CN102297797B - Gas phase-liquid phase online coupling method for purifying dioxin type sample - Google Patents
Gas phase-liquid phase online coupling method for purifying dioxin type sample Download PDFInfo
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Abstract
The invention relates to a method for purifying dioxin type sample, in particular to a method for purifying sample through the following steps: based on the properties of dioxin type semi-volatile organic pollutant, combining GC separation with LC purification, introducing samples with large volume to GC through circular sampling and retention gap column; separating volatile ingredients from non-volatile ingredients through gasification and blowing; separating semi-volatile ingredients from easily volatile ingredients through GC separation, collecting the semi-volatile ingredients through stream switching; and separating the dioxin type semi-volatile organic pollutant from the semi-volatile ingredients through LC separation. Used matching equipment is composed of a high pressure pump, a sample valve, a six-way switching valve, a retention gap column, a GC analytical column, a four-way valve and an LC column. When purifying the dioxin type sample, the invention is advanced in solvent saving, simple operation and low experiment cost, and is applicable to separation and analysis of trace semi-volatile durable organic pollutant.
Description
Technical field
The present invention relates to a kind of GC separates and LC purifying on-line coupling De dioxin sample purification method.
Background technology
Bioxin typically refers to many chloros dibenzodioxin English (polychlorinateddibenzo-pdioxins, PCDDs) and many chloros dibenzofurans (polychlorinateddibenzofurans, PCDFs), different according to the number of chlorine atom and the position of substitution, this compounds has 210 kinds of isomeride, and poisonous De bioxin has 17 kinds, all be 2 mostly, the compound of 3,7,8 chloros, wherein 2, the toxicity of 3,7,8-TCDD is the strongest.Because the chemical constitution of coplanar polychlorinated biphenyl (coplanarpolychlorinated diphenyls, co-PCBs) is similar to bioxin with toxicology character, so also be called dioxin polychlorinated biphenyl (dioxin-like PCBs).They all are persistence organic pollutant (POPs), has the bioaccumulation effect, can enter human body by approach such as skin, alimentary canal, respiratory tracts, cause the diseases such as skin chloracne, headache, insomnia, and the malignant disease such as malignant tumour, hypoimmunity, developmental deformity.The dioxin pollutant often is in the ultratrace level in environmental sample, and the mutual interference component often exceeds several orders of magnitude, so its Sample Purification on Single and quantitative test process are very complicated.
Dioxin sample purification method commonly used mainly is to adopt traditional multistage chromatographic column to purify, and extract is crossed multilayer silicagel column, alumina column, carbon column successively, and the sample purification liquid that analytical instrument requires is satisfied in final acquisition.Wherein, the multilayer silicagel column can be removed the chaff interferences such as palycyclic aromatic, phenols, carboxylic acid, lipoid, the alkali alumina post can be separated PCDD/Fs and co-PCBs from nonplanar PCB isomeride and many chlorination aromatic hydrocarbons compound, carbon column can keep the molecule of plane, hither plane, the on-plane surface molecule is not retained, and is retained molecule and can adopts intensive polar solvent to elute.Whole sample purification process needs the replacing eluting solvent and carries out eluent to concentrate, during operating cost; Consume about the residual level of farming organic solvent 500mL, sample blank value is higher; And when sample substrate is complicated, the stack of impurity and analyte cut can appear; In addition, amount of filler is large and can't reuse.
Carry out the robotization treatment technology of purification method and LC in conjunction with accelerated solvent extraction, traditional multistage chromatographic column, (the Fluid Management Systems of U.S. FMS company, Inc.) developed automatic high pressure extraction/sample purification system (Automated Pressurized LiquidExtraction/Power-Prep Dual Extraction and Clean-up system), with extraction, purifying and concentrated three partly integratedization.Wherein purification part adopts commercial silicagel column, alumina column, carbon column, by selecting suitable elution program, can finish the automatic purifying of PCDD/Fs, PCBs, PBDEs, PAHs and pesticide in the different sample substrates.That the automatic purifying instrument of FMS has is time saving and energy saving, increase result reliability, reduce the advantage to operating personnel's harm, but instrument is expensive, and commercial chromatographic column can not be reused, and the consumption solvent reaches 400mL, and experimental cost has increased nearly one times than classic method.
