CN108828099A - The method that hollow-fibre membrane micro-extraction combines content of plasticizing agent in flash distillation gas chromatography measurement water sample - Google Patents
The method that hollow-fibre membrane micro-extraction combines content of plasticizing agent in flash distillation gas chromatography measurement water sample Download PDFInfo
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- CN108828099A CN108828099A CN201810825930.9A CN201810825930A CN108828099A CN 108828099 A CN108828099 A CN 108828099A CN 201810825930 A CN201810825930 A CN 201810825930A CN 108828099 A CN108828099 A CN 108828099A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The present invention provides a kind of methods that hollow-fibre membrane micro-extraction combines flash distillation gas chromatography measurement Determination of Phthalate Esters in Water kind compound content, the doughnut solid phase micro-extraction technique used in the present invention is a kind of collection sampling, extraction, concentrate in one, the few environmentally friendly Sample Pretreatment Technique Used of consumption of organic solvent, since fiber cinclides is smaller, the macromolecular substances in sample can be hindered to enter in film, therefore this method has good sample purification ability, also has stronger anti-Matrix effects ability simultaneously, in addition doughnut is at low cost, it is disposable, avoid the cross contamination of sample room；The method of the present invention pre-treatment is simple, concentration coefficient is high, at low cost.
Description
(1) technical field
The present invention relates to a kind of measuring methods of plasticiser in water sample, and in particular to a kind of hollow-fibre membrane micro-extraction combination
The method for flashing gas chromatography measurement Determination of Phthalate Esters in Water kind compound content.
(2) background technique
Phthalate (PAEs) is the most common plasticiser, and kind is numerous, it can be by reducing high molecular material
Transition temperature, to make its direct liquefaction or become more soft, be mainly used to the elasticity of reinforced plastics product, durability and
Transparency, PAEs is added in food plastic packaging material can enhance the ductility, durability, plasticity of packaging, therefore often
It is present in plastic package material by the additive as packaging material for food.Current PAEs class compound has 15 kinds all to be recognized
It is set to harmful substance, limitation uses.It, can be with external environment when the plastics package containing PAEs directly contacts food surface
Factor such as temperature, water, grease variation and infiltration migration causes food pollution into food.It has been investigated that PAEs has one
Fixed acute toxicity, after acting on human body, long-term accumulation can interfere the secretion of human hormone, serious to can lead to deformity, mutation
And canceration, seriously threaten human health.The approach that PAEs enters food has 3 kinds：First is that artificially in emulsifying essence, stabilizer
Addition in equal food additives；Second is that the migration in food processing and packaging in the plastic material containing plasticiser；Third is that from
Migration in environmental factor (such as soil).
Traditional detection method is generally adopted by organic solvent ultrasound, concussion or soxhlet extraction method to plasticiser in product
It extracts, because extraction efficiency is lower, is only able to detect the large dosage of plasticiser artificially added and (is plasticized in common product
The limitation of agent is 0.1%, i.e. 1000mg/kg).And lead to the detection method for containing micro plasticiser in food because of process contamination
Then mainly using detection methods such as gas chromatography, gas chromatography mass spectrometry method and Liquid Chromatography/Mass Spectrometries.
(3) summary of the invention
For the deficiencies in the prior art, that the present invention provides a kind of pre-treatments is simple, concentration coefficient is high, at low cost
Measurement Determination of Phthalate Esters in Water class method.
The doughnut solid phase micro-extraction technique used in the present invention is that a kind of collection is sampled, extracted, concentrating in one, organic
The few environmentally friendly Sample Pretreatment Technique Used of solvent usage.Since fiber cinclides is smaller, the macromolecular complex in sample can be hindered
Matter enters in film, therefore this method has good sample purification ability, while also having stronger anti-Matrix effects ability；
In addition doughnut is at low cost, disposable, avoids the cross contamination of sample room.
