CN105823837B - The detection method of phthalate compound and catabolite in environmental water sample - Google Patents

The detection method of phthalate compound and catabolite in environmental water sample Download PDF

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Publication number
CN105823837B
CN105823837B CN201610145218.5A CN201610145218A CN105823837B CN 105823837 B CN105823837 B CN 105823837B CN 201610145218 A CN201610145218 A CN 201610145218A CN 105823837 B CN105823837 B CN 105823837B
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sample
phthalate
water
syringe
catabolite
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CN105823837A (en
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朱方
徐超
孙国茂
薛永来
杜道林
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Jiangsu University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N30/08Preparation using an enricher
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N2030/062Preparation extracting sample from raw material

Abstract

The invention discloses the detection methods of phthalate compound in environmental water sample and catabolite, belong to quality of water environment detection and analysis field.The present invention is according to the polarity of tested substance, the ratio of preferred ion liquid, it is propped up to be downloaded in the micropore of hollow-fibre membrane wall by capillary force and forms liquid film, adjusted suitable sample and receptor acid-base value, receptor is encapsulated in the inner cavity of hollow-fibre membrane and extraction equipment is made.The extraction equipment is placed in sample, that is, forms a water/organic solvent two-phase or water/organic solvent/water three-phase system.After enrichment purification, methanol elution, efficient liquid phase chromatographic analysis target pollutant concentration.This method can be used for the detection of phthalate plasticiser in environment, provide data for the analysis of its environmental behaviour, evaluate the quality of environment water;Method is quick, it is reliable, be simple to operate and friendly to environment.

Description

The detection method of phthalate compound and catabolite in environmental water sample
Technical field
The present invention relates to a kind of detection methods of O-phthalic esters plasticiser in environmental water sample, are adopted more particularly to one kind With doughnut supported ionic liquid liquid-phase micro-extraction method be enriched with and detect environmental water sample in phthalate compound and The method of its catabolite belongs to quality of water environment detection and analysis field.
Background technology
Phthalate compound (Phthalate esters, PAEs) is main as a kind of most common plasticizer It is used for polyvinyl chloride processing industry, it is also possible to make farm chemical carrier, cosmetics, lubricant, detergent, the raw materials for production of paint, Palm oil is even substituted, is illegally added in food.Since such compound only passes through hydrogen bond or Van der Waals force and plastic matrix Connection, is not aggregated in the macromolecule carbochain of plastics, over time, it is easy to can be discharged into environment.PAEs enters After water body, after the reactions such as biodegradation, photodissociation, hydrolysis, a side chain is first opened, is degraded to phthalic monoester (Monoalkyl phthalate esters, MPEs).The study found that phthalic acid ester and its catabolite have oestrogen-like hormone Effect, disturbance endocrine system has humans and animals carcinogenic, teratogenesis, mutagenesis, and reproductive function can be caused abnormal, With potential health risk.Especially phthalic monoester is more easy to the phospholipid bilayer by cell membrane, shows to compare The stronger toxicity of phthalic acid ester.
Phthalate compound is that one of most wide pollutant is propagated in the whole world, in environment such as air, water body, soil Can detect the presence of phthalate substance in medium, and its degradation speed is slow in the environment, be referred to as " second Global PCB (Polychlorinated biphenyls) pollutant ".Phthalate compound solubility is low, and trace is distributed in environmental water sample, Substance classes are also more.The normal octane of PAEs and its catabolite MPEs-water partition coefficient logP, acidity coefficient pKa differences compared with Greatly, water body mesostroma is complicated, and the pre-treatments difficulty such as purification enrichment is larger.
