CN104977382A - Analysis method for simultaneously determining tiny amounts of 6 phenolic endocrine disrupting chemicals in water environment - Google Patents
Analysis method for simultaneously determining tiny amounts of 6 phenolic endocrine disrupting chemicals in water environment Download PDFInfo
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Abstract
The invention discloses an analysis method for simultaneously determining tiny amounts of 6 phenolic endocrine disrupting chemicals (EDCs) in water environment. The method comprises the following steps: enriching the phenolic EDCs by adopting a Sep-Pak-C18 solid phase extraction cartridge, leaching the cartridge by using a methanol-water solution, eluting the enriched phenolic EDCs by dichloromethane to a small reagent bottle, concentrating by using nitrogen, adding BSTFA and pyridine to carry out a derivation reaction, and determining tiny amounts of the phenolic EDCs in an environment water sample by using GC-MS. The derivation reaction can improve the chromatographic peak type, reduces the detection limit, and improves the GC-MS analysis sensitivity and accuracy. The method has the advantages of simplified operation, short phase splitting time, difficult emulsification, high apparatus precision, good reappearance, and great practical application values in water environment related researches.
Description
Technical field
The present invention relates to Environmental Analytical Chemistry field, be specifically related to the analytical approach of 6 kinds of trace phenols environment incretion interferents in a kind of Simultaneously test water environment.
Background technology
Environment incretion interferent (EDCs) refers to the xenobiotics of the bioprocess such as synthesis, secretion, transport, metabolism, combination, reaction, elimination by keeping natural hormone in Equilibrium and adjustment growth course in interference biosome.These organic contaminants have toxicity persistence, harm latency and biological accumulation, enter water environment, and amplify step by step through food chain enrichment, enter human body directly or indirectly and cause health hazard by the industrial and agricultural production of people and life activity.The representational phenols EDCs of most mainly octyl phenol (4-t-OP), cumenyl phenol (4-CP), nonylphenol (4-NP), bisphenol-A (BPA), nonylphenol bis oxyethylene ether (NP2EO) and nonylphenol list oxygen vinethene (NP1EO) in water environment.In existing open patent of invention and Scientific Articles, do not form the analytical approach of phenols EDCs in unified Environmental Water sample, the method especially simultaneously analyzing above-mentioned 6 kinds of typical trace phenols EDCs is still blank so far in China's water monitoring specification, method standard.The inventive method is intended to the analytical approach setting up typical EDCs in a kind of Environmental Water sample.
Publishedly to apply for a patent that the detectable concentration scope that the analysis (publication number: CN 104267129A) of 16 kinds of phenolic compounds " in a kind of Simultaneously test water environment " be characterized as target substance is 5-1000 μ g/L, detection is limited to 0.04-4.0 μ g/L and recovery of standard addition is 77% ~ 112%, adopt PFBBR bromine as derivatization reagent in its derivatization process, and PFBBR bromine chafe and mucous membrane, and have tear-gas effect to eyes, cause corrosive effects, potential risk is constituted to the healthy of researchist.Compared with patented method of the present invention, other is published applies for a patent the detection method (publication number: CN 104280447A) of benzenediol class material " in a kind of water ", " detect the preparation method's (publication number: CN 103267787A) to stupid diphenol and the method for catechol and the nitrogen-doped graphene modified glassy carbon electrode of application " simultaneously, the detection method of phenolic compound " in the environmental wastewater " (publication number: CN 104215696A), " a kind of method (publication number is CN 103558305 A) detecting trace phenols environmental estrogens " and " a kind of method (publication number is CN 102768245A) measuring underwater trace chlorophenols incretion interferent ", the target substance of institute's method for building up is different, and kind is single, sensing range is narrower, there is some difference for its pre-processing device adopted and analytical instrument, significantly limit its using value.In addition, these several openly the detectable concentration scope of method and detectability, far away higher than this method, cannot meet low concentration in Environmental Water sample, requirement that trace phenols EDCs analyzes.What is more important, they do not comprise the octyl phenol (4-t-OP) of this method research, cumenyl phenol (4-CP), nonylphenol (4-NP), nonylphenol bis oxyethylene ether (NP2EO) and the typical phenols EDCs of nonylphenol list oxygen vinethene (NP1EO) 6 kinds.
