CN103163254B - Method of trace quantity persistent organic pollutant in enrichment and separation seawater - Google Patents
Method of trace quantity persistent organic pollutant in enrichment and separation seawater Download PDFInfo
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- CN103163254B CN103163254B CN201310044136.8A CN201310044136A CN103163254B CN 103163254 B CN103163254 B CN 103163254B CN 201310044136 A CN201310044136 A CN 201310044136A CN 103163254 B CN103163254 B CN 103163254B
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Abstract
The invention discloses a method of trace quantity persistent organic pollutant in enrichment and separation seawater. The method comprises a step of installing a solid phase extraction column of polystyrene nanofiber on a solid phase extraction device and dealing with drip washing and activation by using methyl alcohol and ultrapure water; a step of adjusting potential of hydrogen (pH) value of water sample; a step of passing the solid phase extraction column of the polystyrene nanofiber repeatedly twice and pumping dry in vacuum mode; a step of eluting with eluent; a step of waving the eluent to dryness and dealing with constant volume. By adoption of the polystyrene nanofiber as solid phase extraction material, dieldrin and polychlorinated biphenyl of seven types are dealt with separation in an enriched mode in seawater sample in order to conduct detection to a gas chromatography electron capture detector, and therefore usage amount of organic solvent used in the process of the dieldrin and the polychlorinated biphenyl in enrichment and separation seawater can be reduced effectively and interference from other compositions to a target object can be prevented. The method has the advantages of being simple in extraction process, environment-friendly, low in detection limit, high in recovery rate, and good in reproducibility and can meet a detection requirement of the dieldrin and the polychlorinated biphenyl in the seawater.
Description
Technical field
The present invention relates to a kind of enrichment and separation method, specifically, relate to the enrichment and separation method of persistence organic pollutant in seawer system.
Background technology
Dieldrite and polychlorinated biphenyl (PCBs) are " Convention of Stockholm " first definite persistence organic pollutant matter, are found at present in seawater, even if trace exists, also can cause marine organism to reach poisonous level.China's " marine monitoring specification " (GB17378.4-2007) classifies dieldrite and PCBs as monitoring index.Dieldrite and PCBs residual concentration in water quality is low, disturbs morely, must carry out pre-service and enrichment to sample.
" marine monitoring specification " is (GB17378.4-2007) middle adopts resin adsorption concentration method, however a large amount of ultrapure solvents of this Technology Need, workload is larger, and analytical procedure is many, and analyte is easily lost.In water, the method for separating and concentrating of dieldrite and polychlorinated biphenyl also has liquid-liquid extraction, C18 column solid phase extraction, solid-phase microextraction etc.Liquid-liquid extraction organic solvent use amount is large; The materials such as the phthalate ester in C18 column solid phase extraction can disturb measuring to produce; Solid-phase microextraction, because the extracting head cost of coating is high, can not realize disposable use, and along with the increase of its access times, extraction efficiency declines gradually, and enrichment reappearance is poor.
In addition, along with the development of nanometer technology, nanofiber is subject to extensive concern as Solid-Phase Extraction material, and its separation and concentration of organic contaminant in environment has a good application prospect.At present, about the report that utilizes nanofiber to carry out separation and concentration to the organic contaminant in the samples such as biology, fruits and vegetables and tealeaves is more.But because the dieldrite in seawater and polychlorinated biphenyl exist with trace, and seawater component complexity, disturbing factor is more, can not directly use the nanofiber Solid-Phase Extraction method of above-mentioned sample.Therefore, nanofiber Solid-Phase Extraction method is not appeared in the newspapers at present for detection of the detection of dieldrite in seawater and polychlorinated biphenyl.
Summary of the invention
What the present invention will solve is the technical matters that prior art can not accurately detect extra large underwater trace dieldrite and polychlorinated biphenyl, the method of a kind of concentration and separation sea underwater trace persistence organic pollutant is provided, leaching process is easy, environmental protection, with low cost, can meet the testing requirement of extra large underwater trace dieldrite and polychlorinated biphenyl, also widen the range of application of nanofiber Solid-Phase Extraction simultaneously.
