CN103399113A - Solid phase membrane extraction-gas chromatography detection method for chlorobenzene compounds in water body - Google Patents
Solid phase membrane extraction-gas chromatography detection method for chlorobenzene compounds in water body Download PDFInfo
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Abstract
The present invention relates to a solid phase membrane extraction-gas chromatography detection method for chlorobenzene compounds in water body. The method comprises the steps of gathering 500 mL of a water sample with a pH value of 2.5 by flowing through a C18 solid phase extraction membrane at a flow rate of 5-50 mL/min; then eluting with 5 mL of acetone and 3*5 mL of dichloromethane; drying an elution by rotary evaporation; dissolving by n-hexane; diluting to 1 mL; introducing 1 [mu]L of the product into a gas chromatography-electron capture detector for the detection. A detection limit of eleven chlorobenzene compounds ranges from 0.05 ng/L to 4 ng/L; recovery rate ranges from 91% to 115%; and relative standard deviation (n=5) is 3.6-7.6%. The detection method is simple and sensitive, has wide linearity range, good repeatability and high recovery rate, and can rapidly determine concentrations of the chlorobenzene compounds in the water body.
Description
Technical field
The invention belongs to water pollution detection technical field, relate to Isosorbide-5-Nitrae-dichloro-benzenes, 1 in a kind of water body, 3-dichloro-benzenes, 1,2-dichloro-benzenes, 1,3,5-trichloro-benzenes, 1,2,4-trichloro-benzenes, 1,2,3-trichloro-benzenes, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, 1, immobilon-p extraction-gas chromatography electron capture the detection method of 2,3,4-tetrachlorobenzene, pentachlorobenzene, 11 kinds of chlorobenzene compounds of hexachloro-benzene.
Background technology
In recent decades, chlorobenzene compound is widely used in chemical synthetic pesticide, medicine, dyestuff, plastics and other chemical products, because uncontrolled waste water discharges and industrial atmosphere discharges it extensively is distributed in water environment.Chlorobenzene compound belongs to lipophilic compound, and stable chemical nature is difficult for degraded, and long-term suction may cause liver cancer, and they are classified as priority pollutants by Environmental Protection Agency (EPA).Therefore, find chlorobenzene compound detection technique in a kind of simple, quick, highly sensitive water body and seem particularly important.
At present, the trace amounts of chlorine benzene-like compounds in water body detects main by gas chromatography electron capture method or GC-MS.Pretreatment technology commonly used mainly contains liquid-liquid extraction method, solid phase extraction, liquid-phase micro-extraction method, headspace solid-phase microextraction method, headspace liquid-phase microextraction method, dispersive liquid-liquid microextraction method, microwave extraction method and Static Headspace extraction etc.The immobilon-p extraction is as the another kind of form of expression of Solid-Phase Extraction, the solid-phase extraction membrane that it uses, because sectional area is large, mass transfer rate is fast, can use larger flow, simultaneously the particle diameter of the adsorbent of membranaceous medium is less and be evenly distributed, and can make surface area increase and can improve mass transport process, therefore, it can extract the water sample of larger volume.In addition, the immobilon-p extraction can directly extract water sample in the open air, and the transportation volume but also the pollutant that have not only dwindled sample are adsorbed on solid-phase media more stable than the water sample that leaves refrigerator in.
As everyone knows, electron capture detector has high selectivity and sensitivity to organochlorine, is to analyze in the past the important means of chlorinated organics half a century.Chlorobenzene compound contains 1～6 chlorine substituent, and except chlorobenzene is not too sensitive to electron capture detector, other 11 kinds of chlorobenzene compounds are all comparatively sensitive.But consult present domestic and foreign literature, not yet have immobilon-p abstraction technique and the coupling of the gas chromatography electron capture detection method report for detection of 11 kinds of chlorobenzene compounds in water body.
Summary of the invention
Deficiency for above-mentioned present Research, the present invention analyzes present situation according to Chlorobenzens in water body, immobilon-p extraction-gas chromatography electron capture the detection method of chlorobenzene compound in a kind of water body is provided, the method comprises sampling and sample preparation successively, the immobilon-p extraction, concentrated constant volume, gas chromatography-electron capture detector detects, Specification Curve of Increasing, sample and determination of recovery rates.
The inventive method comprises the following steps:
Step (1). sampling and sample preparation:
After the water sample via hole diameter that gathers is the polyvinylidene fluoride microporous filtering film filtration of 0.45 μ m, deposit in Brown Glass Brown glass bottles and jars only, regulate water sample pH value to 2.5, obtain pretreated water sample.
Step (2). the immobilon-p extraction:
2-1. solid-phase extraction membrane need activate before use, concrete activation act is: solid-phase extraction membrane is used 20mL ethyl acetate, the drip washing of 10mL acetone at first successively, then successively with 20mL methyl alcohol, the activation of 20mL redistilled water, the solid-phase extraction membrane that obtains activating; In the reactivation process of solid-phase extraction membrane, can not make the solid-phase extraction membrane ingress of air.
2-2. during extraction, get the pretreated water sample of 500mL, with the solid-phase extraction membrane of speed by activating of 5～50mL/min.After water sample passed through, vacuum pump vacuumized solid-phase extraction membrane 5min, removed the residual moisture in solid-phase extraction membrane, then, successively with 5mL acetone, 3 * 5mL methylene chloride wash-out,, in order to the analyte of enrichment in the wash-out solid-phase extraction membrane, collected eluent.
Described 3 * 5mL methylene chloride is to use 5mL methylene chloride, co-elute three times at every turn.
Step (3). concentrated constant volume:
With the eluent collected with anhydrous sodium sulfate dehydration after, under 35 ℃ of pump vacuum degree 0.1MPa, bath temperature, be evaporated to driedly with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid.
Step (4). gas chromatography-electron capture detector detects:
Sample introduction needle extracts above-mentioned n-hexane dissolution liquid, according to the gas chromatography that sets-electron capture detector condition, detects.Chromatographic condition is: injector temperature is 220 ℃; The electron capture detector temperature is 300 ℃; Carrier gas is high pure nitrogen, and flow velocity is 1mL/min; Sampling volume is 1 μ L; Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1; The gas chromatographic column heating schedule is: 40 ℃ keep 4min, and 10 ℃/min is warming up to 160 ℃, keep 1min, and 10 ℃/min is warming up to 220 ℃, keep 5min, and total run time is 28min.
