CN101537265A - Method of same column extracting and fractionation separation for organic matter with different poles in water - Google Patents
Method of same column extracting and fractionation separation for organic matter with different poles in water Download PDFInfo
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- CN101537265A CN101537265A CN200910030304A CN200910030304A CN101537265A CN 101537265 A CN101537265 A CN 101537265A CN 200910030304 A CN200910030304 A CN 200910030304A CN 200910030304 A CN200910030304 A CN 200910030304A CN 101537265 A CN101537265 A CN 101537265A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000005416 organic matter Substances 0.000 title claims description 16
- 238000000926 separation method Methods 0.000 title abstract description 9
- 238000005194 fractionation Methods 0.000 title abstract 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 89
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000605 extraction Methods 0.000 claims abstract description 26
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 239000003480 eluent Substances 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 231100000419 toxicity Toxicity 0.000 claims description 19
- 230000001988 toxicity Effects 0.000 claims description 19
- 239000012141 concentrate Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 7
- 239000012488 sample solution Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 27
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000012468 concentrated sample Substances 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 22
- 238000011084 recovery Methods 0.000 description 17
- 238000005406 washing Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 4
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 4
- HAXBIWFMXWRORI-UHFFFAOYSA-N Benzo[k]fluoranthene Chemical compound C1=CC(C2=CC3=CC=CC=C3C=C22)=C3C2=CC=CC3=C1 HAXBIWFMXWRORI-UHFFFAOYSA-N 0.000 description 4
- -1 CB-18 Chemical compound 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 230000002280 anti-androgenic effect Effects 0.000 description 4
- 239000000051 antiandrogen Substances 0.000 description 4
- FTOVXSOBNPWTSH-UHFFFAOYSA-N benzo[b]fluoranthene Chemical compound C12=CC=CC=C1C1=CC3=CC=CC=C3C3=C1C2=CC=C3 FTOVXSOBNPWTSH-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000007096 poisonous effect Effects 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 3
- JLYXXMFPNIAWKQ-SHFUYGGZSA-N alpha-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-SHFUYGGZSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
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- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 3
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- 238000010792 warming Methods 0.000 description 3
- SXQBHARYMNFBPS-UHFFFAOYSA-N Indeno[1,2,3-cd]pyrene Chemical compound C=1C(C2=CC=CC=C22)=C3C2=CC=C(C=C2)C3=C3C2=CC=CC3=1 SXQBHARYMNFBPS-UHFFFAOYSA-N 0.000 description 2
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- JLYXXMFPNIAWKQ-CDRYSYESSA-N beta-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@H](Cl)[C@@H](Cl)[C@@H]1Cl JLYXXMFPNIAWKQ-CDRYSYESSA-N 0.000 description 2
- 230000007665 chronic toxicity Effects 0.000 description 2
- 231100000160 chronic toxicity Toxicity 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- JLYXXMFPNIAWKQ-GPIVLXJGSA-N delta-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H](Cl)[C@@H]1Cl JLYXXMFPNIAWKQ-GPIVLXJGSA-N 0.000 description 2
- 229940011871 estrogen Drugs 0.000 description 2
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- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 2
- 231100000567 intoxicating Toxicity 0.000 description 2
- 230000002673 intoxicating effect Effects 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method of same column extracting and fractionation separation for organic matters with different poles in water, comprising the following steps: after a water sample is filtered by a filter film, enrichment is carried out through a solid-phase extraction column, and the extraction column is dried in vacuum under negative pressure after extraction. Solvent of Hexane and solvent of methanol/dichloromethane are sequentially used to elute a step extraction column, and concentration and volume determination are carried out on the eluents. Florisil is weighed to be filled in a glass tube and dried, the concentrated sample solutions are added into a florisil column to be separated and are sequentially and continuously eluted through the Hexane, Hexane/dichloromethane and dichloromethane/methanol, and three effluents are respectively collected and concentrated to be stored at 20 DEG C below zero. The reagent has little consumption, low cost and less steps, can well enrich the organic matters in the water with different pollution levels, and is separated to be components with the different poles.
