CN105738515B - The analysis method of 16 kinds of polycyclic aromatic hydrocarbons in a kind of environmental sample - Google Patents
The analysis method of 16 kinds of polycyclic aromatic hydrocarbons in a kind of environmental sample Download PDFInfo
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- CN105738515B CN105738515B CN201610101319.2A CN201610101319A CN105738515B CN 105738515 B CN105738515 B CN 105738515B CN 201610101319 A CN201610101319 A CN 201610101319A CN 105738515 B CN105738515 B CN 105738515B
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- polycyclic aromatic
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- aromatic hydrocarbons
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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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Abstract
A kind of polycyclic aromatic hydrocarbon HPLC analytical method, it is characterized in that being combined fluorescence detector using PDAD, using acetonitrile and water as mobile phase, gradient elution is carried out in polycyclic aromatic hydrocarbon chromatographic column specially.This method simply and effectively solves 16 kinds of polycyclic aromatic hydrocarbons in environmental sample and separates the shortcomings such as undesirable, sensitivity is low, the more efficient content for separating 16 kinds of polycyclic aromatic hydrocarbons in simultaneously determination of the environment sample.
Description
Technical field
The present invention relates in a kind of water, in gas or in soil moderate environment sample 16 kinds of polycyclic aromatic hydrocarbons liquid-phase chromatographic analysis
Method, the method for being combined separation with ultraviolet and fluorescence detector especially with high performance liquid chromatography.
Background technology
Polycyclic aromatic hydrocarbon (PAHs) is a kind of important environmental contaminants, up to hundreds of kinds of quantity.Wherein 16 kinds of polycyclic aromatic hydrocarbons
Due to significant teratogenesis, carcinogenic, mutagenesis be present, priority pollutants are classified as by Environmental Protection Agency.Especially benzo [a]
Pyrene is a kind of maximum strong carcinogen of polycyclic aromatic hydrocarbon Poisoning.16 kinds of polycyclic aromatic hydrocarbon chemical property are close, most of boiling points compared with
Height, the content in many environmental samples is relatively low in addition, and sample matrices composition is complicated, Matrix effects are serious.At present, more cyclophanes in 16
The analysis of hydrocarbon mainly has 3 kinds of gas-chromatography, gas chromatography mass spectrometry and high performance liquid chromatography analysis means.Gas chromatographic analysis higher boiling
Polycyclic aromatic hydrocarbon certain difficulty be present, to isomer can not be totally separated from similar in several properties below, and GC-MS is then
GC high sensitivity, high distinguishing ability are make use of, particularly selects ion scan quantitative determination PAHs, its instrument detection limit can be with
Up to 2 × 10-9, it is the Main Means that trace PAHs is analyzed in environment in recent years sample.But there is also sample analysis for GC-MS analyses
Temperature is higher, and component separation is preferably difficult not to the utmost.HPLC analyses need not vaporize, suitable for the higher component analysis of boiling point,
It is particularly ultraviolet to be combined with fluorescence detector (FLD), it is this kind of to polycyclic aromatic hydrocarbon to have very high selectivity containing fluorescent characteristic material
And sensitivity.16 kinds of polycyclic aromatic hydrocarbons of HPLC chromatogram post separation can only use the low ultraviolet detection of sensitivity for analysis or bad glimmering of optimization
Optical wavelength detects, and sensitivity for analysis is not high and limits applications of the HPLC in environmental sample.
Simultaneously because the component of polycyclic aromatic hydrocarbon is more, so seeking a kind of simple, degree of accuracy height, the chromatogram side of high sensitivity
Method is particularly important.