Summary of the invention
The object of the invention is to set up the method for a kind of GC separation and LC purifying on-line coupling De dioxin sample purification.The method combines the GC separation with the LC purifying, and has adopted the large volume sample injection technology in GC, comprises that sample introduction, gasification purging, LC purifying, GC separate four steps: at first by ring sampling technique and retention gap post, realize introducing bulk sample among the GC; Secondly utilize gasification to purge, the volatile constituent in the extract is separated from difficult volatility/nonvolatile element; Then adopt GC to separate, the half volatile component in the volatile constituent and volatile component are separated, collect the half volatile component by the stream switching selectivity; Utilize at last LC to separate, De dioxin organic contaminant in the half volatile component is separated, finish the method for sample purification.Compare with classic method, it only be original 1/10th that the method consumes organic solvent, and simplifies purification step, improves analysis speed, and GC post, LC post can Reusabilities, and the reduction experimental cost has reduced the harm of organic reagent to operating personnel.In fact, from Method And Principle, take the most complicated De dioxin of purification process pollutant as research object, the gas phase of setting up-liquid phase on-line coupling De dioxin sample purification method, for different half volatile organic contaminants, the condition of carrying out changes and optimizes, and is effectively equally to the purification of other half volatile organic contaminant, and is significant to the compartment analysis of persistence organic pollutant.
The objective of the invention is to be achieved through the following technical solutions:
Gas phase-liquid phase on-line coupling De dioxin sample purification method, the supporting device that sample purification adopts comprises solvent bottle, high-pressure pump, the one or six direction changeover valve, carrier gas, pressure maintaining valve, flow stabilizing valve, the first transfer valve, quantity tube, sampling valve, retention gap post, three-way connection, the casing with heating element and exhaust fan, GC analytical column, four-way valve, the two or six direction changeover valve, LC post and the second transfer valve with heating element;
Sampling valve is a six-way injection valve, it is position and 6. being connected with the two ends of quantity tube respectively 3., 4. it link to each other the 5. position of position by pipeline and the one or six direction changeover valve, and 5. it link to each other with retention gap post entrance point by pipeline the position, and 1., 2. it link to each other with waste liquid bottle respectively;
4. the position of the one or six direction changeover valve is connected with gas-carrier pipeline through flow stabilizing valve, pressure maintaining valve, and 1. it link to each other with the 2. position of the two or six direction changeover valve by pipeline the position, and 6. it be connected with the solvent bottle pipeline through high-pressure pump the position, its 2. position sealing, 3. position emptying;
The endpiece of retention gap post links to each other by the import of three-way connection with the GC analytical column, two interfaces of three-way connection link to each other with the GC analytical column with the retention gap post respectively, the 3rd interface links to each other with the 3. position of the first transfer valve by pipeline, 2. the position of the first transfer valve links to each other with flow stabilizing valve by pipeline, the 1. position emptying of the first transfer valve;
The outlet of GC analytical column links to each other by the 4. position of pipeline and four-way valve, its 3. the position and 4. the position be connected, 3. position emptying, 2. it link to each other with the 3. position of the two or six direction changeover valve by pipeline the position, 1. 6. it linking to each other through one section collection tube and the two or six direction changeover valve;
3. the position of the two or six direction changeover valve and 4. the position link to each other, 5. with 6. link to each other, 5. position emptying, 4. position sealing, 1. it link to each other by the import of pipeline with the LC post position, the outlet of LC post connects the 3. position of the second transfer valve, and the 1. position of the second transfer valve links to each other with waste liquid bottle, 2. the position links to each other with sample collection bottle;
Wherein retention gap post, GC analytical column and four-way valve all place in the airtight casing, in casing, be provided with four-way valve and retention gap post and the separated dividing plate of GC analytical column, in the residing airtight cavity of four-way valve and in retention gap post and the residing airtight cavity of GC analytical column, be respectively arranged with heating element, and on the outside wall surface of retention gap post and GC analytical column airtight cavity of living in, be provided with exhaust fan.
