CN101126751B - Gas phase chromatogram- ion trap tandem mass spectrometry method for detecting organochlorine pesticide - Google Patents
Gas phase chromatogram- ion trap tandem mass spectrometry method for detecting organochlorine pesticide Download PDFInfo
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Abstract
The invention provides a method for detecting organochlorine pesticides in the atmosphere by means of gas chromatography-ion trap tandem mass spectrometry , which comprises the following steps: collecting samples, extracting samples, purifying and concentrating samples, and detecting the samples by chromatography-ion trap mass spectrometry. The invention enjoys higher selectivity and sensitivity than the prior detection methods of the target compounds through optimization of gas chromatography and tandem mass spectrometry conditional parameters. The invention adopts the selection response monitoring techniques (SRM) of gas chromatography/ion trap tandem mass spectrometry (GC/ITMS) to remove the disadvantage that the selectivity and sensitivity of trace amount OCPs in complex background matrix of the prior detectors can not be achieved at the same time. The invention has the advantages of low detecting cost, and accurate and reliable positioning, thus presenting very obvious superiority over the traditional detection devices GC/ECD, GC/LRMS and GC/HRMS.
Description
Technical field
The present invention relates to fast quantitative measurement method for detecting to trace level organo-chlorine pesticide in the atmospheric environment, specifically, be a kind of utilization gas phase chromatogram-ion trap mass spectrum (ion trap mass spectrometry, ITMS) (selected reaction monitoring, SRM) technology realizes 21 kinds of organochlorine insecticide target compounds in the atmospheric sample of gas, solid binary states are carried out the method that fast quantification detects in choice reaction monitoring.
Background technology
Organo-chlorine pesticide (Organochlorine Pesticides, OCPs) as human important agricultural insecticide, be a persistence organic pollutant that the class range of application is the widest, service time is the most permanent (Persistent OrganicPollutants, POPs).Before half a century, because scientist finds that this compounds has stable chemical property and be difficult for degraded in environment, and possess to have and fat-solublely can carry out enrichment along food chain and amplify, and be proved significantly " three cause " toxicological effect, environmental ecology and health are had bigger harm.Wherein, drinox (Aldrin), dieldrite (Dieldrin), endrin (Endrin), D.D.T. (dichloro-diphenyl-trichloroethane) (DDT), Niran (Chlordane), toxaphene (Toxaphene), mirex (Mirex) and heptachlor (Heptachlor) are as far back as nineteen ninety-five is promptly listed in 12 kinds of POPs compound lists as excellent control by UNEP (United Nations Environment Program) (UNEP) in.China is agricultural production big country, and it is long historical to use organochlorine insecticide to have, and the agricultural chemicals health risk in the environment is than higher.There are some researches show, since the vaporific sprinkling of agricultural chemicals have surpass 70% agricultural chemicals direct or indirect entered atmospheric environment, therefore significant to the relevant monitoring of carrying out organo-chlorine pesticide in China's environment, especially particularly important for atmospheric environment to the Evaluation Environment risk.But mainly there are following two difficult points in the environmental surveys for organo-chlorine pesticide in the air at present: the one, and adopt which kind of detecting device to detect the organo-chlorine pesticide compound of trace level in the atmospheric environment (ppt even ppt); The 2nd, how to solve other chlorinated compounds such as polychlorinated biphenyl (Polychlorinated Biphenyls, PCBs) problem of disturbing organo-chlorine pesticide to measure in the sample.The GC-ECD detecting device is owing to have exclusive selectivity to the electronegativity compound, therefore chlorinated compound there is better sensitivity, can detect the organo-chlorine pesticide target compound of low trace, but owing to be difficult to avoid existing other chlorinated compound such as polychlorinated biphenyl material (PCBs) in the environmental sample, Method 3620 by EPA (EPA) promulgation, even Method 3630 methods point out to use Fo Luoli tripoli (Florisil), deactivated silica gel adsorbents such as (Silica) adopts the solvent elution of opposed polarity also two compounds can't to be separated fully, and therefore two kinds of compounds are understood the phase mutual interference and finally influenced quantitative accuracy when detecting.Introduce a kind of method of using the alkaline compound silica gel chromatography of multistage acidity in 1258 pages of the volume o. 11ths in " analytical chemistry " November in 1999 the 27th and removed that organo-chlorine pesticide disturbs in the sample, and analyzed the method for the polychlorinated biphenyl target compound in the sample with the GC-ECD detecting device.For solving the ECD detecting device optionally not enough, EPA (EPA) after Method TO-4A method in propose to use GC-LRMS as detecting device, utilize mass spectral ion to select (SIM) thus farthest avoid of the interference of other chlorinatedorganics to organo-chlorine pesticide.Although this method improves a lot on selectivity with respect to the ECD detecting device, but during, background matrix complex environment sample detection extremely low for target compound concentration, the mass resolution ability of LRMS then shows very limited, can't effectively eliminate background interference, cause signal to noise ratio (S/N) to decline to a great extent, so sensitivity usually can't reach requirement to target compound.