Summary of the invention
The invention provides the analytical approach of 6 kinds of trace phenols environment incretion interferents in a kind of Simultaneously test water environment, can 6 kinds of typical trace phenols environment incretion interferent (4-t-OP in Simultaneously test environmental water sample, 4-CP, 4-NP, BPA, NP1EO and NP2EO) analytical approach, wherein, to 4-t-octyl phenol (4-t-OP), 4-cumenyl phenol (4-CP), the detection range of linearity of 4-nonylphenol (4-NP) and bisphenol-A (BPA) is 0.5-500ng/L, the detection range of linearity of nonylphenol list oxygen vinethene (NP1EO) and nonylphenol bis oxyethylene ether (NP2EO) is 5-500ng/L, typical curve linear coefficient (R
2) being greater than 0.99, relative standard deviation (RSD) is less than 5.02%, detection limit (LOD), quantitative limit (LOQ) and the recovery are respectively 0.10-2.30ng/L, 0.20-11.50ng/L and 84.65%-101.38%.
For achieving the above object, the technical scheme that the present invention takes is:
In Simultaneously test water environment, the analytical approach of 6 kinds of trace phenols environment incretion interferents, is characterized in that, comprise the steps:
S1, by 1L environmental water sample after 0.45 μm of filtering with microporous membrane, with hydrochloric acid solution regulate pH to 4.5;
S2, use ethyl acetate, methyl alcohol and ultrapure water activation Sep-Pak C-18 solid phase pillar;
S3, the water sample of step S1 gained is entered step S2 gained by large volume sample injection device solid phase pillar after, under condition of negative pressure, post is crossed with the flow velocity lower than 5mL/min, after water sample enrichment, with 10mL methanol-water (1: 9, v/v) mixed solution drip washing solid phase extraction column, to get rid of the interference of little on-column enrichment impurity, vacuum drying 40min;
S4, add 10mL methylene chloride, slowly open solid-phase extracting instrument valve, after making the little column packing of the complete submergence of methylene chloride, rapid valve-off, after immersion 1-2min, open valve, with the elution rate being less than 0.5mL/min, eluent is collected in the brown reagent bottle of 12mL, and be concentrated into about 500 μ L with gentle nitrogen;
S5, the eluent after concentrated is transferred in 1.5mL GC bottle, with 200 μ L methylene chloride, rinse reagent bottle in vortex oscillator, in triplicate, rinse liquid is transferred in the lump in 1.5mL GC bottle;
S6, the solution in GC bottle is dried up with high-purity gentle nitrogen after, add 50 μ L BSTFA and 30 μ L pyridines, cover tightly bottle cap, vibration mixes, and under 70 DEG C of conditions, after derivative reaction 40min, leaves standstill to room temperature;
S7, add mark working fluid in 20 μ L, vibration mixes, and gets 1 μ L and carries out GC-MS analysis.
Preferably, the miillpore filter in described step S1 is GF/F glass fiber filter paper, and water sample is 6mL/min by miillpore filter flow velocity.
Preferably, in described step S2, the reactivation process of solid phase pillar is, first remove bonding agent residual in Sep-Pak C-18 solid phase extraction column filler with 5mL ethyl acetate, post is crossed again with 5mL methyl alcohol low speed, speed is 1-2mL/min, finally add 3 × 5mL ultrapure water, and keep the ultrapure water of more than liquid level about 3mL.
Preferably, in described step S3 extraction process, the interior liquid layer volume of water sample of pillar is greater than 1mL all the time.
Preferably, in described step S4 elution process, for guaranteeing that the object of solid phase extraction column enrichment is by complete wash-out, therefore the rate of outflow of methylene chloride should be less than 0.5mL/min, and after methylene chloride relies on Action of Gravity Field to flow out, slowly should open vacuum pump, and make it be in low-pressure state, liquid in post is all extracted out and collects.