Gas phase-liquid phase on-line coupling De dioxin sample purification method combines the GC separation, and adopted the large volume sample injection technology in GC with the LC purifying, comprise that sample introduction, gasification purge, GC separates and four steps of LC purifying;
Sample introduction: soil, sediment, solid waste, air and waste gas, biological testing sample extract after concentrated are injected in the quantity tube, the switch sampling valve begins sample introduction, adopting the ring input mode, is that 0-0.2MPa, flow velocity are that the first via carrier gas of 0.2-15mL/min is sent in the retention gap post with extract through top hole pressure;
Gasification purges and GC separates: control retention gap post and GC analytical column are in the 30-320 ℃ of scope, carry out temperature programme with 0-45 ℃/min, solvent vapo(u)r is from from the first transfer valve emptying, 0.3-60min switches the first transfer valve behind the sample introduction, making 0-0.2MPa, flow velocity is that the second tunnel carrier gas of 0.2-15mL/min arrives three-way connection by the first transfer valve, difficult volatile constituent/nonvolatile element is retained on the inwall of retention gap post in the extract at this moment, and volatile constituent begins gasification, and separates through the GC analytical column;
The outlet of GC analytical column is connected with four-way valve, four-way valve is in constant temperature in the 30-350 ℃ of scope, volatile component is from the 3. position emptying of four-way valve, 3-90min switches four-way valve behind the sample introduction, make its 1. the position and 4. the position link to each other, 2. with 3. link to each other, will be from the isolated half volatile components condense of GC analytical column in collection tube, carrier gas is from the 5. position emptying of the two or six direction changeover valve;
LC purifying: after the residing airtight cavity temperature programme of retention gap post and GC analytical column finishes, switch four-way valve and the two or six direction changeover valve, make the 1. position of four-way valve and 2. link to each other, 3. position and 4. linking to each other, carrier gas is from the 3. position emptying of four-way valve, make the 1. position of the two or six direction changeover valve and 6. link to each other, 2. position and 3. linking to each other, while opening high pressure pump, adopt nonpolar and/or polar organic solvent 1-10mL to be flushed on the LC post with the half volatile component that the flow velocity of 0.1-2mL/min will be condensate in the collection tube, by selecting nonpolar and polar organic solvent to mix as mobile phase, divide 2-5 stagewise gradient, wherein the volume ratio of non-polar solvent is 100-0%, each gradient differs 2-48%, flow velocity with 0.1-5mL/min carries out wash-out, each gradient elution volume is 8-50mL, by switching the second transfer valve, the 2. position Jiang the cut at dioxin-like compound place from the second transfer valve arrives the sample collection bottle, finishes the purification of dioxin-like compound.
Wherein: the retention gap column length is that 1-20m, internal diameter are quartz ampoule or the glass tube that the 0.20-5mm inwall is not coated with stain, has the effect of restriction solvent gasification rate and some difficult volatile constituents of reservation, prevents that it from polluting chromatographic column, needs periodic replacement; GC analytical column length is that 5-70m, internal diameter are that 0.20-0.53mm, thickness of liquid film are CP Sil 5, DB-5, HP-Ultra 2, Rtx-5ms, DB-DIOX, CP Sil 88, SP 2331, RT-2330 or the Silar 10C of 0.1-5 μ m; The withstand voltage 300psi of four-way valve, 350 ℃ of heatproofs; Fixing in the LC post is 1-20g mutually, granularity is the silica gel (acidic silica gel of 3-50 μ m, alkaline silica gel, silver nitrate silica gel etc.), aluminium oxide, anhydrous sodium sulfate, copper powder, Fo Luoli soil, in the fillers such as activated charcoal one or more, can select according to the purpose of separation and purification, for example acidic silica gel can be removed the lipid material in the sample, silver nitrate silica gel and copper powder can be removed sulphur, activated charcoal has good selectivity to the aromatic on plane, can from nonplanar aromatic, separate the aromatic on plane, adopt dry method or wet method dress post, non-polar solvent in the mobile phase is alkane, naphthenic hydrocarbon such as normal hexane, cyclohexane, sherwood oil, polar solvent is chloralkane, the ester class, ethers, ketone, benzene homologues and alcohols are such as methylene chloride, ethyl acetate, ether, acetone, toluene, isopropyl alcohol, in the methyl alcohol organic solvent one or more mix in proportion.
Gas phase-liquid phase on-line coupling De dioxin sample purification method, the admission pressure by adjusting first via carrier gas and the second tunnel carrier gas and/or length and/or internal diameter, the carrier gas of the control first via and the second tunnel carrier gas of first via carrier gas and the second tunnel carrier gas arrival pipeline that three-way connection passes through are consistent at the pressure of three-way connection.
Gas phase-liquid phase on-line coupling De dioxin sample purification method, fixedly phase, mobile phase and heating schedule condition to GC analytical column, LC post change, other half volatile organic contaminant had same clean-up effect, can finish the purification of other half volatile organic contaminations, such as many chloronaphthalenes, polychlorinated biphenyl ether, palycyclic aromatic etc.