It is the DB-5 capillary gas chromatographic column of 30m * 0.25mm * 0.25 μ m that described gas chromatographic column is selected specification, fixing is the mixed liquor of diphenyl and dimethyl polysiloxane mutually, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 11 kinds of chlorobenzene compounds.
Step (5). Specification Curve of Increasing: qualitative with retention time, external standard method is quantitative.
When retention time is qualitative, standard solution is operated according to the requirement of above-mentioned steps (4) gas chromatogram that obtains standard solution, and with the gas chromatogram of single analyte, carry out retention time relatively, determine the retention time of 11 kinds of chlorobenzene compounds.The retention time of these 11 kinds of chlorobenzene compounds when quantitative as external standard method, the foundations of 11 kinds of chlorobenzene compound chromatographic peak identifications.
In described standard solution, solute is chlorobenzene compound, and solvent is normal hexane; Wherein the concentration of dichloro-benzenes is 100 μ g/L, and the concentration of trichloro-benzenes is 11 μ g/L, and the concentration of tetrachlorobenzene is 2.5 μ g/L, and the concentration of pentachlorobenzene is 1.25 μ g/L, and the concentration of hexachloro-benzene is 1.25 μ g/L.
Described dichloro-benzenes is Isosorbide-5-Nitrae-dichloro-benzenes, 1,3-dichloro-benzenes, 1,2-dichloro-benzenes.
Described trichloro-benzenes is 1,3,5-trichloro-benzenes, 1,2,4-trichloro-benzenes, 1,2,3-trichloro-benzenes.
Described tetrachlorobenzene is 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, 1,2,3,4-tetrachlorobenzene.
The step of preparing standard solution can be: get the dichloro-benzenes that concentration is 0.8mg/L, 0.088mg/L trichloro-benzenes, the 0.02mg/L tetrachlorobenzene, the chlorobenzene compound hybrid standard of 0.01mg/L pentachlorobenzene and 0.01mg/L hexachloro-benzene uses liquid 125 μ L, be settled to 1mL with normal hexane, obtain standard solution.
When external standard method is quantitative, the requirement of the typical curve of six kinds of different mark-on concentration series water sample according to above-mentioned steps (1)～(4) operated, according to the corresponding relation Criterion curve of the chlorobenzene compound concentration that adds and peak area.
In described typical curve series water sample, solute is chlorobenzene compound, and solvent is redistilled water; In the typical curve series water sample of different mark-on concentration, the concentration range of dichloro-benzenes is that the concentration range of 0.02～0.4 μ g/L, trichloro-benzenes is that the concentration range of 0.0022～0.044 μ g/L, tetrachlorobenzene is that the concentration range of 0.0005～0.01 μ g/L, pentachlorobenzene is that the concentration range of 0.00025～0.005 μ g/L, hexachloro-benzene is 0.00025～0.005 μ g/L.
the preparation steps of typical curve series water sample can be: getting respectively concentration is the 0.8mg/L dichloro-benzenes, 0.088mg/L trichloro-benzenes, 0.02mg/L tetrachlorobenzene, 0.01mg/L the chlorobenzene compound hybrid standard of pentachlorobenzene and 0.01mg/L hexachloro-benzene uses liquid 12.5, 25, 37.5, 62.5, 125, 250 μ L, be settled to respectively 500mL with redistilled water, obtaining six kinds of mark-on concentration ranges is dichloro-benzenes 0.02～0.4 μ g/L, trichloro-benzenes 0.0022～0.044 μ g/L, tetrachlorobenzene 0.0005～0.01 μ g/L, pentachlorobenzene and hexachloro-benzene are the typical curve series water sample of 0.00025～0.005 μ g/L.
Table 1 is the range of linearity, equation of linear regression, related coefficient and the detection limit of the inventive method.As shown in Table 1, each chlorobenzene compound in the corresponding range of linearity, has good linear relationship, meets the analytical approach requirement.
The range of linearity of table 1 this method, equation of linear regression and detection limit
Wherein, a: the range of linearity represents the concentration of analyte in typical curve series water sample;
B:y and x represent respectively the peak area of analyte and typical curve series water sample after according to above-mentioned steps (1)～(3), the theoretical concentration of analyte in the 1mL normal hexane.
Step (6). sample and determination of recovery rates:
, with the actual water sample that collects, operate according to the requirement of above-mentioned steps (1)～(4), and the typical curve that obtains with above-mentioned steps (5) relatively, finally obtains the content of 11 kinds of chlorobenzene compounds in actual water sample by converting.
Mark-on water sample with different mark-on concentration, operation repetitive is carried out respectively in requirement according to above-mentioned steps (2)～(4) five times, and compare the mensuration concentration that finally obtains 11 kinds of chlorobenzene compounds in the mark-on water sample by converting with the typical curve that above-mentioned steps (5) obtains.Carrying out according to the following formula the recovery calculates:
In formula: R---the recovery, ﹪;
C
s---the mensuration concentration of 11 kinds of chlorobenzene compounds in the mark-on water sample, μ g/L;
C
0---the concentration of 11 kinds of chlorobenzene compounds in actual water sample, μ g/L;
C---the theoretical mark-on concentration of 11 kinds of chlorobenzene compounds in the mark-on water sample, μ g/L.
Described mark-on water sample is the water sample after adding chlorobenzene compound in the pretreated actual water sample of step (1).
Beneficial effect of the present invention:
The present invention adopts the chlorobenzene compound in immobilon-p extraction-gas chromatography electron capture detection method mensuration water body, the method is simple to operate, energy fast processing water sample with bulk mass, result is accurate, 11 kinds of chlorobenzene compounds detect and are limited to 0.05～4ng/L, and the recovery is 91～115 ﹪, and relative standard deviation (n=5) is 3.6～7.6 ﹪, have higher sensitivity and the gratifying recovery and reappearance, can be used for the assay of water body chlorobenzene compound.