Existing detection phthalate substance pre-treating method, liquid-liquid extraction (LLE), Solid Phase Extraction (SPE) need A large amount of toxic organic solvents, the health of analysis on damage personnel are used, and easily causes the secondary pollution to environment;The micro- extraction of solid phase (SPME) is taken since extracting fiber service life is limited, frangibility, and might have residual in the analysis process, in practical application It is subject to many limitations in the process.Doughnut supported ionic liquid liquid-phase micro extraction technique (HF-LPME), volatility is small, glutinous It spends on ionic liquid attachment doughnut suitable, unmixing with water and forms liquid film, small using quantity of solvent, collection extraction is enriched in One, fiber is disposable, no cross contamination problem, effectively improves the stability and reliability of extraction.By adjusting having The ingredient of machine liquid film selects suitable donor phase, receives phase pH value, donor phase ionic strength, extraction time, matrix effect etc. because Element optimizes enrichment times, realizes and synchronously extracts a variety of phthalate compounds and its catabolite, for understanding its ring Border behavior and return, accurate and effective its influence to Environmental Health of assessment is of great significance.
The content of the invention
The present invention is directed to the above-mentioned deficiency of the prior art, provides neighbour's benzene two in a kind of energy purification, enrichment, synchronous detection water sample The method of formic ether compounds and its catabolite.The organic solvent amount used is few, no cross contamination problem, bioaccumulation efficiency Height, testing result are reproducible.
The purpose of the present invention implements by the following technical programs:Phthalate compound in environmental water sample And the detection method of catabolite, it carries out as steps described below:
(1) preparation of phthalate compound and its catabolite phthalic monoester standard solution;
(2) pre-treatment of environmental water sample:Doughnut is taken, acetone cleaning is dried;With micro-syringe connecing certain pH value By mutually injecting hollow fiber cavity;It is dipped in ionic liquid to form liquid film;Rinse the ionic liquid of fiber surface;Again It is secondary to receive mutually to inject inner cavity until being full of with micro-syringe;With foil sealing circlewise, extraction dress is made in curved fiber, both ends It puts, then with 0.45 μm of filtering with microporous membrane environmental water sample;The pH value of sample solution is adjusted, doughnut extraction equipment is complete It is immersed in entirely in sample solution, is placed in 0.5~4h of oscillation extraction in constant temperature tandem-driving bogie and is enriched with;Extraction terminates, and takes out fiber, Remove aluminium foil, fiber one end is connected to micro-syringe, the other end is positioned in high performance liquid chromatography sample injection bottle, slowly will be micro- 20~200 μ L methanol push-in fiber lumens in syringe, are enriched in liquid film with elution and receive the target analytes of phase.
(3) drafting of standard curve;
(4) high performance liquid chromatography of sample measures.
In the step (1), standard solution using national standard substance prepare, select three kinds of actual productions in dosage compared with Greatly, double (the 2- ethyls of more diethyl phthalate, n-butyl phthalate, phthalic acid are distributed in the environment Hexyl) ester, mono-ethyl phthalate, phthalic acid mono-n-butylester, totally 6 kinds of phthalic acid list (2- ethylhexyls) ester, object No. CAS of matter, chemical structural formula it is as shown in table 1.Three kinds of phthalic acid esters do not show apparent acid-base property, and lipophile compares phase The phthalic monoester answered is strong, and three kinds of phthalic monoesters have moderate acid.The deposit of 1g/L is first configured to methanol Liquid further uses volumetric flask constant volume into a series of mixed standard solution of concentration gradients as needed.
The chemical structural formula of 1 three kinds of phthalic acid esters of table and its catabolite
Preferably, the polypropylene hollow fiber in step (2):280 μm of internal diameter, 50 μm of wall thickness, 0.1 μm of aperture, porosity 60%, length 12cm;Micro syringe:Syringe needle outer diameter 0.3mm, long 8mm, syringe volume 0.5mL;Ionic liquid by 1- butyl- 3- methylimidazoles hexafluorophosphate, 1- hexyl -3- methylimidazoles hexafluorophosphate, 1- octyl group -3- methylimidazole hexafluorophosphates By 1:1:The mixing of 1 volume ratio is made into, and receives to be mutually to adjust the ultra-pure water that pH value is 10 with NaOH.
Preferably, it is 2~3 that sample solution adjusts pH value with HCl in the step (2), and constant temperature tandem-driving bogie temperature is 25 DEG C, The oscillation extraction time is 1.5h under 200rpm speed.