In recent years, along with commercially producing of ion trap mass spectrometry, can realize multipole Mass Spectrometer Method with low cost more with respect to the tandem mass spectrum of before " tandem-in-space " mode.The 33rd the 9th phase of volume of " analytical chemistry " September in 2005 1223 pages of analytical approachs of having introduced 7 kinds of indicative PCBs in the use ion trap tandem mass spectrometry analysis food, the PCBs target compound of studying in the literary composition is less, to only CID voltage (being EV voltage) being optimized in the target compound second order ms Study on Conditions, do not consider MEE parameter (maximum resonance energy) is optimized test.The detection of organo-chlorine pesticide and middle PCBs have differently more in addition, do not retrieve the document that the utilization ion trap tandem mass spectrometry detects organo-chlorine pesticide.
Summary of the invention
1. invent the technical matters that will solve:
Exist other chlorinated compound to disturb at organo-chlorine pesticide in the atmospheric environment sample, pre-treatment step takes time and effort, shortcomings such as detection sensitivity is low, the method that the invention provides organo-chlorine pesticide in the gas chromatography one ion trap tandem mass spectrometry detection atmosphere uses gas chromatography one ion trap mass spectrometry (GC/ITMS) to set up and optimized second order ms (MS/MS) detection method of 21 kinds of organo-chlorine pesticides, by to gas chromatography, the optimization of tandem mass spectrum conditional parameter makes this method that the sensitivity of better choice and Geng Gao can be arranged the conventional detection method of target compound, and utilize the advantage of second order ms on compound is qualitative, having realized need not pre-treatment can be fast, accurately detection by quantitative goes out 21 kinds of organo-chlorine pesticides in the atmospheric sample, can save analysis time and analysis cost greatly.
2. technical scheme:
Principle of the present invention:
Ion trap can be stored in the target compound molecule in the ion trap through the ion (parent ion) that will have certain mass-to-charge ratio (m/z) after the ionization, and by collision-induced cracking (Collision Induced Dissociation, CID) act on suitable exciting voltage (Excitation Voltage, EV) make these parent ions further be cracked into different fragment ion (daughter ion) under, the cracking mode of parent ion is relevant with the chemical constitution of target compound, lysis efficiency mainly be subjected to maximum excitation energy in the ion trap (Maximum Excitation Energy, MEE), the influence of exciting voltage (EV).Detect the response signal of daughter ion at last by detecting device, finish quantitative test compound.The detection technique that a certain specific ion of this selection is carried out the multi-stage ms reaction is referred to as choice reaction monitoring (selectedreaction monitoring, SRM) technology.
