CN109884002A - One kind measuring atmosphere OH and HO for chemical ionization mass spectrometry2The device and method of free radical - Google Patents
One kind measuring atmosphere OH and HO for chemical ionization mass spectrometry2The device and method of free radical Download PDFInfo
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- CN109884002A CN109884002A CN201711272722.2A CN201711272722A CN109884002A CN 109884002 A CN109884002 A CN 109884002A CN 201711272722 A CN201711272722 A CN 201711272722A CN 109884002 A CN109884002 A CN 109884002A
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Abstract
The invention discloses a kind of atmosphere OH and HO2Free radical On-line Measuring Method specifically realizes atmosphere OH and HO based on highly sensitive chemi-ionization ionization time of flight2Free radical in real time, on-line analysis.Including free radical sampling apparatus, chemical ionization source and time of-flight mass spectrometer, free radical sampling apparatus realizes OH and HO2The sampling of free radical, chemical ionization source and time of-flight mass spectrometer realize OH and HO2The measurement of free radical.Main measuring principle are as follows: pass through suitable SO2Titration, OH and HO2Free radical is completely converted into H2SO4, then use NO3 ‑Ion is by chemi-ionization method H2SO4Ionization is HSO4 ‑Ion, the final NO obtained using measurement3 ‑With HSO4 ‑The intensity of ion is completed to OH and HO2The calculating and analysis of free radical real-time concentration.The instrument and method that the present invention is utilized have the remarkable advantages such as high sensitivity, high stability, quick response, meet the analyses demands such as real-time, the online, dynamic change of atmosphere free radical, have broad application prospects in fields such as environmental monitorings.
Description
Technical field
The present invention relates to atmospheric monitoring fields, especially atmosphere free radical fields of measurement, specifically a kind of based on height
Sensitive chemical ionization time of flight mass spectrometry technology realizes atmosphere OH and HO2Free radical in real time, the device and method of on-line analysis.
Background technique
With the propulsion of industrial process, a large amount of uses of fossil fuel, atmospheric environment is influenced by getting worse.Wherein
OH and HO2Free radical is most active oxidant and catalyst in Atmospheric Chemistry, chemistry can occur with most of components in atmosphere
Reaction.But since the free radical time-to-live is less than 1s, and concentration is extremely low, therefore for OH, HO2Real-time, the online survey of free radical
Amount is always the difficult point in atmospheric monitoring field.
Currently used for atmosphere OH and HO2The measuring technique of free radical includes laser differential absorption spectroscopy techniques, chemi-ionization
(the Chinese invention patent CN 104931471A such as mass-spectrometric technique, gas flaring laser Induced Fluorescence Technology；Chinese invention patent CN
103674911A；Chinese invention patent CN 105300952A；Chinese utility model patent CN 205229049U；Chinese invention is special
Sharp CN 101968473A etc.).
Chemical ionization mass spectrometry technology cardinal principle is: by suitable SO2Titration, OH and HO2Free radical is totally converted
For H2SO4, then use NO3 -Ion is by chemi-ionization method H2SO4Ionization is HSO4 -Ion, it is final that measurement is utilized to obtain
NO3 -With HSO4 -The intensity of ion is completed to OH and HO2The calculating and analysis of free radical real-time concentration.With other measurement means phases
Than chemical ionization mass spectrometry technology has many advantages, such as measuring speed is fast, stability is good, high sensitivity.
This laboratory had developed the chemi-ionization flight time mass spectrum of a continuous measurement Atmospheric OH Radical Using in 2014
Instrument (environmental science, 2014,35 (5): 1688-1693).The present invention on the basis of chemical ionization mass spectrometry, to chemical ionization source and
Measuring system sustained improvement is created for atmosphere OH and HO2The new equipment and method of free radical measurement, realize atmosphere OH and HO2
Free radical measurement pattern is switched fast, and is applied successfully in real atmosphere monitoring.
Summary of the invention
The purpose of the present invention is to provide it is a kind of more rapidly, accurate measurement means, be used for atmosphere OH and HO2Free radical is dynamic
State change procedure in real time, on-line measurement.
