CN107589199A - The fingerprint test method of multiring aromatic hydrocarbon substance in a kind of indoor depositing dust - Google Patents
The fingerprint test method of multiring aromatic hydrocarbon substance in a kind of indoor depositing dust Download PDFInfo
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Abstract
The invention discloses a kind of fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust, including：Including：(1) prepared by need testing solution；(2) chromatographic condition：ZORBAX Eclipse PAHs C18Chromatographic column (2.1 × 100mm, 1.8 μm, Agilent, USA), the 1.2mLmin of flow velocity 0.8‑1, the 225nm of Detection wavelength 195, column temperature is 33 37 DEG C, mobile phase：The aqueous solution (B) of the acid tetrahydrofuran of acetonitrile (A) volume ratio 0.01 0.03%, carry out gradient elution；(3) determination method：The μ l of need testing solution 1 20 are drawn, liquid chromatograph is injected, determines, produce under above-mentioned chromatographic condition.The inventive method can be realized to tens of kinds, or even is quickly identified while hundreds of PAHs pollutant, and then characterizes its level of pollution and feature comprehensively, can quickly find problem of environmental pollution and take control measures in time.Present invention reduces testing cost, governance efficiency is improved, the improvement totle drilling cost of pollution can be greatly lowered.
Description
Technical field
The present invention relates to a kind of method for quickly identifying of persistent organic pollutants in indoor depositing dust, particularly indoor depositing dust
The quick identification of middle multiring aromatic hydrocarbon substance.
Background technology
Polycyclic aromatic hydrocarbon (Polycyclic Aromatic Hydrocarbons PAHs) is coal, oil, timber, tobacco, is had
Volatile hydrocarbon caused by the organic matter imperfect combustion such as machine high-molecular compound, it is that important environment and food are dirty
Contaminate thing.Hitherto it is found that there is more than 200 kinds of PAHs, wherein there is considerable part that there is carcinogenicity, such as benzo[α, benzo α anthracenes etc..
PAHs is distributed widely in environment, can be found in each corner that we live, and any organic matter processing, is discarded, burning
Or the place used is likely to produce polycyclic aromatic hydrocarbon.
For PAHs monitors species, monitor 8 kinds of PAHs compounds from early stage and be progressively transitioned into excellent 16 kinds of the control of USEPA recommendations
PAHs compounds.1979 EPA (EPA) promulgated 129 kinds of screen priority pollutants, wherein PAHs pollutants have
16 kinds.In August, 2014, Germany technology equipment and the consumer goods committee (ATAV) disclose the PAHs for needing to carry out GS certified products
Management and control requirement, new standard also add for benzene in addition to 18 kinds of PAH of reservation total amount limit value and the limit value of benzo (a) pyrene
And 10 kinds of PAH such as (e) pyrene, benzo (a) anthracene, benzo (b) fluoranthene, naphthalene limit value, and specification acenaphthylene, acenaphthene, fluorenes, phenanthrene, pyrene,
The total amount limit value of 7 kinds of anthracene, fluoranthene PAH.In this context, the clear and definite PAHs compounds of 18 kinds of toxicity are received including Environmental Studies
The extensive concern of every field inside.But for Environmental Studies field, so far, it has been found that PAHs and its spread out
Biology up to more than 200 is planted, wherein there is considerable part to have stronger carcinogenicity, has the PAHs pollutants of overt toxicity far from
Only the PAHs toxic pollutants outside by 18 kinds of extensive concern, this 18 kinds are far from receiving due attention.PAHs pollutes
Species are various, and composition is complicated, with the existing technology of environmental area and method, is also difficult to tens of kinds, or even hundreds of
Quickly identified while PAHs pollutants, and then characterize its level of pollution and feature comprehensively.
Therefore, prior art, it is difficult to realize to tens of kinds, or even quickly identified while hundreds of PAHs pollutant, nothing
Method characterizes its level of pollution and feature comprehensively, it is impossible to quickly finds problem of environmental pollution, it is impossible to takes control measures to ring in time
Border is administered.Testing cost is high, governance efficiency is low, and the improvement totle drilling cost of pollution is high.
The content of the invention
It is an object of the present invention to provide a kind of fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust.
The inventive method can be realized to tens of kinds, or even is quickly identified while hundreds of PAHs pollutant, and then it is dirty to characterize it comprehensively
Dye level and feature, can quickly find problem of environmental pollution and take control measures in time.Present invention reduces testing cost, carry
High governance efficiency, the improvement totle drilling cost of pollution can be greatly lowered.
