CN103076417B - Method for synchronously extracting organic pollutants in water sample - Google Patents
Method for synchronously extracting organic pollutants in water sample Download PDFInfo
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- CN103076417B CN103076417B CN201210539181.6A CN201210539181A CN103076417B CN 103076417 B CN103076417 B CN 103076417B CN 201210539181 A CN201210539181 A CN 201210539181A CN 103076417 B CN103076417 B CN 103076417B
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Abstract
The invention relates to a method for synchronously extracting organic pollutants in a water sample. The method is suitable for the pretreatment process of the water sample through a gas chromatography-mass spectrometry analyzer. The method for synchronously extracting organic pollutants in the water sample comprises the following steps: 1, sample dehydration: putting 10-20 mL of a sample filtered through a 0.45 mum filter membrane into a watch glass, and placing in a 40-50 DEG C baking box for 10 hours to completely evaporate water in the sample in the watch glass; and 2, organic matter dissolving: carrying out ultrasonic crushing, carrying out oscillation dissolving, centrifuging, and taking the obtained supernatant in a sample bottom as a sample for the gas chromatography-mass spectrometry analyzer. The method for synchronously extracting organic pollutants in the water sample has the advantages of simple and convenient operation, less organic solvent consumption, high extraction efficiency, low cost and the like.
Description
Technical field：
The present invention relates in a kind of water sample organic pollution synchronous extracting process, belong to environmental monitoring.
Background technology：
With the fast development of China's industry, the discharge capacity of organic wastewater increasingly increases, the species of organic pollution also day
Become complicated.Organic pollution in water body mainly includes phenolic compound, amino benzenes compounds, total organic halogen, many cyclophanes
Hydrocarbon compound etc..Some Organic Pollutants can long term accumulation in the environment, ecological environment and human health are caused seriously
Threat.It is the important prerequisite to its quantitative analysis and risk assessment to the qualitative analyses of Organic Pollutants In Water.At present, it is main
To adopt organic pollution pretreatment-gas chromatograph-mass spectrometer (GC-MS)（GC-MS）Qualitative analyses are carried out to organic pollution.
Extraction and concentration of the main purpose of water sample pretreatment for organic pollution.After pretreatment, GC-MS could be adopted
Qualitative detection analysis is carried out to organic pollution.At present, conventional extracting process mainly has liquid-liquid extraction, Solid-Phase Extraction, solid phase
Micro-extraction etc..
Liquid-liquid extraction method mainly uses different solubility of the Organic substance in water and organic solvent, and selection is appropriate to be had
Machine solvent by the organic substance extraction in water sample out.Liquid-liquid extraction method is traditional organic substance extraction method, but need to consume big
The poisonous organic solvent of amount, is detrimental to health, and pollutes environment, and relatively costly, repeatability is poor.
Solid phase extraction（SPE）It is Sample Pretreatment Technique Used developed in recent years, with device is simple, solvent consumption
The advantages of amount is few, can be used for the pre-treatment and enrichment of trace or micro-content organism in environmental sample.Multiple types are had been developed at present
The commercialization solid-phase extraction column of type, including nonpolar, polarity, cation exchange, preparing anion exchange extracting post etc..But using a kind of
Extraction column can only extract the Organic substance of a certain type in water sample, be likely to result in the loss of partial target pollutant.Meanwhile, solid phase
Extraction process needs activation, loading, drip washing, eluting and concentration etc. to operate, time-consuming longer, cumbersome.
Solid phase micro-extraction technique（SPME）It is the non-solvent selective extraction method for growing up the nineties in 20th century, mainly
Using in solid-phase microextraction post fiber head immersion sample solution in or headspace gas in a period of time, while agitating solution with plus
Fiber head is taken out insertion gas chromatogram vaporizer after ready to balance, is adsorbed in thermal desorption coating by fast two alternate balancing speeds
Material.As involved microextraction column and micro-extraction device are expensive, and single microextraction column is to Organic substance in water sample
Selectivity is high, limits its extensive application in actual complex water sample.