Description
Technical field
The present invention relates to the pre-treating method of a kind of different pollution level water body organism toxicity discriminating and toxicity source analysis, a kind of PCB that is used to contain more specifically says so, OCs, PAH, NP, OP, BPA, TBBPA, the same column extracting of the complex environment water sample of common opposed polarity organic pollution such as E2 be the method for classification separation again.
Background technology
Raising along with urbanization, industrialized level, large amount of organic enters into environment with sanitary sewage and industrial wastewater, make environment water be subjected to severe contamination, these organic concentration hypotoxicities are big, life period is long in environment, and may produce chronic toxicity, even cause the occurred frequently of cancer to aquatile and human body.Though the Chinese government has dropped into the safety guarantee Study on Technology such as conventional treatment, sterilization that great amount of manpower and material resources and fund are used for conventional detection, the drinking water of water quality.But conventional chemical detection can only reflect the level of pollution can't satisfy the requirement for health reassurance that people improve day by day, in order to safeguard the stable harmonious development of society, certainly will will pay close attention to the toxicity evaluation and the toxicity source of water quality and follow the trail of.
For a long time, be directed to the PCBs in the water, the organic extraction of multiple opposed polarity such as PAH and phenols, people often need to choose different extraction columns enriching and purifying respectively, such pre-treating method is not only time-consuming, and take reagent, expense sample, also be unfavorable for effective combination that chemical analysis and poisonous effect are estimated.
Last 408 pages of " Environmental Contamination and Toxicology " the 49th phase in 2005 discloses the article " Assessing theDetoxication Efficiencies of Wastewater Treatment Processes Using a Batteryof Bioassays/Biomarkers " that water toxicity is identified in one piece of relevant sewage treatment plant processing procedure, wherein Xu Shu method is with the organic matter in the solid-phase extraction column enrichment water of Oasis HLB cartridges, and is separated into three components and carries out the discussion in toxicity source with silica gel/alumina column classification.This method is many with respect to former method progress, the organic matter of opposed polarity in the water be can extract simultaneously and the evaluation and the tracking of toxicity accomplished, but this method uses single carrene to make that as the eluting solvent of solid-phase extraction column experiment is low for the rate of recovery of polar substances, and its utilization silica gel disturbs bigger as filler, grouping DeGrain for target compound, the analysis of high pollution water body can only be used for, organic extraction and separation in the low-pollution water body of people's growing interest can't be applied to.
By retrieval find domestic and foreign literature not about this opposed polarity organic matter at various pollution level water bodys with the column extracting report of the pre-treating method that separates of classification again.So relevant research has entered Jiangsu Province's plan of science and technology project (BS2007050) and the postgraduate of Jiangsu Province ordinary higher learning school scientific research and innovation programme support projects (CX07B_170z).
Summary of the invention
1. invent the technical problem that will solve:
At the problem that exists in organic extraction in the low-pollution water body of people's growing interest and the separation, the invention provides different pollution level water body organic compounds that collection is located away from one with post enrichment, classification and extract opposed polarity organic matter in the water that separates, can be used for chronic toxicity and identify and the toxicity source analysis with the column extracting classification method of separating again.
2. technical scheme:
The principle of this programme:, must carry out necessary extraction before detecting and concentrate because compound concentration is relatively low in the water environment sample.This method adopts SPE to carry out organic enrichment in the water sample, and the fixing of post is C mutually
18Bonded silica gel uses nonpolar hydrophobic fixing sample solution from polarity, and promptly enrichment organic matter in the water sample can carry out total toxicity test with analyte from fixing eluting mutually with a small amount of organic solvent.Adopt the adsorpting column chromatography method to carry out the organic separation of opposed polarity again, utilize the difference of each component attached ability of absorption-desorption on adsorbent in the mixture and reach the separation purpose, adsorbent commonly used has florisil silica and silica gel.