Advantage of the present invention and good effect are:
1. raising purification efficiency is simplified purification step.Method of the present invention at first adopts ring sampling technique and retention gap post, realizes introducing bulk sample among the GC; Secondly utilize gasification to purge, the volatile constituent in the extract is separated from difficult volatility/nonvolatile element; Then adopt GC to separate, the half volatile component in the volatile constituent and volatile component are separated, collect the half volatile component by the stream switching selectivity; Utilize at last LC to separate, De dioxin organic contaminant in the half volatile component is separated, finish the method for sample purification.The method has been removed the interference of volatile component and difficult volatile constituent effectively, has avoided that the sample extraction thing is crossed multistage chromatographic column successively and has carried out purifying, therefore improves purification efficiency, simplifies purification step, shortens analysis time.
2. reduce the consumption of organic solvent, reduce experimental cost.The required organic solvent of method of the present invention is tens mL only, be equivalent to 1/10th of classic method, the also corresponding minimizing of discarded quantity of solvent that produces, and GC analytical column, collection tube and LC analytical column in the device all can Reusabilities, followed the principle of Green Chemistry and sustainable development, effectively reduce experimental cost, reduced organic reagent to operating personnel's health hazard.
3. be widely used.Method of the present invention in the complex matrices De dioxin Sample Purification on Single as research object, to other half volatile organic contaminant, carry out suitable condition change and have identical clean-up effect with optimizing, can be widely used in the compartment analysis of the trace half volatile persistence organic pollutant in the complex matrices.
Description of drawings
Below by embodiment and accompanying drawing in detail the present invention is described in detail:
Fig. 1 is the schematic flow sheet of gas phase-liquid phase on-line coupling De dioxin sample purification method;
Fig. 2 is the device synoptic diagram that mates with gas phase-liquid phase on-line coupling De dioxin sample purification method;
Fig. 3 is that the flying dust extract adopts the measurement result of the inventive method and the measurement result comparison diagram of Mthod 1613.
Embodiment
Adopt nitrogen as carrier gas, quantity tube 8 volumes are 100 μ L, retention gap post 10 is 4m * 0.53mm ID quartz capillary column, GC analytical column 13 is DB-5 (30m * 0.32mm * 0.25 μ m), adopt self-designed L C post, the alkaline oxygenated Al filler of 3g 18～32 μ m is packed in 15cm * 0.46mmID LC void column pipe, adopt wet method homogenate dress post, normal hexane balance pillar.
The pressure of pressure maintaining valve 5 is 0.22Mpa, first via carrier gas is all consistent with length and internal diameter that the second tunnel carrier gas arrives three-way connection 11 pipeline that passes through, the admission pressure of first via carrier gas and the second tunnel carrier gas is 0.15Mpa, flow rate of carrier gas 1mL/min is so that first via carrier gas is consistent at the pressure of three-way connection 11 with the second tunnel carrier gas;
Sample introduction: soil, sediment, solid waste, air and waste gas, biological testing sample extract after concentrated are injected into quantity tube 8, and switch sampling valve 9 adopts the ring input mode, with extract in carrier gas is sent to retention gap post 10;
Gasification purges and GC separates: retention gap post 10 and GC analytical column 13 residing airtight cavities are heated to 80 ℃ and keep 8min, and solvent vapo(u)r is from the 1. position emptying from the first transfer valve 7.Residual for prevent that sample from having in quantity tube 8, after sample introduction is finished for the first time, introduce in an identical manner the equal-volume solvent, residual sample wash is arrived in the retention gap post 10.Because sample adopts normal hexane to make solvent, its boiling point is 68.7 ℃, so 80 ℃ of initial column temperatures can guarantee that normal hexane is gasified totally.The vapour volume that retention gap post 10 can hold is limited, so sampling volume is 100 μ L at every turn, and complete in the 10 interior gasifications of retention gap post for guaranteeing solvent, wash residual sample