Technical scheme is as follows：
A kind of hollow-fibre membrane micro-extraction combination flash distillation gas chromatography measurement Determination of Phthalate Esters in Water class compound
The method of content, described method includes following steps：
(1) sample pre-treatments
Water sampling, is added NaCl and internal standard compound dicyclohexyl phthalate obtains solution to be measured, by gained solution to be measured
It is placed in ml headspace bottle, is put into hollow-fibre membrane, extract 30min under conditions of temperature 50 C, stirring rate 300rpm, in taking-up
Empty fiber membrane, for use；
Concentration of the NaCl in solution to be measured is 0.15mol/L；
Concentration of the internal standard compound dicyclohexyl phthalate in solution to be measured is 0.1mg/L；
The hollow-fibre membrane is PS membrane, and film outer diameter 0.978mm, internal diameter 0.800mm, aperture 0.2mm can pass through routine
Approach is commercially available；
The hollow-fibre membrane is cut into the segment of length 1cm before use, and impregnates 1h in ethanol, protects after natural drying
It is stored in spare in vial；
(2) sample detection
Ready hollow-fibre membrane in step (1) is placed in the sample of cracker above flash distillation gas chromatograph injection port
In cup, when cracker temperature reaches 300 DEG C, sample introduction button is pressed, specimen cup falls into the furnace heart of pyrolysis furnace, carries out flash distillation gas phase
Chromatography；
It is described flash distillation gas chromatographic analysis condition be：
Chromatographic column：DB-5 (Agilent Labs, 30m × 0.25mm0i.d. × 0.25 μm, the poly- silicon oxygen of 5% phenyl methyl
Alkane)；Column temperature：60 DEG C of initial temperature, 5min is kept, 220 DEG C is raised to 20 DEG C/min rate, keeps 1min, be raised to 5 DEG C/min rate
250 DEG C, 1min is kept, 290 DEG C is raised to 20 DEG C/min rate, keeps 7.5min；The room temperature that gasifies is 300 DEG C, detector temperature
Degree is 320 DEG C；Cracker temperature：It cracks furnace temperature and chromatographic column injector temperature is 300 DEG C；Split ratio 10：1；Carrier gas N2；
Column flow 1.0mL/min；
(3) standard curve is established
The standard substance of DEP, DPRP, DIBP, DBP, DMEP, DPP, DNHP, BBP, DEHP, DNOP are taken, is molten with methanol
Agent is configured to hybrid standard stock solution, and gained hybrid standard stock solution dilutes to obtain standard curve working solution through deionized water,
Gained standard curve working solution is subjected to pre-treatment (i.e. according to step (1) pre-treating method：By water sample in step (1)
Replace with standard curve working solution) and then testing conditions in step (2) under carry out flash distillation gas chromatographic analysis, obtain
To standard substance spectrogram, using the concentration of standard curve working solution Plays substance as abscissa, spectrogram Plays substance with it is interior
Marking the ratio between peak area of object is ordinate, draws standard curve；
The concentration range of each standard substance respectively stands alone as 0.002~1mg/L in the standard curve working solution；
(4) testing result of Determination of Phthalate Esters in Water class compound is obtained
The standard substance spectrogram as obtained by step (3) is compareed with spectrogram obtained by step (2) sample detection, is obtained in water sample
The qualitative results of contained phthalate compound；
By the phthalate compound and the ratio between the peak area of internal standard compound in spectrogram obtained by step (2) sample detection
It substitutes into standard curve obtained by step (3), calculates the content for obtaining Determination of Phthalate Esters in Water class compound.
In the present invention,
The Chinese of DEP is diethyl phthalate；
The Chinese of DPRP is dipropyl phthalate；
The Chinese of DIBP is diisobutyl phthalate；
The Chinese of DBP is n-butyl phthalate；
The Chinese of DMEP is dimethoxyethyl phthalate；
The Chinese of DPP is diamyl phthalate；
The Chinese of DNHP is dihexyl phthalate；
The Chinese of BBP is butyl benzyl phthalate；
The Chinese of DEHP is phthalic acid (2- ethylhexyl) ester；
The Chinese of DNOP is di-n-octyl phthalate.
Compared with prior art, advantages of the present invention is mainly reflected in：Pre-treatment extraction step is few, at low cost, You Jirong
Agent dosage is few, has good sample purification ability, while also having stronger anti-Matrix effects ability；In addition doughnut
It is at low cost, it is disposable, avoid the cross contamination of sample room.
