CN105158395A - Soil analysis method with coupling of solid-liquid extraction and solid phase microextraction - Google Patents
Soil analysis method with coupling of solid-liquid extraction and solid phase microextraction Download PDFInfo
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- CN105158395A CN105158395A CN201510595426.0A CN201510595426A CN105158395A CN 105158395 A CN105158395 A CN 105158395A CN 201510595426 A CN201510595426 A CN 201510595426A CN 105158395 A CN105158395 A CN 105158395A
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Abstract
The invention discloses a soil analysis method with coupling of solid-liquid extraction and solid phase microextraction. The method mainly comprises the following steps: weighing a certain quantity of soil sample, packaging with filter paper and then putting into an extracting device; extracting the soil sample with an extracting solvent to obtain an extracting solution; quantitatively adding the extracting solution obtained in the last step to a volumetric flask, adding an internal standard intermediate working solution and a substitution with certain concentration to the volumetric flask to obtain mixed liquor 1; carrying out secondary extracting, purifying and concentrating on the mixed liquor 1 by using a solid phase microextraction device to obtain mixed liquor 2; analyzing the mixed liquor 2 by using the solid phase microextraction device and a gas chromatography-mass spectrometer; repeatedly measuring a parallel sample and a gradient labeling sample and computing the detection limit and the accuracy. According to the invention, solid-liquid extraction is coupled with solid phase microextraction for the first time, so that the method is suitable for analyzing trace semi-volatile organic compounds in the soil, and is low in cost, small in work load and low in detection limit.
Description
Technical field
The present invention relates to a kind of extracting process being applied to analysizing trace organics, being specifically related to a kind of analytical approach of the liquid-solid extraction coupling solid phase micro extraction for analyzing semi-volatile organic matter in soil.
Background technology
Semi-volatile organic matter is the large class organism slower compared with volatile organic matter volatility, they easier in the media such as soil, air, biology Transport And Transformation, in long-term existence soil, be detrimental to health by biological concentration; Its environment home to return to normally soils and sediments, this kind of organic general character be fat-soluble, be soluble in organic solvent, but also have polarity stronger be slightly soluble in water (as aniline, ester class, aldoketones etc.).Because the molecular weight of semi-volatile organic matter is large, boiling point is high, therefore in the environment can be longer compared with the time of volatile organic matter more difficult degradation, existence.See in the narrow sense, this type organic is thousands of, its environmental hazard because of its physics and chemistry, toxicity difference be also not quite similar; People more pay close attention to those and have physiological-toxicity, carcinogenicity, cause gene mutagenicity, teratogenesis, persistence and belong to the semi-volatile organic matter of environmental hormone.
Current domestic soils/sediments controls in organic analytical approach unsound to organo-chlorine pesticide, palycyclic aromatic, polychlorinated biphenyl isopreference, existing method also comparatively backwardness; Along with the progress of science and technology and the development of environmental science, more poisonous and harmfuls need the semi-volatile organic matter controlled to be found and to study, and must have a kind of analytical approach that generally can be applicable to semi-volatile organic matter in soil.
The pre-treating method of bibliographical information semi-volatile organic matter is had to have the methods such as surname extraction, automatically surname extraction, ultrasonic extraction, microwave abstracting, accelerated solvent extraction, supercritical fluid extraction at present; Also will carry out a series of process such as purifying, concentrate after liquid-solid extraction, this analytical approach consumes quantity of solvent greatly, wastes time and energy.Therefore in order to change this numerous and diverse sample treatment, a kind of soil analysis method of liquid-solid extraction coupling solid phase micro extraction has been invented; And find that domestic and foreign literature does not carry out the report of solid-phase microextraction coupling Solid-Phase Extraction analytical approach to Organic substance in water about employing method by retrieval.
Summary of the invention
Technical matters to be solved by this invention is: the analytical approach of semi-volatile organic matter in existing soil, and detectability is generally higher, cannot under natural situation to soil in semi-volatile organic matter analyze; Or analytic process wastes time and energy very much.
The present invention is for overcoming the deficiencies in the prior art, spy provides a kind of analytical approach being applied to the liquid-solid extraction coupling solid phase micro extraction technology of analysizing trace organics, it comprises the steps:, and (1) takes a certain amount of pedotheque, wraps put into extraction equipment with filter paper; Repeat above step, obtain series of parallel sample.
(2) be made into extraction solvent after acetone and methylene chloride (allocation ratio is 1:1, and all carries out degassed process before use) being mixed in proportion to extract pedotheque, obtain extract.
(3) extract obtained in step (2) is measured a part and add volumetric flask, in volumetric flask, adding use liquid in the middle of interior mark again, (interior mark stock solution concentration is 2mg/mL, comprises following component: phenanthrene-d10, naphthalene-d12, pyrene-d12, Isosorbide-5-Nitrae-dichloro-benzenes-d4, concentration is 10ug/ml) and substitute (nitrobenzene-d5,2-fluorine biphenyl, phenol-d5, terphenyl-d14, concentration is 10ug/ml), obtain mixed liquor 1; Then constant gradient measures extract and adds volumetric flask, adds respectively in the middle of interior mark and uses liquid and substitute, obtain gradient mark-on sample in volumetric flask.
(4) with solid-phase micro-extracting device, the mixed liquor 1 obtained in step (3) is carried out reextraction, purification, concentrated, obtain mixed liquor 2.
(5) with solid-phase micro-extracting device and gas chromatography-mass spectrum instrument apparatus in the mixed liquor 2 obtained in step (4) become to be grouped into and concentration is analyzed.
(6) parallel sample in step (1) is measured according to the operating process of step (2) to step (5) respectively; Gradient mark-on sample in step (3) is measured according to the operating process of step (4) to step (5) respectively; Measurement result is calculated detection limit and accuracy.
The present invention, by coupling liquid-solid extraction and solid-phase microextraction two kinds of methods, realizes on prior art basis, greatly reduce trace semi-volatile organic matter analytic process in soil cost and workload.Remain between 0.1-0.3ug/ml by the detectability of the method, whole analytic process, the related coefficient (R) of 24 kinds of semi-volatile organic matters concentration and instrument responses in soil is more than 0.9932 simultaneously.Efficiently solve pedotheque when carrying out sample analysis after acquisition, the problem of sample preparation complexity.
Embodiment
Below in conjunction with embodiment, the present invention is described further; but it is not as a limitation of the invention; the content that protection scope of the present invention is recorded with claim is as the criterion, and any equivalent technical elements of making according to instructions is replaced, and does not all depart from protection scope of the present invention.
Embodiment: 1) take 20g sample (sample collocation method is attached), wrap with filter paper and put into the device such as surname extraction, accelerated solvent extraction.
2) extraction solvent acetone, methylene chloride (the pure level of pesticide residue analysis should first be carried out degassed, each 150mL before use) extract pedotheque, obtain extract 300mL.
3) from extract, take out 5ml and put into volumetric flask, add in volumetric flask in 100ul and use liquid (interior mark stock solution 2mg/mL in the middle of mark, phenanthrene-d10, naphthalene-d12, pyrene-d12,1,4-dichloro-benzenes-d4) and substitute (nitrobenzene-d5,2-fluorine biphenyl, phenol-d5, terphenyl-d14), interior mark and substitute concentration are as 10ug/ml.
4) with solid-phase micro-extracting device, the 5mL extract adding interior mark and substitute is carried out reextraction, purification, concentrated.
5) solid-phase micro-extracting device and gas chromatograph-mass spectrometer (GCMS) coupling, carry out sample analysis.
6) repeatedly replication parallel sample and gradient mark-on sample (each five points), calculates detection limit and accuracy.
Attached: sample collocation method: to adopt level Four pole technology more advanced in Analysis of environmental samples, select the mass spectral characteristic of 24 kinds of semi-volatile organic matters to carry out qualitative and quantitative analysis.
Accurate preparation contains 24 kinds of semi-volatile organic matters (1, 2, 3-trichloro-benzenes, 1, 2, 4,-trichloro-benzenes, 1, 3, 5-trichloro-benzenes, 1, 2, 3, 4-tetrachlorobenzene, 1, 2, 3, 5-tetrachlorobenzene, 1, 2, 4, 5-tetrachlorobenzene, hexachloro-benzene, nitrobenzene, paradinitrobenzene, meta-dinitro-benzent, o-dinitrobenzene, 2, 4-dinitrotoluene (DNT), 2, 4, 6-trinitro-toluene, paranitrochlorobenzene, m-chloronitrobenzene, o-nitrochlorobenzene, 2, 4-dinitrofluorobenzene, 2, 4-chlorophenesic acid, 2, 4, 6-trichlorophenol, pentachlorophenol, aniline, dibutyl phthalate, dioctyl phthalate, benzo (a) pyrene) soil 20g.