The present invention is realized using following technical scheme：The finger-print test of multiring aromatic hydrocarbon substance in a kind of indoor depositing dust
Method, including：
(1) prepared by need testing solution：Indoor depositing dust sample 0.2g is taken, adds the dehydrogenase and 15- of 0.01-0.05 times of weight
The dichloromethane solution of the acetonitrile containing 20-30% of 25 times of weight, ultrasonic extraction, then Microwave Extraction, filtering, filtrate are concentrated into 0.8-
1.2mL, concentrate are transferred to chromatographic column, with 8-12mL n-hexanes-ether solvent pre-flush chromatographic column, then with 8-12mL just oneself
Alkane-dichloromethane eluent, nitrogen, which blows, to be concentrated to dryness, and residue methanol 0.8-1.2mL dissolves, and crosses 0.45 μm of miillpore filter, collects filter
Liquid produces；
(2) chromatographic condition：ZORBAX Eclipse PAHs C18Chromatographic column (2.1 × 100mm, 1.8 μm, Agilent,
USA), flow velocity 0.8-1.2mLmin-1, Detection wavelength 195-225nm, column temperature is 33-37 DEG C, mobile phase：Acid acetonitrile (A)-
The aqueous solution (B) of volume ratio 0.01-0.03% tetrahydrofurans, carry out gradient elution；
(3) method of testing：Need testing solution 1-20 μ l are drawn, liquid chromatograph is injected, is surveyed under above-mentioned chromatographic condition
Examination, collection of illustrative plates is recorded, is produced.
In foregoing indoor depositing dust in the fingerprint test method of multiring aromatic hydrocarbon substance, described ultrasonic extraction；It is
The ultrasonic extraction 10-14min under 28-32 KHzs.
In foregoing indoor depositing dust in the fingerprint test method of multiring aromatic hydrocarbon substance, described Microwave Extraction；It is
The Microwave Extraction 4-6min under 680-720W.
In foregoing indoor depositing dust in the fingerprint test method of multiring aromatic hydrocarbon substance, described chromatographic column；It is layer
It is anhydrous sodium sulfate, silica and copper powder to analyse post inner stuffing.
In foregoing indoor depositing dust in the fingerprint test method of multiring aromatic hydrocarbon substance, filled in described chromatographic column
Thing is anhydrous sodium sulfate, silica and copper powder；The mass ratio for being anhydrous sodium sulfate, silica and copper powder is 1:1.5-2.5：
0.1-1.0。
In foregoing indoor depositing dust in the fingerprint test method of multiring aromatic hydrocarbon substance, described n-hexane-ether
Solvent；The volume ratio for being n-hexane and ether is 2.5-3.5:1.
In foregoing indoor depositing dust in the fingerprint test method of multiring aromatic hydrocarbon substance, the n-hexane-dichloromethane
Alkane；The volume ratio for being n-hexane-dichloromethane is 0.8-1.2:1.
In foregoing indoor depositing dust in the fingerprint test method of multiring aromatic hydrocarbon substance, described carry out gradient elution
Program；It is that elution program is：0-4.5min, 0% (A) -100% (B)；4.5-15.0min, 8% (A) -92% (B)；15.0-
22.0min, 52% (A) -48% (B)；22.0-35.0,70% (A) -30% (B)；35-50min, 95% (A) -5% (B)；
50min, 95% (A) -5% (B).
Inventor has carried out long-term substantial amounts of experiment to the inventive method, and part is as follows：
First, PAHs fingerprint test methods are as follows in the indoor depositing dust sample of optimization：
1st, prepared by need testing solution
Indoor 0.2 gram of depositing dust sample is taken, the dehydrogenase and 20 times of weight for being separately added into 0.03 times of weight contain 25% acetonitrile
Dichloromethane solution, ultrasonic extraction (30 KHz) 12 minutes, then Microwave Extraction (700W) 5 minutes, filtering, filtrate concentration
To about 1mL, concentrate is transferred to chromatographic column (1g anhydrous sodium sulfate+2g silica+0.5g copper powders), with 10mL n-hexanes-second
Ether solvents (volume ratio 3+1) pre-flush chromatographic column, then eluted with 10mL n-hexanes-dichloromethane (1+1), nitrogen, which blows, to be concentrated to dryness,
Residue methanol 1mL dissolves, and crosses 0.45 μm of miillpore filter, and filtrate is used for efficient liquid phase chromatographic analysis.