Technical scheme of the present invention is as follows:
Gas chromatography one ion trap tandem mass spectrometry detects the method for organo-chlorine pesticide in the atmosphere, the steps include:
(A) sample collecting: the gaseous sample for organo-chlorine pesticide class material in the atmosphere uses polyurethane foam as enrichment material, uses active atmosphere PUF sampling thief to gather atmospheric sample; Adopt the quartz fibre filter membrane to come enrichment for Atmospheric particulates organo-chlorine pesticide class material sample, use to have the air sampler collection atmospheric aerosol samples that particle diameter is cut apart;
(B) sample extraction: use Soxhlet fat-extraction device to do the continuous extracting of extraction solvent gaseous sample with n-hexane/acetone; With collection have the quartzy filter membrane of aerosol sample shred the back use Soxhlet fat-extraction device with n-hexane/acetone be the continuous extracting of extraction solvent;
(C) sample concentration: extract is concentrated into 0.5～1mL, blows to the nearly back isooctane constant volume of doing with nitrogen, testing sample needs to keep in Dark Place in-20 ℃ environment;
(D) testing sample uses chromatogram one ion trap mass spectrometry to detect, and chromatographic condition: chromatographic column can be selected the middle polarity chromatographic column, and injector temperature is at 250 ℃～280 ℃; The mass spectrum condition: the ionization mode is the ionization of EI source, and ionization voltage is 40～70eV, and ion source temperature is at 220～250 ℃; The second order ms condition optimizing method: the second order ms condition of target compound mainly comprises parent ion, daughter ion, maximum resonance energy MEE and resonance voltage EV, in above chromatogram, obtain the one-level mass-spectrogram under the mass spectrum condition, select 1 the highest characteristic ion of abundance as parent ion, parent ion is 0.3 to be that further to be cracked into different fragmentions under the 1.5V condition in ion trap be daughter ion with the EV parameter in the MEE parameter of acquiescence, simultaneously can obtain corresponding second order ms spectrogram, from this collection of illustrative plates, select 2 the highest isotopic characteristic ions of abundance, obtain after the parent ion and corresponding daughter ion of this target compound, under different MEE parameters be from 0.5～3.5V the EV parameter to be set at interval with 0.25V, and the difference of the peak area response that under each parameter, obtains of the target compound of same concentrations relatively, the parameter that the parameter value of the MEE of correspondence and EV can be optimized when selecting peak area response the highest.
Organo-chlorine pesticide class material is tetrachloro m-xylene, α-benzene hexachloride, lindane, β-benzene hexachloride, heptachlor, δ-benzene hexachloride, drinox, Heptachlor epoxide, γ-Niran, Niran, dieldrite, p in the above-mentioned steps (A), p '-drip to drip she, endrin, α-5a,6,9,9a-hexahydro-6,9-methano-2,4, p, p '-dichloro-diphenyl-dichlorothane, different Di Shi aldehyde, p, p '-D.D.T. (dichloro-diphenyl-trichloroethane), 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfate, endrin ketone, methoxychlor, ten chlorobenzenes.Volume ratio with n-hexane/acetone 1:1 in the step (B) is an extraction solvent, and extracting is 8～24 hours continuously.The middle polarity chromatographic column is DB-5, DB-5MS or DB-XLB capillary column in the step (D).
Use active atmosphere PUF sampling thief to gather atmospheric sample in the above-mentioned steps (A), the sampling time is no more than 24h, and sampling flow is 0.07～0.28m
3/ min gathers volume of air at 200～1000m
3Use has the air sampler collection atmospheric aerosol samples that particle diameter is cut apart, and sampling flow is 0.28～1.14m
3/ min, acquisition time is no more than 12h, and the collection volume of air is 100～400m
3
Step (D) second order ms condition: organo-chlorine pesticide class material tetrachloro m-xylene, α-benzene hexachloride, lindane, β-benzene hexachloride, heptachlor, δ-benzene hexachloride, drinox, Heptachlor epoxide, γ-Niran, Niran, dieldrite, p, p '-drip her, endrin, α-5a,6,9,9a-hexahydro-6,9-methano-2,4, p, p '-dichloro-diphenyl-dichlorothane, different Di Shi aldehyde, p, p '-D.D.T. (dichloro-diphenyl-trichloroethane), 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfate, endrin ketone, methoxychlor, the parent ion range of choice of ten chlorobenzenes is respectively 135～250m/z, 100～230m/z, 100～230m/z, 100～230m/z, 100～400m/z, 100～230m/z, 100～350m/z, 200～400m/z, 200～400m/z, 100～400m/z, 100～400m/z, 150～350m/z, 100～350m/z, 150～350m/z, 150～300m/z, 100～400m/z, 100～350m/z, 150～450m/z, 150～400m/z, 150～250m/z, 200～550m/z, corresponding daughter ion scope is respectively at 70～200m/z, 60～180m/z, 60～180m/z, 60～180m/z, 90～270m/z, 60～180m/z, 90～260m/z, 120～350m/z, 125～370m/z, 125～370m/z, 90～260m/z, 85～240m/z, 90～260m/z, 65～190m/z, 80～230m/z, 115～340m/z, 80～230m/z, 90～270m/z, 105～315m/z, 75～225m/z, 170～490m/z, maximum resonance energy MEE scope 0.225～0.3, resonance voltage EV scope 0.5～3.5V.
