CN106053635B - A kind of method of polycyclic aromatic hydrocarbon in measurement plant leaf blade - Google Patents
A kind of method of polycyclic aromatic hydrocarbon in measurement plant leaf blade Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/065—Preparation using different phases to separate parts of sample
Abstract
The invention discloses a kind of methods of polycyclic aromatic hydrocarbon in measurement plant leaf blade, include the following steps: that (1) carries out Soxhlet extraction to plant powder and is concentrated by evaporation；(2) liquid that step (1) obtains successively is used into the purification that hand fills out silicagel column and GPC column carries out sample, is purified liquid；(3) scavenging solution is detected into polycyclic aromatic hydrocarbon therein using gas-chromatography and the method for mass spectrometry.The method that the present invention measures polycyclic aromatic hydrocarbon in plant leaf blade can effectively remove pigment and grease in plant leaf blade, the trace analysis of multicomponent polycyclic aromatic hydrocarbon suitable for plant leaf blade, and the content for polycyclic aromatic hydrocarbon in measurement plant tissue provides technical support.
Description
Technical field
The present invention relates to biological and chemical fields, more particularly to a kind of method of polycyclic aromatic hydrocarbon in measurement plant leaf blade.
Background technique
Polycyclic aromatic hydrocarbon (Polycyclic Aromatic Hydrocarbons, PAHs) is containing 2 or 2 or more benzene
Ring has organic dirt in the organic compound of carcinogenic, aberration inducing and mutagenesis, and a kind of generally existing atmospheric environment
Contaminate one of object.The source of PAHs can be divided into natural source and artificial source in atmosphere, and wherein artificial source is main source, as coal fires
Discharge in burning, vehicle exhaust, steel and petroleum industry production.PAHs can be accumulated in animal and plant body by food chain, seriously
Endanger human health.
PAHs enters plant, and there are mainly two types of approach: soil-plant body and air-plant.PAHs in soil with
Organic matter therein is combined closely, and is not easy to enter plant by plant root absorption.And air-plant is PAHs from sky
Gas is deposited to the wax epidermis of blade by gaseous state and particulate form or is absorbed into plant by stomata.Therefore, air-plant
Object is the main path of plant enrichment PAHs.In recent years, the main right and wrong of study on determination method object in relation to PAHs content
Plant medium, such as water body, deposit and particulate matter.Although there is the content characteristics for having researched and analysed PAHs in plant leaf blade,
The method of PAHs content depends on the analysis method for measuring PAHs in other media mostly in measurement plant leaf blade.Plant leaf blade,
Especially coniferous species such as Chinese pine blade, contains a large amount of lipid, wax and pigment.Existing analysis method is not avoided that these
The interference of ingredient.Therefore, the analysis method for establishing PAHs in general and Accurate Determining leaf is necessary.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of polycyclic aromatic hydrocarbon in measurement plant leaf blade, the methods
The pigment and grease in plant leaf blade can be effectively removed, the trace analysis of multicomponent polycyclic aromatic hydrocarbon suitable for plant leaf blade,
Content for polycyclic aromatic hydrocarbon in measurement plant tissue provides technical support.