The content of the invention：
The invention reside in overcoming problem present in background technology, and provide a kind of synchronous extraction of organic pollution in water sample
Take method.The synchronous extracting process of organic pollution in the water sample, can realize various of different nature in actual complex water sample
The synchronous extraction of organic pollution, extraction efficiency are high, and cost is relatively low, thus has good application prospect.
The present invention solves its problem and can reach by following technical solution：The synchronous extraction of organic pollution in a kind of water sample
Method is taken, is comprised the following steps：
（1）Sample is dehydrated
By 0.45 μm of filtering with microporous membrane of water sample Jing to be measured, the water after filter sample of 10～20mL is taken in surface plate, surface
Ware is positioned in a conventional oven, and temperature setting is 40～50 DEG C, and drying time is about 10h, it is ensured that the moisture of sample in surface plate
To doing, the Organic substance of the micro or trace in water sample will be remained on surface plate evaporating completely；
（2）Organic substance dissolves
A. ultrasonication
The organic solvent of 2mL is added in surface plate, surface plate is placed in into ultrasound 10min in Ultrasound Instrument, is made on surface plate
Debris crush, to be dissolved in added organic solvent；
B. vibration dissolving
By the sample in surface plate, including the debris not being completely dissolved, it is fully transferred in the centrifuge tube of 2mL；
Centrifuge tube is placed in vortex oscillator and vibrates 10min, accelerate Organic substance dissolving in organic solvent；
C. centrifugation
Centrifuge tube is positioned in small-sized high speed centrifugal machine 5min is centrifuged, centrifugal speed is 10000 revs/min；
The supernatant in centrifuge tube is taken after centrifugation with pipettor, you can as the sample of gas chromatography-mass spectrography analyser
Product, carry out qualitative or quantitative analysis to the Organic substance in raw water sample.
Described organic solvent is Methanamide, acetonitrile, methanol, ethanol, isopropanol, pyridine, acetone, tetrahydrofuran, acetic acid
Ethyl ester, ether, diphenyl ether, dichloromethane, chloroform, dichloroethanes, toluene, benzene, carbon tetrachloride, Carbon bisulfide, hexamethylene or stone
One kind in oily ether.Can be according to the property of organic pollution in actual water sample, the organic solvent for selecting polarity close.
During the present invention makes water sample first, hydrone fully evaporates, and is subsequently adding what is remained during appropriate organic solvent makes water sample
Organic substance dissolves, and accelerates Organic substance course of dissolution in organic solvent using ultrasound-vortex oscillation, finally carry out at a high speed from
The heart, you can the sample for obtaining GC-MS is detected.
The present invention know-why be：
（1）The evaporation of moisture in water sample
The evaporation of moisture is relevant with the flowing velocity of the temperature of moisture surface, the surface area of liquid and liquid surface.To treat
Water sample is surveyed after 0.45 μm of filtering with microporous membrane, the water after filter sample of 10～20mL is taken in surface plate, can be greatly increased water sample
Surface area.Surface plate is placed in baking oven, temperature setting is 40～50 DEG C.On the one hand, selected evaporating temperature can be protected
Card and does not cause the Organic substance volatilization in water higher than room temperature with the speed of the evaporation that moisturizes；On the other hand, the sky in baking oven
Flow of air can also accelerate the evaporation of moisture in water sample.In the confined space of baking oven, it is ensured that the evaporation process of water sample is not
By the interference and pollution of particle in outside air.
（2）The dissolving of Organic substance in water sample
In the present invention, the dissolving in organic solvent of the dehydration of water sample and Organic substance is that substep is carried out, and improves Organic substance
Dissolution degree in organic solvent.In water sample after moisture evaporating completely, organic substance residues are on surface plate.Mixed according to similar
Principle, selects the organic solvent similar to the polarity of Organic substance in water sample to be measured, adds organic solvent 2mL in surface plate.