In order to solve the problems of the technologies described above, the present invention is achieved by following technical scheme:
A method for concentration and separation sea underwater trace persistence organic pollutant, described persistence organic pollutant is dieldrite, polychlorinated biphenyl or dieldrite and polychlorinated biphenyl, the method is carried out according to following steps:
(1) pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with methyl alcohol and ultrapure water drip washing activation successively;
(2) regulate water sample pH value to 2.0～12.0;
(3) by water sample with 0.5～2mLmin
-1constant flow rate repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and described pipe/polyhenylethylene nano fiber solid-phase extraction column vacuum is drained;
(4) pipe/polyhenylethylene nano fiber solid-phase extraction column described in eluant, eluent wash-out, the consumption of described eluant, eluent is 100～500 μ L;
(5) volatilize described eluant, eluent constant volume, in order to gas chromatographic analysis, the solvent load of described constant volume is 100～500 μ L.
Preferably, described in step (1), the consumption of methyl alcohol and described ultrapure water is 100～500 μ L.
Preferably, the pH in step (2) is 6.0.
Preferably, the water sample flow velocity in step (3) is 0.5mLmin
-1.
Preferably, the described eluant, eluent in step (4) is selected from methyl alcohol, ethanol, isopropyl alcohol or butanols one wherein.
Preferably, the consumption of the described eluant, eluent in step (4) is 200 μ L.
Preferably, in step (5), be selected from normal hexane, cyclohexane or isooctane one wherein for the solvent of described constant volume.
Preferably, the solvent load of constant volume described in step (5) is 100 μ L.
Along with the development of nanometer technology, nanofiber is subject to extensive concern as Solid-Phase Extraction material, and its diameter is tens of to hundreds of nanometer range, and its high-specific surface area can provide the action site of enormous amount, makes that loading capacity is large and efficiency is high; And nanofiber and other material to interpenetrate power extremely strong, molecule spreads soon in fiber, thereby has shortened absorption and elution time, the consumption of eluting solvent is also corresponding greatly to be reduced.Therefore, the Solid-Phase Extraction based on nanofiber is a kind of sample-pretreating method that has potentiality, and in environment, the separation and concentration of organic contaminant has a good application prospect.
According to the principle of " similar compatibility ", the present invention chooses pipe/polyhenylethylene nano fiber dieldrite in seawater and polychlorinated biphenyl is carried out to separation and concentration, can effectively solve the impact of interfering material.
The invention has the beneficial effects as follows:
The present invention adopts pipe/polyhenylethylene nano fiber to make Solid-Phase Extraction material, dieldrite in seawater sample and polychlorinated biphenyl are carried out to separation and concentration, detect in order to gas chromatography-electron capture detector, effectively reduce the organic solvent use amount in dieldrite and polychlorinated biphenyl process in concentration and separation seawater, prevented the interference of other compositions to object.
Enrichment and separation method leaching process of the present invention is easy, environmental protection, and detection limit is low, and the recovery is high, and reappearance is better, can meet dieldrite and polychlorinated biphenyl testing requirement in seawater.
Brief description of the drawings
Fig. 1 is that dieldrite concentration is 80.0ngL
-1, PCBs concentration is 56.8ngL
-1standard serial solution gained standard colors spectrogram;
Fig. 2 is the chromatogram that the embodiment of the present invention 1 detects water sample.
Embodiment
Below by specific embodiment, the present invention is described in further detail, and following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
The material using in each embodiment is as follows:
Eluant, eluent in each embodiment and select chromatographically pure, Tianjin Concord Technology Co., Ltd. for the solvent of constant volume;
Chinese substandard sea water, dieldrite standard model, pH standard buffer solution, State Standard Matter Research Centre;
Polychlorinated biphenyl (PCBs) standard substance solution, standard model research institute of State Environmental Protection Administration: 2,4,4-trichloro biphenyl (PCB28), 2; 2 ', 5,5 '-tetrachloro biphenyl (PCB52), 2; 2 ', 4,5; 5 '-pentachlorodiphenyl (PCB101), 2,3 ', 4; 4 ', 5-pentachlorodiphenyl (PCB118), 2,2; ' 3,4,4 '; 5 '-chlordene biphenyl (PCB138), 2,2 ', 4; 4 ', 5,5 '-chlordene biphenyl (PCB153), 2; 2 ', 3,4; 4 ', 5,5 '-heptachlor biphenyl (PCB180).