Preferably, micro-syringe is once eluted with 50 μ L methanol in the step (2).
The drafting of step (3) standard curve, specific method are:Take standard made from isometric step (1) molten Liquid is added in ultra-pure water, a series of simulating pollution water sample of 0.1~100 μ g/L concentration is diluted to, before step (2) method Reason, enrichment elute laggard high performance liquid chromatograph analysis, and chromatographic software integration calculates peak area, is fitted to obtain measured object concentration and peak Standard working curve between area, linearly dependent coefficient R2More than 0.99;
Each sample parallel determination 3 times, are averaged;Chromatographic condition is:Eclipse XDB-C18 liquid chromatograies separate Column, 150mm × 4.6mm, 5 μm of grain size;30 DEG C of column temperature;10 μ L of sample size;It is the pure water with acetic acid tune pH value to 3 to flow phase composition And methanol, flow velocity 1mL/min;Condition of gradient elution:0-15min, 70% methanol increase linearly to 100%;Keep 10min;25- 30min, linear reduction to 70%.
The high performance liquid chromatography of sample measures in the step (4), and specific method is as follows:
By the good environmental water sample of step (2) pre-treatment, by the chromatographic condition sample detection of step (3), will be surveyed with external standard method Chromatographic peak is obtained compared with standard curve, conversion obtains phthalate compound and its catabolite in detection environmental water sample The concentration of phthalic monoester.
Advantages of the present invention and advantageous effects are:
The present invention provides the method for phthalate compound and its catabolite in synchronous detection environmental water sample, relates to And three kinds of actual amounts it is larger, be distributed in the environment more phthalate compound and its corresponding primary degradation production Object phthalic monoester, this two classes substance normal octane-water partition coefficient, acidity coefficient differ greatly, the trace in environment water Amount distribution.The present invention integrates extraction, enrichment, purification, with organic solvent usage amount is few, extraction efficiency is high, enrichment times Greatly, the advantages that being simple to operate and friendly to environment can provide data to analyze the environmental behaviour of phthalate plasticiser, be Its Environmental Health risk is assessed to lay the foundation.Detection method can be seen that by the high-efficient liquid phase chromatogram of Fig. 1, it can While by the separation of a variety of phthalate compounds and its clear wash rice of catabolite and detect its content.
Description of the drawings
Attached drawing is used for providing a further understanding of the present invention, and a part for constitution instruction, the reality with the present invention Example is applied together for explaining the present invention, is not construed as limiting the invention.
Fig. 1 is the liquid chromatogram separation figure of 3 kinds of phthalic acid esters and its corresponding catabolite in the embodiment of the present invention.For 10mg/L marks the liquid chromatogram of product solution, retention time MEP:2.656min DEP:3.185min MBP:3.803min DBP:8.426min MEHP:8.909min DEHP:16.428min.
Specific embodiment
Below according to specific embodiments of the present invention, the present invention will be described in detail, and the objects and effects of the present invention will be brighter It is aobvious.
The preferred embodiment of the present invention is illustrated below, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1:
Standard solution is prepared using national standard substance, and dosage is larger, is distributed in the environment in three kinds of actual productions of selection More diethyl phthalate, n-butyl phthalate, phthalic acid double (2- ethylhexyls) ester, O-phthalics Sour mono ethyl ester, phthalic acid mono-n-butylester, totally 6 kinds of phthalic acid list (2- ethylhexyls) ester.First 1g/L is configured to methanol Storing solution, respectively take 100 μ l, 6 kinds of standard reserving solutions in 10mL volumetric flasks, with methanol constant volume to 10ml, be configured to mixing mark product Solution, the concentration of each target contaminant is 10mg/L.