Description of drawings
Fig. 1 is the impacts of different eluents on extraction efficiency;
Fig. 2 is the impacts of different effluent volumes on extraction efficiency;
Fig. 3 is the impacts of different water sample pH on extraction efficiency;
Fig. 4 is the gas chromatogram of 11 kinds of chlorobenzene compounds in three kinds of water samples; Figure (a) is the gas chromatogram of 11 kinds of chlorobenzene compounds in standard solution, and figure (b) is the gas chromatogram of 11 kinds of chlorobenzene compounds in the Zhoushan sea area seawater, the gas chromatogram of 11 kinds of chlorobenzene compounds in figure (c) mark-on Zhoushan sea area seawater; Wherein, 1.1,4-dichloro-benzenes; 2.1, the 3-dichloro-benzenes; 3.1, the 2-dichloro-benzenes; 4.1,3,5-trichloro-benzenes; 5.1,2,4-trichloro-benzenes; 6.1,2,3-trichloro-benzenes; 7.1,2,3,5-tetrachlorobenzene; 8.1,2,4,5-tetrachlorobenzene; 9.1,2,3,4-tetrachlorobenzene; 10. pentachlorobenzene; 11. hexachloro-benzene.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Step (1). sampling and sample preparation:
After the water sample via hole diameter that gathers is the polyvinylidene fluoride microporous filtering film filtration of 0.45 μ m, deposit in Brown Glass Brown glass bottles and jars only, regulate water sample pH value to 2.5, obtain pretreated water sample.
Step (2). the immobilon-p extraction:
2-1. solid-phase extraction membrane need activate before use, concrete activation act is: solid-phase extraction membrane is used 20mL ethyl acetate, the drip washing of 10mL acetone at first successively, then successively with 20mL methyl alcohol, the activation of 20mL redistilled water, the solid-phase extraction membrane that obtains activating; In the reactivation process of solid-phase extraction membrane, can not make the solid-phase extraction membrane ingress of air.
2-2. during extraction, get the pretreated water sample of 500mL, with the solid-phase extraction membrane of speed by activating of 5～50mL/min.After water sample passed through, vacuum pump vacuumized solid-phase extraction membrane 5min, removed the residual moisture in solid-phase extraction membrane, then, successively with 5mL acetone, 3 * 5mL methylene chloride wash-out,, in order to the analyte of enrichment in the wash-out solid-phase extraction membrane, collected eluent.
Described 3 * 5mL methylene chloride is to use 5mL methylene chloride, co-elute three times at every turn.
In carrying out immobilon-p extracting operation process, to eluent, effluent volume, the aqueous sample stream flow velocity through solid-phase extraction membrane, water sample pH and salinity are optimized, with raising method detection sensitivity.Eluent directly affects the elute effect of analyte, more different eluent A(5mL acetone+3 * 5mL methylene chloride), extraction efficiency B(5mL acetone+3 * 5mL normal hexane), C(5mL acetone+3 * 5mL sherwood oil), D(5mL acetone+3 * 5mL ethyl acetate), E(5mL acetone+3 * 5mL acetonitrile), see accompanying drawing 1, why all comprising 5mL acetone in every kind of eluent, is because acetone can dissolve the compound of opposed polarity.By accompanying drawing 1 as can be known, eluent A, B, D have higher extraction efficiency to tetrachlorobenzene, pentachlorobenzene, hexachloro-benzene, and recovery scope is 76～104 ﹪.Except eluent A, the extraction efficiency of other eluent p-dichlorobenzene, trichloro-benzenes is all lower.Consider the extraction efficiency of 11 kinds of chlorobenzene rate compounds, this method selects 5mL acetone+3 * 5mL methylene chloride as eluent.Immobilon-p extraction is adsorb on spe membrane and resolve two processes.Aqueous sample stream is when spe membrane, and the object in water body is extracted film absorption and realizes enrichment, after water sample passes through, then by eluent, is parsed.Choose appropriate effluent volume, both realized the wash-out purpose, saved again solvent.Use acetone and methylene chloride as gradient eluent, studied the impact of different effluent volumes on extraction efficiency, see accompanying drawing 2, when the volume of methylene chloride in eluent increases to 3 * 5mL from 1 * 5mL, extraction efficiency significantly increases, but when increasing to 4 * 5mL, extraction efficiency changes very little.Result shows, when methylene chloride volume was 3 * 5mL, the extraction efficiency of 11 kinds of chlorobenzene compounds was 72～104 ﹪, can meet the analytical approach requirement, need not to increase the volume of methylene chloride again.Different aqueous sample streams have been compared through the impact on extraction efficiency of the flow velocity of solid-phase extraction membrane, result shows in flow velocity 5～50mL/min scope, increase along with flow velocity, extraction efficiency slightly fluctuates, but change not obvious, the water sample flow velocity can be ignored the impact of extraction efficiency, guarantees in operation that therefore the water sample flow velocity gets final product in 5～50mL/min scope.Studied water sample pH in 2.5～9.0 scopes on the impact of extraction efficiency, see accompanying drawing 3.Result shows compares alkalescence and neutrality, and (pH2.5) can obtain better extraction efficiency under acid condition.This may be because chlorobenzene compound more easily is adsorbed on the C18 solid-phase extraction membrane at acid condition (pH2.5).When processing water sample, this method regulates water sample pH2.5.Compared under water sample different salinity condition the impact on extraction efficiency, result show the water sample salinity in 0～5 ﹪ scope on extraction efficiency without impact.Therefore when the actual water sample salinity is in 0～5 ﹪ scope, ignore the effect of salinity of matrix.
Step (3). concentrated constant volume:
With the eluent collected with anhydrous sodium sulfate dehydration after, under 35 ℃ of pump vacuum degree 0.1MPa, bath temperature, be evaporated to driedly with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid.
Step (4). gas chromatography-electron capture detector detects:
Sample introduction needle extracts above-mentioned n-hexane dissolution liquid, according to the gas chromatography that sets-electron capture detector condition, detects.Chromatographic condition is: injector temperature is 220 ℃; The electron capture detector temperature is 300 ℃; Carrier gas is high pure nitrogen, and flow velocity is 1mL/min; Sampling volume is 1 μ L; Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1; The gas chromatographic column heating schedule is: 40 ℃ keep 4min, and 10 ℃/min is warming up to 160 ℃, keep 1min, and 10 ℃/min is warming up to 220 ℃, keep 5min, and total run time is 28min.