Technical scheme of the present invention is as follows:
The opposed polarity organic matter is with the column extracting classification method of separating again in the water, and it mainly may further comprise the steps:
(1) water sample carries out enrichment with the speed of 3～5mL/min by solid-phase extraction column by behind the membrane filtration, before using, extraction column activates with methyl alcohol and distilled water respectively, and after extraction finishes, extraction column negative-pressure vacuum drying,
(2) use 2～6mL n-hexane successively, 4～8mL ethanol/methylene (2～4: the extraction column in the solvent elution step (1) 1), eluent is concentrated respectively, carrene is settled to 1mL,
(3) take by weighing 8～10g florisil silica, utilize the n-hexane wet method to fill out post in glass tube, add anhydrous Na
2SO
4Drying adds the florisil silica post with the sample solution that concentrates and separates, successively use n-hexane, n-hexane/carrene (2～4: 1) and methylene chloride (1～2: 1) wash-out continuously, flow out that liquid are collected respectively and concentrated with three parts ,-20 ℃ of preservations are standby.
Filter membrane is 0.45 μ m filter membrane in the step of the present invention (1).Adopt the C18 enriching column as solid-phase extraction column.General water sampling volume is 5L.The n-hexane of using in the invention, carrene and methyl alcohol are the residual level of farming.
Carry out the test of total toxicity after the organic extract that step (2) obtains can be replaced with the DMSO solvent, also can be used for further classification and separate.
The glass tube internal diameter is 1cm in the step (3), and various elution volumes and proportioning are the optimal conditions that obtains, and the eluent after classification separates concentrates and can be concentrated into about 1mL with Rotary Evaporators earlier, uses N again
2Slowly purge solvent, last DMSO constant volume is used for toxicity to be identified, or with carrying out chemical analysis after n-hexane/methanol constant volume.
3. beneficial effect:
The invention provides opposed polarity organic matter in a kind of water with the column extracting classification method of separating again, reagent consumption is few, cost is low, step is the but better organic matter in the different level of pollution water bodys of enrichment less, and be separated into the component (F1 of opposed polarity, F2, F3), among its weakly polar component F1 among 28 kinds of PCB and the Semi-polarity component F2 among PAH and the F2 PAH reach fully substantially with 5 kinds of phenols among the F3 and separate.The recovery of standard addition of PCB reaches more than 80% among the F1, and the rate of recovery of PAH is more than 70% among the F2, and the rate of recovery of several phenols is more than 80% among the F3.Multiple toxicity authenticate technologies such as the present invention can test with reporter gene, zebrafish embryo experiment, comet experiment combine, and have universality.This technology can be separated classification in the back sample by the bio-toxicity guide, find the intoxicating component, dwindle Instrumental Analysis and follow the trail of the scope of organic pollution, can find out crucial poisonous substance quickly, in addition when the set goal pollutant does not exist in the intoxicating component, also other potential noxious material of trace detection simultaneously.
The specific embodiment
Below further specify the present invention by example.
Enforcement of the present invention also is the process of finishing the postgraduate of Jiangsu Province ordinary higher learning school scientific research and innovation programme support projects (CX07B_170z) and Jiangsu Province's plan of science and technology project (BS2007050).