introduction and the sampling interval 4min first time for the second time.With the 1. position emptying of solvent vapo(u)r from the first transfer valve 7, can prevent that to the fixedly impact of phase of GC analytical column 13 prolong the serviceable life of GC analytical column 13, target analytes carries out enrichment method in retention gap post 10 simultaneously.8min switches the first transfer valve 7 behind the sample introduction, make its 2. position and 3. linking to each other, the the second tunnel carrier gas is by the 2. position arrival three-way connection 11 of the first transfer valve 7, retention gap post 10 and GC analytical column 13 residing airtight cavity start programs heat up simultaneously, be raised to 280 ℃ with 30 ℃/min, keep 40min, difficult volatile constituent/nonvolatile element is retained on the inwall of retention gap post 10 in the extract, and volatile constituent begins gasification, and separates through GC analytical column 13;
Four-way valve 14 is in 280 ℃ of constant temperature, and volatile component is from the 3. position emptying of four-way valve 14; 13min behind the sample introduction, be that retention gap post 10 and GC analytical column 13 residing airtight cavities are when being in 230 ℃, switch four-way valve 14, make its 1. the position and 4. the position link to each other, 2. with 3. link to each other, will be from GC analytical column 13 isolated half volatile components condense in collection tube, carrier gas is from the 5. position emptying of the two or six direction changeover valve 15;
LC purifying: after retention gap post 10 and the 13 residing airtight cavity temperature programmes of GC analytical column finish, switch four-way valve 14 and the two or six direction changeover valve 15, make the 1. position of four-way valve 14 and 2. the position link to each other, 3. with 4. link to each other, carrier gas is from the 3. position emptying of four-way valve 14, make the 1. position of the two or six direction changeover valve 15 and 6. the position link to each other, 2. with 3. link to each other, opening high pressure pump 2 adopts the 3mL normal hexane to be flushed on the LC post 16 with the half volatile component that 0.2mL/min will be condensate in the collection tube simultaneously.The elution program of LC post 16 is: select normal hexane and methylene chloride to do mobile phase, divide 2 stagewise gradients, at first normal hexane/methylene chloride volume is washed impurity than (98: 2) with 0.8mL/min wash-out 24min, waste liquid is discharged into the waste liquid bottle from the 1. position of the second transfer valve 17, then switch the second transfer valve 17, make its 2. position and 3. linking to each other, normal hexane/methylene chloride volume than (1: 1) with identical flow velocity wash-out 20min, the cut at this cut Wei dioxin-like compound place, arrive the sample collection bottle from the 2. position of the second transfer valve 17, finish the purification of dioxin-like compound.With normal hexane balance LC post, use in order to next after the off-test.
The mensuration of PCDD/Fs adopts isotopic dilution HRGC/HRMS method.Sample adds 15 kinds of 10 μ L before adopting apparatus of the present invention to purify
13C
122,3,7 of mark, mark (2,3,7,8-TCDD, 1,2 in the PCDD/Fs that 8-replaces extracts, 3,7,8-PeCDD, 1,2,3,4,7,8-HxCD, 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 1,2,3,7,8,9-HxCDF, 2,3,4,6,7,8-HxCDF, 1,2,3,4,6,7,8-HpCDF, 1,2,3,4,7,8,9-HpCDF is 100ng/mL, and OCDD is 200ng/mL) nonane solution.The eluent rotary evaporation of PCDD/Fs is concentrated into about 2mL, and nitrogen dries up rear adding 10 μ L and contains
13C
12Mark 1,2,3, the nonane solution of 4-TCDD (mark in the recovery) 100ng/mL adopts high-resolution gas chromatography (Agilent, USA) high resolution mass spectrum (Micromass, UK) combined instrument to measure after the sealing.GC conditions: Capillary Column for Gas Chromatography Rtx-5ms (60m * 0.25mm ID * 0.25 μ m df), Splitless injecting samples 1 μ L, heating schedule is 120 ℃ of initial temperatures (1min), be raised to 220 ℃ (15min) with 43 ℃/min, be raised to 250 ℃ (25min) with 2.3 ℃/min, be raised to 260 ℃ with 0.9 ℃/min, be raised to 310 ℃ (20min) with 20 ℃/min again, 250 ℃ of transmission line temperature.Mass spectrum condition: EI source, accelerating potential 8000eV, 260 ℃ of ion source temperatures.Detect the corresponding M of PCDD/Fs
+(M+2)
+Or (M+2)
+(M+4)
+The mass chromatography peak and corresponding isotopic mass chromatographic peak, mass resolution R 〉=10000.