(4) Detailed description of the invention
Fig. 1：The gas chromatogram of phthalate standard items；A PS membrane；B is without extraction (100mg/L)；In c warp
Empty fiber membrane extracts (1mg/L)；
Fig. 2：Hollow fiber membrane extraction-gas chromatogram of actual sample in embodiment 5；A is No. 4 samples；B is No. 6 samples
Product；C is No. 5 samples；D is No. 8 samples.
(5) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
The selection of 1 extraction time of embodiment
The extraction time the long more is conducive to object and enters in film, is further added by extraction time after equilibration had been achieved and imitates to extraction
Rate, which increases, to be influenced less.If will lead to the unstability of film balancing the subsequent long extraction time that renews, so as to cause extraction efficiency
Reduction.Extraction efficiency when extraction 10,20,30,40,50min has been investigated respectively, other experiment conditions are：Extraction temperature is
40 DEG C, stirring rate 300rpm.The result shows that as time increases, the extraction efficiency of object has significantly improved.
When phthalate compound is when 30min or so reaches extraction equilibrium, the time is continued growing, and extraction efficiency drops instead
Low, balancing the subsequent long extraction time that renews will lead to the unstability of film, so as to cause the reduction of extraction efficiency.Therefore it selects
The extraction time of 30min.
The selection of 2 extraction temperature of embodiment
Improving temperature can promote object to enter tunica fibrosa from water sample.However, thermodynamically, adsorption equilibrium is one
A exothermic process, distribution coefficient can decline as the temperature rises, and extraction efficiency is caused to reduce.Extraction temperature has been investigated respectively
Extraction efficiency when being 30,40,50,60,70 DEG C, other experiment conditions are：Extraction time is 30min, and stirring rate is
300rpm.The extraction efficiency highest at 50 DEG C, therefore select 50 DEG C of extraction temperature.
The selection of 3 mixing speed of embodiment
Mass transport process can be improved by accelerating mixing speed, accelerated object and entered film speed, improve extraction efficiency, but mistake
Fast stirring will destroy the structure of film, reduce extraction efficiency.Having investigated mixing speed respectively is 100,200,300,400,
Extraction efficiency when 500rpm, other experiment conditions are：Temperature is 50 DEG C, extraction time 30min.The result shows that in 300rpm
When extraction efficiency highest, therefore stirring rate selects 300rpm.
The selection of 4 salinity of embodiment
Influence of the salt effect to extraction be it is two-way, on the one hand the addition of salt can increase the ionic strength of solution, reduce to
It surveys the solubility of object and then increases extraction efficiency, electrostatic interaction can resist the extraction of organic solvent again but then.It investigates
Influence of the NaCl concentration (0.01,0.05,0.10,0.15 and 0.20mol/L) to extraction efficiency, other conditions in sample solution
For：Extraction temperature is 50 DEG C, stirring rate 300rpm, extraction time 30min.The result shows that the concentration as NaCl is
The extraction efficiency highest of 0.15mol/L phthalate compound, therefore select the concentration of NaCl for 0.15mol/L.
The investigation of 5 methodology of embodiment
(1) instrument and reagent
Japanese Shimadzu GC-2010Plus, Japan Py-2020iD vertical type micro furnace cracker, Germany IKA C-MAG HS4 add
Pyromagnetic force blender.From the bottled pure water of supermarket's purchase different batches.
(2) experimental method
(2-1) sample pre-treatments
Hollow-fibre membrane is cut into 1.0cm segment, and impregnates 1h in ethanol, naturally dry is stored in standby in vial
With.