Preferably, the inner mark solution in described step S7 adopts n-hexane dissolution to be diluted to the androstane solution (S-D) of 5ng/ μ L
Preferably, the GC-MS in step S7 analyzes and adopts DB-5MS capillary chromatograph, and using helium as carrier gas, its flow velocity is 1mL/min; Column oven initial temperature is 60 DEG C, is warming up to 150 DEG C with the heating rate of 15 DEG C/min, then is warming up to 220 DEG C with the heating rate of 8 DEG C/min, keeps 1min, is finally warming up to 290 DEG C with the heating rate of 15 DEG C/min, keeps 5min; Ion gun is EI source, and temperature is 250 DEG C, and electronics bombarding energy is 70eV; Scan mode is that full surface sweeping pattern is qualitative, sweep limit m/z 50-600, and quantitative with Selective ion mode scan pattern (SIM).
Preferably, the input mode that the GC-MS in described step S7 analyzes is Splitless injecting samples, and injector temperature is 260 DEG C, and sampling volume is 1 μ L, and transmission line temperature is 280 DEG C.
The present invention has following beneficial effect:
Adopt Sep-Pak-C18 solid phase extraction column enrichment phenols EDCs, and with methanol-water solution drip washing pillar, with the phenols EDCs of dichloromethane eluent enrichment in reagent vials, after nitrogen is concentrated, add BSTFA and pyridine carries out derivative reaction, finally utilize GC-MS to measure trace phenols EDCs in environmental water sample; By derivative reaction, chromatographic peak type can be improved, reduce detectability, improve sensitivity and the accuracy of GC-MS analysis; This invention simplifies operation, there is the advantages such as short, the not easily emulsification of phase-splitting time, instrument precision are high, favorable reproducibility, in the correlative study of water environment, there is larger actual application value.
Accompanying drawing explanation
Fig. 1 is the selectivity chromatography of ions figure of 6 kinds of phenols EDCs in Environmental Water sample in the embodiment of the present invention.
In figure, abscissa representing time, ordinate represents that phenols EDCs is through BSTFA derivatization afterproduct BST-4-t-OP, BST-4-CP, BST-4-NP, BST-NP 1EO, BST-BPA-d
16, BST-BPA, BST-NP2EO and interior mark I.S. response.
Embodiment
In order to make objects and advantages of the present invention clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
In this concrete enforcement embodiment, all glasswares are all placed in elevated process baking oven by pure water rinsing, and under 450 DEG C of conditions, baking 4h, to remove the organic impurities adhered on wall, preventing pollution; Except specified otherwise, all reagent purity grades are chromatographically pure level, and experimental water is ultrapure water; Agents useful for same comprises 4-t-octyl phenol standard items, and purity is greater than 99%, Sigma-Aldrich; 4-cumenyl phenol standard items, purity is greater than 99%, Sigma-Aldrich; 4-nonylphenol standard items, purity is greater than 99%, Sigma-Aldrich; Androstane standard items, purity is greater than 97%, Sigma-Aldrich; Bisphenol-A standard items, purity is greater than 99%, Sigma-Aldrich; Bisphenol-A-d
16recovery indicant, purity is greater than 98%, Sigma-Aldrich; Nonylphenol list oxygen vinethene standard items, purity is greater than 99%, German Dr.Ehrenstorfer GmbH company; Nonylphenol bis oxyethylene ether standard items, purity is greater than 99%, German Dr.Ehrenstorfer GmbH company; The two trimethyl silicon based trifluoroacetamide of N, O-, Sigma-Aldrich; Pyridine: Fruka company of the U.S.; Methyl alcohol: German Merck company; Methylene chloride: J.T.Baker company of the U.S.; Ethyl acetate: German Merck company; Normal hexane: German Merck company.