To verify high performance liquid chromatography separation effect, above-mentioned mixing mark product solution is taken to carry out HPLC analyses.Experiment liquid phase Chromatograph is Waters, US's Breeze2 liquid chromatographic systems, 1525 binary pumps, 2707 autosamplers, 2489 ultraviolet/ Visible detection device;Eclipse XDB-C18 liquid chromatography separation columns, 150mm × 4.6mm, 5 μm of grain size;30 DEG C of column temperature;Sample size 10μL;It is with the pure water and methanol of acetic acid tune pH value to 3, flow velocity 1mL/min to flow phase composition;Detection wavelength is 280nm;Gradient Elution requirement:0-15min, 70% methanol increase linearly to 100%;Keep 10min;25-30min, linear reduction to 70%.Mesh Mark pollutant mixing mark product solution separation chromatography figure is shown in Fig. 1, and each target contaminant separating effect is preferable, meets analysis requirement.
Embodiment 2:
Standard solution is prepared using national standard substance, and dosage is larger, is distributed in the environment in three kinds of actual productions of selection More diethyl phthalate, n-butyl phthalate, phthalic acid double (2- ethylhexyls) ester, O-phthalics Sour mono ethyl ester, phthalic acid mono-n-butylester, totally 6 kinds of phthalic acid list (2- ethylhexyls) ester.First 1g/L is configured to methanol Storing solution, respectively take 100 μ l, 6 kinds of standard reserving solutions in 10mL volumetric flasks, with methanol constant volume to 10ml, be configured to mixing mark product Solution, the concentration of each target contaminant is 10mg/L.
It is in order to obtain the standard curve of 6 kinds of target contaminants, the mixing mark product solution ultra-pure water of above-mentioned 10mg/L is dilute It is interpreted into a series of simulating pollution water sample (0.1~100 μ g/L) of various concentrations.
The polypropylene hollow fiber (280 μm of internal diameter, 50 μm of wall thickness, 0.1 μm of aperture, porosity 60%) of 12cm long is taken, is placed in It is cleaned by ultrasonic in acetone, to remove surface impurity, dries spare;With micro-syringe (syringe needle outer diameter 0.3mm, long 8mm, needle cylindrical unit Accumulate 0.5mL) ultra-pure water (adjusting pH value 10 by the use of NaOH) is mutually injected into hollow fiber cavity as receiving;By doughnut immerse from Sub- liquid is (by 1- butyl -3- methylimidazoles hexafluorophosphate, 1- hexyl -3- methylimidazoles hexafluorophosphate, 1- octyl group -3- first Base limidazolium hexafluorophosphate presses 1:1:The mixing of 1 volume ratio is made into) in, sonic oscillation 30 seconds, in the micropore of doughnut membranous wall Form liquid film;Ultra-pure water rinses the ionic liquid for remaining in fiber surface;It will be received mutually to inject inner cavity with micro-syringe again Until being full of;With foil sealing circlewise, extraction equipment is made in curved fiber, both ends.
A series of target pollutant concentrations are filtered for 0.1~100 μ g/L simulating pollutions water sample with 0.45 μm of micropore respectively Membrane filtration;It is 3 to adjust water sample pH value with HCl;Doughnut extraction equipment is totally submerged in sample solution, constant temperature is placed in and puts down 25 DEG C in weighing apparatus case, oscillation extraction 1.5h under 200rpm speed.
After extraction, fiber is taken out, removes aluminium foil, fiber one end is connected to micro-syringe, the other end is positioned over height In effect liquid phase chromatogram sample injection bottle, 50 μ L methanol in micro-syringe are slowly pushed into fiber lumens, liquid film is enriched in elution With the target analytes for receiving phase.Sample introduction is analyzed for high performance liquid chromatograph, and each concentration samples parallel determination 3 times is averaged.
Experiment is Waters, US's Breeze2 liquid chromatographic systems with liquid chromatograph, and 1525 binary pumps, 2707 certainly Dynamic injector, 2489 ultraviolet/visible detection devices;Eclipse XDB-C18 liquid chromatography separation columns, 150mm × 4.6mm, grain size 5 μm;30 DEG C of column temperature;10 μ L of sample size;It is with the pure water and methanol of acetic acid tune pH value to 3, flow velocity 1mL/min to flow phase composition;Inspection Survey wavelength is 280nm;Condition of gradient elution:0-15min, 70% methanol increase linearly to 100%;Keep 10min;25- 30min, linear reduction to 70%.
