CN101865898A - Method for determining phthalate ester in soil - Google Patents
Method for determining phthalate ester in soil Download PDFInfo
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- CN101865898A CN101865898A CN 201010208752 CN201010208752A CN101865898A CN 101865898 A CN101865898 A CN 101865898A CN 201010208752 CN201010208752 CN 201010208752 CN 201010208752 A CN201010208752 A CN 201010208752A CN 101865898 A CN101865898 A CN 101865898A
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Abstract
The invention relates to a method for determining phthalate ester in soil, belonging to the filed of analysis of trace contaminants in the environment. The method comprises the following steps: taking dichloromethane as an extract, and extracting by an ultrasonic extraction method; carrying out nitrogen blowing concentration; and finally analyzing and determining by gas chromatography tandem mass spectrometry (GC/MS) so as to accurately and quickly analyze phthalate ester in the soil. The specific analytical determination method comprises the following steps: taking a certain amount of naturally air-dried soil in a conical flask, and adding 10-30mL of dichloromethane; ultrasonically extracting for 5-30min, and collecting the extract after filtering; repeating the steps twice, and combining the extract; nitrogen-blowing to 3-6mL, and transferring to a concentration tube and then continuing to blow to below 2mL; adding internal standard, fixing volume with the dichloromethane, and transferring to an automatic sample bottle; and finally, accurately determining with debugged GC-MS. The determination method developed by the invention is simple and fast, and has the characteristics of high recovery rate, low detection limit, high sensitivity, matrix interference resistance and the like.
Description
[technical field]
The invention belongs to contaminant trace species analysis field in the environment, specifically a kind of accurately quick method of measuring phthalate ester in the soil.
[background technology]
Phthalic ester (phthalate ester) is important plastifier, owing to its material impact to healthy reproduction receives much concern.American National Environmental Protection Agency (US EPA) classifies two (2-ethylhexyl) esters (DEHP) of phthalic acid, phthalic acid dioctyl ester (DOP), benzyl butyl phthalate (BBP), dibutyl phthalate (DBP), repefral (DMP) and diethyl phthalate 6 kinds of phthalate esters such as (DEP) as preferential control toxic pollutant, and China classifies DMP, DBP, DOP as preferential monitoring pollutant.Phthalate ester enters physical environment, and processes such as leaching, volatilization, sedimentation and degraded take place, migration in surrounding mediums such as soil, water body and atmosphere, conversion, and in soil, sediment, accumulate.Phthalate ester in the soil enters atmosphere by volatilization, enters human body via respiratory system; Or, enter human body via digestive system by biological concentration.Phthalate is an environmental hormone class material, has reproduction, development toxicity, has proved that phthalate ester has effects such as carcinogenic, mutagenesis, teratogenesis and genotoxicity to animal.
The extracting method of phthalate ester mainly contains cable-styled extraction method, ultrasonic extraction, Microwave Extraction method in the solid, accelerated solvent extraction is followed the example of and supercritical fluid extraction method etc.The soxhlet extraction solvent load is big, and the extraction time is long, is subject to phthalate ester pollution in the environment, and blank value is big.Microwave abstracting is easy and simple to handle, solvent-oil ratio is few, quantity of sample handling is big.But high temperature can cause the loss of the phthalate ester of half volatile, therefore is not suitable for the extraction of phthalate ester.The accelerated solvent extraction technology is the principle according to solute different solubility in different solvents, utilize accelerated solvent extraction, under higher temperature and pressure condition, select suitable solvent, realize the organic method in solid or the semi-solid sample that extracts efficiently, apace.Accelerated solvent extraction follows the example of that the advantage of measuring phthalate ester in the soil is that security is good, good airproof performance, organic solvent-free leak.Shortcoming is that solvent load is bigger.Because accelerated solvent extraction carries out under High Temperature High Pressure, so for the stronger phthalate ester of volatility, should not adopt this method.Supercritical fluid extraction be a kind of efficient, fast, aftertreatment is simple, be easy to other instrument analytical method couplings, can avoid the desirable sample pre-treatments technology of the loss of sample transfer.But it is had relatively high expectations to pretreatment technology, and instrument is bought relatively more expensive.Ultrasonic extraction is compared advantages such as to have a solvent load few, and the time is short, and the recovery is higher, and is simple and quick, easy to use, and price is lower with other extracting method.