This experiment uses the multi-wavelength emission pattern of fluorescence detector by being optimized to chromatographic column and gradient
Assay is individually carried out to indeno [123-cd] pyrene, avoid indeno [123-cd] pyrene component because temperature fluctuation and and benzo
[ghi] is difficult to separate.Found by experiment before, the appearance time of indeno [123-cd] pyrene and benzo [ghi] connects very much
Closely (the subsequent appearance of indeno [123-cd] pyrene after benzo [ghi] appearance), the launch wavelength of the two keeps off (benzo [ghi] again
λ em are 430nm, and indeno [123-cd] pyrene λ em are 500nm).If gathering indeno [123-cd] pyrene in 430nm, it is substantially
Do not respond to, thus to excite and the time of launch wavelength change point exist a very harsh requirement, once time changing point
In advance or backwardness can all influence the appearance of the two.As knowable to following table and Figure of description 4, excite and launch in 35.8mim changes
Wavelength, it is to gather indeno [123-cd] pyrene.If fluorescence changes time point and shifted to an earlier date, benzo [ghi] non-appearance is complete；And
Once fluorescence times change point rearward, it is complete that indeno [123-cd] pyrene is unable to appearance again, and thus sample can not be carried out accurately
Measure.How in the case where fluorescence mode is fixed, the slight change for avoiding temperature, flowing equal causes to the appearance of the two
Influence.The present invention further optimizes on the basis of original, by the multi emission mode of fluorescence individually to indeno [123-cd] pyrene
It is measured and avoids above mentioned problem, so as to meets the Accurate Determining to 16 kinds of polycyclic aromatic hydrocarbon contents in environmental sample.
The content of the invention
Because the fluorescence response of acenaphthylene is very low, all acenaphthylenes can only use UV-detector, fluorescence be only suitable for 15 kinds it is polycyclic
The detection of aromatic component.Corresponding fluoroscopic examination bar is set according to various Compound Retention times, absorption maximum and launch wavelength
Part.If adjacent several component retention time intervals be not enough to change wavelength, that just select one it is all suitable to several compounds
Excite and launch wavelength.The optimization fluoroscopic examination program of 15 kinds of polycyclic aromatic hydrocarbons is shown in Table.Make each component obtain it is easy, effectively analyze
Purpose, and the sensitivity of the quantitative analysis of each component is improved simultaneously.
Corresponding wavelength unit during the ultraviolet detection polycyclic aromatic hydrocarbon with fluorescence detector of table 1：nm
16 kinds of polycyclic aromatic hydrocarbon components see the table below：
Inventor is by chromatographic column, the equal condition repeated screening of flowing in efficient liquid phase chromatographic analysis, having explored conjunction
Suitable analysis condition.To take into account the requirement of many kinds of substance separation, ratio of suitable flow visualizing and mobile phase etc. have selected
Crucial testing conditions, the method finally established have reached foregoing invention purpose.
Technical scheme is as follows：
The analysis method of polycyclic aromatic hydrocarbon, sample concentrate constant volume to 1ml after pre-treatment, using high performance liquid chromatography,
With the high performance liquid chromatograph separation detection with fluorescence/UV-detector.Using acetonitrile and water as mobile phase,
SUPELCOSILTMGradient elution is carried out in LC-PAH chromatographic columns or the chromatographic column of other similar natures.
Chromatographic condition is：Ultraviolet detection wavelength 220nm；Mobile phase elution rate 1.0ml/min：35 DEG C of chromatogram column temperature：
Sample injection volume：20ul.
The gradient of gradient elution is preferably in the above method：
| Time (min) | Acetonitrile (%) | Water (%) |
| 0 | 55 | 45 |
| 15 | 55 | 45 |
| 30 | 95 | 5 |
| 40 | 95 | 5 |
| 41 | 55 | 45 |
| 45 | 55 | 45 |
The wavelength change program of fluorescence detector is：
The effect and advantage of this method be：
This gradient elution can efficiently separate out 16 kinds of components in polycyclic aromatic hydrocarbon, baseline separation between each component, method
Effectively, reliably；
Component can be efficiently separated in 45min, and 16 kinds of polycyclic aromatic hydrocarbon components are quantified, and have higher spirit
Sensitivity；
The bright spot of the present invention is using fluorescence multi-emission wavelength pattern to indeno [123-cd] pyrene and benzo [ghi]
Content can be quantified accurately, avoided temperature, mobile phase ratio etc. and slightly changed influence to its appearance.