Each embodiment instrument is as follows:
Is furnished with the 7890A gas chromatograph of micro-pond electron capture detector (μ ECD), Agilent company of the U.S.;
HP-5 quartz capillary column (30m × 0.32mm × 0.25 μ m), Agilent company of the U.S.;
Solid-phase extraction device, Agilent company of the U.S.;
Full-automatic nitrogen blows concentrating instrument, Shanghai Xintuo Analytical Instruments Technology Co.ltd;
Pipe/polyhenylethylene nano fiber solid-phase extraction column, Suzhou Xianwei Nano Technology Co., Ltd..
The eluant, eluent of following embodiment is selected methyl alcohol, ethanol, isopropyl alcohol or butanols one wherein, but the invention is not restricted to this, can will be adsorbed on that analyte on pipe/polyhenylethylene nano fiber quantitatively elutes and all can be used for the present invention with the immiscible eluant, eluent of pipe/polyhenylethylene nano fiber.
Embodiment 1
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 100 μ L methyl alcohol and the drip washing activation successively of 200 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 6.0, with 0.5mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 200 μ L methanol-eluted fractions, methyl alcohol volatilizes rear use 100 μ L normal hexanes as solvent constant volume, treats gas chromatographic analysis.
(2) gas chromatography arranges condition:
Carrier gas used is high pure nitrogen; Injector temperature is 260 DEG C; Detecting device (ECD) temperature is made as 310 DEG C; Adopt temperature programme: column temperature initial temperature is 80 DEG C, keep 8min, then with 15 DEG C of min
-1heating rate is warming up to 250 DEG C, then with 25 DEG C of min
-1heating rate is warming up to 280 DEG C, keeps 2min; Carrier gas flux is 1.5mLmin
-1, tail blows 30mLmin
-1; Capillary column is not shunted; External standard method is quantitative.
(3) preparation of standard serial solution and mensuration:
Hybrid standard uses liquid to be mixed with standard reserving solution taking normal hexane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with the serial solution of hybrid standard for solvent.Hybrid standard uses liquid concentration: dieldrite 20.0 μ gL
-1, PCBs is 14.2 μ gL
-1.Getting respectively hybrid standard uses liquid 0.0,0.02,0.05,0.10,0.20,0.50mL to be placed in 6 10mL volumetric flasks, density of scawater (salinity 30) constant volume.Dieldrite concentration is respectively 0.0,8.0,20.0,40.0,80.0,200.0ngL
-1; PCBs concentration is respectively 0.0,5.68,14.2,28.4,56.8,142.0ngL
-1.
According to the pre-treating method in water sample preparation, standard serial solution is carried out after separation and concentration, and with water sample under identical condition by gas Chromatographic Determination, taking its mass concentration as horizontal ordinate, peak area is as ordinate drawing standard curve, obtains typical curve regression equation; Wherein, dieldrite concentration is 80.0ngL
-1, PCBs concentration is 56.8ngL
-1standard serial solution gained standard colors spectrogram see Fig. 1.
(4) result and data:
A. the chromatogram of water sample that the present embodiment detects is shown in Fig. 2, according to the peak area that obtains dieldrite and PCBs, utilizes respectively typical curve regression equation calculation to go out the mass concentration of dieldrite and PCBs in water sample to be analyzed, and test result is in table 2.
B. equation of linear regression, related coefficient and detection sensitivity:
In the present embodiment mensuration seawater, the equation of linear regression of dieldrite and polychlorinated biphenyl and related coefficient are in table 1; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 0.78～1.82ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 1.8%～5.7%.Concrete numerical value is in table 1.