As the Organic substance in water sample is present with solid residue form, its dissolution velocity in organic solvent is have impact on.
Surface plate is placed in Ultrasound Instrument carries out supersound process 10min, can effectively crush debris.Then by surface plate
Sample and the Organic substance not being completely dissolved are fully transferred in the centrifuge tube of 2mL.Centrifuge tube is placed in vortex oscillator and is shaken
10min is swung, Organic substance is fully dissolved in organic solvent.
（3）Sample is centrifuged
Above-mentioned 2mL centrifuge tubes are positioned in small-sized high speed centrifugal machine 5min is centrifuged, centrifugal speed is 10000 revs/min.Take
In sample bottle, used as the detection sample of GC-MS, in sample, the cycles of concentration of Organic substance is about 10 to centrifuge tube supernatant.
The synchronous extracting process of organic pollution in the water sample of the present invention, can be applied to the pre- place of actual complex water sample
Reason.
It is of the invention to have the advantages that compared with above-mentioned background technology：The synchronization of organic pollution in the water sample
Extracting process, using laboratory conventional equipment, it is not necessary to extra equipment, and operating process is simple, reproducible；In the present invention
The consumption of organic solvent is little, low cost, will not produce secondary pollution；In the present invention, the loss of analyte is little, only needs less
Water sample can reach the requirement of micro or organic micro-pollutant extraction；The present invention can be according to goal analysis when actually used
The property of thing selects different types of organic solvent to be dissolved, and realizes the synchronous extraction of Some Organic Pollutants in complicated water sample
Take.The synchronous enrichment and extraction of Some Organic Pollutants in achievable drinking water, ground water and industrial effluents water sample.The extraction side
Method environmental friendliness, with good economy and environmental benefit.
Description of the drawings
Fig. 1 is the extraction procedure figure of organic pollution in water sample of the invention；
Fig. 2 is the chromatogram obtained by waste water from dyestuff is tested and analyzed using GC-MS Jing after extraction process pretreatment of the present invention.
Specific embodiment：
The invention will be further described below in conjunction with the accompanying drawings and the specific embodiments：
Embodiment 1
As shown in figure 1, taking the water sample after azo dye acid orange 7 oxidative degradation 3h, extracted in accordance with the following steps：Water
Sample takes 20mL water after filter sample in the surface plate of a diameter of 15cm Jing after 0.45 μm of filtering with microporous membrane；Surface plate is placed in baking
In case under the conditions of 45 DEG C about 10h, make the moisture evaporating completely of sample in surface plate；Surface plate is taken out from baking oven, and plus
Enter the methanol of 2mL, surface plate is positioned over ultrasound 10min in Ultrasound Instrument；Sample in surface plate is transferred to the centrifuge tube of 2mL
In, centrifuge tube is placed in vortex oscillator and vibrates 10min；Centrifuge tube is placed in small-sized high speed centrifugal machine 5min is centrifuged, from
Heart speed is 10000 revs/min, takes supernatant in sample bottle after centrifugation；Qualitative point is carried out to the sample after extraction using GC-MS
Analysis detection, GC-MS gas phases are separated using DB-5 capillary columns（30mm×320μm×0.5μm）, mass detector（MSD）Using
EI ionization sources（70eV）, ion source temperature is 230 DEG C.Carrier gas（He）Flow is 1.0mL/min, and sample size is 1 μ L, injection port temperature
Spend for 250 DEG C, using not shunt mode.Chromatographic column adopts temperature programming, and heating schedule is as follows：40 DEG C of holding 2min, then with 10
DEG C/ramp of min to 150 DEG C, keep 2min, then with the ramp of 8 DEG C/min to 200 DEG C, and keep 5min.Drop
The NIST08 standard spectrum picture libraries that the identification of solution product is carried using GC-MS, matching degree are more than 90%.