2nd, chromatographic condition
ZORBAX Eclipse PAHs C18Chromatographic column (2.1 × 100mm, 1.8 μm, Agilent, USA), flow velocity 1mL
min-1, Detection wavelength 220nm, column temperature is 35 DEG C, the μ l of sample size 10.
3rd, gradient elution program
With acid acetonitrile (acetic acid containing volume ratio 0.05%) for A phases, the aqueous solution of the tetrahydrofuran containing volume ratio 0.02%
It is as shown in table 1 below for B phases, different analysis time nodes, the situation of change of A, B phase：
The eluent gradient elution program of table 1
2nd, specific research process
1st, sample preparation methods
(1) in sample PAHs extraction
Extracted using following methods, i.e.,：Indoor 0.2 gram of depositing dust sample is taken, is separately added into the dehydrogenation of 0.03 times of weight
The dichloromethane solution containing 25% acetonitrile of enzyme and 20 times of weight, ultrasonic extraction (30 KHz) 12 minutes, then Microwave Extraction
(700W) 5 minutes, filtering, is produced.
(2) PAHs purifying research in extract solution
1) evaluation index
1. the PAHs rate of recovery：Using 2- fluorine biphenyl as substitute, above-mentioned " under (1) item " preparation is added at the beginning of purifying
In the extract solution of gained, to the effect of averagely different purification process.The calculation formula of the rate of recovery is as follows：
2. the time that purge process uses：Timing is carried out from purification process is started, is recorded needed for different purification treating methods
The time wanted.
2) different purification treating methods
1. the selection of filler combination in chromatographic column：The species and volume of fixed eluting solvent, on this condition, to different
Filler combination is studied, and the results are shown in Table 2.
The purification effect of 2 different filler combinations of table
As shown in Table 2, from the perspective of the rate of recovery：" 1g anhydrous sodium sulfate+2g silica+0.5g copper powders " combines
The rate of recovery be 93%, hence it is evident that better than other combination.From the point of view of time-consuming situation：In each combination, taken after addition copper powder obvious few
In the person that is not added with copper powder, illustrate that copper powder is added in filler combination can substantially reduce the used time of purification process.
2. solvent elution system is preferred：According to PAHs physics and chemical property, with " 1g anhydrous sodium sulfate+2g dioxies
SiClx+0.5g copper powders " are combined as filler, and different solvents elution system is optimized, the results are shown in Table 3：
The purification effect of the different solvents elution system of table 3
As shown in Table 3, from the perspective of the rate of recovery：" use 10mL n-hexanes-ether solvent (volume ratio 3+1) pre-flush
The rate of recovery of chromatographic column, then eluted with 10mL n-hexanes-dichloromethane (1+1) " and " use 10mL n-hexanes-ether solvent (body
Product is than 3+1) pre-flush chromatographic column, then eluted with 10mL n-hexanes-chloroform (1+1) " substantially quite, it is significantly better than other
Solvent system；From the point of view of time-consuming situation：" 10mL n-hexanes-ether solvent (volume ratio 3+1) pre-flush chromatographic column is used, then is used
10mL n-hexanes-dichloromethane (1+1) elutes " with " 10mL n-hexanes-ether solvent (volume ratio 3+1) pre-flush chromatographic column is used,
Eluted again with 10mL n-hexanes-chloroform (1+1) " it is required to 22 minutes, take essentially identical.As can be seen here, " with 10mL just
Hexane-ether solvent (volume ratio 3+1) pre-flush chromatographic column, then eluted with 10mL n-hexanes-dichloromethane (1+1) " with " using
10mL n-hexanes-ether solvent (volume ratio 3+1) pre-flush chromatographic column, then eluted with 10mL n-hexanes-chloroform (1+1) "
Eluting power with effect be it is consistent, still, it is contemplated that the toxicity of chloroform is apparently higher than dichloromethane, from environment-friendly
Angle, the solvent elution system of final choice is：With 10mL n-hexanes-ether solvent (volume ratio 3+1) pre-flush chromatographic column,
Eluted again with 10mL n-hexanes-dichloromethane (1+1).
(3) sample preparation methods of optimization gained
What it is by above-mentioned " (1) and (2) " is preferably with research, the optimal sample preparation methods of acquisition：Take indoor depositing dust sample
0.2 gram of product, are separately added into the dehydrogenase of 0.03 times of weight and the dichloromethane solution containing 25% acetonitrile of 20 times of weight, and ultrasound carries
Take (30 KHz) 12 minutes, then Microwave Extraction (700W) 5 minutes, filtering, filtrate are concentrated into about 1mL, concentrate is transferred to layer
Post (1g anhydrous sodium sulfate+2g silica+0.5g copper powders) is analysed, with 10mL n-hexanes-ether solvent (volume ratio 3+1) pre-flush
Chromatographic column, then eluted with 10mL n-hexanes-dichloromethane (1+1), nitrogen, which blows, to be concentrated to dryness, and residue methanol 1mL dissolves, and crosses 0.45
μm miillpore filter, filtrate are used for efficient liquid phase chromatographic analysis.