Related scope all is can the actual scope of implementing in the above step, all is the chromatographic column that can select as DB-5, DB-5MS or DB-XLB capillary column, and we can select in above scope according to experiment condition.
3. beneficial effect:
The invention provides the method that gas chromatography one ion trap tandem mass spectrometry detects organo-chlorine pesticide in the atmosphere, at trace organochlorine insecticide class material in the atmospheric environment is carried out fast detecting, be characterized in utilizing the choice reaction monitoring technology (SRM) of gas chromatography/ion trap tandem mass spectrometry (GC/ITMS) to solve the selectivity of detecting device trace OCPs material in the detection of complex background matrix and the drawback that sensitivity can't get both in the past, background decrease of noise functions by second order ms has not only been simplified the sample pretreatment step greatly, improved the qualitative accuracy of sample, and the detection sensitivity that improves method by optimization to the second order ms condition with satisfy for trace level OCPs target compound quantitatively.Because the SRM technology can have sensitivity and advantage optionally concurrently, testing cost is cheap, accurately and reliably qualitative simultaneously, therefore has very remarkable advantages with respect to traditional GC/ECD, GC/LRMS, GC/HRMS detecting instrument.
Experiment shows: through the GC-ITMS/MS detecting device after optimizing the instrument detecting of 21 kinds of organo-chlorine pesticides being limit (3 times of signal to noise ratio (S/N ratio)s) is 0.22～2.50pg, and detection by quantitative is limited to 0.74～8.33pg, 6 typical curve related coefficient (R
2) between 0.9989-0.9999,21 kinds of target compounds recovery of standard addition be 88.5%～110.1%, satisfy to analyze requirement.
Description of drawings
Fig. 1 is tetrachloro m-xylene (TCMX) daughter ion spectrogram;
Fig. 2 is the relative peak area responses of 21 kinds of OCPs objects under different maximum resonance energy (MEE) parameters.
Embodiment
Further specify the present invention by the following examples in conjunction with the accompanying drawings.Protection scope of the present invention is not restricted to present embodiment.
Chromatogram under the embodiment 1:(starting condition, mass spectrum condition)
(1) configuration of standard solution: compound concentration is 21 kinds of OCPs standard solutions (tetrachloro m-xylene, α-benzene hexachloride, lindane, β-benzene hexachloride, heptachlor, δ-benzene hexachloride, drinox, Heptachlor epoxide, γ-Niran, Niran, dieldrite, p of 1000pg/ μ L, p '-drip to drip she, endrin, α-5a,6,9,9a-hexahydro-6,9-methano-2,4, p, p '-dichloro-diphenyl-dichlorothane, different Di Shi aldehyde, p, p '-D.D.T. (dichloro-diphenyl-trichloroethane), 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfate, endrin ketone, methoxychlor, ten chlorobenzenes).
(2) chromatographic condition: chromatographic column adopting DB-XLB chromatographic column, specification are 15mx0.25mmx0.25m.100 ℃ of temperature programmes (keeping 2min) are warming up to 175 ℃ with 7.5 ℃/min, are warming up to 220 ℃ with 2.5 ℃/min again, are warming up to 270 ℃ (keeping 5min) with 25 ℃/min at last.250 ℃ of injector temperatures; Split sampling 1L not.Carrier gas use helium (purity〉99.999%), flow velocity 1.0mL/min (constant current mode).
(3) mass spectrum condition: the ionization mode is EI ionization, ionization voltage 70eV, and 250 ℃ of ion source temperatures, 260 ℃ of transmission line temperature, mass scanning scope are 50～650m/z.