Embodiment
The efficient liquid phase chromatographic analysis of one 16 kinds of polycyclic aromatic hydrocarbons of embodiment
Instrument and chromatographiccondition-Agilent 1260, chromatographic work station, automatic sampler, column oven.Chromatographic column
For-SUPELCOSILTMLC-PAH (4.6mm × 150mm, 5um), ultraviolet detection wavelength are 220nm, flow velocity 1.0ml/min,
Column temperature is 35 DEG C, and organic phase is acetonitrile, and aqueous phase is water, and gradient elution mode is：
| Time (min) | Acetonitrile (%) | Water (%) |
| 0 | 55 | 45 |
| 15 | 55 | 45 |
| 30 | 95 | 5 |
| 40 | 95 | 5 |
| 41 | 55 | 45 |
| 45 | 55 | 45 |
The wavelength change program of fluorescence detector is：
Experimental procedure：
Polycyclic aromatic hydrocarbon standard reserving solution is diluted step by step, is made into 1.0ug/ml standard liquid.Carried out by above-mentioned condition high
Liquid phase analysis, sample introduction 20ul are imitated, chromatogram refers to Figure of description 1, accompanying drawing 2, accompanying drawing 3.
As a result show, polycyclic aromatic hydrocarbon component can reach good point under the conditions of ultraviolet and fluorescence chromatogram in 45min
From simultaneously because the fluorescence multi emission mode taken, it also avoid the slight change etc. of temperature, mobile phase ratio to indeno
The appearance of [123-cd] pyrene and benzo [ghi] influences, and the two, which is not separated by measure, than before further optimization, before
The two fluorescence pattern for being not separated by measure refers to Figure of description 4；And either uv-spectrogram should fluorescence pattern will
Separating degree in HJ478-2009, HJ478-2009 chromatograms refer to Figure of description 5, accompanying drawing 6；
The methodological study of two analysis method of the present invention of embodiment
It is linear to investigate：The dilution of polycyclic aromatic hydrocarbon standard reserving solution is taken to be formulated as 0.005ug/ml, 0.01ug/ml, 0.05ug/
Ml, 0.1ug/ml, 0.5ug/ml series standard solution, efficient liquid phase chromatographic analysis is carried out, investigate 16 kinds of polycyclic aromatic hydrocarbon components
Linear relationship.It has been observed that good linear relationship is presented in 16 kinds of polycyclic aromatic hydrocarbons.Using peak area A as ordinate, concentration C is horizontal stroke
Coordinate, linear regression is carried out, obtain regression equation respectively.The detection limit of standard substance is calculated with MDL=t (n-1,0.99) S, linearly
Equation, coefficient correlation, detection limit are as shown in the table.
As seen from the above table, each component is in good linear pass with its peak area in the range of 0.005ug/ml~0.5ug/ml
System；The chromatographic process has relatively low detection limit, and 16 kinds of polycyclic aromatic hydrocarbons in environmental sample effectively can be detected.
Chromatographic system precision is investigated：Take the mark that the above-mentioned mixed mark concentration of lower 16 kinds of linear relationship experiment item is 0.005ug/ml
Quasi- solution continuously enters six pins, investigates the precision of method, and precision result is as shown in the table.
16 kinds of polycyclic aromatic hydrocarbon Precision test results
Note：Content data is four after rounding up and retaining decimal point in table, and RSD (%) is then by without the true of choice
Value is calculated
From upper table data, for the RSD of 16 kinds of polycyclic aromatic hydrocarbons within 10%, this method precision is good.
Analysis method Intermediate precision is investigated：
Intermediate precision uses same operating method, and above-mentioned experiment, knot are repeated under different chromatographic systems by different personnel
Fruit see the table below.
16 kinds of polycyclic aromatic hydrocarbon Intermediate precision result of the tests
Note：Content data is four after rounding up and retaining decimal point in table, and RSD (%) is then by without the true of choice
Value is calculated
From upper table data, for the RSD of 16 kinds of polycyclic aromatic hydrocarbons within 10%, this method Intermediate precision is good.
The chromatographic process degree of accuracy is investigated：Take the lower 16 kinds of polycyclic aromatic hydrocarbons of above-mentioned linear relationship experiment item to mix mark to be separately added into
0.01ug, 0.05ug, 0.1ug are in blank sample, after pre-treatment, are analyzed using quantified by external standard method, calculate each component respectively
The rate of recovery.As a result see the table below.
16 kinds of polycyclic aromatic hydrocarbon recovery test results
Note：Rate of recovery data retain one decimal place through rounding up in table, and RSD (%) is then by without the true of choice
Real value is calculated
As seen from the above table, the average recovery rate of lower nine samples of three kinds of concentration is all between 69%-114%, and 9 samples
The RSD of the rate of recovery meets Quality Control requirement, therefore the degree of accuracy of the chromatographic process meets the requirements within 20%.