2nd, the optimization and screening of chromatographic condition
(1) mobile phase compositional optimization and screening
Methanol-water, acetonitrile-water system are the preferred flow phase systems of reversed-phase liquid chromatography, and both are mainly in absorbance, color
It is variant to compose pressure, eluting power and separation selectivity etc..In the ultra-violet absorption spectrum of HPLC levels acetonitrile and methanol, acetonitrile
Absorption it is smaller, especially in short-wave band.HPLC level methanol is mainly used in eliminating the impurity with UV absorption, makes specific wavelength
Lower absorbance control is in specification value.HPLC level acetonitriles are suitable for carrying out the high-sensitivity analysis of sample in short-wave band.In addition,
When carrying out gradient elution, ghost peak caused by HPLC level acetonitriles is less.The stream of different organic solvents species and different mixing proportion
Dynamic phase, which is eluted in the pressure born in chromatographic column, has larger difference.The ratio and chromatogram of methanol-water, acetonitrile-water hybrid system
For pressure dependence, identical proportion of composing methanol-water system is with respect to having higher chromatogram pressure for acetonitrile-water system.
The methanol-water and acetonitrile-water of same ratio, usual acetonitrile-water have stronger eluting power, particularly organic phase ratio compared with
When low, this trend becomes apparent.Because the chemical property of methanol and acetonitrile has a larger difference, methanol belongs to protic, and second
Nitrile belongs to aprotic, therefore, if can not obtain good separation using acetonitrile, methanol can be selected.
Based on above-mentioned analysis, the present invention is successively to CH3CN-water (the 1st group), CH3OH-water (the 2nd group), CH3CN-0.01
H3PO4(the 3rd group) and CH3OH-0.03 H3PO4(the 4th group) four kinds of flow visualizings have made intensive studies.
Four kinds of flow phase system Effectiveness Comparison results are shown in Fig. 1.As shown in figure 1, in terms of separating degree angle, the separation of 1-4 groups
Quantity of the degree more than 1.5, which is respectively the 150,113,108 and 113, the 1st group, has preferable separating effect；For chromatographic peak number,
1-4 groups are respectively that the 160,143,137 and 141, the 1st group of chromatogram peak number is more；In terms of peak area, using the 4th group as reference, 1-
3 groups of peak area is 1.3,1.1 and 0.96 times of the 4th group respectively, illustrates that the 1st group of chromatographic peak area is maximum.Comprehensive separation
From the point of view of degree, chromatographic peak quantity and peak area this three big performance assessment criteria, the 1st group is CH3CN-water system have preferably separation and
Eluting power, therefore, from CH3Flow phase system of the CN-water system as chromatographic isolation.
(2) Detection wavelength
For acquisition Chromatographic information as much as possible, it is same to have selected tetra- wavelength of 220nm, 254nm, 310nm and 340nm
When be measured, meanwhile, carry out full wavelength scanner research using PDAD, the 3D figures of full wavelength scanner are shown in Fig. 2.
Comparative study finds that the chromatographic peak occurred under 220nm wavelength is most, and most of chromatographic peaks absorption intensity at 220m wavelength
Maximum, therefore, the Detection wavelength that finally 220nm is gathered as PAHs finger-prints in the indoor depositing dust sample of the present invention.