In order to achieve the goal above, the technical solution adopted by the present invention are as follows:
Atmosphere OH and HO are measured for chemical ionization mass spectrometry2The device of free radical, including free radical sampling apparatus, be placed in it is close
Chemical ionization source and mass spectrograph in closed chamber room, it is characterised in that:
The free radical sampling apparatus includes drop reaction pipe and atmosphere free radical sample intake passage, for realizing atmosphere freedom
The sampling process of base；Drop reaction Guan Weiyi be horizontally arranged both ends open hollow pipeline, on drop reaction pipe side wall respectively
It is provided with the reaction gas injection port one close to atmosphere free radical sample intake passage, the reaction gas injection port two close to chemical ionization source；
Reaction gas injection port one, reaction gas injection port two are connected with reactant gas source one, reactant gas source two respectively；Atmosphere free radical sample introduction is logical
Road is the hollow pipeline of a both ends open, the left open end of atmosphere free radical sample intake passage and the closed company in the right open end of drop reaction pipe
It connects, the right open end of atmosphere free radical sample intake passage is communicated with ambient air, aperture on the side wall of atmosphere free radical sample intake passage
It is connected by exhaust pipe with aspiration pump, the left open end of drop reaction pipe is connected through chemical ionization source with mass spectrometric injection port；
Atmosphere OH and HO2Free radical is pumped into atmosphere free radical sample intake passage by being evacuated, and in the effect of mass spectrograph pumped vacuum systems
In lower inflow drop reaction pipe；
The drop reaction pipe is for realizing atmosphere OH and HO2The first step of free radical converts；
The chemical ionization source is for realizing atmosphere OH and HO2The second step of free radical converts；；
The mass spectrograph is flight time mass spectrum, and the detection of generated ion is converted for realizing chemical ionization source.
The chemical ionization source successively includes ionization source, 1-3 the middle part plate electrode with through-hole, middle part band from top to bottom
Plate isolation electrode, 2 or more the middle part differential electrodes of the plate electrode with through-hole, middle part with through-hole of through-hole, from top to bottom
Plate electrode, isolation electrode, plate felt pad of the setting middle part with through-hole between differential electrode, plate electrode, isolation electrode,
Middle through-hole coaxial arrangement on differential electrode, felt pad；In ionization source be isolated between electrode be equipped with carrier gas pipe, carrier gas pipe
Outlet towards at plate electrode middle through-hole and with middle through-hole axis perpendicular；
Reagent gas pipe is equipped between isolation electrode and differential electrode, the outlet of reagent gas pipe is towards in plate electrode
Portion through hole and with middle through-hole axis perpendicular；
The left open end of drop reaction pipe is between reagent gas pipe and differential electrode, the left open end of drop reaction pipe
Towards at plate electrode middle through-hole and with middle through-hole axis perpendicular；
Offgas duct is equipped between the left opening and differential electrode of drop reaction pipe, the import of offgas duct is towards plate electrode
At middle through-hole and with middle through-hole axis perpendicular；
Blowback tracheae is equipped between offgas duct and differential electrode, the import of blowback tracheae is towards plate electrode middle through-hole
Locate and with middle through-hole axis perpendicular；
Differential electrode one end far from ionization source is equipped with mass spectrograph；
The cylindrical shape atmosphere free radical sample intake passage and cylindric drop reaction pipe are coaxially disposed.
The atmosphere free radical sample intake passage is the hollow cavity of a transparent both ends open, and cavity material is set as common glass
Glass or quartz glass, it is therefore intended that sunlight can shine directly into atmosphere OH and HO in atmosphere free radical sample intake passage2
Free radical component；
The atmosphere free radical sample intake passage cavity length is set as 100~300mm, and cavity internal diameter is set as 40~
150mm；
The drop reaction pipe is set as the hollow stainless steel cavity of both ends open, and length is 50~400mm, internal diameter setting
For 5~20mm；
The reaction gas injection port one, reaction gas injection port two are located above drop reaction pipe；It is reaction gas injection port one, anti-
Should gas injection port two be connected respectively through valve one, valve two with reactant gas source one, reactant gas source two.
The reagent gas Guan Shangshe flow control valve, flow velocity are adjusted by control valve；
The control valve is mass flowmenter or ball valve or needle-valve；
The ionization source be light source,63Ni radioactive source or discharge source.