The method of polycyclic aromatic hydrocarbon, includes the following steps: in a kind of measurement plant leaf blade
(1) Soxhlet extraction is carried out to plant powder and be concentrated by evaporation；
(2) liquid that step (1) obtains successively is used into the purification that hand fills out silicagel column and GPC column carries out sample, obtained net
Change liquid；
(3) scavenging solution is detected into polycyclic aromatic hydrocarbon therein using gas-chromatography and the method for mass spectrometry.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the present invention, wherein the polycyclic aromatic hydrocarbon be acenaphthylene, acenaphthene,
Fluorenes, anthracene, fluoranthene, pyrene, benzo (a) anthracene, is bent, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, dibenzo (a, h) at phenanthrene
Anthracene, benzo (ghi) and indeno (1,2 3-cd) pyrene.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the present invention, wherein being filled out using hand in the step (2)
The method that silicagel column is purified includes the following steps:
Chromatography one small silica wool of column bottom pad, with 10mL n-hexane rinse inner wall, wet method dress post, from bottom to up successively
Activated silica gel 10g, anhydrous sodium sulfate 6g are filled, silicagel column is eluted with 60mL n-hexane, the sample being concentrated is transferred to silica gel
On column, is eluted, discarded with 25mL n-hexane；Again with the elution of the mixed solution of 80mL n-hexane and methylene chloride, eluent is collected,
Entire elution process elution speed is 1 drop/s, and eluent rotary evaporation is concentrated into 3mL hereinafter, preparing the GPC column purification of next step
Processing.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the present invention, wherein the specification of the chromatographic column are as follows: diameter
The volume ratio of n-hexane and methylene chloride is 4:1 in the mixed solution of 15mm × 30cm, the n-hexane and methylene chloride.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the present invention, wherein the GPC column purification processing includes such as
Lower step:
Entire GPC column purification process is the mixed solution of n-hexane and methylene chloride using solvent, cleaned gel
It is loaded into chromatographic column, filling height is 20cm, elutes GPC column with 100mL mixed solution；The sample being concentrated is transferred to
On GPC column, is eluted, discarded with 50mL mixed solvent；It is eluted, is collected with 100mL mixed solvent again；Finally use 50mL mixed solution
Elution, discards；1~2mL is concentrated in eluent rotary evaporation, is transferred to nitrogen blowpipe, nitrogen is blown to 0.5mL, is added in final sample
50 μ L concentration are the PAHs sample introduction mark of 1 μ g/mL, are vortexed after mixing, are purified liquid, i.e., solution to be measured.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the present invention, wherein the n-hexane and methylene chloride
The volume ratio of n-hexane and methylene chloride is 1:1 in mixed solution；The chromatographic column is that included husky board diameter is 25mm × 30cm
Chromatographic column.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the present invention, wherein GC conditions are such as in step (3)
Under:
Using DB-5MS, 30m × 0.25mm × 0.25 μm capillary column, initial temperature is 50 DEG C, keeps 2min；With 20
DEG C/min rises to 200 DEG C, retain 2min, then rise to 240 DEG C again with 4.5/min, retains 2min, finally with 2.5 DEG C/min liter
To 290 DEG C, retain 2min；Injector temperature is 280 DEG C, and carrier gas is high-purity helium, and purity 99.999%, sampling volume is 1.0 μ
L, Splitless injecting samples.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the present invention, wherein the Mass Spectrometry Conditions in step (3) are such as
Under: the source EI, electron energy: 70eV, transmission line temperature: 270 DEG C, ion source temperature: 250 DEG C, detector voltage: -1300V, from
Sub- galvanic current: 100 μ A, scan method are selective ion SIM.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the present invention, wherein the plant be Chinese juniper, prunus cerasifera,
Chinese pine or Chinese white poplar.
The method difference from prior art that the present invention measures polycyclic aromatic hydrocarbon in plant leaf blade is: the present invention, which measures, to plant
The method of polycyclic aromatic hydrocarbon uses soxhlet extraction, the pretreatment mode of silicagel column and the double purifications of gel column, gas phase color in object blade
Spectrum-mass spectrography carries out analysis detection to Determination of Trace Polycyclic Aromatic Hydrocarbons in common tree blade, since the Experimental Background value of naphthalene is higher, and
It is high volatility, degradable, there is very big uncertainty in the environment, so only determining in plant leaf blade 15 kinds of PAHs' herein
Content does not inquire into naphthalene.
The present invention selects two steps purification (GPC after first silica gel), reason: 1) first crossing silicagel column (disposable pillar), can remove
Complicated impurity, plays a protective role to GPC；2) GPC column is to reuse, and can remove big molecular impurity；3) due to leaf
Polycyclic aromatic hydrocarbon content is less in piece, and the sampling amount needed is big.If only crossing silicagel column, remaining impurity is more；If only crossing gel column,
The impurity being retained in gel column, is not easily cleaned, and clean-up effect is also bad.So from clean-up effect and in terms of saving
It sees, in handling leaf when polycyclic aromatic hydrocarbon, first crosses silicagel column after GPC column.