(3) chromatographic column
Chromatographic column is the carrier of chromatographic isolation, and each compound is needed after realizing separation on a column in sample, into inspection
Device is surveyed, the characteristic signal of compound converts the information (chromatographic peak) on chromatogram after being captured by detector, from according to chromatographic peak
Retention time and peak area carry out analysis qualitative and quantitative analysis.Therefore, suitable chromatographic column refers to for PAHs in depositing dust sample
The collection of line collection of illustrative plates is extremely important.Research process of the present invention, PAHs chemical characteristics are taken into full account, select reversed-phase liquid chromatography pair
It is separated, therefore reverse-phase chromatographic column need to be carried out preferred.The conventional silica gel bonded chromatographic post Eclipse of present invention selection
XDB-C8 (4.6 × 250mm, 5 μm), ZORBAXSB-C18 (4.6 × 250mm, 5 μm) and PAHs chromatographic column speciallies ZORBAX
Eclipse PAHs C18(4.6 × 250mm, 5 μm) is compared.As a result show, conventional chromatogram post Eclipse XDB-C8
(4.6 × 250mm, 5 μm) and ZORBAXSB-C18 (4.6 × 250mm, 5 μm) to PAHs although can separate, to from each
From the point of view of the peak type and separating degree of chromatographic peak, its analytical effect is substantially not so good as ZORBAX Eclipse PAHs C18(4.6×
250mm, 5 μm) chromatographic column.ZORBAX Eclipse PAHs C18(4.6 × 250mm, 5 μm) can be each PAHs in depositing dust sample
It is kept completely separate, and separating degree is preferable, chromatogram peak type is sharp, meets the requirement of chromatography evaluation.Therefore, ZORBAX is selected
Eclipse PAHs C18(4.6 × 250mm, 5 μm) chromatographic column is used for follow-up study.
(4) optimization of gradient elution program
Different gradient elution programs have decisive influence, therefore, this hair to the separating effect of each PAHs components in sample
Bright research process, using the peak type, mathematics and separating degree of chromatographic peak as evaluation index, following different elution programs are ground
Study carefully：
Gradient elution program 1：
| Time (min) | A phases (%) | B phases (%) |
| 0 | 0 | 100 |
| 4.5 | 8 | 92 |
| 15.0 | 52 | 48 |
| 22.0 | 70 | 30 |
| 35.0 | 95 | 5 |
| 50.0 | 95 | 5 |
Gradient elution program 2：
Gradient elution program 3：
| Time (min) | A phases (%) | B phases (%) |
| 0 | 0 | 100 |
| 6 | 6 | 94 |
| 14.0 | 45 | 55 |
| 26.0 | 65 | 35 |
| 40.0 | 95 | 5 |
| 50.0 | 95 | 5 |
Gradient elution program 4：
| Time (min) | A phases (%) | B phases (%) |
| 0 | 0 | 100 |
| 6 | 10 | 90 |
| 17.0 | 40 | 60 |
| 28.0 | 80 | 20 |
| 36.0 | 95 | 5 |
| 50.0 | 95 | 5 |
Gradient elution program 5：
| Time (min) | A phases (%) | B phases (%) |
| 0 | 0 | 100 |
| 7 | 7 | 93 |
| 12.0 | 59 | 41 |
| 24.0 | 75 | 26 |
| 37.0 | 92 | 8 |
| 50.0 | 95 | 5 |
Gradient elution program 6：
| Time (min) | A phases (%) | B phases (%) |
| 0 | 0 | 100 |
| 7.5 | 9 | 91 |
| 16.0 | 54 | 46 |
| 23.0 | 73 | 27 |
| 38.0 | 91 | 9 |
| 50.0 | 95 | 5 |
Gradient elution program 7：
| Time (min) | A phases (%) | B phases (%) |
| 0 | 0 | 100 |
| 6.5 | 5 | 95 |
| 15.5 | 53 | 47 |
| 25.0 | 77 | 23 |
| 38.5 | 93 | 7 |
| 50.0 | 95 | 5 |
As a result show, from the point of view of the peak type, mathematics and separating degree of each chromatographic peak, gradient elution program 1 has best effect
Fruit, separating degree is preferably, chromatogram peak type is sharp, the quantity of chromatographic peak is most, meets the requirement of chromatography evaluation.Therefore, select
Gradient elution program 1 is final analysis condition.
(5) QA and QC
1) Precision Experiment
Precision Experiment is normally used for assessing the accuracy and reliability of a newly-built qualitative or quantitative analysis method, profit
Same test sample is determined simultaneously with defined condition determination, is recorded at least 6 parallel determinations, is calculated different test results
Between relative average standard deviation value (RSD values), if RSD values are less than 3%, then it is assumed that the analysis method established has good
Precision.
Research process of the present invention, system is carried out to PAHs fingerprint test methods in the depositing dust sample established
Precision test is tested.It is specific as follows：Take depositing dust sample appropriate, by preferable sample solution preparation method and chromatographic condition, connect
Continue sample introduction 6 times, record collection of illustrative plates.Using 34min or so big peak as reference, respectively to the reservation of the shared chromatographic peak in chromatogram
Time and chromatographic peak area are recorded, and calculate respective RSD values, the results showed that, peak area (A) and retention time (TR)
RSD values are respectively 0.47% and 2.46%, meet the requirement of precision test.Thus, it is believed that the method that the present invention is established
Its precision is good, available for correlation analysis with assessing.