Embodiment 1:
Accurately preparation contains 28 kinds of PCB (CB-8, CB-18, CB-28, CB-52, CB-44, CB-66, CB-81, CB-77, CB-101, CB-123, CB-118, CB-114, CB-105, CB-126, CB-153, CB-138, CB-128, CB-167, CB-156, CB-157, CB-169, CB-187, CB-180, CB-170, CB-189, CB-195, CB-206, CB-209, concentration is 20ng/L), 8 kinds of OCs (α-BHC, β-BHC, γ-BHC, δ-BHC, p, p ' DDE, o, p ' DDT, p, p ' DDD, p, p ' DDT, concentration is 50ng/L), PAH (acenaphthene, fluorenes, luxuriant and rich with fragrance, anthracene, fluoranthene, pyrene, benzo [a] anthracene, bend, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, indeno [1,2,3-c, d] pyrene, concentration is 200ng/L), NP (200ng/L), OP (200ng/L), BPA (200ng/L), TBBPA (200ng/L), the water sample 5L of E2 (200ng/L) behind 0.45 μ m membrane filtration, passes through the enrichment of C18 solid-phase extraction column with the speed of 4mL/min.Before using, extraction column activates with 10ml methyl alcohol and 10ml distilled water.Extraction column negative-pressure vacuum drying after the enrichment to slough most of moisture, then dries up with nitrogen.Carry out wash-out with the 8mL n-hexane subsequently, the control flow velocity is 2mL/min, and every 2mL collects eluent, blows to 0.1mL in soft nitrogen stream respectively, uses GC-ECD to measure.Analysis condition is as follows:
PCBs and OCs class---GC-ECD
Temperature programming: 80 ℃ of initial temperatures, 20 ℃ of heating rates/min to 165 ℃, be warmed up to 220 ℃ with 2 ℃/min again, be warmed up to 280 ℃ with 4 ℃/min, keep 6min;
Injector temperature: 280 ℃, He is split sampling not, 1.0mL/min; Chromatographic column: DB-5,
30m×250μm×0.25μm；
Sample size: 1 μ L; Split sampling not;
Detector temperature: 320 ℃; Makeup flow:N
2
Observe to find that the rate of recovery scope of this two classes material of PCBs and OCs was between 82%～117% when the n-hexane volume was 4mL, the rate of recovery does not have and significantly improves when the n-hexane volume increases.
Embodiment 2:
Adopt the method configuration water sample among the embodiment 1, filter the back and pass through the enrichment of C18 solid-phase extraction column, dry up with nitrogen after the post negative-pressure vacuum drying with the speed of 4mL/min.Use the 4mL n-hexane to carry out wash-out subsequently, then with ethanol/methylene (4: 1) 8mL wash-out, the control flow velocity is 2mL/min, and every 2ml collects eluent, blows to 0.1ml in soft nitrogen stream respectively; Repeat above enrichment experiment, use the 4ml n-hexane to carry out using ethanol/methylene (2: 1) 10mL wash-out solid-phase extraction column behind the wash-out, every 2ml collects eluent.Use GC-FID to carry out PAH and measure, polar compound is analyzed with HPLC (DVD/FLD), and analysis condition is as follows:
PAHs class---GC-FID
Temperature programming: 40 ℃ of initial temperatures, be warming up to 190 ℃ with the speed of 8.0 ℃/min, the speed with 4.0 ℃/min is warming up to 210 ℃ again, and the speed with 8.0 ℃/min is warming up to 250 ℃/min again, and the speed with 4.0 ℃/min rises to 300 ℃ again, keeps 10min;
Injector temperature: 280 ℃;
Sample size: 2 μ l, not split samplings;
Detector temperature: 320 ℃.
Polar compound class HPLC (DVD/FLD)
Mobile phase: 0-5min, 80% Jia Chun ﹠amp; 20% water; 5-11min, 100% methyl alcohol; Flow: 1ml/min;
Column temperature: 30 ℃.
Detector: the TBBPA:UVD detector, detect wavelength X=210nm;
The BPA:FLD detector, 0-5min, λ
Ex=228nm, λ
Em=315nm;
E
2: FLD detector, 5-7min, λ
Ex=224nm, λ
Em=316nm;
OP, NP:FLD detector, 7-11min, λ
Ex=226nm, λ
Em=314nm.
The analysis result demonstration just can be with PAH during ethanol/methylene (4: 1) 6mL, NP, and OP, BPA, TBBPA, E2 elutes, and ethanol/methylene (2: 1) needs 10mL, and the rate of recovery is basic identical.So select ethanol/methylene (4: 1) as PAH, NP, OP, BPA, TBBPA, the eluting solvent of E2 is better.