It is the DB-5 capillary gas chromatographic column of 30m * 0.25mm * 0.25 μ m that described gas chromatographic column is selected specification, fixing is the mixed liquor of diphenyl and dimethyl polysiloxane mutually, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 11 kinds of chlorobenzene compounds.
Step (5). Specification Curve of Increasing: qualitative with retention time, external standard method is quantitative.
When retention time is qualitative, get the dichloro-benzenes that concentration is 0.8mg/L, 0.088mg/L trichloro-benzenes, 0.02mg/L tetrachlorobenzene, the chlorobenzene compound hybrid standard of 0.01mg/L pentachlorobenzene and 0.01mg/L hexachloro-benzene uses liquid 125 μ L, with normal hexane, is settled to 1mL, obtain that (concentration of dichloro-benzenes is 100 μ g/L, the concentration of trichloro-benzenes is 11 μ g/L, and the concentration of tetrachlorobenzene is 2.5 μ g/L, and the concentration of pentachlorobenzene is that the concentration of 1.25 μ g/L and hexachloro-benzene is 1.25 μ g/L) standard solution.Standard solution is operated according to the requirement of above-mentioned steps (4) gas chromatogram that obtains standard solution, and with the gas chromatogram of single analyte, carry out retention time relatively, determine the retention time of 11 kinds of chlorobenzene compounds.The retention time of these 11 kinds of chlorobenzene compounds when quantitative as external standard method, the foundations of 11 kinds of chlorobenzene compound chromatographic peak identifications.
When external standard method is quantitative, getting respectively concentration is the 0.8mg/L dichloro-benzenes, 0.088mg/L trichloro-benzenes, 0.02mg/L tetrachlorobenzene, 0.01mg/L the chlorobenzene compound hybrid standard of pentachlorobenzene and 0.01mg/L hexachloro-benzene uses liquid 12.5,25,37.5,62.5,125,250 μ L, be settled to respectively 500mL with redistilled water, obtaining six kinds of mark-on concentration ranges is dichloro-benzenes 0.02～0.4 μ g/L, trichloro-benzenes 0.0022～0.044 μ g/L, tetrachlorobenzene 0.0005～0.01 μ g/L, pentachlorobenzene and hexachloro-benzene are the typical curve series water sample of 0.00025～0.005 μ g/L.The requirement of the typical curve of six kinds of different mark-on concentration series water sample according to above-mentioned steps (1)～(4) operated, according to the corresponding relation Criterion curve of the chlorobenzene compound concentration that adds and peak area.
Table 1 is the range of linearity, equation of linear regression, related coefficient and the detection limit of the inventive method.As shown in Table 1, each chlorobenzene compound in the corresponding range of linearity, has good linear relationship, meets the analytical approach requirement.
The range of linearity of table 1 this method, equation of linear regression and detection limit
Wherein, a: the range of linearity represents the concentration of analyte in typical curve series water sample;
B:y and x represent respectively the peak area of analyte and typical curve series water sample after according to above-mentioned steps (1)～(3), the theoretical concentration of analyte in the 1mL normal hexane.
Step (6). sample and determination of recovery rates:
Gather the actual water sample (Wahaha Pure Water, laboratory tap water, Zhoushan sea area seawater) of three kinds of different substrates, requirement according to above-mentioned steps (1)～(4) operates, and with the typical curve that above-mentioned (5) step obtains, compare, finally obtain the content of 11 kinds of chlorobenzene compounds in water sample to be measured by converting.adopt above-mentioned actual water sample, after processing according to the requirement of step (1), get 500mL, add respectively dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 12.5, 62.5, 125 μ L, obtain three kinds and add concentration level (dichloro-benzenes 0.02, 0.1, 0.2 μ g/L, trichloro-benzenes 0.0022, , 0.011, 0.022 μ g/L, tetrachlorobenzene 0.0005, 0.0025, 0.005 μ g/L, pentachlorobenzene and hexachloro-benzene are 0.00025, 0.00125, 0.0025 mark-on water sample μ g/L), according to above-mentioned steps (2), (3), (4) operation repetitive is carried out respectively in requirement five times, and with the typical curve that above-mentioned steps (5) obtains, compare, finally obtain the concentration of 11 kinds of chlorobenzene compounds in the mark-on water sample by converting.Carrying out according to the following formula the recovery calculates:
In formula: R---the recovery, ﹪;
C
s---the mensuration concentration of 11 kinds of chlorobenzene compounds in the mark-on water sample, μ g/L;
C
0---the concentration of 11 kinds of chlorobenzene compounds in actual water sample, μ g/L;
C---the theoretical mark-on concentration of 11 kinds of chlorobenzene compounds in the mark-on water sample, μ g/L.
After testing, heartily in pure water, laboratory tap water, Zhoushan sea area seawater 11 kinds of chlorobenzene compound concentration be and do not detect.In different substrates water body (Wahaha Pure Water, laboratory tap water, Zhoushan sea area seawater), the recovery testu of different mark-on concentration levels the results are shown in Table 2.
In Zhoushan sea area seawater and mark-on Zhoushan sea area seawater, the gas chromatogram of chlorobenzene compound respectively
See (b) and (c) in accompanying drawing 4.
The recovery of table 2 different substrates water body and Precision Experiment result (n=5)
The mensuration of 11 kinds of chlorobenzene compounds in embodiment 2. Wahaha Pure Waters
(1) sampling and sample preparation: Wahaha Pure Water is through 0.45 μ m polyvinylidene fluoride microporous filtering film
After filtration, deposit in the 500mL Brown Glass Brown glass bottles and jars only, regulate its pH value to 2.5.
The mark-on Wahaha Pure Water: adding concentration in the Wahaha Pure Water of handling well to 500mL is dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 12.5 μ L, obtaining concentration is dichloro-benzenes 0.02 μ g/L, trichloro-benzenes 0.0022 μ g/L, tetrachlorobenzene 0.0005 μ g/L, pentachlorobenzene and hexachloro-benzene are the mark-on Wahaha Pure Water of 0.00025 μ g/L.