The planar electrode of the trapezoidal aperture of shaft section, the setting of side hole diameter are provided with centered on the isolation electrode setting
For 4~8mm, other side hole diameter is set as 1~3mm, and the lesser side of aperture internal diameter is placed far from ionization source, it is therefore intended that
Avoid reagent gas that ionization source is interfered or corroded under the action of blowback air.
The port input distance of the exhaust pipe and drop reaction pipe right end is set as 3~15mm；
The aspiration pump pumping speed is set as 0.5~5L/min.
The chemical ionization source length is set as 30~100mm；
The drop reaction pipe is installed on position among chemical ionization source.
It is set as NO in reactant gas source one, is set as SO in reactant gas source two2；
Pass through valve one, the state switching setting OH and HO of valve two in drop reaction pipe2Two kinds of atmosphere free radical measurements
Mode is switched fast；
The reagent gas is set as HNO3Steam, HNO3Steam carries waving on 1-10 DEG C of nitric acid solution liquid level by carrier gas
Obtained by getting angry, flow rate of carrier gas is set as 0.2~3mL/min by flow control valve；
The Atmospheric OH Radical Using measurement pattern: valve one is in an off state, and valve two is in closed state；
Drop reaction is based on following principle and completes the conversion of the Atmospheric OH Radical Using first step in the drop reaction pipe:
SO2+OH→H2SO4
HNO is set as in reagent gas3Steam, HNO3Steam ionizes under the action of ionization source generates NO3 -, NO3 -With it is big
The H that the gas OH free radical first step converts2SO4The conversion of free radical second step is completed based on following principle:
H2SO4+NO3 -→HNO3+HSO4 -
NO is completed in mass spectrograph3 -With HSO4 -Ion detection, and Atmospheric OH Radical Using concentration is obtained by following formula:
Wherein kOHIt is reaction rate constant, reports that its value is 2.6 × 10 in document-9cm3molecule-1s-1；T is ionization
NO in source3 -Ion and H2SO4The ion molecule reaction time of molecule；[OH] represents the concentration of Atmospheric OH Radical Using；I(HSO4 -) generation
Table mass spectrograph detects to obtain HSO4 -Ion signal intensity；I(NO3 -) represent mass spectrograph and detect to obtain NO3 -Ion signal is strong
Degree；
And/or the atmosphere HO2Free radical measurement pattern: valve one is in closed state, and valve two is in closed form
State；
Drop reaction is based on following principle and completes atmosphere HO in the drop reaction pipe2The conversion of the free radical first step:
NO+HO2→NO2+OH
SO2+OH→H2SO4
HNO is set as in reagent gas3Steam, HNO3Steam ionizes under the action of ionization source generates NO3 -, NO3 -With it is big
Gas HO2The H that the free radical first step converts2SO4The conversion of free radical second step is completed based on following principle:
H2SO4+NO3 -→HNO3+HSO4 -
NO is completed in mass spectrograph3 -With HSO4 -Ion detection, and atmosphere HO is obtained by following formula2Free radical is dense in real time
Degree:
Wherein kOHIt is reaction rate constant, reports that its value is 2.6 × 10 in document-9cm3 molecule-1 s-1；T is electricity
From NO in source3 -Ion and H2SO4The ion molecule reaction time of molecule；[OH] represents the concentration of Atmospheric OH Radical Using；I(HSO4 -)
Mass spectrograph is represented to detect to obtain HSO4 -Ion signal intensity；I(NO3 -) represent mass spectrograph and detect to obtain NO3 -Ion signal is strong
Degree；
The reactant gas source one, two flow velocity of reactant gas source are set as 0.5~200mL/min.
The carrier gas, blowback air are set as dry air, nitrogen, helium or argon gas；
The carrier gas, blowback gas velocity are set as 10~200mL/min.
Atmosphere OH and HO provided by the invention2Free radical in real time, on-line analysis, based on chemical ionization source and when flight
Between mass spectrograph, pass through reaction gas NO and SO2Drop reaction and chemi-ionization method are OH and HO2Free radical is completely converted into can
It is detected after the stabilization molecule of ionization using mass spectrum, then is completed by certain formula to OH and HO2Free radical real-time concentration
It calculates and analyzes.