The concrete implementation step of the inventive method is as follows:
S1, preparing standard solution
S11, preparation standard reserving solution S-A (as table 1):
Accurately take 4-t-OP, 4-CP, 4-NP, BPA-d
16, each 40mg of BPA, NP2EO and NP1EO, be dissolved in respectively in the methyl alcohol of 40mL, be made into the phenols EDCs standard reserving solution of 1000ng/ μ L.
S12, preparation standard working solution S-B (as table 1):
Get the above-mentioned standard reserving solution S-A of 10 μ L in 12mL vial, then add 9990 μ L methyl alcohol, being diluted to containing all kinds of target concentration is the standard working solution S-B of 1ng/ μ L.
Mark liquid storing solution S-C (as table 1) in S13, preparation:
Accurately take 40mg androstane to be dissolved in 40mL normal hexane, be made into the interior mark storing solution S-C of 1000ng/ μ L, put into refrigerator (-45 DEG C) freezing stand-by.
Mark working fluid S-D (as table 1) in S14, preparation:
Get the above-mentioned standard reserving solution S-C of 50 μ L in 12mL vial, then add 9950 μ L normal hexanes, being diluted to containing interior mark concentration is the standard working solution S-D of 5ng/ μ L.
Table 1 phenols EDCs standard reserving solution
S2, preparation of samples
S21, water sample filter and pH value regulates: its pH value hydrochloric acid solution by Millipore Millipore filtration system, and is adjusted to 4.5 by environmental water sample;
S22, SPE pillar is chosen and is activated: use 5mL ethyl acetate, 5mL methyl alcohol and 3 × 5mL ultrapure water to activate Sep-Pak C-18 solid phase extraction column successively;
S23, extraction: water sample is passed through Visiprep
tMlarge volume sample injection device enters SPE system, under condition of negative pressure, cross post with the flow velocity lower than 5mL/min.After water sample enrichment, with 10mL methanol-water (1: 9, v/v) mixed liquor drip washing pillar, vacuum drying 40min.
S24, wash-out: add 10mL methylene chloride, make the little column packing of methylene chloride complete submergence SPE, after immersion 1-2min, then collected in the brown reagent bottle of 12mL by eluent with the elution rate being less than 0.5mL/min.
S3, derivatization process
The derivative reaction of phenols EDCs can reduce its polarity, to reaching the top condition that GC-MS analyzes, improving chromatographic peak type, reducing impurity interference, improve instrument detection sensitivity etc.This method adopts trimethyl silicone hydride derivatization method, and the hydroxyl of phenols EDCs is carried out trimethyl silicone hydride process, and concrete steps are as follows:
S31, eluent slowly to be blown to about 500 μ L with gentle nitrogen under normal temperature condition.
S32, concentrate to be transferred in 1.5mL GC bottle, then to use the brown reagent bottle of 3 × 200 μ L methylene chloride rinse, rinse liquid is transferred in GC bottle in the lump.
S33, the high-purity gentle nitrogen of solution in GC bottle slowly to be dried up.
S34, add 50 μ L BSTFA and 30 μ L pyridines, cover tightly bottle cap, vibration mixes.
S35, sample is placed in 70 DEG C of conditions under, after derivative reaction 40min, leave standstill to room temperature.
S36, add mark working fluid (S-D) in 20 μ L, vibration mixes.
S37, get 1 μ L enter GC-MS analyze.In this concrete enforcement, the controlled condition of GC/MS is:
Heating schedule: column oven initial temperature is 60 DEG C, with the ramp to 150 DEG C of 15 DEG C/min, then with the ramp to 220 DEG C of 8 DEG C/min, keeps 1min, finally with the ramp to 290 DEG C of 15 DEG C/min, keeps 5min; Chromatographic column: DB-5MS capillary chromatographic column; Carrier gas: helium, flow velocity 1mL/min; Injection port mode: not shunting mode sample introduction; Injector temperature: 260 DEG C; Sampling volume: 1 μ L; Transmission line temperature: 280 DEG C; Ion gun is: EI source, temperature 250 DEG C, electronics bombarding energy 70eV; Scan pattern: qualitative with full scan pattern (Scan), sweep limit is m/z 50-600; Quantitative with Selective ion mode scan pattern (SIM).