For or the simple sample of matrix higher for polycyclic aromatic hydrocarbon concentration (such as soil or gaseous sample), polycyclic aromatic hydrocarbon one
As only with a kind of chromatographic column (common silicagel column) purification, experiment purpose can be reached.And for complex matrices, such purification is not
It is able to satisfy test request, it is necessary to carry out multistep purification.The present invention merely adds step GPC purification and efficiently low can go to clean
Matter reaches requirement of experiment.
Specifically, the present invention establishes Soxhlet extraction-silicagel column and gel column purification-gas chromatography mass spectrometry method measurement plant
The method of polycyclic aromatic hydrocarbon in blade, the polycyclic aromatic hydrocarbon in blade are mentioned through methylene chloride-n-hexane (volume ratio 1:1) solution Soxhlet
It takes, after extracting solution is using silicagel column and two step of gel column purification (hand fills out silicagel column and GPC column), carries out gas chromatography-mass spectrometry
It is measured with instrument (GC/MS), qualitative, inner mark method ration is carried out according to retention time and characteristic ion；Recovery of standard addition be 82.2~
130%, relative standard deviation is less than 11%.Method detection is limited to 0.0314~5.80ng/g；The method of the invention can be effective
Removal plant leaf blade in pigment and grease, the trace analysis of multicomponent polycyclic aromatic hydrocarbon suitable for plant leaf blade, for measurement
The content of polycyclic aromatic hydrocarbon provides technical support in plant tissue.
The method of polycyclic aromatic hydrocarbon in measurement plant leaf blade of the invention is described further with reference to the accompanying drawing.
Detailed description of the invention
Fig. 1 is the total ion chromatogram of 15 kinds of PAHs in Plays solution of the present invention.
Specific embodiment
Embodiment 1
1, materials and methods
1.1 key instruments and reagent
Gas chromatograph-mass spectrometer (GC-MS) (U.S. Agilent, 7890A GC- Japan Electronics JMS-Q1000)；Rotary evaporation
Instrument (Japanese EYELA, RE-52AA)；Nitrogen evaporator (Beijing general's grace science and technology limited Company SE812)；Grinder (German IKA,
Tube Mill control)；The chromatographic column and diameter that self-control diameter is 15mm × 30cm are the included husky plate of 25mm × 30cm
Chromatographic column.N-hexane, methylene chloride, acetone, anhydrous sodium sulfate, silica gel for chromatography (0.63~0.1mm), chromatography gel (200
~400 mesh) it is that analysis is pure.
PAHs standard solution: 15 kinds of polycyclic aromatic hydrocarbon standard reserving solutions (10ug/mL, Accustandard, USA) include acenaphthylene
(Acenaphthylene), acenaphthene (Acenaphthene), fluorenes (Fluorene), phenanthrene (Phenanthrene), anthracene
(Anthracene), fluoranthene (Fluoranthene), pyrene (Pyrene), benzo (a) anthracene (Benz (a) anthracene), bend
(Chrysene), benzo (b) fluoranthene (Benzo (b) fluoranthene), benzo (k) fluoranthene (Benzo (k)
Fluoranthene), benzo (a) pyrene (Benzo (a) pyrene), dibenzo (a, h) anthracene (Dibenz (a, h) anthracene),
Benzo (ghi) (Benzo (ghi) perylene) and indeno (1,2 3-cd) pyrene (Indeno (1,2,3-cd) pyrene).With
N-hexane is diluted to 1ug/mL as working solution.
PAHs sample introduction mark: benzo (a) anthracene-D12 solution (solvent is nonane), the μ g/ml of ρ=10 are diluted to n-hexane
1ug/mL before working solution examination with computer as being added, for tracking the rate of recovery of sample pre-treatments, analytic process.
PAHs purification mark: acenaphthylene-d10, phenanthrene-d10, fluoranthene-d10, pyrene-d10, benzo (a) pyrene-d12, benzo (g, h, i)
Pyrene-d12 mixed solution (solvent is nonane), the μ g/ml of ρ=10 use n-hexane to be diluted to 1ug/mL and extract as working solution sample
Preceding addition is taken, for quantifying for makings analysis.