The selection that the pre-treatment condition comprises solvent, extraction time and extraction times is a vital step for detecting and measuring of phthalate ester in the soil, therefore selects suitable pre-treatment condition to have great importance.Ultrasonic Extraction extraction agent commonly used have acetone/sherwood oil (3: 5,1: 3 or 1: 1, v/v), acetone/methylene chloride (1: 1), methylene chloride etc. studies show that methylene chloride is the good extraction agent of extracting phthalate ester.Determine that by optimized choice suitable extraction time and number of times can satisfy the requirement of analysis.
Because the soil constitution more complicated generally will be carried out effective pre-separation and purification to component to be measured before mensuration.Promptly select suitable drip washing solvent that the phthalate ester in the extract is leached out, remove the interference of other impurity.Purification method commonly used has silica gel, silica gel/aluminium oxide, florisil silica and S-X3 resin to purify.The advantage that purifies is effectively to have removed the impurity in the sample, and it is effective to go out the peak, and shortcoming is to consume solvent, and has increased operation steps, and introducing blank has in various degree reduced the recovery.
Usually adopt the method for water-bath rotary evaporation when concentrating, promptly the liquid in the flat bottom flask is fully contacted with water in the water-bath, utilize the temperature of water-bath that solvent evaporates is fallen by rotation.But because phthalate ester is the organism of half volatile, therefore heating can be quickened its volatilization, loses bigger.And water-bath Nitrogen evaporator formula is utilized the nitrogen purging liquid surface behind the liquid nitrogen gasification, and temperature is very low, is unfavorable for the volatilization of phthalate ester, and therefore loss is very little.
Phthalate ester exists with trace in surrounding medium, and it is vital therefore selecting suitable detection method.Early stage detection method has colourimetry, titrimetry, thin-layered chromatography and spectrophotometric method etc., but low, the poor selectivity of the sensitivity of these methods, and only can measure the total amount of phthalate ester.In recent years, vapor-phase chromatography, gas chromatography-mass spectrography, liquid phase chromatography, liquid chromatography-mass spectrography etc. are widely used in the mensuration of phthalate ester.The advantage of vapor-phase chromatography is efficient, quick and sensitive, and shortcoming is that detecting device is subject to other organic pollutions, thereby the sensitivity change is bigger, and the pre-treatment of sample is had relatively high expectations.Gas chromatography-mass spectrography has advantages such as qualitative ability is strong, detectability is low, sensitivity height, is a kind of the most ripe, most widely used method.Liquid phase chromatography (HPLC) also is one of main method of analyzing phthalate ester, and the resolution that liquid chromatography has occurred when having solved GC-MS method separating isomerism body potpourri is lower, the overlapping problem of retention time between isostere radical.This method is not considered the detection of isomeride, so the gas chromatography tandem mass spectrometry is comparatively desirable detection method.
In sum, the extraction solvent that optimized choice is suitable, pre-treatment conditions such as extraction time and extraction times are selected appropriate extraction instrument and analytical instrument for use, could set up a kind of method of accurately measuring phthalate ester in the soil efficiently, to satisfy the demand of society.
[summary of the invention]
The purpose of this invention is to provide a kind of method of accurately fast measuring phthalate ester in the soil, this assay method is simple, and is quick, and has high-recovery, low detection limit, high sensitivity, anti-matrix interference, and phthalate ester lays the foundation in the soil in order further to study.
The present invention measures the method for phthalate ester in the soil, is extract with the methylene chloride, and the ultrasonic extraction instrument is an extraction element, and nitrogen blows catches concentrating instrument and concentrate, and measures with the gas chromatography tandem mass spectrometer at last.
Measure the method for phthalate ester in the soil, may further comprise the steps:
Leaching process: the soil of getting a certain amount of natural air drying adds the 10-30mL methylene chloride in conical flask, ultrasonic Extraction 5-30min, and extract is collected after filtering, repeats above step twice;
Concentration process: the extract after the merging is blown away dichloromethane solvent with nitrogen, blows to 3-6mL, is transferred to continue in the concentration tube to blow to 2mL, and mark in adding is used the methylene chloride constant volume;
The mensuration process: the sample transfer behind the constant volume is carried out GC-MS mensuration to brown auto injection bottle.
It is 20-30 ℃ that described ultrasonic extraction instrument extracts temperature, power 250-400w.
Temperature was set at 10-25 ℃ when described nitrogen dried up.
It is helium that described gas chromatography tandem mass spectrometer is measured carrier gas, flow rate of carrier gas: 0.5-2.0mL/min.
The invention has the beneficial effects as follows:
1. the ratio of solvent of Shi Yonging is less.The ultrasonic extraction triplicate that this method adopts, the quantity of solvent of using is 45ml, and cable-styled extraction commonly used repeats twice, the quantity of solvent of using is 150ml.
2. the time ratio of Xiao Haoing is shorter.The time that the ultrasonic extraction that this method adopts consumes is 1/48 of cable-styled extraction time of using always approximately.
3. the recovery is than higher.Use the different extraction conditions of this method optimized choice, several phthalate esters in the soil of mensuration, the recovery all is higher than 79%, is superior to the extracting method of other treatment conditions.
4. simple to operate.This method has been omitted the operation of crossing post, can effectively separate various phthalate esters and can reduce operation steps again, thereby reduce loss, has reduced and has introduced blank possibility.
5. lose less.This method all adopts water-bath nitrogen to blow in concentration process, and temperature is low, has reduced the volatilization of phthalate ester, is better than the rotary evaporation of needs heating, and is effective.
6. accuracy is than higher.This method is selected the gas chromatography tandem mass spectrum for use, and is highly sensitive, and qualitative ability is good, and selectivity ratios is better, has reduced matrix interference, thereby improved the accuracy of analyzing.
Be described in detail below with reference to embodiments of the invention.
[embodiment]
Embodiment
The present invention is extract with the methylene chloride, and with the ultrasonic extraction extraction, nitrogen blows concentrated, uses gas chromatography tandem mass spectrum (GC/MS) assay determination at last, thereby analyzes phthalate ester in the soil accurately and quickly.
84 agricultural soils having selected the 21 kinds of different land use type in Tianjin are as analytic target, and analytical approach and effect are as follows:
Leaching process: the soil of getting a certain amount of natural air drying adds the 15mL methylene chloride according to optimal conditions in conical flask, ultrasonic Extraction 5min, and extract is collected after filtering, repeats above step twice;
Concentration process: the extract after the merging is blown away dichloromethane solvent with nitrogen, blows to 5mL, is transferred to continue in the concentration tube to blow to 2mL, and mark in adding is used the methylene chloride constant volume;
The mensuration process: the sample transfer behind the constant volume is carried out GC-MS mensuration to brown auto injection bottle.
In the detection, described ultrasonic extraction instrument extracts 25 ℃ of temperature, power 300w.
Temperature was set at 16.5 ℃ when described nitrogen dried up.
It is helium that described gas chromatography tandem mass spectrometer is measured carrier gas, flow rate of carrier gas: 1.0mL/min.Sample transfer behind the constant volume directly enters gas chromatography tandem mass spectrometer mensuration to brown auto injection bottle.
The qualitative condition of this experimental technique of table 1 phthalate ester
The content (μ g/kg) of table 2 Tianjin soil different land use type PAEs
Table 3 rotary evaporation, nitrogen blow and the recovery (%) of this method
Claims (5)
1. a method of measuring phthalate ester in the soil is characterized in that described method is extract with the methylene chloride, and the ultrasonic extraction instrument is an extraction element, and nitrogen blows catches concentrating instrument and concentrate, and measures with the gas chromatography tandem mass spectrometer at last.
2. the method for phthalate ester in the mensuration soil according to claim 1 is characterized in that said method comprising the steps of:
Leaching process: the soil of getting a certain amount of natural air drying adds the 10-30mL methylene chloride in conical flask, ultrasonic Extraction 5-30min, and extract is collected after filtering, repeats above step twice;
Concentration process: the extract after the merging is blown away dichloromethane solvent with nitrogen, blows to 3-6mL, is transferred to continue in the concentration tube to blow to 2mL, and mark in adding is used the methylene chloride constant volume;
The mensuration process: the sample transfer behind the constant volume is carried out GC-MS mensuration to brown auto injection bottle.
