CN106501391B - Solid phase membrane extraction-gas-chromatography tandem mass spectrum detection method of organochlorine compound in a kind of water body - Google Patents
Solid phase membrane extraction-gas-chromatography tandem mass spectrum detection method of organochlorine compound in a kind of water body Download PDFInfo
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Abstract
The invention discloses a kind of solid phase membrane extraction of organochlorine compound in water body-gas-chromatography tandem mass spectrum detection methods, with C18Solid-phase extraction membrane realizes the enrichment of organochlorine compound in water body, is detected using gas chromatography tandem mass spectrometry detection method, and this method operating procedure is few, high sensitivity, favorable reproducibility, the assay that can be used for organochlorine compound in water body.
Description
Technical field
The present invention relates to Water quality safety detection technology field, in particular to organochlorine compound consolidates in a kind of water body
Phase membrane extraction-gas-chromatography tandem mass spectrum detection method.
Background technique
Six six six, DDT are a kind of organo-chlorine pesticides difficult to degrade, have to many pests tag, stomach toxicity, it is stifling and
A degree of systemic action, the half-life period of organo-chlorine pesticide are about 2~20 years or so, can accumulate and pass through in vivo
Food chain transmitting, causes to seriously threaten to ecological environment and human health.Although many countries are prohibited already and limit use,
Since six six six, DDT chemical property are stablized, further investigation reveals that having in the surrounding medium of domestic each department and in human body residual
It stays, some are even higher by standard regulation manyfold.As the contamination characteristics investigation of Min River water body six six six, DDT shows water body six
Six or six and DDT mass concentration range be respectively 1.031-1.804 and 0.767-1.156ng/L.Organo-chlorine pesticide in soil
Residual has direct harm to terrestrial life, and influence on water body aquatile can be also discharged by rainwash.More chlorine connection in environment
Benzene (PCBs) mostlys come from the production of industrial goods.The commodity production of PCBs starts from nineteen twenty-nine.Although the production and application of PCBs
It has been prohibited in worldwide in early stage the 1970s, the production of whole world PCBs alreadys exceed 1,300,000 tons.
It is produced since nineteen sixty-five, ends (production of PCBs is prohibited) in 1974, China about produces 10000 tons of PCBs.In addition,
The 1950s, electrical equipment of the China also constantly from other countries' import containing PCBs, these also became between the eighties
The potential source that PCBs pollutes in Chinese environmental.In soils and sediments, according to existing PCB data, PCB in China s's is dense
Degree range is 0.01~1840 μ g/kg.7 kinds of PCBs total standard Limited Doses are 0.02 μ in " water environment quality standard "
G/L, the Limited Doses of DDT are 0.2 μ g/L.Scholar has studied the residual level of PCBs and its environment in the water body of reservoir area of Three Gorges and hands over
It changes, the results showed that the content range of PCBs is that~48.67ng/L is not detected in the water body of reservoir area.In the big estuary water body of the Zhujiang River eight
The content range of PCBs is 0.19~7.04ng/L.Waste electric products, deposit are in suspension, atmospheric sedimentation and waste water treatment plant
Discharge is the significant contributor of water body PCBs pollution.
Since organochlorine compound concentration is extremely low in environmental water sample, it usually needs could be measured by enrichment.Traditional richness
Catchment middle organochlorine compound method be liquid-liquid extraction method, it is cumbersome time-consuming, need to consume a large amount of organic solvent,
And solid phase extraction is because having easy to operate, consumption solvent is few and enrichment times are high to be widely used in the analysis of pesticide.
Find a kind of simpler, the pre-treating method of organochlorine compound becomes research hotspot in environmentally friendly water body.Solid phase membrane extraction is made
For one kind of Solid Phase Extraction, solid-phase extraction membrane used in it can handle large volume of water sample, and enrichment times faster
It is high.In addition, solid phase membrane extraction can directly handle water sample, convenient and efficient stabilization at the scene.The instrument of organochlorine compound detects
Technology has gas-chromatography, gas chromatography-mass spectrography etc..Gas-chromatography-electron capture detection is as selectively highly sensitive
The detecting instrument of degree detects sensitivity with higher and accuracy to organochlorine compound, but interferes vulnerable to impurity, it is qualitative not
It is enough accurate.In recent years, researcher has carried out the research to certain Hekou Area organochlorine residues and distribution, but about in water body
The remaining research of trace organochlorine compound is few.
Summary of the invention
The purpose of the present invention is to provide a kind of solid phase membrane extraction of organochlorine compound in water body-gas-chromatography series connection matter
Spectrum detection method can fast and accurately measure trace organochlorine compound in water body, to realize trace organic chloride in water body
Close the quantitative and qualitative analysis of object.