Table 1 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (dieldrite concentration is respectively 8.0,20.0,40.0ngL in same water sample, to add respectively three kinds of concentration levels
-1; PCBs concentration is respectively 5.68,14.2,28.4ngL
-1) hybrid standard use liquid, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 2.Recovery of standard addition, between 80.5%～124.8%, is applicable to dieldrite and PCBs analysis in seawater.
The measurement result of table 2 accuracy
Embodiment 2
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 200 μ L methyl alcohol and the drip washing activation successively of 100 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 2.0, with 2.0mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 100 μ L ethanol elution, it is solvent constant volume that ethanol volatilizes rear use 200 μ L cyclohexane gives, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Hybrid standard uses liquid to be mixed with standard reserving solution taking cyclohexane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with the serial solution of hybrid standard for solvent.Other are with embodiment 1.
(4) result and data:
A. according to obtaining the peak area of dieldrite and PCBs, utilize respectively typical curve regression equation calculation to go out the mass concentration of dieldrite and PCBs in water sample to be analyzed, test result is in table 4.
B. equation of linear regression, related coefficient and detection sensitivity:
In the present embodiment mensuration seawater, the equation of linear regression of dieldrite and polychlorinated biphenyl and related coefficient are in table 3; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 1.22～1.51ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 4.14%～8.02%.Concrete numerical value is in table 3.
Table 3 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (dieldrite concentration is respectively 8.0,20.0,40.0ngL in same water sample, to add respectively three kinds of concentration levels
-1; PCBs concentration is respectively 5.68,14.2,28.4ngL
-1) hybrid standard use liquid, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 4.Recovery of standard addition, between 81.3%～119.3%, is applicable to dieldrite and PCBs analysis in seawater.
The measurement result of table 4 accuracy
Embodiment 3
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 500 μ L methyl alcohol and the drip washing activation successively of 200 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 12.0, with 1.0mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 500 μ L isopropyl alcohol wash-out, isopropyl alcohol volatilizes rear use 500 μ L isooctane as solvent constant volume, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Hybrid standard uses liquid to be mixed with standard reserving solution taking isooctane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with the serial solution of hybrid standard for solvent.Other are with embodiment 1.
(4) result and data:
A. according to obtaining the peak area of dieldrite and PCBs, utilize respectively typical curve regression equation calculation to go out the mass concentration of dieldrite and PCBs in water sample to be analyzed, test result is in table 6.
B. equation of linear regression, related coefficient and detection sensitivity:
In the present embodiment mensuration seawater, the equation of linear regression of dieldrite and polychlorinated biphenyl and related coefficient are in table 5; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 1.30～2.06ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 3.68%～7.68%.Concrete numerical value is in table 5.
Table 5 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (dieldrite concentration is respectively 8.0,20.0,40.0ngL in same water sample, to add respectively three kinds of concentration levels
-1; PCBs concentration is respectively 5.68,14.2,28.4ngL
-1) hybrid standard use liquid, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 6.Recovery of standard addition, between 82.8%～122.9%, is applicable to dieldrite and PCBs analysis in seawater.
The measurement result of table 6 accuracy
Embodiment 4
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 100 μ L methyl alcohol and the drip washing activation successively of 500 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 4.0, with 0.8mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 300 μ L butanols wash-out, butanols volatilizes rear use 100 μ L normal hexanes as solvent constant volume, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Hybrid standard uses liquid to be mixed with standard reserving solution taking normal hexane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with the serial solution of hybrid standard for solvent.Other are with embodiment 1.
(4) result and data:
A. according to obtaining the peak area of dieldrite and PCBs, utilize respectively typical curve regression equation calculation to go out the mass concentration of dieldrite and PCBs in water sample to be analyzed, test result is in table 8.
B. equation of linear regression, related coefficient and detection sensitivity:
In the present embodiment mensuration seawater, the equation of linear regression of dieldrite and polychlorinated biphenyl and related coefficient are in table 7; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 0.59～1.76ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 3.49%～7.50%.Concrete numerical value is in table 7.