Detailed description of the invention
Fig. 1 is of the invention for chemical ionization mass spectrometry measurement atmosphere OH and HO2The structure of the device and method of free radical
Schematic diagram.
Fig. 2 is of the invention for chemical ionization mass spectrometry measurement atmosphere OH and HO2It is in the device and method of free radical
Measure the switch state schematic diagram of Atmospheric OH Radical Using mode.
Fig. 3 is of the invention for chemical ionization mass spectrometry measurement atmosphere OH and HO2It is in the device and method of free radical
Measure atmosphere HO2The switch state schematic diagram of free radical mode.
Fig. 4 is on 04 30th, 2017 real-time in the biotechnology Lou Wulou roof of ZhongShan Road, Shahekou District, DaLian City 457
Monitor Atmospheric OH Radical Using concentration trend chart in the daytime.
Specific embodiment
Referring to Fig. 1, being structural schematic diagram of the invention.
Of the invention measures atmosphere OH and HO for chemical ionization mass spectrometry2The device of free radical, including free radical sampling cartridge
The chemical ionization source 2 and mass spectrograph 3 setting 1, being placed in airtight chamber, it is characterised in that:
The free radical sampling apparatus 1 includes drop reaction pipe 4 and atmosphere free radical sample intake passage 5, for realizing atmosphere
The sampling process of free radical；Drop reaction pipe 4 is the hollow pipeline of a horizontal positioned both ends open, in 4 side wall of drop reaction pipe
On be respectively arranged with close to atmosphere free radical sample intake passage 5 reaction gas injection port 1, close to chemical ionization source 2 reaction gas
Injection port 2 10；Reaction gas injection port 1, reaction gas injection port 2 10 respectively with reactant gas source 1,2 12 phase of reactant gas source
Even；Atmosphere free radical sample intake passage 5 is the hollow pipeline of a both ends open, the left open end of atmosphere free radical sample intake passage 5 and drop
Determine the right open end airtight connection of reaction tube 4, the right open end of atmosphere free radical sample intake passage 5 is communicated with ambient air 6, and atmosphere is certainly
It is connected by exhaust pipe 8 with aspiration pump 7 by aperture on the side wall of base sample intake passage 5, the left open end of drop reaction pipe 4 is through chemistry
Ionization source 2 is connected with the injection port of mass spectrograph 3；Atmosphere OH and HO2Free radical is pumped into atmosphere free radical sample intake passage by aspiration pump 7
In 5, and flowed into drop reaction pipe 4 under the action of 3 pumped vacuum systems of mass spectrograph；
The drop reaction pipe 4 is for realizing atmosphere OH and HO2The first step of free radical converts；
The chemical ionization source 2 is for realizing atmosphere OH and HO2The second step of free radical converts；；
The mass spectrograph 3 is flight time mass spectrum, and the detection of generated ion is converted for realizing chemical ionization source 2.
The chemical ionization source 2 successively include from top to bottom ionization source 15, the plate electrode with through-hole in the middle part of 1-3, in
19,2, electrode or more the middle part differential electrodes of the plate electrode with through-hole, middle part with through-hole are isolated in plate of the portion with through-hole, from
Plate electrode under, isolation electrode, plate felt pad of the setting middle part with through-hole between differential electrode, plate electrode, every
From the middle through-hole coaxial arrangement on electrode, differential electrode, felt pad；In ionization source 15 be isolated between electrode 19 be equipped with carrier gas
Pipe 16, the outlet of carrier gas pipe 16 towards at plate electrode middle through-hole and with middle through-hole axis perpendicular；
Reagent gas pipe 20 is equipped between isolation electrode 19 and differential electrode, the outlet of reagent gas pipe 20 is towards plate
At electrode middle through-hole and with middle through-hole axis perpendicular；
Between reagent gas pipe 20 and differential electrode, a left side for drop reaction pipe 4 is opened for the left open end of drop reaction pipe 4
Mouthful end face at plate electrode middle through-hole and with middle through-hole axis perpendicular；
Offgas duct 18 is equipped between the left opening and differential electrode of drop reaction pipe 4, the import of offgas duct 18 is towards plate
At shape electrode middle through-hole and with middle through-hole axis perpendicular；
Blowback tracheae 17 is equipped between offgas duct 18 and differential electrode, the import of blowback tracheae 17 is towards in plate electrode
Portion through hole and with middle through-hole axis perpendicular；
Differential electrode one end far from ionization source 15 is equipped with mass spectrograph 3；
The cylindrical shape atmosphere free radical sample intake passage 5 is coaxially disposed with cylindric drop reaction pipe 4.
The atmosphere free radical sample intake passage 5 is the hollow cavity of a transparent both ends open, and cavity material is set as common
Glass or quartz glass, it is therefore intended that sunlight can shine directly into atmosphere OH in atmosphere free radical sample intake passage 5 and
HO2Free radical component；
5 cavity length of atmosphere free radical sample intake passage is set as 100~300mm, and cavity internal diameter is set as 40~
150mm；
The drop reaction pipe 4 is set as the hollow stainless steel cavity of both ends open, and length is 50~400mm, and internal diameter is set
It is set to 5~20mm；
The reaction gas injection port 1, reaction gas injection port 2 10 are located at 4 top of drop reaction pipe；Reaction gas injection port
One 9, reaction gas injection port 2 10 is connected through valve 1, valve 2 14 with reactant gas source 1, reactant gas source 2 12 respectively.
Flow control valve 21 is set on the reagent gas pipe 20, flow velocity is adjusted by control valve 21；
The control valve 21 is mass flowmenter or ball valve or needle-valve；
The ionization source 15 be light source,63Ni radioactive source or discharge source.
The isolation electrode 19 is provided with the planar electrode of the trapezoidal aperture of shaft section centered on being arranged, side hole diameter is set
It is set to 4~8mm, other side hole diameter is set as 1~3mm, and the lesser side of aperture internal diameter is placed far from ionization source 15, purpose
It is to avoid reagent gas 20 that ionization source 15 is interfered or corroded under the action of blowback air 17.
The port input distance of the exhaust pipe 8 and 4 right end of drop reaction pipe is set as 3~15mm；
7 pumping speed of aspiration pump is set as 0.5~5L/min.
2 length of chemical ionization source is set as 30~100mm；
The drop reaction pipe 4 is installed on the intermediate position of chemical ionization source 2.
It is set as NO in reactant gas source 1, is set as SO in reactant gas source 2 122；
Pass through valve 1, the state switching setting OH and HO of valve 2 14 in drop reaction pipe 42Two kinds of atmosphere free radicals
Measurement pattern is switched fast；
The reagent gas is set as HNO3Steam, HNO3Steam carries waving on 1-10 DEG C of nitric acid solution liquid level by carrier gas
Obtained by getting angry, flow rate of carrier gas is set as 0.2~3mL/min by flow control valve 21；
The Atmospheric OH Radical Using measurement pattern: valve 1 is in an off state, and valve 2 14 is in closed state；
Drop reaction is based on following principle and completes the conversion of the Atmospheric OH Radical Using first step in the drop reaction pipe 4:
SO2+OH→H2SO4
HNO is set as in reagent gas3Steam, HNO3Steam ionizes under the action of ionization source 15 generates NO3 -, NO3 -With
The H that the Atmospheric OH Radical Using first step converts2SO4The conversion of free radical second step is completed based on following principle:
H2SO4+NO3 -→HNO3+HSO4 -
NO is completed in mass spectrograph 33 -With HSO4 -Ion detection, and Atmospheric OH Radical Using concentration is obtained by following formula:
Wherein kOHIt is reaction rate constant, reports that its value is 2.6 × 10 in document-9cm3 molecule-1 s-1；T is electricity
From NO in source3 -Ion and H2SO4The ion molecule reaction time of molecule；[OH] represents the concentration of Atmospheric OH Radical Using；I(HSO4 -)
Mass spectrograph 3 is represented to detect to obtain HSO4 -Ion signal intensity；I(NO3 -) represent mass spectrograph 3 and detect to obtain NO3 -Ion signal
Intensity；
And/or the atmosphere HO2Free radical measurement pattern: valve 1 is in closed state, and valve 2 14 is in closure
State；
Drop reaction is based on following principle and completes atmosphere HO in the drop reaction pipe 42The conversion of the free radical first step:
NO+HO2→NO2+OH
SO2+OH→H2SO4
HNO is set as in reagent gas3Steam, HNO3Steam ionizes under the action of ionization source 15 generates NO3 -, NO3 -With
Atmosphere HO2The H that the free radical first step converts2SO4The conversion of free radical second step is completed based on following principle:
H2SO4+NO3 -→HNO3+HSO4 -
NO is completed in mass spectrograph 33 -With HSO4 -Ion detection, and atmosphere HO is obtained by following formula2Free radical is dense in real time
Degree:
Wherein kOHIt is reaction rate constant, reports that its value is 2.6 × 10 in document-9cm3 molecule-1 s-1；T is electricity
From NO in source3 -Ion and H2SO4The ion molecule reaction time of molecule；[OH] represents the concentration of Atmospheric OH Radical Using；I(HSO4 -)
Mass spectrograph 3 is represented to detect to obtain HSO4 -Ion signal intensity；I(NO3 -) represent mass spectrograph 3 and detect to obtain NO3 -Ion signal
Intensity；
The reactant gas source 1,2 12 flow velocity of reactant gas source are set as 0.5~200mL/min.
The carrier gas 16, blowback air 17 are set as dry air, nitrogen, helium or argon gas；
The carrier gas 16,17 flow velocity of blowback air are set as 10~200mL/min.
Provided by the present invention for measuring atmosphere OH and HO for chemical ionization mass spectrometry2The device and method of free radical, base
It is realized in highly sensitive chemi-ionization ionization time of flight.Cardinal principle is: passing through suitable SO2Titration, OH and HO2
Free radical is completely converted into H2SO4, then use NO3 -Ion is by chemi-ionization method H2SO4Ionization is HSO4 -Ion, final benefit
The NO obtained with measurement3 -With HSO4 -The intensity of ion is completed to OH and HO2The calculating and analysis of free radical real-time concentration.With it
He compares measurement means, and chemical ionization mass spectrometry technology has many advantages, such as measuring speed is fast, stability is good, high sensitivity.
Embodiment 1
Atmosphere OH and HO are measured for chemical ionization mass spectrometry for of the present invention2The property of the device and method of free radical
It can be carried out investigation.In on 04 30th, 2017, in the daytime to the biotechnology Lou Wulou roof of ZhongShan Road, Shahekou District, DaLian City 457
Atmospheric OH Radical Using concentration variation tendency continuously monitors, as a result as shown in figure 4, showing in 05:00~12:00 atmosphere OH
Number of free radical gradually rises, and obtains peak value, then in 12:00~18:00 with the decrease Atmospheric OH Radical Using of sunlight
Concentration gradually decays, gained changing rule and document report (Atmospheric Environment 154 (2017) 167-178；
Journal of Environmental Sciences 20 (2008) 28-32) it is consistent.
Claims (9)
1. one kind measures atmosphere OH and HO for chemical ionization mass spectrometry2The device of free radical, including free radical sampling apparatus (1), set
Chemical ionization source (2) and mass spectrograph (3) in airtight chamber, it is characterised in that:
The free radical sampling apparatus (1) includes drop reaction pipe (4) and atmosphere free radical sample intake passage (5), for realizing big
The sampling process of gas free radical；Drop reaction pipe (4) is the hollow pipeline of a horizontal positioned both ends open, in drop reaction pipe
(4) the reaction gas injection port one (9) close to atmosphere free radical sample intake passage (5) is respectively arranged on side wall, close to chemi-ionization
The reaction gas injection port two (10) in source (2)；Reaction gas injection port one (9), reaction gas injection port two (10) respectively with reactant gas source
One (11), reactant gas source two (12) are connected；Atmosphere free radical sample intake passage (5) is the hollow pipeline of a both ends open, and atmosphere is certainly
By base sample intake passage (5) left open end and drop reaction pipe (4) right open end airtight connection, atmosphere free radical sample intake passage (5)
Right open end communicated with ambient air (6), on the side wall of atmosphere free radical sample intake passage (5) aperture pass through exhaust pipe (8)
It is connected with aspiration pump (7), drop reaction pipe (4) left open end is connected through chemical ionization source (2) with the injection port of mass spectrograph (3)；
Atmosphere OH and HO2Free radical is pumped into atmosphere free radical sample intake passage (5) by aspiration pump (7), and is vacuumized in mass spectrograph (3) and be
It is flowed into drop reaction pipe (4) under the action of system；
The drop reaction pipe (4) is for realizing atmosphere OH and HO2The first step of free radical converts；
The chemical ionization source (2) is for realizing atmosphere OH and HO2The second step of free radical converts；；
The mass spectrograph (3) is flight time mass spectrum, and the detection of generated ion is converted for realizing chemical ionization source (2).