The technical solution adopted by the present invention to solve the technical problems is:
Solid phase membrane extraction-gas-chromatography tandem mass spectrum detection method of organochlorine compound in a kind of water body, including it is as follows
Step:
(1)C18The cleaning and activation of solid-phase extraction membrane: C18Solid-phase extraction membrane uses 5mL n-hexane/methylene chloride mixing in advance
Liquid impregnates 3min, then successively activates C with 10mL methanol, 10mL water18Solid-phase extraction membrane allows solvent all to flow through C18Solid phase extraction
Film is taken, in the process, avoids solid-phase extraction membrane ingress of air；
(2) extraction of water sample: water sample must be pre-processed with 0.45 μm of glass fiber filter filtering water sample in advance, then will be located in advance
The 1000mL water sample of reason is added to equipped with the C after step (1) activation18In the glass filter of solid-phase extraction membrane, vacuum pump, water sample are opened
After passing through with the flow velocity of 10mL/min, continue to vacuumize to remove C18Residual moisture in solid-phase extraction membrane；
(3) 10mL n-hexane and 10mL dichloromethane eluent step (2) successively the elution and concentration of organochlorine compound: are used
Treated C18Solid-phase extraction membrane, eluent, in 40 DEG C of water-bath rotary evaporated to dryness, add just after anhydrous sodium sulfate crosses column water removal
Hexane, which dissolves and is settled to 1.0mL, obtains liquid to be detected；
(4) gas chromatography tandem mass spectrometry detects: liquid to be detected is using Agilent 7890B-7000C gas-chromatography series connection matter
Spectrometer detection, configures the source EI, realizes that component separates using DB-5 capillary gas chromatographic column (30m × 0.25mm × 0.25 μm),
It is detected according to the gas chromatography tandem mass spectrometry testing conditions set, MRM mode scans, quantified by external standard method.
Preferably, n-hexane/methylene chloride mixed liquor is the body of n-hexane and methylene chloride according to 1:1 in step (1)
The mixture of product ratio.
Preferably, gas chromatographic column temperature program in step (4) are as follows: 80 DEG C of holdings 2min, 25 DEG C/min are warming up to 150
DEG C, 3 DEG C/min is warming up to 200 DEG C, then is warming up to 280 DEG C of holding 10min with 8 DEG C/min.
Preferably, Mass Spectrometry Conditions in step (4) are as follows: 280 DEG C of chromatography-mass spectroscopy interface temperature, 300 DEG C of ion source temperature,
Electron bombardment ionization source (EI) energy 70eV, 150 DEG C of level four bars temperature, throughput 2.25mL/ is quenched in collision gas flow 1.5mL/min
Min, solvent delay time 4.5min, MRM mode scan.
Preferably, in water body organochlorine compound include α-six six six, β-six six six, γ-six six six, δ-six six six,
p,p'-DDE、p,p'-DDD、o,p'-DDT、p,p'-DDT、PCB28、PCB52、PCB155、PCB101、PCB112、PCB118、
PCB153、PCB138、PCB180、PCB198。
The beneficial effects of the present invention are: the present invention is with C18Solid-phase extraction membrane realizes the enrichment of organochlorine compound in water body,
It is detected using gas chromatography tandem mass spectrometry detection method, this method operating procedure is few, high sensitivity, favorable reproducibility, can be used for water
The assay of organochlorine compound in body.
Detailed description of the invention
Fig. 1 is the gas-chromatography tandem mass spectrum MRM scanning figure of 18 kinds of organochlorine compound standard solution；1. α-six six six,
2. β-six six six, 3. γ-six six six, 4. δ-six six six, 5.PCB28,6.PCB52,7.PCB155,8.PCB101,9.PCB112,
10.p, p'-DDE, 11.PCB118,12.p, p'-DDD, 13.o, p'-DDT, 14.PCB153,15.p, p'-DDT,
16.PCB138,17.PCB180,18.PCB198.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art.
Method in following embodiments is unless otherwise instructed the conventional method of this field.
Gas-chromatography tandem mass spectrum MRM scanning is able to achieve efficiently separating for 18 kinds of organochlorine compounds, as shown in Fig. 1.
Table 2 is the recovery testu of the different scalar quantities in different water bodys (laboratory tap water and Zhoushan sea area seawater)
As a result.The content of organochlorine in certain reservoir water body of table 3.