In summary, the inventive method can efficiently separate 16 kinds of polycyclic aromatic hydrocarbon components, can accurately, quickly determine 16
The component of kind of polycyclic aromatic hydrocarbon, this method is simple, quick, accurate and effective, and precision is high, be in determination of the environment sample 16 kinds it is polycyclic
The preferable chromatographic process of arene content.
[brief description of the drawings]
Fig. 1 is 16 kinds of ultraviolet high-efficient liquid phase chromatograms of polycyclic aromatic hydrocarbon.
Fig. 2 is 14 kinds of polycyclic aromatic hydrocarbon fluorescence high-efficient liquid phase chromatograms.
Fig. 3 is indeno [123-cd] pyrene fluorescence high-efficient liquid phase chromatogram.
Fig. 4 is 15 kinds of polycyclic aromatic hydrocarbon fluorescence high-efficient liquid phase chromatograms.
Fig. 5 is 16 kinds of ultraviolet high-efficient liquid phase chromatograms of polycyclic aromatic hydrocarbon in HJ478-2009 standards.
Fig. 6 is 15 kinds of polycyclic aromatic hydrocarbon fluorescence high performance liquid chromatography in HJ478-2009 standards.
Claims (1)
- A kind of 1. analysis method of 16 kinds of polycyclic aromatic hydrocarbons in environmental sample, it is characterized in that using high performance liquid chromatography, using purple It is combined outside with fluorescence detector, using acetonitrile and water as mobile phase, in the mm of 4.6 mm × 150,5 μm of the special chromatogram of polycyclic aromatic hydrocarbon Gradient elution is carried out on post, testing conditions are：The nm of ultraviolet detection wavelength 220；Mobile phase elution rate：1.0 mL/min；Chromatogram Column temperature：35 ℃；Sample injection volume：20 µl；Gradient elution program is：,Using the multi-wavelength emission pattern of fluorescence detector, indeno [123-cd] the pyrene component of 16 kinds of polycyclic aromatic hydrocarbons is carried out individually Measure, avoid its appearance with benzo [ghi] and disturb, the wavelength change program of fluorescence detector is：。
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| CN106841490B (en) * | 2017-03-10 | 2019-04-05 | 环境保护部华南环境科学研究所 | A kind of method of contained polycyclic aromatic hydrocarbon in detection surrounding air |
| CN107202838B (en) * | 2017-05-10 | 2020-05-19 | 大连理工大学 | Method for detecting polycyclic aromatic hydrocarbon adsorbed in atmospheric environment by textile |
| CN112763637B (en) * | 2020-12-25 | 2022-06-28 | 上海仪电分析仪器有限公司 | Variable wavelength data acquisition and processing method of liquid chromatograph ultraviolet detector |
Citations (2)
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| CN101706480A (en) * | 2009-11-27 | 2010-05-12 | 沈阳大学 | Method for analyzing polycyclic aromatic hydrocarbon content of soil |
| JP2010249647A (en) * | 2009-04-15 | 2010-11-04 | Isuzu Motors Ltd | Recovery rate evaluation method of polycyclic aromatic hydrocarbons |
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| JP2010249647A (en) * | 2009-04-15 | 2010-11-04 | Isuzu Motors Ltd | Recovery rate evaluation method of polycyclic aromatic hydrocarbons |
| CN101706480A (en) * | 2009-11-27 | 2010-05-12 | 沈阳大学 | Method for analyzing polycyclic aromatic hydrocarbon content of soil |
Non-Patent Citations (4)
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| 快速溶剂提取⁃高效液相色谱⁃二极管紫外阵列/荧光串联法同时测定土壤中18种多环芳烃;张纯淳等;《环境化学》;20150630;第34卷(第6期);第1232-1233页 * |
| 紫外-荧光检测器高效液相色谱法测定PM2.5中16种多环芳烃;高庚申等;《环境污染与防治》;20130531;第35卷(第5期);摘要、第1.3部分 * |
| 荧光一紫外检测器高效液相色谱法检测地下水中16种多环芳烃;曹攽等;《岩矿测试》;20101031;第29卷(第5期);第539-542页 * |
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