15 kinds of 10 μ L
13C
122,3,7 of mark, mark was diluted to 100 μ L as sample with normal hexane in the PCDD/Fs that 8-replaces extracted, and adopted apparatus of the present invention that it is carried out gas chromatography gasification separation and liquid chromatography purifies and separates, and the PCDD/Fs cut of collecting is measured.15 kinds
13C
122,3,7 of mark, the recovery result of the PCDD/Fs that 8-replaces is: 2,3,7,8-TCDD is 68.71%, 1,2,3,7,8-PeCDD is 75.47%, 1,2,3,4,7,8-HxCD is 75.49%, 1,2,3,6,7,8-HxCDD is 71.23%, 1,2,3,4,6,7,8-HpCDD is that 42.19%, OCDD is 36.29%, 2,3,7,8-TCDF is that 59.13%, 1,2,3,7,8-PeCDF is 72.08%, 2,3,4,7,8-PeCDF is 66.66%, 1,2,3,4,7,8-HxCDF is 73.13%, 1,2,3,6,7,8-HxCDF is 73.38%, 1,2,3,7,8,9-HxCDF is that 51.41%, 2,3,4,6,7,8-HxCDF is 59.67%, 1,2,3,4,6,7,8-HpCDF is 44.76%, 1,2,3,4,7,8,9-HpCDF is 36.31%.Experimental result shows, adopts the inventive method that the PCDD/Fs standard specimen is carried out purifying, and recovery result satisfies the recovery requirement among the Mthod 1613 of Environmental Protection Agency (EPA), can be used for actual sample and measure.Subordinate list 1 is the comparison that the Mthod 1613 of the purification method recovery of the present invention and Environmental Protection Agency (EPA) allows the recovery.
The table 1 purification method recovery of the present invention and Mthod 1613 allow the comparison of the recovery
| This method recovery % | The recovery scope % that Mthod 1613 allows | |
| 2378-TCDD 13C12 STD | 68.71 | 25-164 |
| 12378-PeCDD 13C12 STD | 75.47 | 25-181 |
| 123478-HxCDD 13C12 STD | 75.49 | 32-141 |
| 123678-HxCDD 13C12 STD | 71.23 | 28-130 |
| 1234678-HpCDD 13C12 STD | 42.19 | 23-140 |
| OCDD 13C12 STD | 36.29 | 17-157 |
| 2378-TCDF 13C12 STD | 59.13 | 24-169 |
| 12378-PeCDF 13C12 STD | 72.08 | 24-185 |
| 23478-PeCDF 13C12 STD | 66.66 | 21-178 |
| 123478-HxCDF 13C12 STD | 73.13 | 26-152 |
| 123678-HxCDF 13C12 STD | 73.38 | 26-123 |
| 123789-HxCDF 13C12 STD | 51.41 | 29-147 |
| 234678-HxCDF 13C12 STD | 59.67 | 28-136 |
| 1234678-HpCDF 13C12 STD | 44.76 | 28-143 |
| 1234789-HpCDF 13C12 STD | 36.31 | 26-138 |
Embodiment 2
Experimental technique condition and device add 15 kinds of 10 μ L with embodiment 1,90 μ L flying dust extract
13C
122,3,7 of mark, mark in the PCDD/Fs that 8-replaces extracts adopts apparatus of the present invention that it is carried out gas chromatography gasification separation and liquid chromatography purifies and separates, and the PCDD/Fs cut of collecting is measured.Total toxic equivalent of 90 μ L flying dust extracts is 855.486ng/L, wherein 15 kinds
13C
122,3,7 of mark, the recovery result of the PCDD/Fs that 8-replaces is: 2,3,7,8-TCDD is 51.84%, 1,2,3,7,8-PeCDD is 74.21%, 1,2,3,4,7,8-HxCD is 84.94%, 1,2,3,6,7,8-HxCDD is 80.43%, 1,2,3,4,6,7,8-HpCDD is that 51.12%, OCDD is 56.43%, 2,3,7,8-TCDF is that 46.11%, 1,2,3,7,8-PeCDF is 64.94%, 2,3,4,7,8-PeCDF is 68.62%, 1,2,3,4,7,8-HxCDF is 76.13%, 1,2,3,6,7,8-HxCDF is 72.72%, 1,2,3,7,8,9-HxCDF is that 82.26%, 2,3,4,6,7,8-HxCDF is 76.22%, 1,2,3,4,6,7,8-HpCDF is 44.50%, 1,2,3,4,7,8,9-HpCDF is 58.50%.Experimental result shows, adopt the inventive method that the flying dust extract that contains PCDD/Fs is carried out purifying, sample after the purification can satisfy high-resolution gas chromatography/high resolution mass spectrum testing requirement, and recovery result satisfies the recovery requirement among the Mthod 1613 of Environmental Protection Agency (EPA).To adopt simultaneously the measurement result of the inventive method and the measurement result of Mthod 1613 to compare, both have good consistance, see accompanying drawing 3, illustrate that the method has preferably clean-up effect to the actual sample extract that contains PCDD/Fs.