The structure of S4, typical curve
S41, get a certain amount of standard working solution S-B and be placed in 1.5mL GC bottle, then add methyl alcohol, be mixed with the standard solution that concentration is 5,10,25,50,75,100,150,250,400,600 and 800pg/ μ L respectively;
S42, get the above-mentioned standard solution of 100 μ L respectively and slowly dry up with high-purity gentle nitrogen at normal temperatures;
S43, add 50 μ L BSTFA and 30 μ L pyridines, cover tightly bottle cap, vibration mixes;
S44, be placed in 70 DEG C of conditions under, after derivative reaction 40min, leave standstill to room temperature;
S45, add mark working fluid (S-D) in 20 μ L respectively, vibration mixes;
S46, get 1 μ L enter GC-MS analyze;
S47, drawing standard curve.
The calculating of S5, the recovery
S51, get 100 μ L standard working solution S-B and be dissolved in 1L ultrapure water, regulate water sample pH to 4.5;
S52, SPE pillar uses 5mL ethyl acetate, 5mL methyl alcohol and 3 × 5mL ultrapure water to activate successively; 1L environmental water sample under condition of negative pressure to be not more than the flow velocity of 5mL/min by SPE pillar; After water sample crosses post, with 10mL methanol-water (1: 9, v/v) solution drip washing SPE pillar, vacuum drying 40min.S53, add 10mL methylene chloride in the SPE pillar of enrichment phenols EDCs, filler in pillar is flooded completely by methylene chloride; After immersion 1-2 minute, open SPE system valve, collect eluent with the brown reagent bottle of 12mL; For guaranteeing that the phenols EDCs of SPE pillar enrichment is collected completely, eluent flow rate is too fast (≤be not more than 0.5mL/min) not easily.When 10mL methylene chloride is after gravity flows out, slowly opens vacuum pump, make whole liquid under lower negative pressure condition, all flow out, collect.
S53, eluent is slowly blown to about 500 μ L with gentle nitrogen at normal temperatures; Concentrate is transferred in 1.5mL GC bottle.With the brown reagent bottle of 3 × 200 μ L methylene chloride rinse, rinse liquid is transferred in bottle in the lump; Solution is slowly dried up with gentle nitrogen at normal temperatures.Add 50 μ L BSTFA and 30 μ L pyridines, cover tightly bottle cap, vibration mixes; Under being placed in 70 DEG C of conditions, after derivative reaction 40min, leave standstill to room temperature; Add mark working fluid (S-D) in 20 μ L, after vibration mixes, get 1 μ L and enter GC-MS analysis; Calculate average recovery rate.
S6, sample analysis
(1) with blank assay, whole process supervision is carried out to pre-treatment and analytic process.
(2) Back ground Information such as the residence time, characteristic ion, molion of target substance is obtained by full scan pattern.
After (3) ten continuous sample introductions, enter pin standard items and carry out quality control.
If this concrete sample amounts response of implementing reduces gradually, then should check contaminating impurity situation in chromatographic column and injection port, change capillary chromatograph, injection port pad, cleaning bushing pipe, ion gun etc.When occurring following situation should reanalysing sample a) relative deviation be greater than 15%; B) mark-on sample recovery rate be greater than 140% or be less than 60% time.