1-10 water sample is taken, NaCl is separately added into and internal standard compound dicyclohexyl phthalate obtains solution to be measured, make
Concentration of the NaCl in solution to be measured is 0.15mol/L, concentration of the internal standard compound dicyclohexyl phthalate in solution to be measured
For 0.1mg/L, 4mL solution to be measured is taken to be placed in ml headspace bottle, places into stirring magneton and be placed on magnetic stirring apparatus, then take two
Root 1.0cm doughnut is put into ml headspace bottle, unlatching magnetic stirring apparatus, extracts 30min at 50 DEG C with the mixing speed of 300rpm,
Hollow-fibre membrane is taken out, for use；
(2-2) sample detection
Ready hollow-fibre membrane in step (2-1) is placed in the sample of cracker above flash distillation gas chromatograph injection port
In product cup, when cracker temperature reaches 300 DEG C, sample introduction button is pressed, specimen cup falls into the furnace heart of pyrolysis furnace, carries out flashed vapour
Analysis of hplc；
It is described flash distillation gas chromatographic analysis condition be：
Chromatographic column：DB-5 (i.d. × 0.25 μm Agilent Labs, 30m × 0.25mm, the poly- silicon oxygen of 5% phenyl methyl
Alkane)；Column temperature：60 DEG C of initial temperature, 5min is kept, 220 DEG C is raised to 20 DEG C/min rate, keeps 1min, be raised to 5 DEG C/min rate
250 DEG C, 1min is kept, 290 DEG C is raised to 20 DEG C/min rate, keeps 7.5min；The room temperature that gasifies is 300 DEG C, detector temperature
Degree is 320 DEG C；Cracker temperature：It cracks furnace temperature and chromatographic column injector temperature is 300 DEG C；Split ratio 10：1；Carrier gas N2；
Column flow 1.0mL/min；
(2-3) establishes standard curve
The standard substance of DEP, DPRP, DIBP, DBP, DMEP, DPP, DNHP, BBP, DEHP, DNOP are taken, is molten with methanol
Agent is configured to hybrid standard stock solution, and gained hybrid standard stock solution dilutes to obtain standard curve working solution through deionized water,
Gained standard curve working solution is subjected to pre-treatment (i.e. according to step (1) pre-treating method：By water in step (2-1)
Sample replaces with standard curve working solution) and then testing conditions in step (2-2) under carry out flash distillation gas-chromatography point
Analysis, obtains standard substance spectrogram, using the concentration of standard curve working solution Plays substance as abscissa, spectrogram Plays substance
It is ordinate with the ratio between the peak area of internal standard compound, draws standard curve；
The concentration range of each standard substance respectively stands alone as 0.002~1mg/L in the standard curve working solution；
The testing result of (2-4) acquisition Determination of Phthalate Esters in Water class compound
The standard substance spectrogram as obtained by step (2-3) is compareed with spectrogram obtained by step (2-2) sample detection, must be discharged
The qualitative results of contained phthalate compound in sample；
By the peak area of phthalate compound and internal standard compound in spectrogram obtained by step (2-2) sample detection it
Than substituting into standard curve obtained by step (2-3), the content for obtaining Determination of Phthalate Esters in Water class compound is calculated.
(3) results and discussion
The parameters such as the linear of this method, detection limit and quantitative limit are investigated, the results are shown in Table 1.It can see from table 1, it is to be measured
Object is linear good within the scope of 0.002-1mg/L, and r is greater than 0.98, RSD less than 9.5%, therefore, it is considered that this method accuracy is good
It is good, it can be used to measure the phthalate in water sample.
Table 1：The linear of 10 kinds of phthalic acid esters, concentration coefficient, detection limit and quantitative limit result
Content, precision and the rate of recovery of 10 kinds of phthalic acid esters in sample are measured respectively.Fig. 2 is real
Border sample doughnut solid phase microextraction-gas chromatogram.Using internal standard method to the phthalate content in sample into
Row is quantitative, and RSD is respectively less than 5.7%, the results are shown in Table 2, the rate of recovery the results are shown in Table 3.