2) repeated experiment
Repeated experiment refers to that using identical sample be research object, and parallel test is carried out to the analysis method established
Research, in the case of ensureing that operating personnel, instrument and equipment, place etc. do not change, in prescribed limit, take same concentration
Test sample, evaluated with the result at least determining 6 parts, if relative mean standard deviation (RSD) value of measurement result is less than
3%, then it is considered as the reproducible of method.Research process of the present invention, depositing dust sample powder 0.5g is taken, totally 6 parts, respectively by above-mentioned
The method of foundation prepares need testing solution, measure, records chromatogram.Using 34min or so big peak as reference, shared peak is recorded
Relative peak area and relative retention time, and calculate its RSD value, investigate the reappearance of experiment.As a result Fig. 3 is seen, the results showed that,
Peak area (A) and retention time (T between the shared chromatographic peak shown in chromatogram in 6 parts of samplesR) RSD values are respectively
0.50% and 2.51%, meet the requirement of replica test, illustrate that established PAHs finger-prints acquisition method can repeat
Reproduction test result, available for correlation analysis with assessing.
3) stability experiment
Stability experiment be usually used in assessing in need testing solution target substance how long in the range of it is stable, do not decompose,
Never degenerate, so as to instruct established analysis test method to carry out analysis test in rational time range, ensure test knot
Fruit is accurately and reliably.Stability test need to generally use same sample solution to carry out test analysis in different time node, and count
Calculate the relative standard deviation between test result.Research process of the present invention, take depositing dust need testing solution, by it is above-mentioned preferably after
Chromatographic condition, it is measured respectively in 6 different times 0h, 2h, 4h, 8h, 12h and 24h.As a result show, share peak peak area
And retention time (T (A)R) RSD values respectively 0.49% and 2.51%, show that need testing solution is good in 24h internal stabilities.
(6) sample test
By taking the Indoor Residential Ecological depositing dust sample of Guiyang Region as an example, using the assay method of above-mentioned foundation, to certain family Indoor Residential Ecological
Sample has carried out determining fingerprint pattern, and measurement result is shown in Table 4, as follows：
It by Fig. 4, can intuitively find, about 38 chromatographic peaks be contained in the indoor depositing dust, i.e.,：Illustrate the depositing dust sample
In contain 38 kinds of PAHs class materials.By the test of the finger-print, realize in the depositing dust sample PAHs class materials it is fast
Speed identification.
Simply from material, qualitatively angle has carried out the identification of PAHs pollutants for above-mentioned quick identification, in order to further characterize
PAHs classes content of material in sample is horizontal, has carried out quantitative test to each specific PAHs, the results are shown in Table 10.
PAHs measurement result tables in certain the depositing dust sample of table 10
Therefore, the inventive method can be realized to tens of kinds, or even is quickly identified while hundreds of PAHs pollutant, and then
Its level of pollution and feature are characterized comprehensively, can quickly be found problem of environmental pollution and be taken control measures in time.Reduce detection
Cost, governance efficiency is improved, so the improvement totle drilling cost of pollution can be greatly lowered in the present invention.
Brief description of the drawings
Fig. 1 is different flow phase system efficiency figures；
Fig. 2 is indoor depositing dust sample full wavelength scanner 3D figures；
Fig. 3 is repeated experiment research chromatogram；
Fig. 4 is PAHs class substance finger-prints in certain family Indoor Residential Ecological depositing dust sample.
Embodiment 1.
The fingerprint test method of multiring aromatic hydrocarbon substance in a kind of indoor depositing dust, including：
(1) prepared by need testing solution：Indoor depositing dust sample 0.2g is taken, adds the dehydrogenase and 20 times of weight of 0.03 times of weight
The dichloromethane solution containing 25% acetonitrile, ultrasonic extraction, then Microwave Extraction, filtering, filtrate is concentrated into 1.0mL, and concentrate turns
Chromatographic column is moved to, is blown with 10mL n-hexanes-ether solvent pre-flush chromatographic column, then with 10mL n-hexanes-dichloromethane eluent, nitrogen
It is concentrated to dryness, residue methanol 1.0mL dissolves, and crosses 0.45 μm of miillpore filter, collects filtrate and produces；
(2) chromatographic condition：ZORBAX Eclipse PAHs C18Chromatographic column (2.1 × 100mm, 1.8 μm, Agilent,
USA), flow velocity 1.0mLmin-1, Detection wavelength 220nm, column temperature is 35 DEG C, mobile phase：Acid acetonitrile (A)-volume ratio 0.02%
The aqueous solution (B) of tetrahydrofuran, carry out gradient elution；
(3) determination method：The μ l of need testing solution 10 are drawn, liquid chromatograph is injected, is determined under above-mentioned chromatographic condition, i.e.,
.