(2) immobilon-p extraction: solid-phase extraction membrane is used 20mL ethyl acetate, the drip washing of 10mL acetone before using successively, more successively with 20mL methyl alcohol, 20mL redistilled water activation (in this process, can not make the solid-phase extraction membrane ingress of air).During extraction, get Wahaha Pure Water or mark-on Wahaha Pure Water that 500mL above-mentioned steps (1) is handled well, with the speed of 5mL/min, pass through preactivated good solid-phase extraction membrane.After water sample passes through, vacuum pump vacuumizes 5min to remove the residual moisture in solid-phase extraction membrane,, successively with the analyte of enrichment in 5mL acetone and 3 * 5mL methylene chloride (each 5mL methylene chloride, wash-out is three times respectively) wash-out solid-phase extraction membrane, collect simultaneously eluent again.
(3) concentrated constant volume: the eluent that above-mentioned steps (2) is collected with anhydrous sodium sulfate dehydration after,, at pump vacuum degree 0.1MPa, under 35 ℃ of bath temperatures, be evaporated to driedly with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL.
(4) gas chromatography-electron capture detector detects: sample introduction needle extracts the 1mL n-hexane dissolution liquid that above-mentioned (3) step obtains, and according to the gas chromatography that sets-electron capture detector condition, detects.Concrete grammar is: sample introduction needle extracts the 1mL n-hexane dissolution liquid 1 μ L that above-mentioned steps (3) obtains, and according to the gas chromatography that sets-electron capture detector condition, detects, and chromatographic condition is: injector temperature is 220 ℃; The electron capture detector temperature is 300 ℃; Carrier gas is high pure nitrogen, and flow velocity is 1mL/min; Sampling volume is 1 μ L; Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1; The gas chromatographic column heating schedule is: 40 ℃ keep 4min, and 10 ℃/min is warming up to 160 ℃, keep 1min, and 10 ℃/min is warming up to 220 ℃, keep 5min, and total run time is 28min.
It is the DB-5 capillary gas chromatographic column of 30m * 0.25mm * 0.25 μ m that described gas chromatographic column is selected specification, fixing is the mixed liquor of diphenyl and dimethyl polysiloxane mutually, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 11 kinds of chlorobenzene compounds.
(5) Specification Curve of Increasing: qualitative with retention time, external standard method is quantitative.when retention time is qualitative, getting concentration is dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 125 μ L, be settled to 1mL with normal hexane, obtaining concentration is dichloro-benzenes 100 μ g/L, trichloro-benzenes 11 μ g/L, tetrachlorobenzene 2.5 μ g/L, pentachlorobenzene and hexachloro-benzene are the standard solution of 1.25 μ g/L, requirement according to above-mentioned steps (4) operates the gas chromatogram that obtains standard solution, and with the gas chromatogram of single analyte, carry out retention time relatively, determine the retention time of 11 kinds of chlorobenzene compounds, use when quantitative as external standard method, the foundation of 11 kinds of chlorobenzene compound chromatographic peak identifications.In accompanying drawing 4, (a) is the standard solution gas chromatogram.when external standard method is quantitative, getting respectively concentration is dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 12.5, 25, 37.5, 62.5, 125, 250 μ L, be settled to 500mL with redistilled water, obtaining six mark-on concentration ranges is dichloro-benzenes 0.02～0.4 μ g/L, trichloro-benzenes 0.0022～0.044 μ g/L, tetrachlorobenzene 0.0005～0.01 μ g/L, pentachlorobenzene and hexachloro-benzene are the typical curve series water sample of 0.00025～0.005 μ g/L, according to above-mentioned steps (1), (2), (3), (4) requirement operates, corresponding relation Criterion curve according to the chlorobenzene compound concentration that adds and peak area.Table 1 is the range of linearity of this method, equation of linear regression, related coefficient and detection limit.As shown in Table 1, each chlorobenzene compound in the corresponding range of linearity, has good linear relationship, meets the analytical approach requirement.
(6) sample and determination of recovery rates: after the requirement operation of Wahaha Pure Water according to above-mentioned steps (1), (2), (3), (4), the typical curve that obtains with above-mentioned steps (5) compares, and the mensuration concentration that finally obtains 11 kinds of chlorobenzene compounds in Wahaha Pure Water by converting is and does not detect.The mark-on Wahaha Pure Water, operation repetitive is carried out respectively in requirement according to above-mentioned steps (1), (2), (3), (4) five times, and with the typical curve that above-mentioned steps (5) obtains, compare, the mensuration concentration that finally obtains 11 kinds of chlorobenzene compounds in the mark-on Wahaha Pure Water by converting, and calculate recovery rate, the relative standard deviation of five replicate determinations.As shown in Table 1, the mark-on Wahaha Pure Water recovery is 99～115 ﹪, and relative standard deviation (n=5) is 4.5～7.6 ﹪, meets analytical approach to the recovery and reappearance requirement.
The mensuration of 11 kinds of chlorobenzene compounds in embodiment 3. laboratory tap water
(1) sampling and sample preparation: the laboratory tap water after 0.45 μ m polyvinylidene fluoride microporous filtering film filters, is deposited in the 500mL Brown Glass Brown glass bottles and jars only, regulates its pH value to 2.5.
Mark-on laboratory tap water: to adding concentration in the laboratory tap water that 500mL handles well, be dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 62.5 μ L, obtaining concentration is dichloro-benzenes 0.1 μ g/L, trichloro-benzenes 0.011 μ g/L, tetrachlorobenzene 0.0025 μ g/L, pentachlorobenzene and hexachloro-benzene are the mark-on laboratory tap water of 0.00125 μ g/L.
(2) immobilon-p extraction: solid-phase extraction membrane is used 20mL ethyl acetate, the drip washing of 10mL acetone before using successively, more successively with 20mL methyl alcohol, 20mL redistilled water activation (in this process, can not make the solid-phase extraction membrane ingress of air).During extraction, get laboratory tap water or mark-on laboratory tap water that 500mL above-mentioned steps (1) is handled well, with the speed of 25mL/min, pass through preactivated good solid-phase extraction membrane.After water sample passes through, vacuum pump vacuumizes 5min to remove the residual moisture in solid-phase extraction membrane,, successively with the analyte of enrichment in 5mL acetone and 3 * 5mL methylene chloride (each 5mL methylene chloride, wash-out is three times respectively) wash-out solid-phase extraction membrane, collect simultaneously eluent again.