Table 7 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (dieldrite concentration is respectively 8.0,20.0,40.0ngL in same water sample, to add respectively three kinds of concentration levels
-1; PCBs concentration is respectively 5.68,14.2,28.4ngL-
1) hybrid standard use liquid, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 8.Recovery of standard addition, between 80.2%～101.1%, is applicable to dieldrite and PCBs analysis in seawater.
The measurement result of table 8 accuracy
Embodiment 5
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 200 μ L methyl alcohol and the drip washing activation successively of 300 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 8.0, with 1.5mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 400 μ L methanol-eluted fractions, it is solvent constant volume that methyl alcohol volatilizes rear use 300 μ L cyclohexane gives, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Hybrid standard uses liquid to be mixed with standard reserving solution taking cyclohexane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with the serial solution of hybrid standard for solvent.Other are with embodiment 1.
(4) result and data:
A. according to obtaining the peak area of dieldrite and PCBs, utilize respectively typical curve regression equation calculation to go out the mass concentration of dieldrite and PCBs in water sample to be analyzed, test result is in table 10.
B. equation of linear regression, related coefficient and detection sensitivity:
In the present embodiment mensuration seawater, the equation of linear regression of dieldrite and polychlorinated biphenyl and related coefficient are in table 9; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 0.45～1.69ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 2.72%～7.91%.Concrete numerical value is in table 9.
Table 9 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (dieldrite concentration is respectively 8.0,20.0,40.0ngL in same water sample, to add respectively three kinds of concentration levels
-1; PCBs concentration is respectively 5.68,14.2,28.4ngL
-1) hybrid standard use liquid, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 10.Recovery of standard addition, between 80.0%～108.7%, is applicable to dieldrite and PCBs analysis in seawater.
The measurement result of table 10 accuracy
Embodiment 6
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 300 μ L methyl alcohol and the drip washing activation successively of 100 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 10.0, with 0.5mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 200 μ L methanol-eluted fractions, methyl alcohol volatilizes rear use 400 μ L isooctane as solvent constant volume, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Hybrid standard uses liquid to be mixed with standard reserving solution taking isooctane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with the serial solution of hybrid standard for solvent.Other are with embodiment 1.
(4) result and data:
A. according to obtaining the peak area of dieldrite and PCBs, utilize respectively typical curve regression equation calculation to go out the mass concentration of dieldrite and PCBs in water sample to be analyzed, test result is in table 12.
B. equation of linear regression, related coefficient and detection sensitivity:
In the present embodiment mensuration seawater, the equation of linear regression of dieldrite and polychlorinated biphenyl and related coefficient are in table 11; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 1.05～2.04ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 3.49%～5.50%.Concrete numerical value is in table 11.
Table 11 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (dieldrite concentration is respectively 8.0,20.0,40.0ngL in same water sample, to add respectively three kinds of concentration levels
-1; PCBs concentration is respectively 5.68,14.2,28.4ngL
-1) hybrid standard use liquid, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 12.Recovery of standard addition, between 81.1%～127.7%, is applicable to dieldrite and PCBs analysis in seawater.
The measurement result of table 12 accuracy
Embodiment 7
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 100 μ L methyl alcohol and the drip washing activation successively of 200 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 6.0, with 0.5mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 200 μ L methanol-eluted fractions, methyl alcohol volatilizes rear use 100 μ L normal hexanes as solvent constant volume, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Standard solution is mixed with standard reserving solution taking normal hexane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with standard serial solution as solvent.Standard solution concentration: dieldrite 20.0 μ gL
-1.Get respectively standard solution 0.0,0.02,0.05,0.10,0.20,0.50mL is placed in 6 10mL volumetric flasks, density of scawater (salinity 30) constant volume.Dieldrite concentration is respectively 0.0,8.0,20.0,40.0,80.0,200.0ngL
-1.
According to the pre-treating method in water sample preparation, standard serial solution is carried out after separation and concentration, and with water sample under identical condition by gas Chromatographic Determination, taking its mass concentration as horizontal ordinate, peak area is as ordinate drawing standard curve, obtains typical curve regression equation.