Described ultrasonic extraction；It is the ultrasonic extraction 12min under 30 hertz.
Described Microwave Extraction；It is the Microwave Extraction 5min under 700W.
Described chromatographic column；It is that chromatographic column inner stuffing is anhydrous sodium sulfate, silica and copper powder；Described anhydrous sulphur
The mass ratio of sour sodium, silica and copper powder is 1:2.0：0.8.
Described n-hexane-ether solvent；The volume ratio for being n-hexane and ether is 3.0:1.
Described n-hexane-dichloromethane；The volume ratio for being n-hexane-dichloromethane is 1.0:1.
The carry out gradient elution；Elution program is：0-4.5min, 0% (A) -100% (B)；4.5-15.0min, 8%
(A) -92% (B)；15.0-22.0min, 52% (A) -48% (B)；22.0-35.0,70% (A) -30% (B)；35-50min,
95% (A) -5% (B)；50min, 95% (A) -5% (B).
Embodiment 2.
The fingerprint test method of multiring aromatic hydrocarbon substance in a kind of indoor depositing dust, including：
(1) prepared by need testing solution：Indoor depositing dust sample 0.2g is taken, adds the dehydrogenase and 25 times of weight of 0.05 times of weight
The dichloromethane solution containing 30% acetonitrile, ultrasonic extraction, then Microwave Extraction, filtering, filtrate is concentrated into 1.2mL, and concentrate turns
Chromatographic column is moved to, is blown with 12mL n-hexanes-ether solvent pre-flush chromatographic column, then with 12mL n-hexanes-dichloromethane eluent, nitrogen
It is concentrated to dryness, residue methanol 1.2mL dissolves, and crosses 0.45 μm of miillpore filter, collects filtrate and produces；
(2) chromatographic condition：ZORBAX Eclipse PAHs C18Chromatographic column (2.1 × 100mm, 1.8 μm, Agilent,
USA), flow velocity 1.2mLmin-1, Detection wavelength 225nm, column temperature is 37 DEG C, mobile phase：Acid acetonitrile (A)-volume ratio 0.03%
The aqueous solution (B) of tetrahydrofuran, carry out gradient elution；
(3) determination method：The μ l of need testing solution 20 are drawn, liquid chromatograph is injected, is determined under above-mentioned chromatographic condition, i.e.,
.
Described ultrasonic extraction；It is the ultrasonic extraction 14min under 32 KHzs.
Described Microwave Extraction；It is the Microwave Extraction 6min under 720W.
Described chromatographic column；It is that chromatographic column inner stuffing is anhydrous sodium sulfate, silica and copper powder；The anhydrous slufuric acid
The mass ratio of sodium, silica and copper powder is 1:1.5：0.1.
Described n-hexane-ether solvent；The volume ratio for being n-hexane and ether is 3.5:1.
Described n-hexane-dichloromethane；The volume ratio for being n-hexane-dichloromethane is 1.2:1.
Described carry out gradient elution；It is that gradient elution program is：0-4.5min, 0% (A) -100% (B)； 4.5-
15.0min, 8% (A) -92% (B)；15.0-22.0min, 52% (A) -48% (B)；22.0-35.0 70% (A) -30%
(B)；35-50min, 95% (A) -5% (B)；50min, 95% (A) -5% (B).
Embodiment 3.
The fingerprint test method of multiring aromatic hydrocarbon substance in a kind of indoor depositing dust, including：
(1) prepared by need testing solution：Indoor depositing dust sample 0.2g is taken, adds the dehydrogenase and 15 times of weight of 0.01 times of weight
The dichloromethane solution containing 20% acetonitrile, ultrasonic extraction, then Microwave Extraction, filtering, filtrate is concentrated into 0.8mL, and concentrate turns
Chromatographic column is moved to, with 8mL n-hexanes-ether solvent pre-flush chromatographic column, then with 8mL n-hexanes-dichloromethane eluent, nitrogen blows dense
Dry, residue methanol 0.8mL dissolvings are reduced to, cross 0.45 μm of miillpore filter, collection filtrate produces；
(2) chromatographic condition：ZORBAX Eclipse PAHs C18Chromatographic column (2.1 × 100mm, 1.8 μm, Agilent,
USA), flow velocity 0.8mLmin-1, Detection wavelength 195nm, column temperature is 33 DEG C, mobile phase：Acid acetonitrile (A)-volume ratio 0.01%
The aqueous solution (B) of tetrahydrofuran, carry out gradient elution；
(3) determination method：The μ l of need testing solution 1 are drawn, liquid chromatograph is injected, determines, produce under above-mentioned chromatographic condition.