Chromatographic software integration calculates peak area, the standard curve being fitted between measured object concentration and peak area, this method The range of linearity is in 0.200-50 μ g/L, linearly dependent coefficient R2Relative standard deviation more than 0.99, three parallel sample exists Between 4.1-8.9%, detection limit is shown in Table 2, meets water environment in 0.028-0.072 μ g/L, linear equation, the enrichment times of method The testing requirements of middle Trace Phthalate Esters class compound and its catabolite.
The efficient liquid phase of 2 three kinds of phthalic acid esters of the table and its catabolite detection range of linearity, enrichment times, detection limit
Embodiment 3:
Adjacent benzene is carried out to 2 kinds of laboratory tap water, Beijing-Hangzhou Grand Canal Zhenjiang section river water environmental water samples using institute's method for building up The enrichment and detection of diformic ester compound and its catabolite.
The polypropylene hollow fiber (280 μm of internal diameter, 50 μm of wall thickness, 0.1 μm of aperture, porosity 60%) of 12cm long is taken, is placed in It is cleaned by ultrasonic in acetone, to remove surface impurity, dries spare;With micro-syringe (syringe needle outer diameter 0.3mm, long 8mm, needle cylindrical unit Accumulate 0.5mL) ultra-pure water (adjusting pH value 10 by the use of NaOH) is mutually injected into hollow fiber cavity as receiving;By doughnut immerse from Sub- liquid is (by 1- butyl -3- methylimidazoles hexafluorophosphate, 1- hexyl -3- methylimidazoles hexafluorophosphate, 1- octyl group -3- first Base limidazolium hexafluorophosphate presses 1:1:The mixing of 1 volume ratio is made into) in, sonic oscillation 30 seconds, in the micropore of doughnut membranous wall Form liquid film;Ultra-pure water rinses the ionic liquid for remaining in fiber surface;It will be received mutually to inject inner cavity with micro-syringe again Until being full of;With foil sealing circlewise, extraction equipment is made in curved fiber, both ends.
By environmental water sample respectively with 0.45 μm of filtering with microporous membrane;It is 3 to adjust water sample pH value with HCl;By doughnut Extraction equipment is totally submerged in sample solution, is placed in constant temperature tandem-driving bogie 25 DEG C, oscillation extraction 1.5h under 200rpm speed.
After extraction, fiber is taken out, removes aluminium foil, fiber one end is connected to micro-syringe, the other end is positioned over height In effect liquid phase chromatogram sample injection bottle, 50 μ L methanol in micro-syringe are slowly pushed into fiber lumens, liquid film is enriched in elution With the target analytes for receiving phase.Sample introduction is analyzed for high performance liquid chromatograph, and each concentration samples parallel determination 3 times is averaged.
Experiment is Waters, US's Breeze2 liquid chromatographic systems with liquid chromatograph, and 1525 binary pumps, 2707 certainly Dynamic injector, 2489 ultraviolet/visible detection devices;Eclipse XDB-C18 liquid chromatography separation columns, 150mm × 4.6mm, grain size 5 μm;30 DEG C of column temperature;10 μ L of sample size;It is with the pure water and methanol of acetic acid tune pH value to 3, flow velocity 1mL/min to flow phase composition;Inspection Survey wavelength is 280nm;Condition of gradient elution:0-15min, 70% methanol increase linearly to 100%;Keep 10min;25- 30min, linear reduction to 70%.
Chromatographic peak will be measured compared with standard curve with external standard method, and conversion obtains phthalic acid ester in detection environmental water sample The concentration of class compound and its catabolite phthalic monoester.The results show is shown in Table 3, tap water, Jing Hang great in laboratory DBP, DEHP are all detected in the Zhenjiang section river water of canal, other four kinds of substances do not detect, and 10 μ g/L of mark-on, measure back in water sample Yield is 84.0-106.2%.