Embodiment 1
Certain municipal sewage plant discharges water
Gather certain municipal sewage plant and discharge water, add a certain amount of methyl alcohol, through 0.45 μm of GF/F glass fiber filter with after 6mL/min flow filtration, filtrate pH value is adjusted to 4.5.Use 5mL ethyl acetate, 5mL methyl alcohol and 3 × 5mL ultrapure water to cross post successively, flow velocity is 1.5mL/min, activation Sep-PakC-18 solid phase extraction column.After pillar activation, filter water sample with the loading rate vacuum lower than 5mL/min, in overall process SPE pillar, liquid layer is all greater than 1mL.After mixed solution (methanol/water=1/9, v/v) the drip washing SPE pillar of 10mL first alcohol and water, vacuum drying SPE pillar 40min.With 0.5mL/min flow velocity, wash-out is carried out to SPE pillar with 10mL methylene chloride, collect eluent to the brown reagent bottle of 12mL.Eluent nitrogen is slowly blown to about 500 μ L, transfers them in 1.5mL GC bottle, slowly dry up with gentle nitrogen at normal temperatures.Add 50 μ L BSTFA and 30 μ L pyridines, derivatization 40min under 70 DEG C of conditions.Be cooled to room temperature, add the inner mark solution that 20 μ L concentration are 5ng/ μ L, vibration mixes, and gets 1 μ L and enters GC-MS analysis.By analyzing, in riverway sludge, the recovery of phenols EDCs and RSD are respectively 80.58%-102.82% and 1.72%-5.90%.In this sewage disposal plant effluent the concentration of 4-t-OP, 4-CP, 4-NP, NP1EO, BPA and NP2EO be respectively 2.97,2.69,4.45,177.16,168.80,117.21ng/L.This method can meet the analysis requirement of trace phenols EDCs in sewage disposal plant effluent well.
Embodiment 2
Lake Water
Gather in certain Lake Water 1mL to brown reagent bottle, with 6mL/min flow velocity by 0.45 μm of GF/F glass fiber filter, then adjust pH to 4.5.Cross post with 5mL ethyl acetate, 5mL methyl alcohol low speed, then add 3 × 5mL ultrapure water successively, cross post speed and be about 1.5mL/min.After pillar activation, filter water sample with the loading rate vacuum being not more than 5mL/min, in SPE extraction process pillar, liquid layer is all greater than 1mL.After 10mL mixed solution (methanol/water=1/9, v/v) drip washing SPE pillar, vacuum drying 40min.With 0.5mL/min flow velocity, wash-out is carried out to SPE pillar with 10mL methylene chloride, collect eluent in the brown reagent bottle of 12mL.Eluent nitrogen is slowly blown to about 500 μ L, transfers them in 1.5mL GC bottle, slowly dry up with gentle nitrogen at normal temperatures.Add 50 μ L BSTFA and 30 μ L pyridines, under 70 DEG C of conditions, derivatization 40min, is cooled to room temperature.Then, add the inner mark solution that 20 μ L concentration are 5ng/ μ L, vibration mixes, and gets 1 μ L and carries out GC-MS analysis.By analyzing, in Lake Water, the recovery of phenols EDCs and RSD are respectively 85.05%-100.96% and 1.89%-6.25%.In this lake sampled point water body the concentration of 4-t-OP, 4-CP, 4-NP, NP1EO, BPA and NP2EO be respectively 3.58,5.07,10.03,67.30,36.04,75.59ng/L.This method can meet the analysis requirement of lake Trace Phenols in Water class EDCs well.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. the analytical approach of 6 kinds of trace phenols environment incretion interferents in Simultaneously test water environment, is characterized in that, comprise the steps:
S1, by 1L environmental water sample after 0.45 μm of filtering with microporous membrane, with hydrochloric acid solution regulate pH to 4.5;
S2, use ethyl acetate, methyl alcohol and ultrapure water activation Sep-Pak C-18 solid phase pillar;
S3, the water sample of step S1 gained is entered step S2 gained by large volume sample injection device solid phase pillar after, under condition of negative pressure, cross post with the flow velocity lower than 5mL/min, after water sample enrichment, with 10mL methanol-water mixed solution drip washing solid phase extraction column, vacuum drying 40min;
S4, add 10mL methylene chloride, slowly open solid-phase extracting instrument valve, after making the little column packing of the complete submergence of methylene chloride, rapid valve-off, after immersion 1-2min, open valve, with the elution rate being less than 0.5mL/min, eluent is collected in the brown reagent bottle of 12mL, and be concentrated into about 500 μ L with gentle nitrogen;
S5, the eluent after concentrated is transferred in 1.5mL GC bottle, with 200 μ L methylene chloride, rinse reagent bottle in vortex oscillator, in triplicate, rinse liquid is transferred in the lump in 1.5mL GC bottle;
S6, the solution in GC bottle is dried up with high-purity gentle nitrogen after, add 50 μ L BSTFA and 30 μ L pyridines, cover tightly bottle cap, vibration mixes, and under 70 DEG C of conditions, after derivative reaction 40min, leaves standstill to room temperature;
S7, add mark working fluid in 20 μ L, vibration mixes, and gets 1 μ L and carries out GC-MS analysis.