Described ultrasonic extraction；It is the ultrasonic extraction 10min under 28 KHzs.
Described Microwave Extraction；It is the Microwave Extraction 4min under 680W.
Described chromatographic column；It is that chromatographic column inner stuffing is anhydrous sodium sulfate, silica and copper powder；The anhydrous slufuric acid
The mass ratio of sodium, silica and copper powder is 1:2.5：1.0.
Described n-hexane-ether solvent；The volume ratio for being n-hexane and ether is 2.5:1.
Described n-hexane-dichloromethane；The volume ratio for being n-hexane-dichloromethane is 0.8:1.
Described carry out gradient elution；It is that elution program is, 0-4.5min, 0% (A) -100% (B)； 4.5-
15.0min, 8% (A) -92% (B)；15.0-22.0min, 52% (A) -48% (B)；22.0-35.0 70% (A) -30%
(B)；35-50min, 95% (A) -5% (B)；50min, 95% (A) -5% (B).
Claims (8)
- A kind of 1. fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust, it is characterised in that：Including：(1) prepared by need testing solution：Take indoor depositing dust sample 0.2g, add 0.01-0.05 times of weight dehydrogenase and 15-25 times The dichloromethane solution of the acetonitrile containing 20-30% of weight, ultrasonic extraction, then Microwave Extraction, filtering, filtrate are concentrated into 0.8- 1.2mL, concentrate are transferred to chromatographic column, with 8-12mL n-hexanes-ether solvent pre-flush chromatographic column, then with 8-12mL just oneself Alkane-dichloromethane eluent, nitrogen, which blows, to be concentrated to dryness, and residue methanol 0.8-1.2mL dissolves, and crosses 0.45 μm of miillpore filter, collects filter Liquid produces；(2) chromatographic condition：ZORBAX Eclipse PAHs C18Chromatographic column (2.1 × 100mm, 1.8 μm, Agilent, USA), stream Fast 0.8-1.2mLmin-1, Detection wavelength 195-225nm, column temperature is 33-37 DEG C, mobile phase：Acid acetonitrile (A)-volume ratio The aqueous solution (B) of 0.01-0.03% tetrahydrofurans, carry out gradient elution；(3) method of testing：Draw need testing solution 1-20 μ l, note Enter liquid chromatograph, tested under above-mentioned chromatographic condition, record collection of illustrative plates, produce.
- 2. the fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust as claimed in claim 1, it is characterised in that： Described ultrasonic extraction；It is the ultrasonic extraction 10-14min under 28-32 KHzs.
- 3. the fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust as claimed in claim 1, it is characterised in that： Described Microwave Extraction；It is the Microwave Extraction 4-6min under 680-720W.
- 4. the fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust as claimed in claim 1, it is characterised in that： Described chromatographic column；It is that chromatographic column inner stuffing is anhydrous sodium sulfate, silica and copper powder.
- 5. the fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust as claimed in claim 4, it is characterised in that： Described chromatographic column inner stuffing is anhydrous sodium sulfate, silica and copper powder；It is anhydrous sodium sulfate, silica and copper powder Mass ratio is 1:1.5-2.5：0.1-1.0.
- 6. the fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust as claimed in claim 1, it is characterised in that： Described n-hexane-ether solvent；The volume ratio for being n-hexane and ether is 2.5-3.5:1.
- 7. the fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust as claimed in claim 1, it is characterised in that： N-hexane-the dichloromethane；The volume ratio for being n-hexane-dichloromethane is 0.8-1.2:1.
- 8. the fingerprint test method of multiring aromatic hydrocarbon substance in indoor depositing dust as claimed in claim 1, it is characterised in that： Described carry out gradient elution program；It is that elution program is：0-4.5min, 0% (A) -100% (B)；4.5-15.0min, 8% (A) -92% (B)；15.0-22.0min, 52% (A) -48% (B)；22.0-35.0,70% (A) -30% (B)；35-50min, 95% (A) -5% (B)；50min, 95% (A) -5% (B).
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