(4) result and data:
A. according to the peak area that obtains dieldrite, utilize typical curve regression equation calculation to go out the mass concentration of dieldrite in water sample to be analyzed, test result is in table 14.
B. equation of linear regression, related coefficient and detection sensitivity:
In the present embodiment mensuration seawater, the equation of linear regression of dieldrite and related coefficient are in table 13; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 1.26ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 3.04%.Concrete numerical value is in table 13.
Table 13 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (dieldrite concentration is respectively 8.0,20.0,40.0ngL in same water sample, to add respectively three kinds of concentration levels
-1) standard solution, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 14.Recovery of standard addition, between 92.1%～110.1%, is applicable to dieldrite analysis in seawater.
The measurement result of table 14 accuracy
Embodiment 8
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 500 μ L methyl alcohol and the drip washing activation successively of 200 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 2.0, with 2.0mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 500 μ L ethanol elution, it is solvent constant volume that ethanol volatilizes rear use 200 μ L cyclohexane gives, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Standard solution is mixed with standard reserving solution taking cyclohexane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with standard serial solution as solvent.Other are with embodiment 7.
(4) result and data:
A. according to the peak area that obtains dieldrite, utilize typical curve regression equation calculation to go out the mass concentration of dieldrite in water sample to be analyzed, test result is in table 16.
B. equation of linear regression, related coefficient and detection sensitivity:
In the present embodiment mensuration seawater, the equation of linear regression of dieldrite and related coefficient are in table 15; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 1.48ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 2.97%.Concrete numerical value is in table 15.
Table 15 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (dieldrite concentration is respectively 8.0,20.0,40.0ngL in same water sample, to add respectively three kinds of concentration levels
-1) standard solution, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 16.Recovery of standard addition, between 90.0%～112.8%, is applicable to dieldrite analysis in seawater.
The measurement result of table 16 accuracy
Embodiment 9
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 100 μ L methyl alcohol and the drip washing activation successively of 200 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 6.0, with 0.5mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 200 μ L methanol-eluted fractions, methyl alcohol volatilizes rear use 100 μ L normal hexanes as solvent constant volume, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Hybrid standard uses liquid to be mixed with standard reserving solution taking normal hexane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with the serial solution of hybrid standard for solvent.Hybrid standard uses liquid concentration: PCBs is 14.2 μ gL
-1.Getting respectively hybrid standard uses liquid 0.0,0.02,0.05,0.10,0.20,0.50mL to be placed in 6 10mL volumetric flasks, density of scawater (salinity 30) constant volume.PCBs concentration is respectively 0.0,5.68,14.2,28.4,56.8,142.0ngL
-1.
According to the pre-treating method in water sample preparation, standard serial solution is carried out after separation and concentration, and with water sample under identical condition by gas Chromatographic Determination, taking its mass concentration as horizontal ordinate, peak area is as ordinate drawing standard curve, obtains typical curve regression equation.
(4) result and data:
A. according to the peak area that obtains PCBs, utilize respectively typical curve regression equation calculation to go out the mass concentration of PCBs in water sample to be analyzed, test result is in table 18.
B. equation of linear regression, related coefficient and detection sensitivity:
The equation of linear regression of the present embodiment mensuration Polychlorinated Biphenyls In Sea Water and related coefficient are in table 17; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 0.90～1.80ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 1.40%～3.89%.Concrete numerical value is in table 17.
Table 17 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (PCBs concentration is respectively 5.68,14.2,28.4ngL in same water sample, to add respectively three kinds of concentration levels
-1) hybrid standard use liquid, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 18.Recovery of standard addition, between 90.2%～109.4%, is applicable to phosphorus CBs and analyzes.
The measurement result of table 18 accuracy
Embodiment 10
(1) water sample preparation:
Pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with 100 μ L methyl alcohol and the drip washing activation successively of 500 μ L ultrapure waters;
Get 50mL water sample, regulate after its pH value to 12.0, with 1.0mLmin
-1flow velocity repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and its vacuum is drained;
The above-mentioned extraction column of 500 μ L ethanol elution, it is solvent constant volume that ethanol volatilizes rear use 200 μ L cyclohexane gives, treats gas chromatographic analysis.
