining method and terminal equipment based on ultra-high resolution mass spectrometer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10473642B2 (en) | Effect-directed identification of targeted and non-targeted androgen disruptors | |
| Hsu et al. | Petroleomics: advanced molecular probe for petroleum heavy ends | |
| Dwivedi et al. | Metabolic profiling by ion mobility mass spectrometry (IMMS) | |
| Newton et al. | Identification of nitroaromatics in diesel exhaust particulate using gas chromatography/negative ion chemical ionization mass spectrometry and other techniques | |
| Eljarrat et al. | Quantitative analysis of polychlorinated n-alkanes in environmental samples | |
| Junot et al. | Fourier transform mass spectrometry for metabolome analysis | |
| Weggler et al. | Advanced scripting for the automated profiling of two-dimensional gas chromatography-time-of-flight mass spectrometry data from combustion aerosol | |
| CN104237436A (en) | Qualitative screening method of semi-volatile halogenated organic pollutants in sediments | |
| Kuang et al. | Aromatic formulas in ambient PM 2.5 samples from Hong Kong determined using FT-ICR ultrahigh-resolution mass spectrometry | |
| CA2843648C (en) | Chemical identification using a chromatography retention index | |
| Kim et al. | Combination of ring type HPLC separation, ultrahigh-resolution mass spectrometry, and high field NMR for comprehensive characterization of crude oil compositions | |
| Grimm et al. | Grouping of petroleum substances as example UVCBs by ion mobility-mass spectrometry to enable chemical composition-based read-across | |
| Clingenpeel et al. | Comprehensive characterization of petroleum acids by distillation, solid phase extraction separation, and Fourier transform ion cyclotron resonance mass spectrometry | |
| Wang et al. | Determination of n-alkanes, polycyclic aromatic hydrocarbons and hopanes in atmospheric aerosol: evaluation and comparison of thermal desorption GC-MS and solvent extraction GC-MS approaches | |
| Getzinger et al. | Illuminating the exposome with high-resolution accurate-mass mass spectrometry and nontargeted analysis | |
| Kates et al. | The application of comprehensive two-dimensional gas chromatography to the analysis of wildfire debris for ignitable liquid residue | |
| Zeigler et al. | Total alkylated polycyclic aromatic hydrocarbon characterization and quantitative comparison of selected ion monitoring versus full scan gas chromatography/mass spectrometry based on spectral deconvolution | |
| CN111855790A (en) | Method for identifying specific aromatic compounds in complex environment sample | |
| CN102818791A (en) | Fluorescence detection method of polycyclic aromatic hydrocarbons (PAHs) in water body | |
| Ahn et al. | Analysis of polycyclic aromatic hydrocarbons in ambient aerosols by using one-dimensional and comprehensive two-dimensional gas chromatography combined with mass spectrometric method: a comparative study | |
| CA2906720C (en) | Mass spectrometry (ms) identification algorithm | |
| Zweigle et al. | PFΔ Screen—an open-source tool for automated PFAS feature prioritization in non-target HRMS data | |
| Roman-Hubers et al. | Analytical chemistry solutions to hazard evaluation of petroleum refining products | |
| Kidwell et al. | Comparing two analytical methods: minimal standards in forensic toxicology derived from information theory | |
| Nowak et al. | Quantification of isomerically summed hydrocarbon contributions to crude oil by carbon number, double bond equivalent, and aromaticity using gas chromatography with tunable vacuum ultraviolet ionization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |