CN103616458A - Method for quantitatively detecting six kinds of nitrobenzene compounds in fine atmospheric particles PM2.5 - Google Patents
Method for quantitatively detecting six kinds of nitrobenzene compounds in fine atmospheric particles PM2.5 Download PDFInfo
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Abstract
The invention provides a method for quantitatively detecting six kinds of nitrobenzene compounds in fine atmospheric particles PM2.5. The method comprises the following steps: acquiring a sample, extracting the sample, concentrating and purifying the sample and quantitatively detecting by adopting chromatography-tandem mass spectrometry. By optimizing parameters of secondary mass spectrometry conditions, the method is better in selectivity and higher in sensitivity on target compounds in comparison with an existing detection method reported in literature. According to the method, the disadvantage that the selectivity and the sensitivity of a conventional detector in the process of detecting the trace quantity of nitrobenzene compounds in a complex background matrix cannot be ensured at the same time is overcome by virtue of a gas chromatography/tandem mass spectrometry selective reaction monitoring technology, and the qualitative operation is accurate and reliable, so that the method has very remarkable advantages in comparison with conventional GC/ECDs (gas chromatography/election capture detectors), GC/NPDs (gas chromatography/nitrogen-phosphorus detector), GC/LRMS (gas chromatography/low resolution mass spectrometry) detectors or GC/HRMS (gas chromatography/high resolution mass spectrometry) detectors.
Description
Technical field
The present invention relates to a kind of Quantitative Monitoring method for nitrobenzene compounds in Fine Particles PM2.5, be particularly related to the method for 6 kinds of nitrobenzene compounds in a kind of quantitative detection Fine Particles PM2.5, specifically, to use gas chromatography separation, plural serial stage mass spectrum (tandem mass) to select monitoring (selected reaction monitoring, SRM) quantitative measurement technology 6 kinds of nitrobenzene compounds in Atmospheric particulates PM2.5 sample to be carried out to a kind of method of Quantitative detection.
Background technology
Nitrobenzene compounds is the general name of nitro-aromatic compounds of group, is that dyestuff is synthetic, the intermediate of paint, plastics, explosive, medicine and agricultural chemicals manufacture etc.Nitrobenzene class pollutant in environment mainly comprises the materials such as nitrobenzene, nitro-chlorobenzene, nitrotoluene, nitrophenol, nitroaniline.
Most of nitrobenzene compounds has the feature of stable chemical nature, high toxicity and biological concentration, belongs to high toxicity pollutant, is put in the screen priority pollutants list of American National Environmental Protection Administration (EPA) and China.This compounds can cause human body poisoning through respiratory tract, alimentary canal and skin, and Main Function, in blood, liver and central nervous system, can make haemoglobin become methemoglobin, loses the ability of transportation oxygen, causes anoxic.Nitrobenzene belongs to lasting toxicity organic contaminant, there is the sudden change of causing, cause cancer, lead deforming health risk, in industries such as printing and dyeing, agricultural chemicals as intermediate; Dinitro benzene when concentration reaches 10mg/L in water body, can cause fish and hydrobiological death, inflammable, explosive, has severe toxicity, has carcinogenicity.
It is one of current environmental problem meriting attention most of China that Fine Particles PM2.5 pollutes.Atmosphere polluting problem is directly connected to population health, and the harm bringing than water, soil pollution is more direct and have a chronicity risk.But every basic work of China's prevention and control of air pollution is made slow progress, environmental supervision and administration system is unsound, weak for the monitoring capability of the various high risk pollutants in Atmospheric particulates, and the relevant Study on Monitoring Technology of therefore carrying out nitrobenzene toxic organics in Atmospheric particulates is significant to assessment China atmospheric environmental security risk.
The domestic quantitative detecting method of not yet promulgating nitrobenzene compounds in relevant Atmospheric particulates PM2.5, has only issued the standard method of nitrobenzene compounds in water environment at present.As the mensuration vapor-phase chromatography > > (GB13194-91) of the < < water quality nitrobenzene in existing method standard, nitrotoluene, nitro-chlorobenzene, dinitrotoluene (DNT); The mensuration vapor-phase chromatography > > (HJ592-2010) of < < water quality nitrobenzene compounds; Mensuration resin adsorption/vapor-phase chromatography > > (SL/T273.1-2001) of Analysis of Organic Substances method Trace Nitrobenzene compounds in the industry standard < < of Ministry of Water Resources water; And the method for stipulating in mensuration liquid-liquid extraction/organophosphorous pesticides method > > (HJ648-2013) of the standard method < < water quality nitrobenzene compounds of issue in up-to-date 2013.
External relevant monitoring standard aspect, mainly contain the correlation technique of Environmental Protection Agency's issue, method has adopted based on single-stage mass spectrum (mass spectrum, MS) and electron capture detector (Electron Capture Detector, ECD) technical method detecting, as used GC/MS for measuring solid waste in the EPA8270C method of Environmental Protection Agency's issue, soil, gas, the detection of water sample, detect object and comprised dinitro benzene, 2, 4-dinitrotoluene (DNT) and 2, the mensuration of 6-dinitrotoluene (DNT), use dichloromethane extraction, DB-5MS capillary column and gas chromatography/mass spectrometry detect.In the EPA8091 method of Environmental Protection Agency, measure nitrobenzene and cyclic ketones compounds in water, useless water and soil, wherein nitrobenzene compounds kind is more, comprise nitrobenzene, nitrotoluene, nitro-chlorobenzene, dinitrotoluene (DNT), dichloronitrobenzene, trichloronitrobenzene, tecnazene, nitrobenzene n-hexane extraction in water, use DB-5 and 1701 capillary column separations, used gas phase ECD detecting device to detect.Study on determination method report about Detection of aromatic nitrocompounds in air is as follows:
In < < occupational medicine > > the 2nd phase 38-40 pages in 1997, introduced a kind of method of using nitrobenzene in oscillopolarographic detection air, this law detects down and is limited to 0.05 μ g/10ml.In < < Guangzhou chemistry > > the 2nd phase 23-26 pages in 2003, introduced a kind of employing wide bore capillary column separated, the quantitative analysis method of using nitrogen phosphorous detector (NPD) to set up water and benzene in air amine and nitrobenzene, the range of linearity 0～80 μ g/L, detects lower limit 1 μ g/L.Within 2007, in < < chemical analysis metering > > the 5th phase 51-52 page, introduced the method for Trace Nitrobenzene in a kind of Tenax of utilization enrichment-gas chromatograph for determination surrounding air, the main airborne Trace Nitrobenzene of Tenax sampling pipe absorption environment that uses, nitrobenzene with 1.0mL sherwood oil drip washing Dissociative adsorption, with gas chromatography-electron capture detector, detect, linearly dependent coefficient is 0.9992, average recovery rate is that 95.9%～97.1%, RSD is not more than 5.2% (n=5).By sampling, 10L calculates, and detects and is limited to 0.0002mg/m3.In < < occupational health in 2007 and emergency management and rescue > > the 5th phase 274-275 page, introduced a kind of method of using nitrobenzene in determined by ultraviolet spectrophotometry air, in air, nitrobenzene gathers with ethanol, in the acid solution of sulfur acid copper, the nascent hydrogen being produced by zinc powder reaction, nitrobenzene reduction is become to aniline, after diazotising, in the solution that is 1.5～2.0 in pH value, generate purple compound with hydrochloride naphthodiamide coupling, , under 560nm wavelength, with pure water reference, carry out the measurement of absorbance.
In sum, at present the domestic mensuration about nitrobenzene compounds in atmosphere is mainly for some gaseous contaminants, and the assay method of the nitrobenzene compounds at present more concerned Atmospheric particulates PM2.5 be there is not yet to report.
Summary of the invention
1. the technical matters that invention will solve:
For nitrobenzene compounds in current Atmospheric particulates environmental sample, exist background matrix to disturb, pre-treatment purifying step is complicated, easily produce the problems such as false positive, the invention provides the method for 6 kinds of nitrobenzene compounds in a kind of quantitative detection Fine Particles PM2.5, set up and optimized second order ms (MS/MS) detection method of 6 kinds of nitrobenzene compounds, method after optimization has the sensitivity of better selectivity and Geng Gao compared with conventional sense method, this kind of second order ms detection technique advantage on compound is qualitative, can meet the demand that gets final product 6 kinds of nitrobenzene compounds in Quantitative detection ambient atmosphere aerosol sample without complicated pre-treatment, greatly save analysis time and analysis cost.
2. technical scheme:
Principle of the present invention: tandem mass spectrum is used two level Four mass analyzers (quadrupole mass analyzer) to be used as quantitative, the qualitative analysis tool of unknown compound by the mode of tandem-in-space, after compound molecule is through ionization ionization, voltage acceleration electronics by 70eV obtains stable ion current, and the ionization potential of organic compound molecule is generally all at 7-15eV, therefore considerable molion M+(is even whole) all can chipping generation fragmention.And tandem mass spectrometry can bombard by secondary electron, obtain further confirming fragment ion, by changing exciting voltage (Excitation Voltage, EV) one-level parent ion is further cracked into different fragment ion (daughter ion), the cracking mode of parent ion is relevant to the chemical constitution of target compound, the qualitative foundation of Here it is compound; Finally by second level mass detector, detect the response signal of daughter ion, thereby complete the quantitative test to compound.The detection technique that a certain specific ion of this selection is carried out multi-stage ms reaction is referred to as to select reaction monitoring (selected reaction monitoring, SRM) technology.
Technical scheme of the present invention is as follows:
In quantitative detection Fine Particles PM2.5, a method for 6 kinds of nitrobenzene compounds, the steps include:
(A) target compound is selected 6 kinds of nitrobenzene compounds;
(B) sample collection: flow or mass flow atmospheric sampling thief in use, use inorganic glass fiber filter membrane or quartz fibre filter membrane to gather Atmospheric particulates PM2.5 sample;
(C) sample extraction: after using stainless steel scissors to shred in the PM2.5 sample collecting, utilize extraction solvent, use the continuous extracting of Soxhlet extraction equipment for fat, extraction time is 8～24 hours;
(D) sample concentration: the extract obtaining after sample extraction is concentrated into 0.5～1.0mL, blows near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 ℃;
(E) instrumental analysis condition:
Instrument chromatographic condition: chromatographic column can be selected medium or low pole chromatographic column, injector temperature is at 230 ℃～280 ℃, and transmission line temperature is at 250 ℃～300 ℃;
Mass spectrum condition: ionization mode is the ionization of EI source, and ionization voltage is 40～70eV, and ion source temperature is at 200～280 ℃.
Second order ms condition: the foundation of quantitative and qualitative method: in above chromatogram, under mass spectrum condition, obtain one-level mass spectrogram, select 1 characteristic ion that its abundance is the highest as parent ion (being designated as Q1), EV voltage parameter selects 15v as initial EV voltage, under certain resonance voltage, according to the architectural characteristic of functional group, to be further cracked into different fragmentions be daughter ion to parent ion, from daughter ion spectrogram, screen again 1-2 stable cleaved fragment ion and (be designated as Q2 as daughter ion, Q3), with mother, daughter ion is to as qualitative foundation, using the peak area of daughter ion as its quantitative basis.After obtaining the parent ion and corresponding daughter ion of this target compound, take 5V as interval from EV voltage parameter is set between 5～40v, and the peak area that comparison object compound obtains under parameters is big or small, therefrom select EV magnitude of voltage that response peak area is the highest as the foundation of best approach sensitivity, find the method for optimum voltage, in this electric reduction method, could have a best sensitivity response to target compound.
In step (A), target compound is selected 6 kinds of nitrobenzene compounds, and described target compound is: nitrobenzene, o-dinitrobenzene, meta-dinitro-benzent, paradinitrobenzene, 2,4-dinitrotoluene (DNT), TNT.
In can using in above-mentioned steps (A), flow air sampler gathers aerosol sample, and the sampling time is no more than 24h, and sampling flow is 0.1～0.3m
3/ min, gathers volume of air at 144～432m
3; Also can use the air sampler of cutting apart with particle diameter to gather atmospheric aerosol samples, sampling flow is 0.8～1.2m
3/ min, acquisition time is no more than 12h, and collection volume of air is 576～792m
3.
Step B) the hybrid extraction dicyandiamide solution in is: n-hexane/acetone mixed extractant solvent system, with 50/50 volume ratio, mix respectively, and extraction time is 8-24 hour.
Step (E) middle polarity chromatographic column is the HP-5 of Agilent company, HP-5MS, DB-5 or DB-5MS capillary column
Step (E) second order ms condition: 6 kinds of target compounds are nitrobenzene, o-dinitrobenzene, meta-dinitro-benzent, paradinitrobenzene, 2,4-dinitrotoluene (DNT), 2,4, the parent ion range of choice of 6-trinitro-toluene is: 50～150m/z, 50～300m/z, 50～300m/z, 50～300m/z, 50～300m/z, 50～350m/z, the daughter ion mass range of respective compound is: 30～80m/z, 50～170m/z, 50～170m/z, 50～170m/z, 50～170m/z, 50～220m/z, resonance voltage EV scope 5～40V.
In above step, related scope is all can the actual scope of implementing, and according to experiment condition, we can select in above scope.
3. beneficial effect:
(1) compare the recording camera that uses in detection method in method in the past, nitrogen phosphorous detector, electron capture detector, spectrophotometer etc., these detecting devices have certain matter selective, but for polluting the sample that background is complicated, interfering material is many, often cannot realize accurately quantitatively, this mensuration that is about tens of trace organic components to the air particle of every cube of hundreds of microgram for content is cannot meet its quantitative requirement far away.
(2) along with the fast development of Modern Instrument Analytical Technique, mass spectrum is as the detecting device of organic analysis, aspect qualitative, have advantages of that other gas chromatography detectors are incomparable, especially two-stage tandem mass spectrum detection has more larger advantage aspect compound qualitative.The present invention has developed a kind of for the nitrobenzene compounds under complicated environmental condition in Atmospheric particulates, can realize collection, Rapid Extraction rapidly and efficiently, possess the more assay method of high selectivity and sensitivity.
(3) monitoring that at present China is used gas chromatography/tandem mass spectrum method about nitrobenzene compounds in Atmospheric particulates in the relevant monitoring technology of China also in blank.
The invention provides the method that gas chromatography-tandem mass spectrometry quantitatively detects 6 kinds of nitrobenzene compounds in Atmospheric particulates PM2.5, nitrobenzene compounds for trace in Atmospheric particulates PM2.5 quantitatively detects accurately, be characterized in utilizing the selection reaction monitoring technology (SRM) of gas chromatography/tandem mass spectrum (GC-MS/MS) to solve conventional detecting device as ECD, NPD, the selectivity of spectrophotometer trace target components in detection of complex background matrix, the drawback existing in sensitivity, utilize the background decrease of noise functions of second order ms greatly to simplify sample pretreatment step, improved the qualitative accuracy of sample, this patent also the detection sensitivity by the optimization of second order ms condition further being improved to method with meet for trace level nitrobenzene compounds quantitatively.Because SRM technology can have sensitivity and advantage optionally concurrently, qualitative results accurately and reliably, detects and has very significantly advantage with respect to traditional gas chromatography GC/ECD/NPD, single level Four bar mass spectrum (LRMS), high resolution mass spectrum (HRMS).
Experiment shows: the GC-MS/MS detection method after optimizing is 0.003～0.015pg to the instrument detectability of 6 kinds of nitrobenzene compounds nitrobenzene compounds (3 times of signal to noise ratio (S/N ratio)s), quantitatively detect and be limited to 0.009～0.05pg, 5 typical curve related coefficient (R
2) between 0.9989-0.9999,6 kinds of target compounds recovery of standard addition be 88.5%～105.1%, can meet the requirement of quantitative test.
Accompanying drawing explanation
Fig. 1 is nitrobenzene daughter ion response curve of (EV) under different exciting voltages.
Fig. 2 is o-dinitrobenzene daughter ion response curve of (EV) under different exciting voltages.
Fig. 3 is meta-dinitro-benzent daughter ion response curve of (EV) under different exciting voltages.
Fig. 4 is paradinitrobenzene daughter ion response curve of (EV) under different exciting voltages.
Fig. 5 is 2,4-dinitrotoluene (DNT) at the daughter ion response curve of (EV) under different exciting voltages.
Fig. 6 is TNT daughter ion response curve of (EV) under different exciting voltages.
Embodiment
Further illustrate by reference to the accompanying drawings by the following examples the present invention.Protection scope of the present invention is not restricted to the present embodiment.
Embodiment 1:
(A) target compound is selected nitrobenzene compound;
(B) sample collection: use glass fiber filter or quartz fibre filter membrane as Enrichment filter membrane, use the air sampler of cutting apart with particle diameter to gather atmospheric aerosol samples, sampling flow is 0.8～1.2m
3/ min, acquisition time is no more than 12h, and collection volume of air is 576～792m
3;
(C) sample extraction: after the filter membrane that gathers aerosol sample is shredded, utilize extraction solvent, use the continuous extracting of Soxhlet extraction equipment for fat, extraction time is 12 hours, and extraction solvent is normal hexane and the acetone solution that 1:1 is mixed into by volume;
(D) sample concentration: the extract after sample extraction is concentrated into 1mL, blows near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 ℃;
(E) testing sample is used chromatogram-detect from tandem mass spectrum,
Chromatographic column is selected DB-5MS chromatographic column, and injector temperature is at 250 ℃, and transmission line temperature is at 280 ℃; Mass spectrum condition: ionization mode is the ionization of EI source, and ionization voltage is 70eV, and ion source temperature is at 250 ℃;
Second order ms condition: the second order ms condition of target compound comprises choosing of parent ion, daughter ion and exciting voltage EV value,
Under above chromatogram, mass spectrum condition, obtain under one-level mass-spectrogram condition, select 1～2 characteristic ion that abundance is the highest as parent ion, EV voltage parameter selects 15v as initial EV voltage, it is daughter ion that parent ion is further cracked into different fragmentions with this understanding, can obtain corresponding second order ms spectrogram, selects 2 the highest daughter ions of abundance, in Table 2, obtain after the parent ion and daughter ion of this target compound, it is 5V that EV voltage parameter is set, and adds up corresponding peak area response.Repeat above step, parent ion, daughter ion are constant, and EV voltage is set as to 10V, 15V, 20V, 25V, 30V, 35V, 40V successively.And add up corresponding peak area.The peak area response difference obtaining under each parameter by comparison object compound, the parameter that while selecting peak area response the highest, corresponding EV parameter value can be optimized.Refer to Fig. 1.
Embodiment 2:
(A) target compound is selected o-dinitrobenzene compound, 6 kinds of nitrobenzene standard solutions that compound concentration is 1000ug/mL, as shown in Figure 2;
(B) sample collection: use glass fiber filter or quartz fibre filter membrane as Enrichment filter membrane, use the air sampler of cutting apart with particle diameter to gather atmospheric aerosol samples, sampling flow is 0.8m
3/ min, acquisition time is no more than 12h, and collection volume of air is 576m
3;
(C) sample extraction: after the filter membrane that gathers aerosol sample is shredded, utilize extraction solvent, use the continuous extracting of Soxhlet extraction equipment for fat, extraction time is 8 hours, and extraction solvent is normal hexane and the acetone solution that 1:1 is mixed into by volume;
(D) sample concentration: the extract obtaining after extraction is concentrated into about 1mL, blows near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 ℃;
(E) testing sample is used chromatogram-detect from tandem mass spectrum,
Chromatographic condition:
Chromatographic column is selected DB-5MS chromatographic column, specification is 30m * 0.25mm * 0.25 μ m, and 40 ℃ of temperature programmes (keeping 2min), are warming up to 220 ℃ with 20 ℃/min, with 15 ℃/min, be warming up to 280 ℃ again, finally with 5 ℃/min, be warming up to 300 ℃ (keeping 3min).Injector temperature is at 250 ℃, Splitless injecting samples 1uL.Helium (purity > 99.999%), flow velocity 1.2mL/min (constant current mode), 280 ℃ of transmission line temperature are used in carrier gas.
Mass spectrum condition:
Ionization mode is EI ionization, ionization voltage 70eV, and 250 ℃ of ion source temperatures, mass scanning scope is 50～650m/z.
Second order ms condition: the second order ms condition of target compound comprises parent ion, choosing of daughter ion and exciting voltage EV value, in above chromatogram, under mass spectrum condition, obtain under one-level mass-spectrogram condition, select 1～2 characteristic ion that abundance is the highest as parent ion, EV voltage parameter selects 15v as initial EV voltage, it is daughter ion that parent ion is further cracked into different fragmentions under this voltage conditions, can obtain corresponding second order ms spectrogram, select 2 the highest daughter ions of abundance, in Table 2, obtain after the parent ion and daughter ion of this target compound, it is 5V that EV voltage parameter is set, add up corresponding peak area response.Repeat above step, parent ion, daughter ion are constant, and EV voltage is set as to 10V, 15V, 20V, 25V, 30V, 35V, 40V successively.And add up corresponding peak area.The difference of the peak area response obtaining under each parameter by comparison object compound, the parameter that while selecting peak area response the highest, corresponding EV parameter value can be optimized.Refer to Fig. 2.
Embodiment 3:
(A) target compound is selected meta-dinitro-benzent compound;
(B) sample collection: use glass fiber filter or quartz fibre filter membrane as Enrichment filter membrane, use the air sampler of cutting apart with particle diameter to gather atmospheric aerosol samples, sampling flow is 1.2m
3/ min, acquisition time is no more than 24h, and collection volume of air is 792m
3;
(C) sample extraction: after the filter membrane that gathers aerosol sample is shredded, utilize extraction solvent, use the continuous extracting of Soxhlet extraction equipment for fat, extraction time is 24 hours, and extraction solvent is normal hexane and the methylene chloride solution that 1:1 is mixed into by volume;
(D) sample concentration: the extract obtaining after extraction is concentrated into about 0.5mL, blows near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 ℃;
(E) testing sample is used chromatogram-detect from tandem mass spectrum,
Chromatographic condition: chromatographic column is selected HP-5 chromatographic column, and injector temperature is at 230 ℃, and transmission line temperature is at 250 ℃;
Mass spectrum condition: ionization mode is the ionization of EI source, and ionization voltage is 40eV, and ion source temperature is at 200 ℃, and mass scanning scope is 50～650m/z;
Second order ms condition: the second order ms condition of target compound comprises parent ion, choosing of daughter ion and exciting voltage EV value, in above chromatogram, under mass spectrum condition, obtain under one-level mass-spectrogram condition, select 1～2 characteristic ion that abundance is the highest as parent ion, EV voltage parameter selects 15v as initial EV voltage, it is daughter ion that parent ion is further cracked into different fragmentions under this voltage conditions, can obtain corresponding second order ms spectrogram, select 2 the highest daughter ions of abundance, in Table 2, obtain after the parent ion and daughter ion of this target compound, it is 5V that EV voltage parameter is set, add up corresponding peak area response.Repeat above step, parent ion, daughter ion Information invariability, be set as 10V, 15V, 20V, 25V, 30V, 35V, 40V successively by EV voltage.And add up corresponding peak area.The difference of the peak area response obtaining under each parameter by comparison object compound, the parameter that while selecting peak area response the highest, corresponding EV parameter value can be optimized.Refer to Fig. 3.
Embodiment 4:
(A) with embodiment 2 target compounds, select paradinitrobenzene.
(B) sample collection: use glass fiber filter or quartz fibre filter membrane as Enrichment filter membrane, use the air sampler of cutting apart with particle diameter to gather atmospheric aerosol samples, sampling flow is 1.0m
3/ min, acquisition time is no more than 18h, and collection volume of air is 660m
3;
(C) sample extraction: after the filter membrane that gathers aerosol sample is shredded, utilize extraction solvent, use the continuous extracting of Soxhlet extraction equipment for fat, extraction time is 12 hours, and extraction solvent is normal hexane and the acetone solution that 1:1 is mixed into by volume;
(D) sample concentration: the extract obtaining after extraction is concentrated into about 0.8mL, blows near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 ℃;
(E) testing sample is used chromatogram-detect from tandem mass spectrum,
Chromatographic condition: chromatographic column is selected DB-5MS chromatographic column, and injector temperature is at 250 ℃, and transmission line temperature is at 280 ℃;
Mass spectrum condition: ionization mode is the ionization of EI source, and ionization voltage is 70eV, and ion source temperature is at 250 ℃, and mass scanning scope is 50～650m/z;
Second order ms condition: the second order ms condition of target compound comprises parent ion, choosing of daughter ion and exciting voltage EV value, in above chromatogram, under mass spectrum condition, obtain under one-level mass-spectrogram condition, select 1～2 characteristic ion that abundance is the highest as parent ion, EV voltage parameter selects 15v as initial EV voltage, it is daughter ion that parent ion is further cracked into different fragmentions under this voltage conditions, can obtain corresponding second order ms spectrogram, select 2 the highest daughter ions of abundance, in Table 2, obtain after the parent ion and daughter ion of this target compound, it is 5V that EV voltage parameter is set, add up corresponding peak area response.Repeat above step, parent ion, daughter ion Information invariability, be set as 10V, 15V, 20V, 25V, 30V, 35V, 40V successively by EV voltage.And add up corresponding peak area.The difference of the peak area response obtaining under each parameter by comparison object compound, the parameter that while selecting peak area response the highest, corresponding EV parameter value can be optimized.Refer to Fig. 4.
Embodiment 5:
(A) target compound is selected 2,4-dinitro benzene Toluene compound;
(B) sample collection: use glass fiber filter or quartz fibre filter membrane as Enrichment filter membrane, use the active middle flow air sampler collected specimens with PM2.5 cutting head, sampling time 8h, sampling flow is 0.1m
3/ min, gathers volume of air at 144m
3;
(C) sample extraction: after the filter membrane that gathers aerosol sample is shredded, utilize extraction solvent, use the continuous extracting of Soxhlet extraction equipment for fat, extraction time is 12 hours, and extraction solvent is normal hexane and the acetone solution that 1:1 is mixed into by volume;
(D) sample concentration: the extract obtaining after extraction is concentrated into about 1mL, blows near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 ℃;
(E) testing sample is used chromatogram-detect from tandem mass spectrum,
Chromatographic column is selected HP-5MS chromatographic column, and injector temperature is at 250 ℃, and transmission line temperature is at 280 ℃;
Mass spectrum condition: ionization mode is the ionization of EI source, and ionization voltage is 70eV, and ion source temperature is at 250 ℃, and mass scanning scope is 50～650m/z;
Second order ms condition: the second order ms condition of target compound comprises parent ion, choosing of daughter ion and exciting voltage EV value, in above chromatogram, under mass spectrum condition, obtain under one-level mass-spectrogram condition, select 1～2 characteristic ion that abundance is the highest as parent ion, EV voltage parameter selects 15v as initial EV voltage, it is daughter ion that parent ion is further cracked into different fragmentions under certain voltage conditions, can obtain corresponding second order ms spectrogram, select 2 the highest daughter ions of abundance, in Table 2, obtain after the parent ion and daughter ion of this target compound, it is 5V that EV voltage parameter is set, add up corresponding peak area response.Repeat above step, parent ion, daughter ion Information invariability, be set as 10V, 15V, 20V, 25V, 30V, 35V, 40V successively by EV voltage.And add up corresponding peak area.The difference of the peak area response obtaining under each parameter by comparison object compound, the parameter that while selecting peak area response the highest, corresponding EV parameter value can be optimized.Refer to Fig. 5.
Embodiment 6:
(A) target compound is selected TNT compound;
(B) sample collection: use glass fiber filter or quartz fibre filter membrane as Enrichment filter membrane, use the active middle flow air sampler collected specimens with PM2.5 cutting head, sampling time 24h, sampling flow is 0.3m
3/ min, gathers volume of air at 432m
3;
(C) sample extraction: after the filter membrane that gathers aerosol sample is shredded, utilize extraction solvent, use the continuous extracting of Soxhlet extraction equipment for fat, extraction time is 12 hours, and extraction solvent is normal hexane and the acetone solution that 1:1 is mixed into by volume;
(D) sample concentration: the extract obtaining after extraction is concentrated into about 1mL, blows near doing and use isooctane constant volume with nitrogen, testing sample keeps in Dark Place in the environment of-20 ℃;
(E) testing sample is used chromatogram-detect from tandem mass spectrum,
Chromatographic column is selected DB-5 chromatographic column, and injector temperature is at 250 ℃, and transmission line temperature is at 280 ℃; Mass spectrum condition: ionization mode is the ionization of EI source, and ionization voltage is 70eV, and ion source temperature is at 250 ℃, and mass scanning scope is 50～650m/z;
Second order ms condition: the second order ms condition of target compound comprises choosing of parent ion, daughter ion and exciting voltage EV value,
Under above chromatogram, mass spectrum condition, obtain under one-level mass-spectrogram condition, select 1～2 characteristic ion that abundance is the highest as parent ion, EV voltage parameter selects 15v as initial EV voltage, it is daughter ion that parent ion is further cracked into different fragmentions under certain voltage conditions, can obtain corresponding second order ms spectrogram, select 2 the highest daughter ions of abundance, in Table 2, obtain after the parent ion and daughter ion of this target compound, it is 5V that EV voltage parameter is set, and adds up corresponding peak area response.Repeat above step, parent ion, daughter ion Information invariability, be set as 10V, 15V, 20V, 25V, 30V, 35V, 40V successively by EV voltage.And add up corresponding peak area.The difference of the peak area response obtaining under each parameter by comparison object compound, the parameter that while selecting peak area response the highest, corresponding EV parameter value can be optimized.Refer to Fig. 6.
Table 1,6 kinds of nitrobenzene compounds information
| Sequence number | Chinese | English name | CAS | Molecular weight |
| 1 | Nitrobenzene | Nitrobenzene | 98-95-3 | 123.11 |
| 2 | O-dinitrobenzene | o-Dinitrobenzene | 528-29-0 | 168.11 |
| 3 | Meta-dinitro-benzent | m-Dinitrobenzene | 99-65-0 | 168.11 |
| 4 | Paradinitrobenzene | p-Dinitrobenzene | 100-25-4 | 168.11 |
| 5 | 2,4-dinitrotoluene (DNT) | 2,4-Dinitrotoluene | 121-14-2 | 182.14 |
| 6 | |
2,4,6-trinitro-Toluene | 118-96-7 | 227.13 |
The second order ms parent ion of table 2,6 kinds of nitrobenzene compounds and daughter ion Parameter Conditions
The exciting voltage (EV) of the daughter ion of table 3,6 kinds of nitrobenzene compounds target compounds after optimizing, wherein m/z is proton number/charge number
In sum, by the embodiment of embodiment 1-6, can obtain parent ion, the daughter ion Parameter Conditions (table 1) of the optimization tandem mass spectrum of six kinds of nitrobenzene compounds, the second order ms that obtains is optimized voltage conditions (referring to table 3), and nitrobenzene parent ion m/z is that 77.1 to be cracked into m/z be that the exciting voltage of 50 daughter ion is 25V and to be cracked into m/z be that the exciting voltage of 49 daughter ion is 40V; O-dinitrobenzene parent ion m/z is that 168 to be cracked into m/z be that the exciting voltage of 75 daughter ion is 25V and to be cracked into m/z be that the exciting voltage of 63 daughter ion is 30V; Meta-dinitro-benzent parent ion m/z is that 168 to be cracked into m/z be that the exciting voltage of 75 daughter ion is 30V and to be cracked into m/z be that the exciting voltage of 63 daughter ion is 30V; Paradinitrobenzene parent ion m/z is that 168 to be cracked into m/z be that the exciting voltage of 51 daughter ion is 25V and to be cracked into m/z be that the exciting voltage of 63 daughter ion is 35V; 2,4-dinitrotoluene (DNT) parent ion m/z is that 165 to be cracked into m/z be that the exciting voltage of 63 daughter ion is 25V and to be cracked into m/z be that the exciting voltage of 90 daughter ion is 15V, 2,4,6-trinitro-toluene parent ion m/z is that 210 to be cracked into m/z be that the exciting voltage of 90 daughter ion is 15V and to be cracked into m/z be that the exciting voltage of 117 daughter ion is 15V, has so far set up the method for quantitatively determining that the gas chromatography-tandem mass spectrum for six class nitrobenzene compounds in atmosphere PM2.5 detects.
Claims (7)
1. quantitatively detect a method for 6 kinds of nitrobenzene compounds in Fine Particles PM2.5, the steps include:
(A) target compound is selected 6 kinds of nitrobenzene compounds;
(B) sample collection: use glass fiber filter or quartz fibre filter membrane as Enrichment filter membrane, use the active large flow with PM2.5 cutter or middle traffic sampling device to gather atmospheric sample;
(C) sample extraction: after the filter membrane that gathers aerosol sample is shredded, utilize extraction solvent, use the continuous extracting of Soxhlet extraction equipment for fat, extraction time is 8 ~ 24 hours;
(D) sample concentration: the extract obtaining after sample extraction is concentrated, with nitrogen, blow near doing and use isooctane constant volume, testing sample keeps in Dark Place in the environment of-20 ℃;
(E) testing sample use chromatogram-from tandem mass spectrum detection, chromatographic column is selected medium or low pole chromatographic column, and injector temperature is at 230 ℃～280 ℃, and transmission line temperature is at 250 ℃～300 ℃, mass spectrum condition: ionization mode is the ionization of EI source, and ionization voltage is 40～70eV, and ion source temperature is at 200～280 ℃, second order ms condition: the second order ms condition of target compound comprises parent ion, choosing of daughter ion and exciting voltage EV value, in above chromatogram, under mass spectrum condition, obtain under one-level mass-spectrogram condition, select 1 characteristic ion that abundance is the highest as parent ion, EV voltage parameter selects 15v as initial EV voltage, it is daughter ion that parent ion is further cracked into different fragmentions under this voltage conditions, can obtain corresponding second order ms spectrogram, select 2 the highest isotopic characteristic ions of abundance, obtain after the parent ion and daughter ion of this target compound, the 5V of take arranges EV parameter as interval from 5 ~ 40V, and the difference of the peak area response that relatively target compound of same concentrations obtains under each parameter, corresponding EV parameter value while selecting peak area response the highest: nitrobenzene parent ion m/z is that 77.1 exciting voltages when to be cracked into m/z be 50 daughter ion are 25V, the exciting voltage that is cracked into m/z and is 49 daughter ion is 40V, o-dinitrobenzene parent ion m/z is that 168 to be cracked into m/z be that the exciting voltage of 75 daughter ion is 25V and to be cracked into m/z be that the exciting voltage of 63 daughter ion is 30V, meta-dinitro-benzent parent ion m/z is that 168 to be cracked into m/z be that the exciting voltage of 75 daughter ion is 30V and to be cracked into m/z be that the exciting voltage of 63 daughter ion is 30V, paradinitrobenzene parent ion m/z is that 168 to be cracked into m/z be that the exciting voltage of 51 daughter ion is 25V and to be cracked into m/z be that the exciting voltage of 63 daughter ion is 35V, 2,4-dinitrotoluene (DNT) parent ion m/z is that 165 to be cracked into m/z be that the exciting voltage of 63 daughter ion is 25V and to be cracked into m/z be that the exciting voltage of 90 daughter ion is 15V, 2,4,6-trinitro-toluene parent ion m/z is that 210 to be cracked into m/z be that the exciting voltage of 90 daughter ion is 15V and to be cracked into m/z be that the exciting voltage of 117 daughter ion is 15V.
2. the method for 6 kinds of nitrobenzene compounds in quantitative detection Fine Particles PM2.5 according to claim 1, it is characterized in that, in described step (A), 6 kinds of nitrobenzene compounds are nitrobenzene, o-dinitrobenzene, meta-dinitro-benzent, paradinitrobenzene, 2,4-dinitrotoluene (DNT), 2,4,6-trinitro-toluene.
3. the method for 6 kinds of nitrobenzene compounds in quantitative detection Fine Particles PM2.5 according to claim 2, it is characterized in that, extraction solvent in described step (C) is normal hexane and the acetone solution that 1:1 is mixed into by volume, or normal hexane and the methylene chloride solution that 1:1 is mixed into by volume, or acetone/methylene chloride solution that 1:1 is mixed into is by volume extraction solvent.
4. according to the method for 6 kinds of nitrobenzene compounds in the quantitative detection Fine Particles PM2.5 described in claim 3, it is characterized in that, the middle polarity chromatographic column in described step (E) is HP-5, HP-5MS, DB-5 or DB-5MS capillary column.
5. according to the method for 6 kinds of nitrobenzene compounds in the quantitative detection Fine Particles PM2.5 described in any one in claim 1～4, it is characterized in that, in described step (B), use the active middle flow air sampler collected specimens with PM2.5 cutting head, sampling time is no more than 24h, and sampling flow is 0.1～0.3m
3/ min, gathers volume of air at 144～432 m
3.
6. according to the method for 6 kinds of nitrobenzene compounds in the quantitative detection Fine Particles PM2.5 described in any one in claim 1～4, it is characterized in that, in described step (B), use or use the air sampler of cutting apart with particle diameter to gather atmospheric aerosol samples, sampling flow is 0.8～1.2 m
3/ min, acquisition time is no more than 12h, and gathering volume of air is 576～792 m
3.
7. according to the method for 6 kinds of nitrobenzene compounds in the quantitative detection Fine Particles PM2.5 described in any one in claim 1～4, it is characterized in that, second order ms condition setting in described step (E): nitrobenzene, o-dinitrobenzene, meta-dinitro-benzent, paradinitrobenzene, 2, 4-dinitrotoluene (DNT), 2, 4, the parent ion range of choice of 6-trinitro-toluene is: 50 ~ 150m/z, 50 ~ 300m/z, 50 ~ 300m/z, 50 ~ 300m/z, 50 ~ 300m/z, 50 ~ 350m/z, the daughter ion mass range of respective compound is: 30 ~ 80 m/z, 50 ~ 170 m/z, 50 ~ 170 m/z, 50 ~ 170 m/z, 50 ~ 170 m/z, 50 ~ 220 m/z, resonance voltage EV scope 5～40V.
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