Point four steps that work below are carried out, the first step, and scan type is set as full scan scan pattern, scanmode is set as msmode, adopt MS as detecting device, quality of scanning scope: 35-450amu; Ionization energy: 70eV; Level Four bar temperature is set as 150 DEG C, and ion source temperature is set as 280 DEG C, and interface temperature is set as 280 DEG C, the solvent delay time: 5min; Tuning manner: DFTPP, other arrange and all adopt instrument default setting.
Second step, sample introduction, after obtaining mass spectrogram, selects the maximum abundance ion of each compound, carries out standard spectrum storehouse signals assigned; 3rd step, with main ion in mass spectrogram as the peak area of quota ion or peak height quantitative, inner mark method ration, when the main ion of object in sample has interference, can use characteristic ion quantitative; 4th step, draws the typical curve of each compound.
condition determination:gC-MS is the 5977A-7890B (U.S.A) that AgilentScientific company produces.
Gas phase portion: chromatographic column is capillary column DB-5MS (30m × 0.25mm × 0.25 μm) (5%-phenyl-95% methyl polysiloxane; Immobile liquid).Carrier gas is helium, and post flow is constant current, and flow velocity is 1ml/min.Heating schedule is: initial 35 DEG C, and keep 2min, 15 DEG C/min rises to 150 DEG C, and keep 5min, 3 DEG C/min rises to 290 DEG C, keeps 1min.Sample size is 1 μ l.
Mass spectrum part: the ionization mode adopting chemi-ionization, transmission line temperature 280 DEG C; Ion source temperature 280 DEG C, fragment ion scan pattern is Scan (full scan pattern).
Comprehensive the method step Quality Control data, 24 kinds of SVOCs are within the scope of the spiked levels of 0.5-50ug/ml, and the related coefficient of spiked levels and instrument response size is all greater than 0.9935, show that this step still has in wider concentration range one constant linear; Under the spiked levels of 10ug/ml, the recovery of 24 kinds of SVOCs, between 46.2% to 125.7%, shows that, in whole analytic process, the loss amount of SVOCs is low, without exogenous pollution; Repeat to make sample 5 times, the relative standard deviation of 24 kinds of SVOCs, between 6.7% to 15.2%, shows that this analytical approach is stablized; Adopt the method analysis water-like, the detectability of 24 kinds of SVOCs is between 0.1-0.3ug/ml.
Testing result shows, and the method measures for the SVOCs in actual pedotheque, has detectability low, the advantage that workload is little.This illustrates that the solid phase micro-extraction method improved is simple, economical, effectively, may be used for low concentration small size Analysis of environmental samples.The present invention, in conjunction with other method for chromatographic determination, can be widely used in the Analysis of Organic Substances that other are relevant.
Claims (5)
1. a soil analysis method for liquid-solid extraction coupling solid phase micro extraction, it comprises the steps:, and (1) takes a certain amount of pedotheque, wraps put into extraction equipment with filter paper; Repeat above step, obtain series of parallel sample; (2) be made into extraction solvent after acetone and methylene chloride being mixed in proportion to extract pedotheque, obtain extract; (3) extract obtained in step (2) is measured a part and add volumetric flask, add again in volumetric flask in the middle of interior mark and use liquid and substitute, obtain mixed liquor 1; Then constant gradient measures extract and adds volumetric flask, adds respectively in the middle of interior mark and uses liquid and substitute, obtain gradient mark-on sample in volumetric flask; (4) with solid-phase micro-extracting device, the mixed liquor 1 obtained in step (3) is carried out reextraction, purification, concentrated, obtain mixed liquor 2; (5) with solid-phase micro-extracting device and gas chromatography-mass spectrum instrument apparatus in the mixed liquor 2 obtained in step (4) become to be grouped into and concentration is analyzed; (6) parallel sample in step (1) is measured according to the operating process of step (2) to step (5) respectively; Gradient mark-on sample in step (3) is measured according to the operating process of step (4) to step (5) respectively; Measurement result is calculated detection limit and accuracy.
2. the soil analysis method of a kind of liquid-solid extraction coupling solid phase micro extraction according to claim 1, the extraction equipment that it is characterized in that in step (1) is one in surname extraction, accelerated solvent extraction device or all.