The GC-MS analysis results of the sample are shown, the waste water from dyestuff still contains various arene chemical combination Jing after processing
Thing, analysis of spectra are as shown in Figure 2.As shown in table 1, in spectrogram, a is benzofuran, b for the organic pollution relevant information that detected
For 1 (3) hydrogen-isobenzofuranone, c is 1,3- indandiones, and d is paranitroanisole, and e is coumarin, and f is phthalic acid
Dimethyl ester, g are phthalimide, and h is 1- aminoidans.Therefore, the present invention is to Some Organic Pollutants in waste water from dyestuff
It is respectively provided with higher extraction efficiency.
The organic pollution information of the detection of table 1
Claims (2)
1. in a kind of water sample organic pollution synchronous extracting process, comprise the following steps：
（1）Sample is dehydrated
By 0.45 μm of filtering with microporous membrane of water sample Jing to be measured, the water after filter sample of 10 ~ 20 mL is taken in surface plate, surface plate is put
It is placed in a conventional oven, temperature setting is 40 ~ 50 DEG C, and drying time is about 10 h, it is ensured that in surface plate, the moisture of sample is complete
It is evaporated to dryness, the Organic substance of the micro or trace in water sample will be remained on surface plate；
（2）Organic substance dissolves
A. ultrasonication
The organic solvent of 2 mL is added in surface plate, surface plate is placed in into ultrasonic 10 min in Ultrasound Instrument, is made on surface plate
Debris are crushed, to be dissolved in added organic solvent；
B. vibration dissolving
By the sample in surface plate, including the debris not being completely dissolved, it is fully transferred in the centrifuge tube of 2 mL；Will be from
Heart pipe is placed in vortex oscillator and vibrates 10 min, accelerates Organic substance dissolving in organic solvent；
C. centrifugation
Centrifuge tube is positioned in small-sized high speed centrifugal machine 5 min are centrifuged, centrifugal speed is 10000 revs/min；
The supernatant in centrifuge tube is taken after centrifugation with pipettor, you can as the sample of gas chromatography-mass spectrography analyser, right
Organic substance in raw water sample carries out qualitative or quantitative analysis；
The organic pollution for being detected is benzofuran, 1 (3) hydrogen-isobenzofuranone, 1,3- indandiones, p-nitrophenyl first
Ether, coumarin, dimethyl phthalate, phthalimide, 1- aminoidans；
Described organic solvent is acetonitrile, methanol, ethanol, isopropanol, pyridine, acetone, ethyl acetate, dichloromethane
One kind in alkane or chloroform；
The gas chromatography-mass spectrography analyser gas phase is separated using DB-5 capillary columns, capillary column length 30mm, internal diameter
320 μm, 0.5 μm of thickness, EI ionization source of the MSD mass detectors using 70 eV, ion source temperature are 230 DEG C；Carrier gas He flows
Measure as 1.0 mL/min, sample size is 1 μ L, and injector temperature is 250 DEG C, using not shunt mode；Chromatographic column is using intensification
Program is as follows：40 DEG C of 2 min of holding, then with the ramp of 10 DEG C/min to 150 DEG C, keep 2 min, then with 8 DEG C/
The ramp of min is to 200 DEG C, and keeps 5 min.
2. in a kind of water sample described in claim 1 organic pollution synchronous extracting process be used for actual complex water sample in it is organic
The extraction and enrichment of pollutant.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106582058B (en) * | 2016-12-20 | 2018-10-30 | 山东京博石油化工有限公司 | A method of separation petroleum coke Soluble Organic Matter |
| CN108362791B (en) * | 2018-01-30 | 2020-07-28 | 中国农业科学院茶叶研究所 | Method for detecting phthalimide in tea |
| CN114441700A (en) * | 2021-12-24 | 2022-05-06 | 江苏赫尔斯检测技术有限公司 | Method for determining deltamethrin in water based on gas-mass linkage method |
| CN114965799B (en) * | 2022-08-02 | 2022-10-25 | 山东杰诺检测服务有限公司 | Method for rapidly determining residual quantity of various pesticides in food |
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