The measurement result of 10 kinds of phthalates in 2 actual sample of table
The recovery of standard addition of 10 kinds of phthalates in 3 actual sample of table
Claims (3)
1. a kind of hollow-fibre membrane micro-extraction combines flash distillation gas chromatography measurement Determination of Phthalate Esters in Water class compound to contain
The method of amount, which is characterized in that described method includes following steps：
(1) sample pre-treatments
Water sampling, is added NaCl and internal standard compound dicyclohexyl phthalate obtains solution to be measured, and gained solution to be measured is placed in
In ml headspace bottle, it is put into hollow-fibre membrane, 30min is extracted under conditions of temperature 50 C, stirring rate 300rpm, takes out hollow fibre
Film is tieed up, for use；
Concentration of the NaCl in solution to be measured is 0.15mol/L；
Concentration of the internal standard compound dicyclohexyl phthalate in solution to be measured is 0.1mg/L；
(2) sample detection
Ready hollow-fibre membrane in step (1) is placed in the specimen cup of cracker above flash distillation gas chromatograph injection port
In, when cracker temperature reaches 300 DEG C, sample introduction button is pressed, specimen cup falls into the furnace heart of pyrolysis furnace, carries out flash distillation gas phase color
Spectrum analysis；
It is described flash distillation gas chromatographic analysis condition be：
Chromatographic column：I.d. × 0.25 μm DB-5,30m × 0.25mm, 5% methyl-polysiloxane；Column temperature：It 60 DEG C of initial temperature, protects
5min is held, 220 DEG C is raised to 20 DEG C/min rate, keeps 1min, 250 DEG C is raised to 5 DEG C/min rate, 1min is kept, with 20
DEG C/min rate is raised to 290 DEG C, keep 7.5min；The room temperature that gasifies is 300 DEG C, and detector temperature is 320 DEG C；Cracker temperature
Degree：It cracks furnace temperature and chromatographic column injector temperature is 300 DEG C；Split ratio 10：1；Carrier gas N2；Column flow 1.0mL/min；
(3) standard curve is established
The standard substance for taking DEP, DPRP, DIBP, DBP, DMEP, DPP, DNHP, BBP, DEHP, DNOP, matches by solvent of methanol
Hybrid standard stock solution is made, gained hybrid standard stock solution dilutes to obtain standard curve working solution through deionized water, by institute
It obtains standard curve working solution and carries out pre-treatment and then the detection in step (2) according to step (1) pre-treating method
Under the conditions of carry out flash distillation gas chromatographic analysis, standard substance spectrogram is obtained, with the dense of standard curve working solution Plays substance
Degree is abscissa, and the ratio between spectrogram Plays substance and the peak area of internal standard compound are ordinate, draws standard curve；
The concentration range of each standard substance respectively stands alone as 0.002~1mg/L in the standard curve working solution；
(4) testing result of Determination of Phthalate Esters in Water class compound is obtained
The standard substance spectrogram as obtained by step (3) is compareed with spectrogram obtained by step (2) sample detection, is obtained contained in water sample
The qualitative results of phthalate compound；
The ratio between the peak area of phthalate compound and internal standard compound in spectrogram obtained by step (2) sample detection is substituted into
In standard curve obtained by step (3), the content for obtaining Determination of Phthalate Esters in Water class compound is calculated.
2. hollow-fibre membrane micro-extraction as described in claim 1 combines phthalic acid in flash distillation gas chromatography measurement water sample
The method of ester type compound content, which is characterized in that the hollow-fibre membrane is PS membrane, film outer diameter 0.978mm, internal diameter
0.800mm, aperture 0.2mm.
3. hollow-fibre membrane micro-extraction as described in claim 1 combines phthalic acid in flash distillation gas chromatography measurement water sample
The method of ester type compound content, which is characterized in that the hollow-fibre membrane is cut into the segment of length 1cm before use, and
1h is impregnated in ethyl alcohol, is stored in after natural drying spare in vial.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106979986A (en) * | 2017-05-04 | 2017-07-25 | 南京大学 | It is a kind of to analyze the method that micro- plastics carrying phthalate compound is enriched with content in vivo |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106979986A (en) * | 2017-05-04 | 2017-07-25 | 南京大学 | It is a kind of to analyze the method that micro- plastics carrying phthalate compound is enriched with content in vivo |
Non-Patent Citations (4)
| Title |
|---|
| ELEFTERIA PSILLAKIS ET AL.: "Hollow-fibre liquid-phase microextraction of phthalate esters from water", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| JAVIER GONZ_ALEZ-S_ALAMO ET AL.: "Determination of phthalic acid esters in water samples by hollow fiber liquid-phase microextraction prior to gas chromatography tandem mass spectrometry", 《CHEMOSPHERE》 * |
| 吴惠勤 等: "不同类别食品中21种邻苯二甲酸酯的气相色谱-质谱测定及其分布情况研究", 《分析测试学报》 * |
| 张伟: "裂解气相色谱/质谱法测定聚氯乙烯中邻苯二甲酸酯类增塑剂的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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