1.2 experimental method
1.2.1 the extraction of sample
Plant powder (5g) is weighed, is added in glass fiber filter cylinder, the PAHs that 50 μ L concentration of addition are 1 μ g/mL is purified
After mark, filter cylinder is put into Soxhlet extractor, with 200mL n-hexane/methylene chloride mixed solution (V/V=1/1) with per hour
Reflux no less than 4 speed continuously extracts 16~for 24 hours.
After Soxhlet extraction, extracting solution rotary evaporation is concentrated, temperature control is concentrated into 1~2mL at 45 DEG C or less, is added
10mL n-hexane continues to rotate, and solvent is switched to n-hexane completely, is concentrated into 1mL or so, is ready for purified treatment.
1.2.2 the purification of sample
Hand fills out silicagel column: in chromatographic column (diameter 15mm × 30cm) one small silica wool of bottom pad, being rushed with 10mL n-hexane
Inner wall is washed, wet method dress post is sequentially filled activated silica gel 10g, anhydrous sodium sulfate 6g from bottom to up, elutes silica gel with 60mL n-hexane
Column.The sample being concentrated is transferred on silicagel column.It is eluted, is discarded with 25mL n-hexane；80mL n-hexane/methylene chloride is used again
Eluent is collected in mixed solution (V/V=4/1) elution, and entire elution process elution speed is 1 drop/s.Eluent rotary evaporation
3mL is concentrated into hereinafter, preparing to handle in next step.
GPC column: entire GPC column purification process is positive hexanes/ch mixed solution (V/V=1/1) using solvent, is made
The chromatographic column for being 25mm × 30cm with included husky board diameter.Cleaned gel is loaded into chromatographic column, filling height is
20cm elutes GPC column with 100mL mixed solution.The sample being concentrated is transferred on GPC column, is eluted with 50mL mixed solvent,
It discards；It is eluted, is collected with 100mL mixed solvent again；It is finally eluted, is discarded with 50mL mixed solution.Eluent rotary evaporation is dense
1~2mL of contraction is transferred to nitrogen blowpipe, and nitrogen is blown to 0.5mL, be added in final sample 50 μ L concentration be 1 μ g/mL PAHs into
Sample mark is vortexed after mixing, to be measured.
1.2.3 instrument condition
GC conditions: using DB-5MS (30m × 0.25mm × 0.25 μm) capillary column, and initial temperature is 50 DEG C,
Keep 2min；200 DEG C are risen to 20 DEG C/min, retains 2min, then rises to 240 DEG C again with 4.5/min, retains 2min, finally
290 DEG C are risen to 2.5 DEG C/min, retains 2min.Injector temperature is 280 DEG C, and carrier gas is high-purity helium (purity 99.999%).
1.0 μ L of sampling volume, Splitless injecting samples.
Mass Spectrometry Conditions: the source EI, electron energy 70eV, 270 DEG C of transmission line temperature, 250 DEG C of ion source temperature, detector electricity
Pressure: -1300V, ionization current: 100 μ A, scan method are selective ion (SIM).
2, results and discussion
The optimization of 2.1 sample purification methods
The layer that the purification method of PAHs generally has silica gel column purification or silica gel and Fu Luoli soil to load according to a certain percentage
Column purification is analysed, but all methods are all step purifications.Since PAHs is half volatile pollutants, PAHs's contains in plant sample
Amount is far smaller than the content of the PAHs in environmental sample, it is necessary to which lower method detection limit is just able to satisfy analysis and requires.But
Contain a large amount of pigment and a small amount of grease in plant sample, these impurity understand the measurement of disturbed specimen and can not obtain lower inspection
Rising limit, it is necessary to optimize purification method completely remove as far as possible impurity be just able to satisfy analysis require.This method has selected two steps to purify,
Silica gel column purification and GPC purification.
Silica gel is the analysis most suitable solid phase extraction adsorbents of PAHs, has separation using PAHs in silica gel column purification sample
The features such as performance is stable, leacheate dosage is few, clean-up effect is obvious.Common 1g silicagel column is adapted to soil, deposit etc., but
For plant leaf blade sample, it is not suitable with.Because plant leaf blade contains a large amount of lipid and wax, it is easy blocking pillar.This literary grace
Formula silica gel (10g) column is filled out with hand, has achieved the effect that not only to be not easy stifled column but also can have centainly to purify.But silicagel column is only crossed, elution
Liquid be it is orange and sticky, do not meet testing conditions.