Embodiment 2:(optimizes the second order ms condition: select parent ion, daughter ion)
The concentration of (1) 21 kind of organo-chlorine pesticide standard items, chromatographic condition, mass spectrum condition are with embodiment 1;
(2) second order ms (MS
2) condition: with 21 kinds of OCPs standard items of 1000pg/ μ L concentration at present embodiment
(1) operation obtains corresponding one-level mass spectrum (MS under the chromatogram in, the mass spectrum condition
1) collection of illustrative plates, note the retention time (RT) of each target compound according to target compound at the peak sequence of chromatographic column, select the highest characteristic ion peak [M] of abundance
+As the parent ion in the MS/MS condition, the MEE default parameter value is made as 0.3, and the EV parameter value is made as 1.5V, and selecting 2 fragmentions of abundance maximum in the parent ion cleaved fragment is quota ion as daughter ion.
(3) can draw 21 kinds of daughter ion spectrograms in the OCPs compound by above experimental procedure, the daughter ion spectrogram of tetrachloro m-xylene (TCMX) is seen accompanying drawing 1, determines that finally parent ion, the daughter ion parameter of target compound sees table 1 for details.
The second order ms parameter condition of 21 kinds of OCPs target compounds after table 1 is optimized
Embodiment 3:(optimizes the second order ms condition: the MEE Parameter Optimization)
The concentration of (1) 21 kind of organo-chlorine pesticide standard items, chromatographic condition, mass spectrum condition are with embodiment 1:
(2) second order ms (MS
2) condition: the parent ion of 21 kinds of organo-chlorine pesticide target compounds, the selection of daughter ion are referring to embodiment 2 (2).The parameter value of MEE (maximum resonance energy) is made as 0.225, the parameter area of EV (disassociation voltage) is at interval with 0.25V from 0.25～3.5V, amount to 14 parameters, select 2 daughter ions, can obtain the corresponding peak area of each compound by integration as quota ion;
Embodiment 4:(optimizes the second order ms condition: the MEE Parameter Optimization)
The concentration of (1) 21 kind of organo-chlorine pesticide standard items, chromatographic condition, mass spectrum condition are with embodiment 1;
(2) second order ms (MS
2) condition: the parent ion of 21 kinds of organo-chlorine pesticide target compounds, the selection of daughter ion are referring to embodiment 2 (2).The parameter value of MEE (maximum resonance energy) is made as 0.3, the parameter area of EV (disassociation voltage) is at interval with 0.25V from 0.25～3.5V, amount to 14 parameters, select 2 daughter ions, can obtain the corresponding peak area of each compound by integration as quota ion;
Embodiment 5:(optimizes the second order ms condition: the MEE Parameter Optimization)
The concentration of (1) 21 kind of organo-chlorine pesticide standard items, chromatographic condition, mass spectrum condition are with embodiment 1;
(2) second order ms (MS2) condition: the parent ion of 21 kinds of organo-chlorine pesticide target compounds, the selection of daughter ion are referring to embodiment 2 (2).The parameter value of MEE (maximum resonance energy) is made as 0.45, the parameter area of EV (disassociation voltage) is at interval with 0.25V from 0.25～3.5V, amount to 14 parameters, select 2 daughter ions, can obtain the corresponding peak area of each compound by integration as quota ion;
(3) the maximum peak area of each compound under different MEE parameter conditions can be drawn by comparing embodiment 3～5, the optimum sensitivity of this compound can be obtained in this MEE parameter condition.The best MEE parameter of each target compound that test is determined sees table 1 for details.
Embodiment 6:(optimizes the second order ms condition: the optimization of EV voltage parameter)
The concentration of (1) 21 kind of organo-chlorine pesticide standard items, chromatographic condition, mass spectrum condition are with embodiment 1.
(2) second order ms (MS
2) condition: the parent ion of 21 kinds of organo-chlorine pesticide target compounds, the selection of daughter ion see explanation among the embodiment 2 (2) for details, the MEE parameter of each compound is set to test the optimal value that obtains by embodiment 3～5, is to test at interval the parameter area of EV with 0.25V from 0.5～3.5V, usually select 2 daughter ions peak area to be carried out integration as quota ion, obtain the peak area of 21 groups of OCPs compounds under each EV voltage, the pairing EV voltage of best peak area response is the best EV parameter of target compound.The best EV parameter of 21 kinds of OCPs target compounds that test is determined sees table 1 for details.