Embodiment 3:
Accurately take by weighing 8g florisil silica (60-100 order, 650 ℃ of calcination 5h activate 4-6h in 130 ℃ before using), the 1g anhydrous Na
2SO
4, it is in the glass tube of 1cm to internal diameter that wet method is filled out post, beats tube wall to remove the bubble in the glass column with hose, and florisil silica is tamped in glass column.Extraction column is with 10mL left and right sides n-hexane drip washing twice, to remove foreign body in the post.The sample solution that concentrates that will obtain with the concentration method of embodiment 2 is added on the florisil silica column top, in the time of in sample infiltrates post, with the polluter that is adsorbed in the 60mL hexane solution drip washing post, and eluent is collected in the 100mL pyriform bottle, use the hexane solution wash-out again, every 20mL collects once, and eluent is concentrated into about 1mL with Rotary Evaporators earlier respectively, uses N again
2Slowly purge solvent, concentrate and with n-hexane solvent constant volume.Measure analysis condition such as embodiment 1 immediately with GC-ECD.Analysis result shows that the 60mL n-hexane can be collected part PCB, and the PCB accumulative total rate of recovery reaches 83%-111% when the drip washing of 120mL n-hexane.Continue subsequently to continue drip washing with 120mL n-hexane/carrene (4: 1), the rate of recovery that concentrated post analysis obtains PAH in second component is 35%-80%.
Embodiment 4:
Accurately take by weighing 10g florisil silica (60-100 order, 650 ℃ of calcination 5h activate 4-6h in 130 ℃ before using), the 1g anhydrous Na
2SO
4, it is in the glass tube of 1cm to internal diameter that wet method is filled out post, beats tube wall to remove the bubble in the glass column with hose, and florisil silica is tamped in glass column.Extraction column is with 10mL left and right sides n-hexane drip washing twice, to remove foreign body in the post.The sample solution that concentrates that will obtain with the concentration method of embodiment 2 is added on the florisil silica column top, in the time of in sample infiltrates post, with the polluter that is adsorbed in the 60mL hexane solution drip washing post, and eluent is collected in the 100mL pyriform bottle, use the hexane solution wash-out again, every 20mL collects once, and eluent is concentrated into about 1mL with Rotary Evaporators earlier respectively, uses N again
2Slowly purge solvent, concentrate and with n-hexane solvent constant volume.Measure analysis condition such as embodiment 1 immediately with GC-ECD.Analysis result shows that the PCB accumulative total rate of recovery reaches 80%-110% when the drip washing of 100mL n-hexane.Continue subsequently to continue drip washing with 100mL n-hexane/carrene (4: 1), the rate of recovery that concentrated post analysis obtains PAH is 79%-115%, analysis condition such as embodiment 2, and no PCB detects in this component.Continue with 40mL n-hexane/carrene (4: 1) drip washing, detect through GC-FID that no PAH detects among this 40mL, two components are separated fully.
Embodiment 5:
Accurately take by weighing 10g florisil silica (60-100 order, 650 ℃ of calcination 5h activate 4-6h in 130 ℃ before using), the 1g anhydrous Na
2SO
4, it is in the glass tube of 1cm to internal diameter that wet method is filled out post, beats tube wall to remove the bubble in the glass column with hose, and florisil silica is tamped in glass column.Extraction column is with 10mL left and right sides n-hexane drip washing twice, to remove foreign body in the post.The sample solution that concentrates that will obtain with the concentration method of embodiment 2 is added on the florisil silica column top, in the time of in sample infiltrates post, with the polluter that is adsorbed in the 100mL hexane solution drip washing post, and eluent is collected in the 100mL pyriform bottle, use 100mL n-hexane/carrene (4: 1) wash-out again, use 80mL methylene chloride (1: 1) drip washing subsequently, continue with methylene chloride (1: 1) eluant solution, every 20mL collects once, eluent concentrates with Rotary Evaporators earlier respectively, analyzes with HPLC (DVD/FLD).Analysis result shows, when 120mL methylene chloride (1: 1), accumulative total NP, OP, BPA, TBBPA, the E2 rate of recovery reach 81%-98%.Add that methylene chloride (1: 1) drip washing florisil silica post has not had NP, OP, BPA, TBBPA, E2 detects, three components all reach fully separates again.