3. the soil analysis method of a kind of liquid-solid extraction coupling solid phase micro extraction according to claim 1, it is characterized in that extraction solvent acetone in step (2) and methylene chloride are the pure level of pesticide residue analysis, allocation ratio is 1:1, and all carries out degassed process before use.
4. the soil analysis method of a kind of liquid-solid extraction coupling solid phase micro extraction according to claim 1, it is characterized in that using the interior mark stock solution concentration in liquid to be 2mg/mL in the middle of the interior mark in step (3), liquid is used to comprise following component wherein in the middle of mark: phenanthrene-d10, naphthalene-d12, pyrene-d12, Isosorbide-5-Nitrae-dichloro-benzenes-d4, concentration is 10ug/ml; Substitute comprises following component: nitrobenzene-d5,2-fluorine biphenyl, phenol-d5, terphenyl-d14, concentration is 10ug/ml.
5. the soil analysis method of a kind of liquid-solid extraction coupling solid phase micro extraction according to claim 1, is characterized in that parallel sample in step (6) and gradient mark-on sample size are all not less than 5.
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Cited By (10)
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| CN106770703A (en) * | 2016-11-18 | 2017-05-31 | 韩超 | The method that GC-MS determines chlorobenzene class organic pollution in leather |
| CN108152397A (en) * | 2017-12-14 | 2018-06-12 | 浙江工业大学 | Method for simultaneously detecting hexachlorobutadiene, pentachlorobenzene and hexachlorobenzene in waste incineration fly ash |
| CN108548812A (en) * | 2018-03-21 | 2018-09-18 | 江苏实朴检测服务有限公司 | The method for measuring triethylamine in soil |
| CN109839454A (en) * | 2018-09-30 | 2019-06-04 | 天津大学 | Research method of the farm antibiotics in soil particle airwater mist cooling interface degradation rule |
| CN111474261A (en) * | 2020-04-24 | 2020-07-31 | 山东省济南生态环境监测中心 | Method for measuring aniline in soil and sediment |
| CN112147246A (en) * | 2020-09-23 | 2020-12-29 | 浙江求实环境监测有限公司 | Rapid detection method for polybrominated diphenyl ethers in soil |
| CN113552267A (en) * | 2021-05-20 | 2021-10-26 | 山东省物化探勘查院 | Method for simultaneously measuring aniline, nitrobenzene and polycyclic aromatic hydrocarbon in soil |
| CN114487220A (en) * | 2020-10-27 | 2022-05-13 | 天津市职业大学 | Method for measuring semi-volatile organic compounds in soil based on temperature programming sample introduction-gas chromatography-mass spectrometry |
| CN115112791A (en) * | 2022-06-13 | 2022-09-27 | 永春县产品质量检验所(福建省香产品质量检验中心、国家燃香类产品质量监督检验中心(福建)) | Method for determining benzene series in incense by microwave extraction-gas chromatography-mass spectrometry |
| CN115184524A (en) * | 2022-08-22 | 2022-10-14 | 普研（上海）标准技术服务有限公司 | Method for detecting content of 1,3, 5-trichlorobenzene in soil |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106770703A (en) * | 2016-11-18 | 2017-05-31 | 韩超 | The method that GC-MS determines chlorobenzene class organic pollution in leather |
| CN108152397A (en) * | 2017-12-14 | 2018-06-12 | 浙江工业大学 | Method for simultaneously detecting hexachlorobutadiene, pentachlorobenzene and hexachlorobenzene in waste incineration fly ash |
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| CN113552267A (en) * | 2021-05-20 | 2021-10-26 | 山东省物化探勘查院 | Method for simultaneously measuring aniline, nitrobenzene and polycyclic aromatic hydrocarbon in soil |
| CN115112791A (en) * | 2022-06-13 | 2022-09-27 | 永春县产品质量检验所(福建省香产品质量检验中心、国家燃香类产品质量监督检验中心(福建)) | Method for determining benzene series in incense by microwave extraction-gas chromatography-mass spectrometry |
| CN115112791B (en) * | 2022-06-13 | 2023-11-28 | 永春县产品质量检验所(福建省香产品质量检验中心、国家燃香类产品质量监督检验中心(福建)) | Method for measuring benzene series in incense by using microwave extraction-gas chromatography mass spectrometry |
| CN115184524A (en) * | 2022-08-22 | 2022-10-14 | 普研（上海）标准技术服务有限公司 | Method for detecting content of 1,3, 5-trichlorobenzene in soil |
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