In order to reach the thoroughly purification of sample, more preferably extracting solution is obtained, it is further to fill out formula gel (10g) column using hand
Infiltration purification.GPC column can separate the substance of different molecular size, herein can be grease remaining after silica gel purification and pigment
It completely removes, obtains colorless and transparent eluent.Therefore, successively crossing silicagel column and gel column can make sample sufficiently cleaned up, obtain
To highly reliable result.
The drafting of 2.2 standard curves
This method uses inner mark method ration, has prepared the standard solution (table 1) of 7 various concentrations.Wherein minimum point concentration
Should be equal to or below sample concentration, remaining point should refer to the concentration range of actual sample, should be no more than the quantitative model of GC/MS
It encloses, according to the sample concentration range of test, at least five concentration series is selected to make standard curve.To the mark of production standard curve
The every bit of quasi- solution at least carries out the measurement of 3 sample introductions, should be obtained in entire concentration range 15 numbers accordingly on.
The concentration (CS, ng/mL) of each standard solution of table 1
Each concentration point is marked and each 100ng/mL of sample introduction mark (table 1) containing purification accordingly.With standard substance and corresponding internal standard
The concentration of the ratio between peak area of substance and standard solution Plays substance and internal standard substance is than production standard curve.15 kinds of polycyclic virtues
The standard curve data of hydrocarbon are shown in Table 2.15 kinds of polycyclic aromatic hydrocarbons are linearly good, and instrument detection limit range is 1.07~3.26ng/mL.Figure
1 is the total ion chromatogram of polycyclic aromatic hydrocarbon.15 kinds of PAHs realizations are kept completely separate.Table 2 and Fig. 1's the result shows that, this method
Instrument condition meets the instrument test requirement for the sample that PAHs monomer concentration range is 10~1000ng/mL.
The equation of linear regression of 15 kinds of PAHs in 2 blade of table, related coefficient (r), detection limit (LOD) and lower limit of quantitation
(LOQ)
2.3 analysis method performance evaluations
2.3.1 precision and accuracy
25uL PAHs standard solution (1ng/uL) is added in glass fiber filter paper and is used as blank mark-on sample, according to complete
Parallel 3 measurements of program, calculate target concentration average value, the rate of recovery (REC) and relative standard deviation (RSD) (table 3).As a result
Show that recovery of standard addition is 82.2~130%, relative standard deviation is less than 11%.
The recovery of standard addition and relative standard deviation (n=3) of 15 kinds of PAHs in 3 blank sample of table
* the content to deduct PAHs in blank sample
Preci-sion and accuracy experiment is carried out using plant leaf blade matrix mark-on sample, can more reflect the performance of method.It is real
250uL PAHs standard is added as blank in tree species prunus cerasifera (Prunus cerasifera) leaf sample in border in leaf sample
Solution (1ng/uL) carries out preci-sion and accuracy experiment as blade mark-on sample.Purple Leaf Plum sample and Purple Leaf Plum
According to parallel 3 measurements of Whole Process, it is inclined to calculate target concentration average value, the rate of recovery (REC) and relative standard for mark-on sample
Poor (RSD) (table 4).The result shows that recovery of standard addition is 46.7~132%, relative standard deviation meets experiment and wants less than 15%
It asks.Compared with blank mark-on tests (table 3), the rate of recovery range of PAHs becomes larger in blade matrix mark-on sample, and relative standard is inclined
Difference is larger.These differences be primarily due to low ring PAHs belong to volatile environmental organic pollutant, especially acenaphthylene, acenaphthene, fluorenes,
Luxuriant and rich with fragrance, fluoranthene and pyrene have detection (table 3) in blank sample, and there is uncertainties.In addition, experiment discovery blade matrix pair
The existing enhancing of the matrix effect of analyte, also there is inhibition.But the data obtained result and the research phase for PAHs in other media
Closely, in environment trace analysis tolerance interval.