Embodiment 6:
Accurately preparation contains 28 kinds of PCB (CB-8, CB-18, CB-28, CB-52, CB-44, CB-66, CB-81, CB-77, CB-101, CB-123, CB-118, CB-114, CB-105, CB-126, CB-153, CB-138, CB-128, CB-167, CB-156, CB-157, CB-169, CB-187, CB-180, CB-170, CB-189, CB-195, CB-206, CB-209, concentration is 20ng/L), 8 kinds of OCs (α-BHC, β-BHC, γ-BHC, δ-BHC, p, p ' DDE, o, p '-DDT, p, p '-DDD, p, p '-DDT, concentration is 50ng/L), PAH (acenaphthene, fluorenes, luxuriant and rich with fragrance, anthracene, fluoranthene, pyrene, benzo [a] anthracene, bend, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, indeno [1,2,3-c, d] pyrene, concentration is 200ng/L), NP (200ng/L), OP (200ng/L), BPA (200ng/L), TBBPA (200ng/L), the distillation water sample 5L of E2 (200ng/L) passes through the enrichment of C18 solid-phase extraction column with the speed of 3～5ml/min.Before using, extraction column activates with 10ml methyl alcohol and 10ml distilled water.Extraction column negative-pressure vacuum drying after the enrichment to slough most of moisture, then dries up with nitrogen.Use the 4ml n-hexane to carry out wash-out, then with ethanol/methylene (4: 1) 6mL wash-out, the control flow velocity is 2ml/min.Eluent is mixed, and be concentrated into 1-2mL with rotary evaporation.
Accurately take by weighing 10g florisil silica (60-100 order, 650 ℃ of calcination 5h activate 4-6h in 130 ℃ before using), the 1g anhydrous Na
2SO
4, it is in the glass tube of 1cm to internal diameter that wet method is filled out post, beats tube wall to remove the bubble in the glass column with hose, and florisil silica is tamped in glass column.Extraction column is with 10mL left and right sides n-hexane drip washing twice, to remove foreign body in the post.The sample solution that the SPE column extracting is concentrated is added on the florisil silica column top, in the time of in sample infiltrates post, with the polluter that is adsorbed in the 100mL hexane solution drip washing post, and eluent is collected in the 100mL pyriform bottle, use 100mL n-hexane/carrene (4: 1) wash-out again, use 120mL methylene chloride (1: 1) drip washing subsequently, eluent is collected respectively and is concentrated into about 1mL with Rotary Evaporators earlier, uses N again
2Slowly purge solvent, non-polar component and middle polarity component n-hexane constant volume, the polar compound methanol constant volume, and adopt analysis condition among embodiment 1 and the embodiment 2 to PCB, and OCs, PAH, NP, OP, BPA, TBBPA, E2 analyzes.
Analysis result shows that the rate of recovery of 28 kinds of PCB in first component is 65%-103%, α-BHC and p, and the rate of recovery of p '-DDE is respectively 81% and 99%; The rate of recovery of PAH is 54%-124% in second component, and all the other OCs rate of recovery are 91%-114%; NP in the 3rd component, OP, BPA, TBBPA, the rate of recovery of E2 also can reach 70%-98%.
Embodiment 7:
Gather water outlet 15L in chemical industry garden, Zhenjiang sewage treatment plant, behind the 0.45um membrane filtration, carry out on-the-spot enrichment by a C18 solid-phase extraction column, take back the laboratory with the every 5L of the speed of 3～5ml/min.Before using, extraction column activates with 10ml methyl alcohol and 10ml distilled water.Extraction column negative-pressure vacuum drying after the enrichment to slough most of moisture, then dries up freezing preservation with nitrogen.Adopt the method among the embodiment 6 to carry out the organic matter enrichment, the organic solvent equal-volume after the enrichment is divided into three parts, be respectively applied for total toxotest (A group), toxicity tracking (B group) and chemical analysis (C group).The A group is utilized reporter gene test carrying out toxotest, find that the water outlet organic extract has strong estrogen active and reaches the centinormal 1 E2 of 35.1ng/L (document shows that the E2 of 1ng/L can influence the hormone secretion of fish), have strong antiandrogen activity simultaneously.For toxicity is followed the trail of, B group and two parts of organic extracts of C group are carried out classification respectively separate, adopt the method among the embodiment 6, every group all obtain three components (F1, F2, F3).Three secondary components to the B group carry out toxicity test respectively, find the antiandrogen activity from the F1 component, and estrogen active are from the F3 component.Again F1 and F3 component are carried out chemical analysis, find that PCB concentration is lower among the F1, all be lower than 0.2ng/L, but p, p '-DDE concentration is higher to be 67.7 μ g/L, and p, p '-DDE can cause strong antiandrogen activity, is the main source of toxicity; Among the F3 NP concentration higher be 28.3 μ g/L, be the main source of toxicity.Be in the sewage disposal plant effluent mainly to poisonous substance matter be p, p '-DDE and NP.
