CN110261527A - It is a kind of for correcting the reaction unit and method of biomass combustion indicant concentration in snow ice - Google Patents
It is a kind of for correcting the reaction unit and method of biomass combustion indicant concentration in snow ice Download PDFInfo
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Abstract
It is a kind of for correcting the reaction unit and method of biomass combustion indicant concentration in snow ice, device includes two-way compression N2Input port and all the way O2Input port, for every road gas setting flowmeter, contain 30%H2O2(weight) aqueous solution reagent bottle, low pressure mercury lamp ultraviolet source, OH free-radical generator, flowing reactive cavity, Mega-Ray simulated solar light source, sample disc, thermometer and salicylic acid sampling head.The device and method are used to study the stability difference of various burning and exhausting indicants under different OH number of free radical, reaction time, reaction temperature, and calculate its second order reaction constant；The initial settlement concentration for calculating biomass combustion indicant in snow and ice, eliminating as much as influences since OH free radical can aoxidize biomass combustion indicant bring in snow.
Description
Technical field
The present invention relates to a kind of for correcting the reaction unit and method of biomass combustion indicant concentration in snow ice, belongs to
Snow ice chemical field.
Background technique
Snow ice has widely been accepted as the good carrier of climatic environment information.Snow ice not only records nature change
Change information, and records influence of the mankind's activity to climatic environment.A large number of studies show that the greenhouse gas of biomass combustion discharge
The carbonaceous aerosols such as body and black carbon, brown carbon can significantly change the chemical composition of atmosphere, and then rough atmosphere circulation patterns,
Influence Global climate change.After carbonaceous aerosol is deposited to snow ice surface, the albedo of accumulated snow can be significantly reduced, accelerates snow ice
Ablation.Simultaneously as the features such as unique low temperature environment of snow ice, disturbance lack, is very beneficial for the preservation of biomass combustion signal.
Therefore, the modern process and historical record discharged using snow ice as study on the carrier biomass combustion is to system cognizant terrestrial climate
Environmental change is of great significance.In recent years, levoglucosan, partially aromatic organic acid (P-hydroxybenzoic acid, vanillic acid,
Dehydroabietic acid) it is widely used as typical biomass combustion indicant.
The research of (2010 before) in early days think using levoglucosan as the biomass combustion indicant of representative be stabilization,
Hardly possible volatilization.However, recent studies have indicated that, (OH is free in atmospheric oxidant for some organic tracers for being usually used in source resolution
Base etc.) in the presence of a degree of reaction can occur, so as to cause their concentration during propagation in atmosphere, sedimentation and preservation
It can change；In addition, gaseous oxidation will be very big studies have pointed out that levoglucosan has half volatile when more than 20 DEG C
Ground shortens its retention time, especially under certain specified conditions such as summer high temperature, atmospheric lifetime even only 1-2 days.Cause
This, uses levoglucosan etc. to carry out source resolution research as indicant, may underestimate biomass combustion row to a certain extent
The contribution put, so that the photochemical reaction rate and accuracy to quantitative source resolution result are brought greater impact.
And up to now until, the research for the burning indicant stability such as levoglucosan in snow ice medium still belongs to empty
It is white.OH free radical is widely present inside snow/vapor interface and snow ice, and the burning indicant such as levoglucosan is deposited to snow ice surface
Afterwards, in this case it is still possible to continue to degrade.Domine etc. (2002) writes articles on " Science " points out largely exist in accumulated snow
OH free radical can aoxidize certain organic matters and halide ion in snow, generate carbonyls and halogen, change snow and its
The composition of clearance air, and especially emphasize to carry out needing to carry out complicated correction when ancient Atmospheric composition is rebuild using ice core.
Therefore, a kind of for correcting the reaction unit of biomass combustion indicant concentration in snow ice there is an urgent need to design, and
Experimental method is established, the application for biomass combustion indicant in snow ice chemical research field is offered reference, to establish big compression ring
The quantitative relationship of border and snow ice record provides scientific basis, expands the research category of snow ice chemical field.
Summary of the invention
The present invention provides a kind of for correcting the reaction unit of biomass combustion indicant concentration in snow ice, and establishes in fact
Proved recipe method, can the photochemical stability to biomass combustion indicant in snow ice effectively assessed and corrected.