2. according to claim 1 measure atmosphere OH and HO for chemical ionization mass spectrometry2The device of free radical, feature exist
In:
The chemical ionization source (2) successively include from top to bottom ionization source (15), the plate electrode with through-hole in the middle part of 1-3, in
Plate isolation electrode (19) of the portion with through-hole, 2 or more the middle part differential electrodes of the plate electrode with through-hole, middle part with through-hole,
Plate electrode from top to bottom, isolation electrode, plate felt pad of the setting middle part with through-hole between differential electrode, plate electrode,
Electrode, differential electrode, the middle through-hole coaxial arrangement on felt pad is isolated；It sets in ionization source (15) with being isolated between electrode (19)
Have carrier gas pipe (16), the outlet of carrier gas pipe (16) towards at plate electrode middle through-hole and with middle through-hole axis perpendicular；
Reagent gas pipe (20) are equipped between isolation electrode (19) and differential electrode, the outlet of reagent gas pipe (20) is towards plate
At shape electrode middle through-hole and with middle through-hole axis perpendicular；
The left open end of drop reaction pipe (4) is located between reagent gas pipe (20) and differential electrode, a left side for drop reaction pipe (4)
Open end at plate electrode middle through-hole and with middle through-hole axis perpendicular；
Be equipped with offgas duct (18) between the left opening and differential electrode of drop reaction pipe (4), the import of offgas duct (18) towards
At plate electrode middle through-hole and with middle through-hole axis perpendicular；
Blowback tracheae (17) are equipped between offgas duct (18) and differential electrode, the import of blowback tracheae (17) is towards plate electrode
At middle through-hole and with middle through-hole axis perpendicular；
Differential electrode one end far from ionization source (15) is equipped with mass spectrograph (3)；
The cylindrical shape atmosphere free radical sample intake passage (5) and cylindric drop reaction pipe (4) are coaxially disposed.
3. according to claim 1 measure atmosphere OH and HO for chemical ionization mass spectrometry2The device of free radical, feature exist
In:
The atmosphere free radical sample intake passage (5) is the hollow cavity of a transparent both ends open, and cavity material is set as common glass
Glass or quartz glass, it is therefore intended that sunlight can shine directly into atmosphere OH in atmosphere free radical sample intake passage (5) and
HO2Free radical component；
Atmosphere free radical sample intake passage (5) cavity length is set as 100~300mm, and cavity internal diameter is set as 40~
150mm；
The drop reaction pipe (4) is set as the hollow stainless steel cavity of both ends open, and length is 50~400mm, internal diameter setting
For 5~20mm；
The reaction gas injection port one (9), reaction gas injection port two (10) are located above drop reaction pipe (4)；Reaction gas sample introduction
One (9) of mouth, reaction gas injection port two (10) are respectively through valve one (13), valve two (14) and reactant gas source one (11), reaction gas
Source two (12) is connected.
4. according to claim 1 measure atmosphere OH and HO for chemical ionization mass spectrometry2The device of free radical, feature exist
In:
It is set flow control valve (21) on the reagent gas pipe (20), flow velocity is adjusted by control valve (21)；
The control valve (21) is mass flowmenter or ball valve or needle-valve；
The ionization source (15) be light source,63Ni radioactive source or discharge source.
5. according to claim 1 measure atmosphere OH and HO for chemical ionization mass spectrometry2The device of free radical, feature exist
In:
The planar electrode of the trapezoidal aperture of shaft section, the setting of side hole diameter are provided with centered on isolation electrode (19) setting
For 4~8mm, other side hole diameter is set as 1~3mm, and the lesser side of aperture internal diameter is placed far from ionization source (15), purpose
It is that reagent gas (20) is avoided to interfere under the action of blowback air (17) or corrode ionization source (15).