Embodiment 8:
Gather water inlet 15L in waterworks, the south of a city, Nanjing, adopt method among the embodiment 7 to carry out organic enrichment and separation etc. in the filtration of water sample, the water.Find that by the test of total toxicity the water sample organic extract has weak antiandrogen activity.Toxotest after the classified separation finds that polar compound and non-polar component do not have poisonous effect, and toxicity derives from middle polarity component (F2).So only carry out chemical analysis at the middle polarity component, find that PAH concentration is higher in water factory's water inlet, ∑ PAH reaches 158.3ng/L, is the main source of toxicity.
Claims (5)
1, the opposed polarity organic matter is with the column extracting classification method of separating again in a kind of water, and it may further comprise the steps:
(1) water sample carries out enrichment with the speed of 3～5mL/min by solid-phase extraction column by behind the membrane filtration, before using, extraction column activates with methyl alcohol and distilled water respectively, and after extraction finishes, extraction column negative-pressure vacuum drying;
(2) use 2～6mL n-hexane successively, 4～8mL volume ratio is the extraction column in the mixed solvent elution step (1) of 2～4: 1 methyl alcohol and carrene, and eluent is concentrated respectively, and carrene is settled to 1mL;
(3) sample solution that concentrates being added the florisil silica post separates, be that 2～4: 1 n-hexane and carrene mixed solvent and volume ratio are 1～2: 1 carrene and the continuous wash-out of methyl alcohol mixed solvent successively with n-hexane, volume ratio, three parts of outflow liquid are collected respectively and concentrated, and-20 ℃ of preservations are standby.
2, the opposed polarity organic matter is characterized in that with the column extracting classification method of separating again filter membrane is 0.45 μ m filter membrane in the step (1) in the water according to claim 1.
3, the opposed polarity organic matter is characterized in that with the column extracting classification method of separating again solid-phase extraction column is the C18 enriching column in the step (1) in the water according to claim 2.
4, the opposed polarity organic matter is characterized in that carrying out after the organic extract that obtains in the step (2) can be replaced with the DMSO solvent test of total toxicity with the column extracting classification method of separating again in the water according to claim 2.
5, in the water according to claim 3 the opposed polarity organic matter with the column extracting classification method of separating again, it is characterized in that the florisil silica post prepares by the following method in the step (3): take by weighing 8～10g florisil silica, utilize the n-hexane wet method to fill out post in glass tube, add anhydrous Na
2SO
4Dry.
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| CN104667572A (en) * | 2015-02-09 | 2015-06-03 | 湖北民族学院 | Industrial gardenia yellow pigment purification device and method for extracting gardenia yellow pigment |
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| CN109682897A (en) * | 2019-01-17 | 2019-04-26 | 南京大学 | A kind of method of a variety of incretion interferents in while determination of the environment water sample |
| CN114324670A (en) * | 2021-04-23 | 2022-04-12 | 新疆生产建设兵团第十三师红星医院 | Solid phase extraction column and application thereof |
| CN114324670B (en) * | 2021-04-23 | 2024-05-28 | 新疆生产建设兵团第十三师红星医院 | Solid phase extraction column and application thereof |
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| CN117438123B (en) * | 2023-12-22 | 2024-05-07 | 中国核电工程有限公司 | Method and device for determining uranium extraction zone in extraction column and method for controlling position of uranium extraction zone |
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