The testing result of three kinds of phthalic acid esters and its catabolite in 3 actual water sample of table
Note:ND- is not detected

Claims (1)

1. the detection method of phthalate compound and catabolite in environmental water sample, it is characterised in that according to following steps It is rapid to carry out:
(1)The preparation of phthalate compound and its catabolite phthalic monoester standard solution;
(2)The pre-treatment of environmental water sample:Doughnut is taken, acetone cleaning is dried;Certain pH value is received into phase with micro-syringe Inject hollow fiber cavity;It is dipped in ionic liquid to form liquid film;Rinse the ionic liquid of fiber surface;It uses again Micro-syringe will receive mutually to inject inner cavity until being full of;With foil sealing circlewise, extraction equipment is made in curved fiber, both ends, Then with 0.45 μm of filtering with microporous membrane environmental water sample;The pH value of sample solution is adjusted, doughnut extraction equipment is complete It is immersed in sample solution, is placed in 0.5~4h of oscillation extraction in constant temperature tandem-driving bogie and is enriched with;Extraction terminates, and takes out fiber, goes Fall aluminium foil, fiber one end is connected to micro-syringe, the other end is positioned in high performance liquid chromatography sample injection bottle, slowly by micro- note 20~200 μ L methanol push-in fiber lumens in emitter, are enriched in liquid film with elution and receive the target analytes of phase;(3)Mark The drafting of directrix curve;
(4)The high performance liquid chromatography of sample measures;
The step(1)In, standard solution using national standard substance prepare, select three kinds of actual productions in dosage it is larger, It is double that more diethyl phthalate, n-butyl phthalate, phthalic acid are distributed in environment(2- ethylhexyls) Ester, mono-ethyl phthalate, phthalic acid mono-n-butylester, totally 6 kinds of phthalic acid list (2- ethylhexyls) ester, first use methanol The storing solution of 1g/L is configured to, further uses volumetric flask constant volume as needed into a series of mixed standard solution of concentration gradients;
Step(2)In polypropylene hollow fiber:280 μm of internal diameter, 50 μm of wall thickness, 0.1 μm of aperture, porosity 60%, length 12cm;Micro syringe:0.3 mm of syringe needle outer diameter, long 8 mm, 0.5 mL of syringe volume;Ionic liquid is by 1- butyl -3- methyl Limidazolium hexafluorophosphate, 1- hexyl -3- methylimidazoles hexafluorophosphate, 1- octyl group -3- methylimidazoles hexafluorophosphate press 1:1:1 Volume ratio mixing is made into, and receives to be mutually to adjust the ultra-pure water that pH value is 10 with NaOH;
The step(2)It is 2~3 that middle sample solution adjusts pH value with HCl, and constant temperature tandem-driving bogie temperature is 25 DEG C, 200rpm speed The lower oscillation extraction time will be 1.5h;
The step(2)Middle micro-syringe is once eluted with 50 μ L methanol;
The step(3)The drafting of standard curve, specific method are:Take isometric step(1)Standard solution obtained adds Enter in ultra-pure water, a series of simulating pollution water sample of 0.1~100 μ g/L concentration is diluted to, using step(2)Method pre-treatment, Enrichment elutes laggard high performance liquid chromatograph analysis, and chromatographic software integration calculates peak area, is fitted to obtain measured object concentration and peak face Standard working curve between product, linearly dependent coefficient R2More than 0.99;Each sample parallel determination 3 times, are averaged;Chromatography Condition is:Eclipse XDB-C18 liquid chromatography separation columns, 150mm × 4.6mm, 5 μm of grain size;30 DEG C of column temperature;10 μ of sample size L;It is with the pure water and methanol of acetic acid tune pH value to 3, flow velocity 1mL/min to flow phase composition;Condition of gradient elution:0-15min, 70% methanol increases linearly to 100%;Keep 10 min;25-30min, linear reduction to 70%;
The step(4)The high performance liquid chromatography of middle sample measures, and specific method is as follows:
By step(2)The good environmental water sample of pre-treatment, by step(3)Chromatographic condition sample detection, will measure color with external standard method For spectral peak compared with standard curve, conversion obtains phthalate compound and its catabolite neighbour's benzene in detection environmental water sample The concentration of dioctyl phthalate monoesters.
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