(2) gas chromatography arranges condition with embodiment 1.
(3) preparation of standard serial solution and mensuration:
Hybrid standard uses liquid to be mixed with standard reserving solution taking cyclohexane as solvent, taking standard reserving solution as solute, density of scawater (salinity 30) is mixed with the serial solution of hybrid standard for solvent.Other are with embodiment 9.
(4) result and data:
A. according to the peak area that obtains PCBs, utilize respectively typical curve regression equation calculation to go out the mass concentration of PCBs in water sample to be analyzed, test result is in table 20.
B. equation of linear regression, related coefficient and detection sensitivity:
The equation of linear regression of the present embodiment mensuration Polychlorinated Biphenyls In Sea Water and related coefficient are in table 19; Measure blank solution 11 times, obtain average signal-to-noise ratio, calculate it according to signal to noise ratio (S/N ratio) S/N=3 and detect and be limited to 1.12～1.80ngL
-1; The relative standard deviation (RSD) of measuring parallel water sample 7 times is 1.80%～3.73%.Concrete numerical value is in table 19.
Table 19 equation of linear regression, related coefficient and detection sensitivity
C. the accuracy of detection method:
The mode that the present embodiment adopts mark-on to reclaim has been verified the accuracy detecting, and (PCBs concentration is respectively 5.68,14.2,28.4ngL in same water sample, to add respectively three kinds of concentration levels
-1) hybrid standard use liquid, each sample replicate determination 6 times, calculates the average recovery of standard addition under three kinds of concentration levels, the results are shown in Table 20.Recovery of standard addition, between 82.2%～127.0%, is applicable to phosphorus CBs and analyzes.
The measurement result of table 20 accuracy
Although above the preferred embodiments of the present invention are described; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing from the scope situation that aim of the present invention and claim protect, can also make the concrete conversion of a lot of forms, within these all belong to protection scope of the present invention.
Claims (6)
1. a method for concentration and separation sea underwater trace persistence organic pollutant, is characterized in that, described persistence organic pollutant is dieldrite and polychlorinated biphenyl, and the method is carried out according to following steps:
(1) pipe/polyhenylethylene nano fiber solid-phase extraction column is placed in to solid-phase extraction device, respectively with methyl alcohol and ultrapure water drip washing activation successively;
(2) regulate water sample pH value to 6.0;
(3) by water sample with 0.5～2mLmin
-1constant flow rate repeat by pipe/polyhenylethylene nano fiber solid-phase extraction column 2 times, and described pipe/polyhenylethylene nano fiber solid-phase extraction column vacuum is drained;
(4) pipe/polyhenylethylene nano fiber solid-phase extraction column described in eluant, eluent wash-out, the consumption of described eluant, eluent is 100～500 μ L;
(5) volatilize described eluant, eluent constant volume, in order to gas chromatographic analysis, the solvent load of described constant volume is 100～500 μ L; The solvent of described constant volume is selected from normal hexane, cyclohexane or isooctane one wherein.
2. the method for a kind of concentration and separation according to claim 1 sea underwater trace persistence organic pollutant, is characterized in that, described in step (1), the consumption of methyl alcohol and described ultrapure water is 100～500 μ L.
3. the method for a kind of concentration and separation according to claim 1 sea underwater trace persistence organic pollutant, is characterized in that, the water sample flow velocity in step (3) is 0.5mLmin
-1.
4. the method for a kind of concentration and separation according to claim 1 sea underwater trace persistence organic pollutant, is characterized in that, the described eluant, eluent in step (4) is selected from methyl alcohol, ethanol, isopropyl alcohol or butanols one wherein.
5. the method for a kind of concentration and separation according to claim 1 sea underwater trace persistence organic pollutant, is characterized in that, the consumption of the described eluant, eluent in step (4) is 200 μ L.
6. the method for a kind of concentration and separation according to claim 1 sea underwater trace persistence organic pollutant, is characterized in that, the solvent load of constant volume described in step (5) is 100 μ L.
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