3. according to the method for phthalate ester in claim 2 or the 3 described mensuration soil, it is characterized in that it is 20-30 ℃ that described ultrasonic extraction instrument extracts temperature, power 250-400w.
4. the method for phthalate ester in the mensuration soil according to claim 1, temperature is set at 10-25 ℃ when it is characterized in that described nitrogen dries up.
5. according to the method for phthalate ester in claim 1 or 2, the 3 described mensuration soil, it is characterized in that it is helium that described gas chromatography tandem mass spectrometer is measured carrier gas, flow rate of carrier gas: 0.5-2.0mL/min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102128888A (en) * | 2010-12-13 | 2011-07-20 | 上海富臣化工有限公司 | Method for measuring phthalate plasticizer in paint |
| CN103913518A (en) * | 2012-12-31 | 2014-07-09 | 天士力制药集团股份有限公司 | Method for detecting content of plasticizer in white spirit and application thereof in detection of migration rate of plasticizer |
| WO2016155347A1 (en) * | 2015-03-27 | 2016-10-06 | 北京市环境保护监测中心 | System and method for measuring phthalic acid ester in atmospheric particulates |
| CN107607648A (en) * | 2017-09-14 | 2018-01-19 | 浙江省海洋水产研究所 | The solid phase extraction GC MS detection method of phthalate compound in a kind of deposit |
| CN107655991A (en) * | 2017-09-21 | 2018-02-02 | 国家烟草质量监督检验中心 | The assay method of 6 kinds of phthalic acid esters in soil |
| CN107703236A (en) * | 2017-09-26 | 2018-02-16 | 广东工业大学 | A kind of extraction detection method of Phthalate Esters In Soil |
| CN107991405A (en) * | 2017-11-23 | 2018-05-04 | 湖北文理学院 | The assay method of phthalate ester in soil |
| CN114062543A (en) * | 2021-11-09 | 2022-02-18 | 江苏省农业科学院 | Method for extracting plasticizer in environment at high flux |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102128888A (en) * | 2010-12-13 | 2011-07-20 | 上海富臣化工有限公司 | Method for measuring phthalate plasticizer in paint |
| CN102128888B (en) * | 2010-12-13 | 2013-09-11 | 上海富臣化工有限公司 | Method for measuring phthalate plasticizer in paint |
| CN103913518A (en) * | 2012-12-31 | 2014-07-09 | 天士力制药集团股份有限公司 | Method for detecting content of plasticizer in white spirit and application thereof in detection of migration rate of plasticizer |
| WO2016155347A1 (en) * | 2015-03-27 | 2016-10-06 | 北京市环境保护监测中心 | System and method for measuring phthalic acid ester in atmospheric particulates |
| CN107607648A (en) * | 2017-09-14 | 2018-01-19 | 浙江省海洋水产研究所 | The solid phase extraction GC MS detection method of phthalate compound in a kind of deposit |
| CN107607648B (en) * | 2017-09-14 | 2020-04-07 | 浙江省海洋水产研究所 | Solid phase extraction-gas chromatography mass spectrometry detection method for phthalate compounds in sediments |
| CN107655991A (en) * | 2017-09-21 | 2018-02-02 | 国家烟草质量监督检验中心 | The assay method of 6 kinds of phthalic acid esters in soil |
| CN107703236A (en) * | 2017-09-26 | 2018-02-16 | 广东工业大学 | A kind of extraction detection method of Phthalate Esters In Soil |
| CN107991405A (en) * | 2017-11-23 | 2018-05-04 | 湖北文理学院 | The assay method of phthalate ester in soil |
| CN114062543A (en) * | 2021-11-09 | 2022-02-18 | 江苏省农业科学院 | Method for extracting plasticizer in environment at high flux |
| CN114062543B (en) * | 2021-11-09 | 2023-11-21 | 江苏省农业科学院 | Method for extracting plasticizer in environment with high flux |
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