Embodiment 7:(optimizes pre-treating method: the optimization of gaseous sample extraction time)
(1) sample extraction.To the OCPs standard items of 3 parts of blank PUF adding 100ng, as extraction solvent difference soxhlet extraction 8h, 16h, 24h (return velocity 4 times/hour), sample number into spectrum is 1 to the apparatus,Soxhlet's of use 1000mL with 600mL n-hexane/acetone (1: 1)
#, 2
#, 3
#
(2) sample concentration.Three duplicate samples extractions finishes the back and uses rotary evaporator to be concentrated into 0.5mL, uses the unhurried current high pure nitrogen instead and blows to the nearly back of doing and be settled to 200 μ L with isooctane, and sample keeps in Dark Place in-20 ℃ environment.Sample adds 4ng's before sample introduction is analyzed
13C-PCB194 is as marking last machine analysis in the sample introduction.
(3) sample detection.Chromatogram, mass spectrum, ion trap second order ms testing conditions are with condition among the embodiment 6.
(4) result shows: 1 of soxhlet extraction asynchronism(-nization)
#, 2
#, 3
#The average recovery of standard addition of sample is respectively 65.6%, 88.1%, 91.71%.This shows that to gaseous state PUF sample, extraction 16h can reach recovery requirement.
Embodiment 8:(optimizes pre-treating method: the optimization of particulate form sample extraction time)
(1) sample extraction.The OCPs standard items that 3 parts of blank quartz fibre filter membranes (quartz fiber filter) added 100ng, shred the apparatus,Soxhlet's that the back adds 500mL with scissors, as extraction solvent difference soxhlet extraction 8h, 16h, 24h (return velocity 4 times/hour), the sample number into spectrum note does 1 with 300mL n-hexane/acetone (1: 1)
#, 2
#, 3
#
(2) sample concentration.Three duplicate samples extractions finishes the back and uses rotary evaporator to be concentrated into 0.5mL, uses the unhurried current high pure nitrogen instead and blows to the nearly back of doing and be settled to 200 μ L with isooctane, and sample keeps in Dark Place in-20 ℃ environment.Sample adds 4ng's before sample introduction is analyzed
13C-PCB194 is as marking last machine analysis in the sample introduction.
(3) sample detection.Chromatogram, mass spectrum, ion trap second order ms testing conditions are with embodiment 6.
(4) result shows: 1
#, 2
#, 3
#The average recovery of standard addition of sample is respectively 89.2%, 87.5%, 92.4%.Therefore, for the particulate form atmospheric sample, extraction 8h can reach recovery requirement.
Embodiment 9:(is applied to pre-treating method, the detection method of optimizing in the actual gaseous state PUF sample detection)
(1) gaseous sample collection.As enrichment material, (flow is 0.14m to use atmosphere PUF sampling thief with PUF (polyurethane foam)
3/ min) the about 200m of continuous acquisition 24h
3Atmospheric sample.
(2) sample extraction.The sample extraction step is with embodiment 7, and the extraction time is 16h.
(3) sample concentration.The sample concentration step is with (2) step among the embodiment 7.
(4) chromatogram of sample/ion trap second order ms testing conditions is with embodiment 9.
(5) verification of OCPs standard solution working curve.The OCPs standard solution configuration concentration that will contain 21 kinds of monomeric compounds is 1,5,10,25,100, the standard solution of 500pg/ μ L, and sample size is 1 μ L,
13The mark addition is 40pg in the C-PCB194 isotope.The ratio of target compound and internal standard compound peak area and the ratio of object and internal standard compound concentration are carried out linear regression analysis, the linearity curve related coefficient (R that obtains
2) between 0.9989-0.9999, satisfy quantitative requirement.
(6) recovery of standard addition experiment.Target compound to 5 parts of blank PUF samples adding 100ng repeats (2)～(5) step in the present embodiment, and the recovery of 21 kinds of OCPs target compounds is 89.1%-105.5%, and relative standard deviation (RSD) is 8.4%-19.3%, satisfies and analyzes requirement.
(7) actual sample detects.The result shows, detects 21 kinds of target compounds in gaseous sample, and the aerial content of all cpds is 1.9～36.0pg/m3, and the mean concentration of total organo-chlorine pesticide is 142.4pg/m3.