15 kinds of PAHs mark-on preci-sion and accuracies (n=3) in 4 leaf sample of table
* the content to deduct PAHs in plant leaf blade sample
2.3.2 method detection limit
5uL PAHs standard solution (1ng/uL) is added in 5g quartz sand, totally 6 parts of parallel mark-on samples.Calculate Duplicate Samples
The standard deviation (SD) of product searches t value, method detection limit MDL=t*SD, method Determination Limit MQL=4*MDL (table 5).As a result
Show that method detection is limited to 0.0314~5.80ng/g.Since the background of low ring PAHs is higher, so method detection limit is inclined
It is high.
The method detection limit and lower limit of quantitation of 5 15 kinds of PAHs of table
The detection of 2.4 actual samples
This method is to picking up from Xizhimen North Street, Beijing City (E116 ° of 21', N39 ° 57 ') Chinese juniper (Sabina
Chinensis), prunus cerasifera (Prunus cerasifera), Chinese pine (Pinus tabuliformis) and Chinese white poplar (Populus
Tomentosa) 15 kinds of polycyclic aromatic hydrocarbons in 4 kinds of plant leaf samples are detected.Accurately weigh 5g plant leaf blade sample (dry sample
Product), pre-treatment, upper machine measurement are carried out according to the method described above, and sample analysis the results are shown in Table 6.As seen from the table, 15 kinds of PAHs' is total
For content between 509.58ng/g~1476.54ng/g, detection is limited to 0.29~2.50ng/g.4 kinds of total PAHs' of tree species blade
Content is followed successively by Chinese juniper > prunus cerasifera > Chinese pine > Chinese white poplar, this may be related with plant leaf surface structure and leaf rouge content.
The measurement result (ng/g, dry-eye disease) of PAHs content in 6 actual sample of table
BDL: it is lower than Monitoring lower-cut
3 conclusions
The present invention establishes the measuring method of Determination of Trace Polycyclic Aromatic Hydrocarbons in plant leaf blade sample.Soxhlet extraction can be mentioned effectively
The polycyclic aromatic hydrocarbon in sample is taken, it is miscellaneous that self-control silicagel column and gel column can effectively purify pigment and grease in extract etc.
Matter meets the analysis requirement of gas chromatography-mass spectrum.Impurity can be effectively removed in this method, reduces the interference of impurity, quantitative standard
Really, suitable for common tree leaf sample 15 kinds of PAHs measurement, mention to measure PAHs in large quantities of plant tree species blades from now on
For reference, there is certain application value.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (3)
1. a kind of method of polycyclic aromatic hydrocarbon in measurement plant leaf blade, characterized by the following steps:
(1) Soxhlet extraction is carried out to plant powder and is concentrated by evaporation: weighed plant powder 5g, be added in glass fiber filter cylinder,
After adding the PAHs purification mark that 50 μ L concentration are 1 μ g/mL, filter cylinder is put into Soxhlet extractor, with 200mL n-hexane/dichloro
Methane blended solution V/V=1/1, extract 16 continuously with the no less than 4 times speed of flowing back per hour ~ for 24 hours；
After Soxhlet extraction, extracting solution rotary evaporation is concentrated, temperature control is concentrated into 1 ~ 2mL at 45 DEG C or less, and 10mL is being added just
Hexane continues to rotate, and solvent is switched to n-hexane completely, is concentrated into 1mL or so, is ready for purified treatment；
PAHs purification mark: acenaphthylene-d10, phenanthrene-d10, fluoranthene-d10, pyrene-d10, benzo (a) pyrene-d12, benzo (g, h, i) pyrene-
D12 mixed solution, the solvent used is nonane, the μ g/ml of ρ=10, uses n-hexane to be diluted to 1ug/mL and extracts as working solution sample
Preceding addition is taken, for quantifying for makings analysis；
(2) liquid that step (1) obtains successively is used into the purification that hand fills out silicagel column and GPC column carries out sample, is purified liquid；
The method that silicagel column is purified is filled out using hand to include the following steps:
In chromatography one small silica wool of column bottom pad, inner wall is rinsed with 10 mL n-hexanes, wet method dress post is successively filled out from bottom to up
10 g of activated silica gel, 6 g of anhydrous sodium sulfate are filled, silicagel column is eluted with 60 mL n-hexanes, the sample being concentrated is transferred to silica gel
On column, is eluted, discarded with 25 mL n-hexanes；It is eluted again with the mixed solution of 80 mL n-hexanes and methylene chloride, collects elution
Liquid, entire elution process elution speed are 1 drop/s, and eluent rotary evaporation is concentrated into 3mL hereinafter, preparing the GPC column of next step
Purified treatment；The specification of the chromatographic column are as follows: the diameter cm of 15 mm × 30, the mixed solution of the n-hexane and methylene chloride
The volume ratio of middle n-hexane and methylene chloride is 4:1；
The GPC column purification processing includes the following steps:
Entire GPC column purification process is the mixed solution of n-hexane and methylene chloride using solvent, and cleaned gel is loaded
Into chromatographic column, filling height is 20 cm, elutes GPC column with 100 mL mixed solutions；Wherein, the n-hexane and dichloromethane
The volume ratio of n-hexane and methylene chloride is 1:1 in the mixed solution of alkane；The chromatographic column be included husky board diameter be 25 mm ×
The chromatographic column of 30 cm；The sample being concentrated is transferred on GPC column, is eluted, is discarded with 50 mL mixed solvents；100mL is used again
Mixed solvent elution, is collected；It is finally eluted, is discarded with 50mL mixed solution；1 ~ 2mL is concentrated in eluent rotary evaporation, is transferred to
Nitrogen blowpipe, nitrogen are blown to 0.5 mL, and the PAHs sample introduction mark that 50 μ L concentration are 1 μ g/mL is added in final sample, is vortexed and mixes
Afterwards, it is purified liquid, i.e., solution to be measured；
(3) scavenging solution is detected polycyclic aromatic hydrocarbon therein using gas-chromatography and the method for mass spectrometry: GC conditions are such as
Under:
Using DB-5MS, the mm × 0. 25 μm capillary column of 30 m × 0. 25, initial temperature is 50 DEG C, keeps 2 min；With
20 DEG C/min rises to 200 DEG C, retains 2 min, then rises to 240 DEG C again with 4.5/min, retains 2 min, finally with 2.5 DEG C/
Min rises to 290 DEG C, retains 2 min；Injector temperature is 280 DEG C, and carrier gas is high-purity helium, purity 99.999%, sampling volume
For 1.0 μ L, Splitless injecting samples；
Mass Spectrometry Conditions are as follows: the source EI, electron energy: 70eV, transmission line temperature: 270 DEG C, ion source temperature: and 250 DEG C, detector
Voltage: -1300V, ionization current: 100 μ A, scan method are selective ion SIM.
2. the method for polycyclic aromatic hydrocarbon in measurement plant leaf blade according to claim 1, it is characterised in that: the polycyclic aromatic hydrocarbon
For acenaphthylene, acenaphthene, fluorenes, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, bend, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, two
Benzo (a, h) anthracene, benzo (g, h, i) and indeno (1,2,3-c, d) pyrene.
3. the method for polycyclic aromatic hydrocarbon in measurement plant leaf blade according to claim 1, it is characterised in that: the plant is circle
Cypress, prunus cerasifera, Chinese pine or Chinese white poplar.
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| CN110161165B (en) * | 2019-05-17 | 2021-08-24 | 广东工业大学 | Analysis method for simultaneously detecting levels of polycyclic aromatic hydrocarbon and hydroxyl metabolites thereof in hair |
| CN112946241B (en) * | 2021-02-03 | 2022-04-15 | 中国科学院生态环境研究中心 | Morphological analysis method of organic pollutants in soil based on graded extraction |
| CN113447580A (en) * | 2021-06-11 | 2021-09-28 | 南方医科大学顺德医院(佛山市顺德区第一人民医院) | Method for analyzing content of polycyclic aromatic hydrocarbon in plant leaves |
| CN113567596A (en) * | 2021-06-28 | 2021-10-29 | 中国科学院南京土壤研究所 | Purification column for extracting polycyclic aromatic hydrocarbon and preparation method thereof |
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