Claims (4)
1. gas-liquid phase on-line coupling De dioxin sample purification method, the supporting device that sample purification adopts comprises solvent bottle (1), high-pressure pump (2), the one or six direction changeover valve (3), carrier gas (4), pressure maintaining valve (5), flow stabilizing valve (6), the first transfer valve (7), quantity tube (8), sampling valve (9), retention gap post (10), three-way connection (11), casing (12) with heating element and exhaust fan, GC analytical column (13), four-way valve (14) with heating element, the two or six direction changeover valve (15), LC post (16) and the second transfer valve (17);
Sampling valve (9) is a six-way injection valve, it is position and 6. being connected with the two ends of quantity tube (8) respectively 3., 4. it link to each other with the 5. position of the one or six direction changeover valve (3) by pipeline the position, 5. it link to each other with retention gap post (10) entrance point by pipeline the position, and 1., 2. it link to each other with waste liquid bottle respectively;
4. the position of the one or six direction changeover valve (3) is connected with carrier gas (4) pipeline through flow stabilizing valve (6), pressure maintaining valve (5), 1. it link to each other with the 2. position of the two or six direction changeover valve (15) by pipeline the position, 6. it be connected with solvent bottle (1) pipeline through high-pressure pump (2) position, its 2. position sealing, 3. position emptying;
The endpiece of retention gap post (10) links to each other with the import of GC analytical column (13) by three-way connection (11), (11) two interfaces of three-way connection link to each other with GC analytical column (13) with retention gap post (10) respectively, the 3rd interface links to each other with the 3. position of the first transfer valve (7) by pipeline, 2. the position of the first transfer valve (7) links to each other with flow stabilizing valve (6) by pipeline, the 1. position emptying of the first transfer valve (7);
The outlet of GC analytical column (13) links to each other with the 4. position of four-way valve (14) by pipeline, its 3. the position and 4. the position be connected, 3. position emptying, 2. it link to each other with the 3. position of the two or six direction changeover valve (15) by pipeline the position, and 1. it link to each other with the 6. position of the two or six direction changeover valve (15) through one section collection tube the position;
3. the position of the two or six direction changeover valve (15) and 4. the position link to each other, 5. with 6. link to each other, 5. position emptying, 4. position sealing, 1. it link to each other by the import of pipeline with LC post (16) position, the outlet of LC post (16) connects the 3. position of the second transfer valve (17), and the 1. position of the second transfer valve (17) links to each other with waste liquid bottle, 2. the position links to each other with sample collection bottle;
Retention gap post (10) wherein, GC analytical column (13) and four-way valve (14) all place in the airtight casing (12), in casing (12), be provided with four-way valve (14) and retention gap post (10) and the separated dividing plate of GC analytical column (13), in the residing airtight cavity of four-way valve (14), and be respectively arranged with heating element in retention gap post (10) and the residing airtight cavity of GC analytical column (13), and on the outside wall surface of retention gap post (10) and GC analytical column (13) airtight cavity of living in, be provided with exhaust fan;
It is characterized in that: GC is separated combining with the LC purifying, and in GC, adopted the large volume sample injection technology, comprise that sample introduction, gasification purge, GC separates and four steps of LC purifying;
Sample introduction: soil, sediment, solid waste, air, waste gas or biological testing sample extract after concentrated are injected in the quantity tube (8), switch sampling valve (9) beginning sample introduction, adopting the ring input mode, is that 0-0.2MPa, flow velocity are that the first via carrier gas of 0.2-15mL/min is sent in the retention gap post (10) with extract through top hole pressure;
Gasification purges and GC separates: control retention gap post (10) and GC analytical column (13) are in the 30-320 ℃ of scope, carry out temperature programme with 0-45 ℃/min, solvent vapo(u)r is from from the first transfer valve (7) emptying, switch the first transfer valve (7) behind the sample introduction 0.3-60min, make 0-0.2MPa, flow velocity is that the second tunnel carrier gas of 0.2-15mL/min arrives three-way connection (11) by the first transfer valve (7), difficult volatile constituent/nonvolatile element is retained on the inwall of retention gap post (10) in the extract at this moment, and volatile constituent begins gasification, and separates through GC analytical column (13);