(3) concentrated constant volume: the eluent that above-mentioned steps (2) is collected with anhydrous sodium sulfate dehydration after,, at pump vacuum degree 0.1MPa, under 35 ℃ of bath temperatures, be evaporated to driedly with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL.
(4) gas chromatography-electron capture detector detects: sample introduction needle extracts the 1mL n-hexane dissolution liquid that above-mentioned steps (3) obtains, and according to the gas chromatography that sets-electron capture detector condition, detects.Concrete grammar is: sample introduction needle extracts the 1mL n-hexane dissolution liquid 1 μ L that above-mentioned (3) step obtains, and according to the gas chromatography that sets-electron capture detector condition, detects, and chromatographic condition is: injector temperature is 220 ℃; The electron capture detector temperature is 300 ℃; Carrier gas is high pure nitrogen, and flow velocity is 1mL/min; Sampling volume is 1 μ L; Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1; The gas chromatographic column heating schedule is: 40 ℃ keep 4min, and 10 ℃/min is warming up to 160 ℃, keep 1min, and 10 ℃/min is warming up to 220 ℃, keep 5min, and total run time is 28min.
It is the DB-5 capillary gas chromatographic column of 30m * 0.25mm * 0.25 μ m that described gas chromatographic column is selected specification, fixing is the mixed liquor of diphenyl and dimethyl polysiloxane mutually, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 11 kinds of chlorobenzene compounds.
(5) Specification Curve of Increasing: qualitative with retention time, external standard method is quantitative.when retention time is qualitative, getting concentration is dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 125 μ L, be settled to 1mL with normal hexane, obtaining concentration is dichloro-benzenes 100 μ g/L, trichloro-benzenes 11 μ g/L, tetrachlorobenzene 2.5 μ g/L, pentachlorobenzene and hexachloro-benzene are the standard solution of 1.25 μ g/L, requirement according to above-mentioned steps (4) operates the gas chromatogram that obtains standard solution, and with the gas chromatogram of single analyte, carry out retention time relatively, determine the retention time of 11 kinds of chlorobenzene compounds, use when quantitative as external standard method, the foundation of 11 kinds of chlorobenzene compound chromatographic peak identifications.In accompanying drawing 4, (a) is the standard solution gas chromatogram.when external standard method is quantitative, getting respectively concentration is dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 12.5, 25, 37.5, 62.5, 125, 250 μ L, be settled to 500mL with redistilled water, obtaining six kinds of mark-on concentration ranges is dichloro-benzenes 0.02～0.4 μ g/L, trichloro-benzenes 0.0022～0.044 μ g/L, tetrachlorobenzene 0.0005～0.01 μ g/L, pentachlorobenzene and hexachloro-benzene are the typical curve series water sample of 0.00025～0.005 μ g/L, according to above-mentioned steps (1), (2), (3), (4) requirement operates, corresponding relation Criterion curve according to the chlorobenzene compound concentration that adds and peak area.Table 1 is the range of linearity of this method, equation of linear regression, related coefficient and detection limit.As shown in Table 1, each chlorobenzene compound in the corresponding range of linearity, has good linear relationship, meets the analytical approach requirement.
(6) sample and determination of recovery rates: after the requirement operation of laboratory tap water according to above-mentioned steps (1), (2), (3), (4), the typical curve that obtains with above-mentioned steps (5) compares, and the mensuration concentration that finally obtains 11 kinds of chlorobenzene compounds in the tap water of laboratory by converting is and does not detect.Mark-on laboratory tap water, operation repetitive is carried out respectively in requirement according to above-mentioned steps (1), (2), (3), (4) five times, and with the typical curve that above-mentioned steps (5) obtains, compare, finally obtain the concentration of 11 kinds of chlorobenzene compounds in the tap water of mark-on laboratory by converting, and calculate recovery rate, the relative standard deviation of five replicate determinations.As shown in Table 1, the mark-on laboratory tap water recovery is 91～106 ﹪, and relative standard deviation (n=5) is 4.2～6.8 ﹪, meets analytical approach to the recovery and reappearance requirement.
The mensuration of 11 kinds of chlorobenzene compounds in embodiment 4. Zhoushan sea area seawater
(1) sampling and sample preparation: the Zhoushan sea area seawater after 0.45 μ m polyvinylidene fluoride microporous filtering film filters, is deposited in the 500mL Brown Glass Brown glass bottles and jars only, regulates its pH value to 2.5.
Mark-on Zhoushan sea area seawater: to adding concentration in the good Zhoushan sea area seawater of 500mL pre-service, be dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 125 μ L, obtaining concentration is dichloro-benzenes 0.2 μ g/L, trichloro-benzenes 0.022 μ g/L, tetrachlorobenzene 0.005 μ g/L, pentachlorobenzene and hexachloro-benzene are the mark-on Zhoushan sea area seawater of 0.0025 μ g/L.
(2) immobilon-p extraction: solid-phase extraction membrane is used 20mL ethyl acetate, the drip washing of 10mL acetone before using successively, more successively with 20mL methyl alcohol, 20mL redistilled water activation (in this process, can not make the solid-phase extraction membrane ingress of air).During extraction, get Zhoushan sea area seawater or mark-on Zhoushan sea area seawater that 500mL above-mentioned steps (1) is handled well, with the speed of 50mL/min, pass through preactivated good solid-phase extraction membrane.After water sample passes through, vacuum pump vacuumizes 5min to remove the residual moisture in solid-phase extraction membrane,, successively with the analyte of enrichment in 5mL acetone and 3 * 5mL methylene chloride (each 5mL methylene chloride, wash-out is three times respectively) wash-out solid-phase extraction membrane, collect simultaneously eluent again.
(3) concentrated constant volume: the eluent that above-mentioned steps (2) is collected with anhydrous sodium sulfate dehydration after,, at pump vacuum degree 0.1MPa, under 35 ℃ of bath temperatures, be evaporated to driedly with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL.