6. according to claim 1 measure atmosphere OH and HO for chemical ionization mass spectrometry2The device of free radical, feature exist
In:
The port input distance of the exhaust pipe (8) and drop reaction pipe (4) right end is set as 3~15mm；
Aspiration pump (7) pumping speed is set as 0.5~5L/min.
Chemical ionization source (2) length is set as 30~100mm；
The drop reaction pipe (4) is installed on the intermediate position of chemical ionization source (2).
7. a kind of any described device of claim 1-6 measures atmosphere OH and HO for chemical ionization mass spectrometry2The method of free radical,
It is characterized by:
It is set as NO in reactant gas source one (11), is set as SO in reactant gas source two (12)2；
Pass through valve one (13), the state switching setting OH and HO of valve two (14) in drop reaction pipe (4)2Two kinds of atmosphere freedom
Base measurement pattern is switched fast；
The reagent gas is set as HNO3Steam, HNO3Steam is carried the Volatile Gas on 1-10 DEG C of nitric acid solution liquid level by carrier gas
Gained, flow rate of carrier gas are set as 0.2~3mL/min by flow control valve (21)；
The Atmospheric OH Radical Using measurement pattern: valve one (13) is in an off state, and valve two (14) is in closed state；
The interior drop reaction of the drop reaction pipe (4) is based on following principle and completes the conversion of the Atmospheric OH Radical Using first step:
SO2+OH→H2SO4
HNO is set as in reagent gas3Steam, HNO3Steam ionizes under the action of ionization source (15) generates NO3 -, NO3 -With it is big
The H that the gas OH free radical first step converts2SO4The conversion of free radical second step is completed based on following principle:
H2SO4+NO3 -→HNO3+HSO4 -
NO is completed in mass spectrograph (3)3 -With HSO4 -Ion detection, and Atmospheric OH Radical Using concentration is obtained by following formula:
Wherein kOHIt is reaction rate constant, reports that its value is 2.6 × 10 in document-9cm3molecule-1s-1；T is in ionization source
NO3 -Ion and H2SO4The ion molecule reaction time of molecule；[OH] represents the concentration of Atmospheric OH Radical Using；I(HSO4 -) represent matter
Spectrometer (3) detects to obtain HSO4 -Ion signal intensity；I(NO3 -) represent mass spectrograph (3) and detect to obtain NO3 -Ion signal is strong
Degree；
And/or the atmosphere HO2Free radical measurement pattern: valve one (13) is in closed state, and valve two (14) is in closure
State；
The interior drop reaction of the drop reaction pipe (4) is based on following principle and completes atmosphere HO2The conversion of the free radical first step:
NO+HO2→NO2+OH
SO2+OH→H2SO4
HNO is set as in reagent gas3Steam, HNO3Steam ionizes under the action of ionization source (15) generates NO3 -, NO3 -With it is big
Gas HO2The H that the free radical first step converts2SO4The conversion of free radical second step is completed based on following principle:
H2SO4+NO3 -→HNO3+HSO4 -
NO is completed in mass spectrograph (3)3 -With HSO4 -Ion detection, and atmosphere HO is obtained by following formula2Free radical real-time concentration:
Wherein kOHIt is reaction rate constant, reports that its value is 2.6 × 10 in document-9cm3molecule-1s-1；T is in ionization source
NO3 -Ion and H2SO4The ion molecule reaction time of molecule；[OH] represents the concentration of Atmospheric OH Radical Using；I(HSO4 -) represent matter
Spectrometer (3) detects to obtain HSO4 -Ion signal intensity；I(NO3 -) represent mass spectrograph (3) and detect to obtain NO3 -Ion signal is strong
Degree.
8. according to the method described in claim 7, it is characterized by:
The reactant gas source one (11), reactant gas source two (12) flow velocity are set as 0.5~200mL/min.
9. according to the method described in claim 7, it is characterized by:
The carrier gas (16), blowback air (17) are set as dry air, nitrogen, helium or argon gas；
The carrier gas (16), blowback air (17) flow velocity are set as 10~200mL/min.
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