Embodiment 1: the measurement of 18 kinds of organochlorine compounds in the tap water of laboratory
(1)C18The cleaning and activation of solid-phase extraction membrane: C18Solid-phase extraction membrane use in advance 5mL n-hexane/methylene chloride (1:
1) 3min is impregnated, successively activates C with 10mL methanol, 10mL water18Solid-phase extraction membrane allows solvent all to flow through solid-phase extraction membrane,
During this, solid-phase extraction membrane ingress of air cannot be made；
(2) extraction of water sample: pretreated in advance with 0.45 μm of glass fiber filter filtration experiment room originally water sample
Originally water sample is added to equipped with C in the laboratory 1000mL18In the glass filter of solid-phase extraction membrane, vacuum pump is opened, water sample is with 10mL/
After the flow velocity of min passes through, continue to vacuumize to remove the residual moisture in solid-phase extraction membrane；
(3) 10mL n-hexane and 10mL dichloromethane eluent C successively the elution and concentration of organochlorine compound: are used18Solid phase
Spe membrane, eluent, in 40 DEG C of water-bath rotary evaporated to dryness, are settled to after anhydrous sodium sulfate crosses column water removal with n-hexane
1.0mL, it is to be analyzed；
(4) gas chromatography tandem mass spectrometry detects: using Agilent 7890B-7000C gas-chromatography tandem mass spectrometer, configuration
The source EI realizes that component separates using DB-5 capillary gas chromatographic column (30m × 0.25mm × 0.25 μm).Gas chromatographic column heating
Program are as follows: 80 DEG C of holdings 2min, 25 DEG C/min are warming up to 150 DEG C, and 3 DEG C/min is warming up to 200 DEG C, then is warming up to 8 DEG C/min
280 DEG C of holding 10min.It is detected (table 1) according to the gas chromatography tandem mass spectrometry testing conditions set, MRM mode is swept
It retouches, quantified by external standard method.
The MRM of 1 organochlorine compound of table scans mass spectrometry parameters
(5) Specification Curve of Increasing (external standard method): suitable organochlorine compound standard reserving solution is taken respectively, is matched with n-hexane
Concentration is set as the organochlorine compound mixing of 0.02 μ g/L, 0.05 μ g/L, 0.10 μ g/L, 0.50 μ g/L, 1.0 μ g/L, 2.0 μ g/L
Standard solution.It is operated according to the requirement of above-mentioned (1), (2), (3), (4) step, according to the organochlorine compound concentration of addition
Standard curve is established with the corresponding relationship of product ion peak area.
Using the external standard method, measuring 18 kinds of organochlorine class content of material in the tap water of laboratory is to be not detected, and mark-on is real
The rate of recovery for testing each organochlorine compound of room tap water is 83%-104% (being shown in Table 2), meets analysis method and wants to the rate of recovery
It asks.
The recovery of standard addition and precision experiment result of 2 different substrates water body of table
Embodiment 2: the measurement of 18 kinds of organochlorine compounds in Zhoushan sea area seawater
Method is with embodiment 1, and measuring 18 kinds of organochlorine class content of material in Zhoushan sea area seawater is to be not detected, mark-on boat
The rate of recovery of each organochlorine compound is 85%-115% (being shown in Table 2) in the seawater of mountain and sea domain, meets analysis method to the rate of recovery
It is required that.
The measurement of 18 kinds of organochlorine compounds in certain reservoir water of embodiment 3
(1)C18The cleaning and activation of solid-phase extraction membrane: C18Solid-phase extraction membrane use in advance 5mL n-hexane/methylene chloride (1:
1) 3min is impregnated, successively activates C with 10mL methanol, 10mL water18Solid-phase extraction membrane allows solvent all to flow through solid-phase extraction membrane,
During this, solid-phase extraction membrane ingress of air cannot be made；
(2) certain reservoir water sample, pretreated 1000mL the extraction of water sample: are filtered with 0.45 μm of glass fiber filter in advance
Reservoir water sample is added to equipped with C18In the glass filter of solid-phase extraction membrane, vacuum pump is opened, water sample is passed through with the flow velocity of 10mL/min
Afterwards, continue to vacuumize to remove the residual moisture in solid-phase extraction membrane；
(3) 10mL n-hexane and 10mL dichloromethane eluent C successively the elution and concentration of organochlorine compound: are used18Solid phase
Spe membrane, eluent, in 40 DEG C of water-bath rotary evaporated to dryness, are settled to after anhydrous sodium sulfate crosses column water removal with n-hexane
1.0mL, it is to be analyzed；
(4) gas chromatography tandem mass spectrometry detects: using Agilent 7890B-7000C gas-chromatography tandem mass spectrometer, configuration
The source EI realizes that component separates using DB-5 capillary gas chromatographic column (30m × 0.25mm × 0.25 μm).Gas chromatographic column heating
Program are as follows: 80 DEG C of holdings 2min, 25 DEG C/min are warming up to 150 DEG C, and 3 DEG C/min is warming up to 200 DEG C, then is warming up to 8 DEG C/min
280 DEG C of holding 10min.It is detected (table 1) according to the gas chromatography tandem mass spectrometry testing conditions set, MRM mode is swept
It retouches, quantified by external standard method；
(5) Specification Curve of Increasing (external standard method): suitable organochlorine compound standard reserving solution is taken respectively, is matched with n-hexane
Concentration is set as the organochlorine compound mixing of 0.02 μ g/L, 0.05 μ g/L, 0.10 μ g/L, 0.50 μ g/L, 1.0 μ g/L, 2.0 μ g/L
Standard solution.It is operated according to the requirement of above-mentioned (1), (2), (3), (4) step, according to the organochlorine compound concentration of addition
Standard curve is established with the corresponding relationship of product ion peak area.