(4) gas chromatography-electron capture detector detects: sample introduction needle extracts the 1mL n-hexane dissolution liquid that above-mentioned steps (3) obtains, and according to the gas chromatography that sets-electron capture detector condition, detects.Concrete grammar is: sample introduction needle extracts the 1mL n-hexane dissolution liquid 1 μ L that above-mentioned steps (3) obtains, and according to the gas chromatography that sets-electron capture detector condition, detects, and chromatographic condition is: injector temperature is 220 ℃; The electron capture detector temperature is 300 ℃; Carrier gas is high pure nitrogen, and flow velocity is 1mL/min; Sampling volume is 1 μ L; Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1; The gas chromatographic column heating schedule is: 40 ℃ keep 4min, and 10 ℃/min is warming up to 160 ℃, keep 1min, and 10 ℃/min is warming up to 220 ℃, keep 5min, and total run time is 28min.
It is the DB-5 capillary gas chromatographic column of 30m * 0.25mm * 0.25 μ m that described gas chromatographic column is selected specification, fixing is the mixed liquor of diphenyl and dimethyl polysiloxane mutually, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 11 kinds of chlorobenzene compounds.
(5) Specification Curve of Increasing: qualitative with retention time, external standard method is quantitative.when retention time is qualitative, getting concentration is dichloro-benzenes 0.8mg/L, trichloro-benzenes 0.088mg/L, tetrachlorobenzene 0.02mg/L, the chlorobenzene compound hybrid standard that pentachlorobenzene and hexachloro-benzene are 0.01mg/L uses liquid 125 μ L, be settled to 1mL with normal hexane, obtaining concentration is dichloro-benzenes 100 μ g/L, trichloro-benzenes 11 μ g/L, tetrachlorobenzene 2.5 μ g/L, pentachlorobenzene and hexachloro-benzene are the standard solution of 1.25 μ g/L, requirement according to above-mentioned steps (4) operates the gas chromatogram that obtains standard solution, and with the gas chromatogram of single analyte, carry out retention time relatively, determine the retention time of 11 kinds of chlorobenzene compounds, use when quantitative as external standard method, the foundation of 11 kinds of chlorobenzene compound chromatographic peak identifications.In accompanying drawing 4, (a) is the standard solution gas chromatogram.when external standard method is quantitative, getting respectively concentration is the 0.8mg/L dichloro-benzenes, 0.088mg/L trichloro-benzenes, 0.02mg/L tetrachlorobenzene, 0.01mg/L the chlorobenzene compound hybrid standard of pentachlorobenzene and 0.01mg/L hexachloro-benzene uses liquid 12.5, 25, 37.5, 62.5, 125, 250 μ L, be settled to 500mL with redistilled water, obtaining six mark-on concentration ranges is dichloro-benzenes 0.02～0.4 μ g/L, trichloro-benzenes 0.0022～0.044 μ g/L, tetrachlorobenzene 0.0005～0.01 μ g/L, pentachlorobenzene and hexachloro-benzene are the typical curve series water sample of 0.00025～0.005 μ g/L, according to above-mentioned steps (1), (2), (3), (4) requirement operates, corresponding relation Criterion curve according to the chlorobenzene compound concentration that adds and peak area.Table 1 is the range of linearity of this method, equation of linear regression, related coefficient and detection limit.As shown in Table 1, each chlorobenzene compound in the corresponding range of linearity, has good linear relationship, meets the analytical approach requirement.
(6) sample and determination of recovery rates: after the requirement operation of Zhoushan sea area seawater according to above-mentioned steps (1), (2), (3), (4), the typical curve that obtains with above-mentioned steps (5) relatively, finally obtains in the Zhoushan sea area seawater concentration of 11 kinds of chlorobenzene compounds and is and does not detect by converting.Mark-on Zhoushan sea area seawater, operation repetitive is carried out respectively in requirement according to above-mentioned steps (1), (2), (3), (4) five times, and with the typical curve that above-mentioned steps (5) obtains, compare, finally obtain the concentration of 11 kinds of chlorobenzene compounds in mark-on Zhoushan sea area seawater by converting, and calculate recovery rate, the relative standard deviation of five replicate determinations.As shown in Table 1, the mark-on Zhoushan sea area seawater recovery is 96～110 ﹪, and relative standard deviation (n=5) is 3.6～6.6 ﹪, meets analytical approach to the recovery and reappearance requirement.
Instrument and equipment used in the present invention mainly contains the CP3380 gas chromatograph (configuration electron capture detector) of U.S. Varian company production and membranous disc solid-phase extraction device and the 47mm C18 immobilon-p that Britain Gast manufacturing company produces.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention,, as long as meet requirement of the present invention, all belongs to protection scope of the present invention.