2. the analytical approach of 6 kinds of trace phenols environment incretion interferents in a kind of Simultaneously test water environment according to claim 1, it is characterized in that: the miillpore filter in described step S1 is GF/F glass fiber filter paper, water sample is 6mL/min by miillpore filter flow velocity.
3. the analytical approach of 6 kinds of trace phenols environment incretion interferents in Simultaneously test water environment according to claim 1, it is characterized in that: in described step S2, the reactivation process of solid phase pillar is, first remove bonding agent residual in Sep-Pak C-18 solid phase extraction column filler with 5mL ethyl acetate, post is crossed again with 5mL methyl alcohol low speed, speed is 1-2mL/min, finally add 3 × 5mL ultrapure water, and keep the ultrapure water of more than liquid level about 3mL.
4. the analytical approach of 6 kinds of trace phenols environment incretion interferents in Simultaneously test water environment according to claim 1, is characterized in that: in described step S3 extraction process, the interior liquid layer volume of water sample of pillar is greater than 1mL all the time.
5. the analytical approach of 6 kinds of trace phenols environment incretion interferents in Simultaneously test water environment according to claim 1, it is characterized in that: in described step S4 elution process, after methylene chloride relies on Action of Gravity Field to flow out, slowly should open vacuum pump, and make it be in low-pressure state, liquid in post is all extracted out and collects.
6. the analytical approach of 6 kinds of trace phenols environment incretion interferents in Simultaneously test water environment according to claim 1, is characterized in that: the inner mark solution in described step S7 adopts n-hexane dissolution to be diluted to the androstane solution of 5ng/ μ L.
7. the analytical approach of 6 kinds of trace phenols environment incretion interferents in Simultaneously test water environment according to claim 1, is characterized in that: the GC-MS in step S7 analyzes and adopts DB-5MS capillary chromatograph, and using helium as carrier gas, its flow velocity is 1mL/min; Column oven initial temperature is 60 DEG C, is warming up to 150 DEG C with the heating rate of 15 DEG C/min, then is warming up to 220 DEG C with the heating rate of 8 DEG C/min, keeps 1min, is finally warming up to 290 DEG C with the heating rate of 15 DEG C/min, keeps 5min; Ion gun is EI source, and temperature is 250 DEG C, and electronics bombarding energy is 70eV; Scan mode is that full surface sweeping pattern is qualitative, sweep limit m/z 50-600, and quantitative with Selective ion mode scan pattern (SIM).
8. the analytical approach of 6 kinds of trace phenols environment incretion interferents in Simultaneously test water environment according to claim 1, it is characterized in that: the input mode that the GC-MS in described step S7 analyzes is Splitless injecting samples, injector temperature is 260 DEG C, sampling volume is 1 μ L, and transmission line temperature is 280 DEG C.
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| CN109142557A (en) * | 2018-06-27 | 2019-01-04 | 广州海沁天诚技术检测服务有限公司 | A kind of detection method of phenols endocrine disruptors matter |
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| CN111024846A (en) * | 2019-12-23 | 2020-04-17 | 华南理工大学 | Method for measuring bisphenol A in water body |
| CN114324627A (en) * | 2021-11-24 | 2022-04-12 | 贵阳学院 | Method for detecting pollution of trace estrogen endocrine disrupting compounds in reclaimed water by biological-chemical combination |
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