Pre-treatment after embodiment 10:(will optimize, detection method are applied in the analysis of real atmosphere aerosol sample)
(1) aerosol sample collection.Is example with the more particle diameter of present research less than the PM2.5 particle of 2.5 μ m, uses quartz fibre filter membrane (quartz fiber filter) as enrichment material, with the active big traffic sampling device collection that has PM2.5 particle diameter cutting head.Sampling flow is 1.12m
3/ min, the collection volume of air is 200m
3
(2) sample extraction.Step is with embodiment 8 (1) steps.
(3) sample concentration.With (2) step among the embodiment 8.
(4) sample detection.Chromatogram/ion trap second order ms testing conditions is with condition among the embodiment 6.
(5) verification of standard solution working curve.The OCPs standard solution configuration concentration that will contain 21 kinds of monomeric compounds is 1,5,10,25,100, the standard solution of 500pg/L, and sample size is 1L,
13The mark addition is 40pg in the C-PCB194 isotope.The ratio of target compound and internal standard compound peak area and the ratio of object and internal standard compound concentration are carried out linear regression analysis, the linearity curve related coefficient (R that obtains
2) between 0.9989-0.9999.
(6) recovery of standard addition experiment.The target compound that 5 parts of blank quartz fibre filter membranes is added 100ng, repeat (2)～(5) step in the present embodiment, the recovery of 21 kinds of OCPs target compounds is 85.3%-95.9%, and relative standard deviation (RSD) is 3.7%-17.2%, satisfies and analyzes requirement.
(7) actual sample detects.The result shows, has also detected 21 kinds of all organo-chlorine pesticides in the PM2.5 aerosol sample, and aerial content distribution is 2.5～95.4pg/m
3, the OCPs total concentration is 242.6pg/m
3
Claims (7)
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| CN101498692B (en) * | 2008-08-18 | 2012-05-02 | 通标标准技术服务（天津）有限公司 | Method for measuring pesticide residue in leather |
| CN102636603B (en) * | 2011-02-12 | 2014-05-07 | 湖北省烟草科研所 | Method for detecting organochlorine pesticide residue in soil |
| CN102520101A (en) * | 2011-12-14 | 2012-06-27 | 广西壮族自治区环境监测中心站 | Pre-treatment and analysis methods of organochlorine pesticides in soil |
| CN102735778A (en) * | 2012-07-09 | 2012-10-17 | 吴桂玲 | Pretreatment method for detecting organochlorine pesticide residue |
| CN113945667A (en) * | 2021-09-09 | 2022-01-18 | 国家粮食和物资储备局科学研究院 | Method for extracting and purifying persistent organic pollutants in grains |
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| CN1563976A (en) * | 2004-03-24 | 2005-01-12 | 南京大学 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
-
2007
- 2007-09-11 CN CN2007101320596A patent/CN101126751B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2069111U (en) * | 1990-04-06 | 1991-01-09 | 沈阳环境科学研究所 | Multi-purpose head for sampling atmosphere pollutant substance |
| DE10042074A1 (en) * | 2000-08-16 | 2002-03-07 | Ufz Leipzighalle Gmbh | Passive collector for extraction of dissolved organic compounds, useful for monitoring pesticides, comprises sorbent body placed inside membrane chamber |
| CN1341855A (en) * | 2001-08-23 | 2002-03-27 | 中国科学院南京土壤研究所 | Determination method of trace organic chlorine pesticide and polychlorobiphenyl residual amount |
| CN1382969A (en) * | 2002-04-09 | 2002-12-04 | 中国科学院生态环境研究中心 | In-situ sampler based on membane extraction technique for pollutants in natural water |
| CN1563976A (en) * | 2004-03-24 | 2005-01-12 | 南京大学 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
Non-Patent Citations (8)
| Title |
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| CN 2069111 U,全文. |
| 刘咸德 |
| 刘文杰 |
| 刘文杰;陈大舟;刘咸德;谢文明;李炳伟;戴天有.被动采样技术在监测大气有机氯污染物中的应用.环境科学研究20 4.2007,20(4),9-14. * |
| 戴天有.被动采样技术在监测大气有机氯污染物中的应用.环境科学研究20 4.2007,20(4),9-14. |
| 李炳伟 |
| 谢文明 |
| 陈大舟 |
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