Claims (3)
1. the immobilon-p of chlorobenzene compound extraction gas-chromatography detection method in a water body is characterized in that the method comprises the following steps:
Step (1). sampling and sample preparation:
After the water sample via hole diameter is the polyvinylidene fluoride microporous filtering film filtration of 0.45 μ m, deposit in Brown Glass Brown glass bottles and jars only, regulate water sample pH value to 2.5, obtain pretreated water sample;
Step (2). the immobilon-p extraction:
2-1. solid-phase extraction membrane need activate before use, concrete activation act is: solid-phase extraction membrane is used 20 mL ethyl acetate, 10 mL acetone drip washing at first successively, then successively with 20 mL methyl alcohol, 20 mL redistilled water activation, the solid-phase extraction membrane that obtains activating; In the reactivation process of solid-phase extraction membrane, can not make the solid-phase extraction membrane ingress of air;
2-2. during extraction, get the 500 pretreated water samples of mL, with the solid-phase extraction membrane of speed by activating of 5～50 mL/min; After water sample passed through, vacuum pump vacuumized solid-phase extraction membrane 5min, removed the residual moisture in solid-phase extraction membrane, then, successively with 5 mL acetone, 3 * 5 mL methylene chloride wash-outs,, in order to the analyte of enrichment in the wash-out solid-phase extraction membrane, collected eluent;
Described 3 * 5 mL methylene chloride are at every turn with 5 mL methylene chloride, co-elute three times;
Step (3). concentrated constant volume:
With the eluent collected with anhydrous sodium sulfate dehydration after, under 35 ℃ of pump vacuum degree 0.1MPa, bath temperature, be evaporated to driedly with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0 mL, obtain n-hexane dissolution liquid;
Step (4). gas chromatography-electron capture detector detects:
Sample introduction needle extracts above-mentioned n-hexane dissolution liquid, according to the gas chromatography that sets-electron capture detector condition, detects;
Step (5). Specification Curve of Increasing: qualitative with retention time, external standard method is quantitative;
When retention time is qualitative, standard solution is operated according to the requirement of above-mentioned steps (4) gas chromatogram that obtains standard solution, and with the gas chromatogram of single analyte, carry out retention time relatively, determine the retention time of 11 kinds of chlorobenzene compounds; The retention time of these 11 kinds of chlorobenzene compounds when quantitative as external standard method, the foundations of 11 kinds of chlorobenzene compound chromatographic peak identifications;
In described standard solution, solute is chlorobenzene compound, and solvent is normal hexane; Wherein the concentration of dichloro-benzenes is 100 μ g/L, and the concentration of trichloro-benzenes is 11 μ g/L, and the concentration of tetrachlorobenzene is 2.5 μ g/L, and the concentration of pentachlorobenzene is that the concentration of 1.25 μ g/L and hexachloro-benzene is 1.25 μ g/L;
The step of preparing standard solution is: get the dichloro-benzenes that concentration is 0.8 mg/L, 0.088 mg/L trichloro-benzenes, 0.02 mg/L tetrachlorobenzene, 0.01 the chlorobenzene compound hybrid standard of mg/L pentachlorobenzene and 0.01 mg/L hexachloro-benzene uses liquid 125 μ L, be settled to 1 mL with normal hexane, obtain standard solution;
When external standard method is quantitative, the requirement of the typical curve of six kinds of different mark-on concentration series water sample according to above-mentioned steps (1)～(4) operated, according to the corresponding relation Criterion curve of the chlorobenzene compound concentration that adds and peak area;
In described typical curve series water sample, solute is chlorobenzene compound, and solvent is redistilled water; In the typical curve series water sample of different mark-on concentration, the concentration range of dichloro-benzenes is that the concentration range of 0.02～0.4 μ g/L, trichloro-benzenes is that the concentration range of 0.0022～0.044 μ g/L, tetrachlorobenzene is that the concentration range of 0.0005～0.01 μ g/L, pentachlorobenzene is that the concentration range of 0.00025～0.005 μ g/L, hexachloro-benzene is 0.00025～0.005 μ g/L;
the preparation steps of typical curve series water sample is: getting respectively concentration is 0.8 mg/L dichloro-benzenes, 0.088 mg/L trichloro-benzenes, 0.02 mg/L tetrachlorobenzene, 0.01 the chlorobenzene compound hybrid standard of mg/L pentachlorobenzene and 0.01 mg/L hexachloro-benzene uses liquid 12.5, 25, 37.5, 62.5, 125, 250 μ L, be settled to respectively 500 mL with redistilled water, obtaining six kinds of mark-on concentration ranges is dichloro-benzenes 0.02～0.4 μ g/L, trichloro-benzenes 0.0022～0.044 μ g/L, tetrachlorobenzene 0.0005～0.01 μ g/L, pentachlorobenzene and hexachloro-benzene are the typical curve series water sample of 0.00025～0.005 μ g/L,
Step (6). sample and determination of recovery rates:
, with the actual water sample that collects, operate according to the requirement of above-mentioned steps (1)～(4), and the typical curve that obtains with above-mentioned steps (5) relatively, finally obtains the content of 11 kinds of chlorobenzene compounds in actual water sample by converting;
Mark-on water sample with different mark-on concentration, operation repetitive is carried out respectively in requirement according to above-mentioned steps (2)～(4) five times, and compare the mensuration concentration that finally obtains 11 kinds of chlorobenzene compounds in the mark-on water sample by converting with the typical curve that above-mentioned steps (5) obtains; Carrying out according to the following formula the recovery calculates:
In formula: R---the recovery, ﹪;
C
s---the mensuration concentration of 11 kinds of chlorobenzene compounds in the mark-on water sample, μ g/L;
C
0---the concentration of 11 kinds of chlorobenzene compounds in actual water sample, μ g/L;
C---the theoretical mark-on concentration of 11 kinds of chlorobenzene compounds in the mark-on water sample, μ g/L;
Described mark-on water sample is the water sample after adding chlorobenzene compound in the pretreated actual water sample of step (1).
2. in a kind of water body as claimed in claim 1, the immobilon-p of chlorobenzene compound extracts gas-chromatography detection method, and it is characterized in that the chromatographic condition that step (4) gas chromatography-electron capture detector detects is: injector temperature is 220 ℃; The electron capture detector temperature is 300 ℃; Carrier gas is high pure nitrogen, and flow velocity is 1 mL/min; Sampling volume is 1 μ L; Input mode is Splitless injecting samples, and after 0.75 min, split ratio is 50:1; The gas chromatographic column heating schedule is: 40 ℃ keep 4 min, and 10 ℃/min is warming up to 160 ℃, keep 1 min, and 10 ℃/min is warming up to 220 ℃, keep 5 min, and total run time is 28 min;
It is the DB-5 capillary gas chromatographic column of 30m * 0.25mm * 0.25 μ m that described gas chromatographic column is selected specification, fixing is the mixed liquor of diphenyl and dimethyl polysiloxane mutually, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 11 kinds of chlorobenzene compounds.
3. the immobilon-p of chlorobenzene compound extraction gas-chromatography detection method in a kind of water body as claimed in claim 1, is characterized in that described dichloro-benzenes is Isosorbide-5-Nitrae-dichloro-benzenes, 1,3-dichloro-benzenes, 1,2-dichloro-benzenes; Trichloro-benzenes is 1,3,5-trichloro-benzenes, 1,2,4-trichloro-benzenes, 1,2,3-trichloro-benzenes; Tetrachlorobenzene is 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, 1,2,3,4-tetrachlorobenzene.
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