GC analytical column (13) outlet is connected with four-way valve (14), four-way valve (14) is in constant temperature in the 30-350 ℃ of scope, volatile component is from the 3. position emptying of four-way valve (14), switch four-way valve (14) behind the sample introduction 3-90min, make its 1. the position and 4. the position link to each other, 2. with 3. link to each other, will be from the isolated half volatile components condense of GC analytical column (13) in collection tube, carrier gas is from the 5. position emptying of the two or six direction changeover valve (15);
LC purifying: after the residing airtight cavity temperature programme of retention gap post (10) and GC analytical column (13) finishes, switch four-way valve (14) and the two or six direction changeover valve (15), make the 1. position of four-way valve (14) and 2. link to each other, 3. position and 4. linking to each other, carrier gas is from the 3. position emptying of four-way valve (14), make the 1. position of the two or six direction changeover valve (15) and 6. link to each other, 2. position and 3. linking to each other, while opening high pressure pump (2), adopt nonpolar and/or polar organic solvent 1-10mL to be flushed on the LC post (16) with the half volatile component that the flow velocity of 0.1-2mL/min will be condensate in the collection tube, by selecting nonpolar and polar organic solvent to mix as mobile phase, divide 2-5 stagewise gradient, wherein the volume ratio of non-polar solvent is 100-0%, each gradient differs 2-48%, flow velocity with 0.1-5mL/min carries out wash-out, each gradient elution volume is 8-50mL, arrive the sample collection bottle by switching the 2. position of the second transfer valve (17) Jiang the cut at dioxin-like compound place from the second transfer valve (17), finish the purification of dioxin-like compound.
2. by the described gas-liquid phase on-line coupling of claim 1 De dioxin sample purification method, it is characterized in that: length is that 1-20m, internal diameter are the retention gap post (10) that 0.20-5mm and inwall are not coated with stain quartz ampoule or glass tube; Length is that 5-70m, internal diameter are that 0.20-0.53mm, thickness of liquid film are the GC analytical column (13) of CP Sil 5, DB-5, HP-Ultra 2, Rtx-5ms, DB-DIOX, CP Sil 88, SP 2331, RT-2330 or the Silar 10C type of 0.1-5 μ m; The withstand voltage 300psi of four-way valve (14), 350 ℃ of heatproofs; Fixing in the LC post (16) is in the fillers such as silica gel, aluminium oxide, anhydrous sodium sulfate, copper powder, Fo Luoli soil, activated charcoal of 3-50 μ m one or more for 1-20g, granularity mutually, adopt dry method or wet method dress post, non-polar solvent in the mobile phase is alkane, naphthenic hydrocarbon, and polar solvent is that in chloralkane, ester class, ethers, ketone, benzene homologues and the alcohols one or more mix in proportion.
3. by the described gas-liquid phase on-line coupling of claim 1 De dioxin sample purification method, it is characterized in that: the admission pressure by adjusting first via carrier gas and the second tunnel carrier gas and/or length and/or internal diameter, the carrier gas of the control first via and the second tunnel carrier gas of first via carrier gas and the second tunnel carrier gas arrival three-way connection (11) pipeline that passes through are consistent at the pressure of three-way connection (11).
4. by gas-liquid phase on-line coupling De dioxin sample purification method claimed in claim 1, fixedly phase, mobile phase and heating schedule condition to GC analytical column (13), LC post (16) change, other half volatile organic contaminant is had same clean-up effect, can finish the purification of other half volatile organic contaminations.
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| CN104458925B (en) * | 2013-09-16 | 2016-06-22 | 中国科学院大连化学物理研究所 | The detection method of 2,3,4,7,8-PeCDF in incinerator flying dust and flue gas |
| CN105158380B (en) * | 2015-05-13 | 2020-03-31 | 上海烟草集团有限责任公司 | Interface device for high performance liquid chromatography and gas chromatography/mass spectrometry |
| CN107656002B (en) * | 2016-07-26 | 2020-04-14 | 上海烟草集团有限责任公司 | Large-volume sample introduction technology on gas chromatography column and application thereof |
| CN109987668B (en) * | 2019-04-30 | 2024-01-30 | 正大新科科技有限公司 | Dual-rotation gas-liquid separation device and wastewater treatment equipment |
| CN112730651B (en) * | 2020-12-15 | 2022-08-05 | 湖北微谱技术有限公司 | Rapid pretreatment method for dioxin sample |
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