Using quantified by external standard method, it is as shown in table 3 to measure 18 kinds of organochlorine content of material in certain reservoir water body.
The content (ng/L) of organochlorine in certain reservoir water body of table 3
Note: ND expression is not detected.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (1)
1. the solid phase membrane extraction of organochlorine compound-gas-chromatography tandem mass spectrum detection method in a kind of water body, which is characterized in that
Include the following steps:
(1) cleaning and activation of C18 solid-phase extraction membrane: C18 solid-phase extraction membrane uses 5mL n-hexane/methylene chloride mixed liquor in advance
3min is impregnated, then successively C18 solid-phase extraction membrane is activated with 10mL methanol, 10mL water, solvent is allowed all to flow through C18 Solid Phase Extraction
Film avoids solid-phase extraction membrane ingress of air in the process；
(2) extraction of water sample: must pre-process water sample with 0.45 μm of glass fiber filter filtering water sample in advance, then will be pretreated
1000mL water sample is added in the glass filter equipped with the C18 solid-phase extraction membrane after step (1) activation, opens vacuum pump, water sample with
After the flow velocity of 10mL/min passes through, continue to vacuumize to remove the residual moisture in C18 solid-phase extraction membrane；
(3) it the elution and concentration of organochlorine compound: is successively handled with 10mL n-hexane and 10mL dichloromethane eluent step (2)
C18 solid-phase extraction membrane afterwards, eluent, in 40 DEG C of water-bath rotary evaporated to dryness, add n-hexane after anhydrous sodium sulfate crosses column water removal
It dissolves and is settled to 1.0mL and obtain liquid to be detected；
(4) gas chromatography tandem mass spectrometry detects: liquid to be detected uses Agilent 7890B-7000C gas-chromatography tandem mass spectrometer
Detection configures the source EI, realizes that component separates using DB-5 capillary gas chromatographic column, according to the gas-chromatography-series connection set
Mass Spectrometer Method condition is detected, quantified by external standard method；
N-hexane/methylene chloride mixed liquor is the mixture of n-hexane and methylene chloride according to the volume ratio of 1:1 in step (1)；
Gas chromatographic column temperature program in step (4) are as follows: 80 DEG C of holdings 2min, 25 DEG C/min are warming up to 150 DEG C, 3 DEG C/min liter
Temperature is warming up to 280 DEG C of holding 10min to 200 DEG C, then with 8 DEG C/min；
Mass Spectrometry Conditions in step (4) are as follows: 280 DEG C of chromatography-mass spectroscopy interface temperature, 300 DEG C of ion source temperature, electron bombardment ionization source (EI)
150 DEG C of level four bars temperature, collision gas flow 1.5mL/min, throughput 2.25mL/min is quenched in energy 70eV, when solvent delay
Between 4.5min, MRM mode scans；
Organochlorine compound includes α-six six six, β-six six six, γ-six six six, δ-six six six, p, p'-DDE, p, p'- in water body
DDD、o,p'-DDT、p,p'-DDT、PCB28、PCB52、PCB155、PCB101、PCB112、PCB118、PCB153、PCB138、
PCB180、PCB198。
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| CN107132305B (en) * | 2017-07-18 | 2020-05-26 | 泉州出入境检验检疫局综合技术服务中心 | Method for detecting organic chlorine compounds in leather |
| CN107643347A (en) * | 2017-09-14 | 2018-01-30 | 浙江省海洋水产研究所 | The immobilon-p extraction gaschromatographic mass spectrometry detection method of phthalate compound in a kind of water body |
| CN108680687A (en) * | 2018-04-19 | 2018-10-19 | 浙江省海洋水产研究所 | The detection method of Polychlorinated biphenyls in a kind of marine product |
| CN108931588A (en) * | 2018-04-27 | 2018-12-04 | 中国地质大学（武汉） | A kind of method that qualitative, quantitative measures organochlorine in Oilfield Chemicals |
| CN110146618A (en) * | 2019-06-06 | 2019-08-20 | 中国科学院新疆生态与地理研究所 | A kind of method that rapidly extracting analyzes 10 kinds of polycyclic aromatic hydrocarbons in water |
| CN113376305A (en) * | 2021-07-13 | 2021-09-10 | 浙江省海洋水产研究所 | Solid-phase membrane extraction gas chromatography-mass spectrometry detection method for carbazole and polyhalogen carbazole in water body |
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