In order to solve the above technical problems, the present invention adopts the following technical scheme that: one kind is raw in snow ice for correcting
The reaction unit of substance combustion indicant concentration, which is characterized in that the device includes two-way compression N2Input port and all the way O2Input
Mouthful, for every road gas setting flowmeter, contain 30%H2O2(weight) aqueous solution reagent bottle, low pressure mercury lamp ultraviolet source, OH are free
Base generator, flowing reactive cavity, Mega-Ray simulated solar light source, sample disc, for measure reaction when specific temperature temperature
The components composition such as degree meter and salicylic acid sampling head.First via N2By first flowmeter and 30%H is housed2O2Aqueous solution reagent bottle phase
Even, H is had2O and H2O2Air-flow enter OH free-radical generator, H2O and H2O2It is free to generate OH for photodissociation under ultraviolet light irradiation
Base；Second road N2Directly it is connected with OH free-radical generator by second flowmeter, O2With the N for flowing through OH free-radical generator2It is mixed
Flowing reactive cavity is directly accessed after conjunction, herein N2And O2Ratio is set according to ratio both in air；By adjusting the first via and
Second road N2Flow velocity and ratio control the concentration of OH free radical.OH free radical generating device is placed on laboratory room temperature ring
Border facilitates parameter regulation, and flowing reactive cavity is placed in miniature cold storage (- 20 DEG C to -5 DEG C controllable), and there are dedicated for cold storage wall
Experiment mouth, the two passes through piping connection；Flowing reactive cavity design is upper opening ways, convenient for picking and placing sample, flowing reactive
Cavity upper cover integrates Mega-Ray simulated solar light source simultaneously, convenient for simulation available light environment, can individually carry out simulated solar
Light exposes experiment to the open air, is removed at this time containing 30%H2O2(weight) aqueous solution reagent bottle, low pressure mercury lamp ultraviolet source and OH free radical occur
Device is only exposed to the open air by simulated solar irradiation and generates OH free radical；Sample disc size about 40cm(long) × 30cm(wide) × 10cm(depth),
Sample laying depth is 5cm or so when experiment, and snow and ice is enable more adequately to contact with OH free radical or sufficiently receive
The irradiation of Mega-Ray analog light source.Flowing reactive cavity outlet is docked with salicylic acid sampling head, certainly using chemical reaction trapping OH
By base, the concentration of OH free radical is obtained indirectly by the production quantity of its reaction product.Salicylic acid is free in the OH of various concentration
Degradation reaction under basic ring border is first order reaction.
The principal ray of low pressure mercury lamp is two wavelength of 185nm and 254nm, H2O and H2O2Two length ultraviolets can be absorbed respectively
The energy of ray generates OH free radical, while carrier gas uses pure N2And non-air, avoid O2Introducing in advance generate oxidisability gas
Body O3, influence experimental result.The reaction mechanism is as follows:
H2O + hv H + OH
H2O2 + hv OH + OH 。
In addition to irradiating 30%H using low pressure mercury lamp2O2The mode of (weight) aqueous solution, OH free radical can also be only with
The mode of Mega-Ray simulated solar light source irradiation, at this time two-way N2Input and all the way O2Input is all closed, and the OH generated at this time is certainly
It is basicly stable by base concentration, in the case where not requiring OH number of free radical to change.
For correcting the reaction method of biomass combustion indicant concentration in snow ice on the basis of reaction unit, Ke Yishi
Now the photochemical reaction rate to biomass combustion indicant in snow ice and stability carry out accurate evaluation, and corresponding method is:
It is tested after melting with the snow and ice before and after OH radical reaction with ultra performance liquid chromatography mass spectrometer (UPLC-MSMS)
The concentration of biomass combustion indicant calculates its second order reaction constant, obtains two under each indicant specific temperature in laboratory
On the basis of order reaction constant, the initial settlement concentration of biomass combustion indicant in snow and ice is obtained, correction is due to OH freedom
Biomass combustion indicant bring influences in base oxidation snow, and then assesses the stability of various burning indicants.
Further, in order to make flowing reactive cavity quickly reach balance with environment temperature, cavity main body is reacted by thermal conductivity
Good red copper material is made；Mega-Ray analog light source shelling machine is antifog material, prevents fogging under low temperature from influencing light transmission
Intensity；In addition, reactor wall covers Teflon film, enhance the reactionlessness of inside cavity.
The corresponding correction mode of the device is, using reaction unit above-mentioned, which is characterized in that specifically include following step
It is rapid: setting two-way N2Certain N2Salicylic acid is dispersed on sampling film by flow rate, and the sampling head of sampling film will be housed
It is connect by union with flowing reactive cavity, reacts the OH free radical generated sufficiently with salicylic acid, the primary product of generation
Sampling film is removed, is extracted with methanol, and filters, dry up, silanization after reacting a period of time for 2,3-DHBA and 2,5-DHBA
It is analyzed after derivative, n-hexane constant volume with gas chromatography-mass spectrometry (GC-MS), the concentration of OH free radical (unit:
molecule.cm-3) formula can be usedIt calculates, in formula: M1To be detected on reaction post-sampling film
2,3-DHBA or 2, the amount of the substance of 5-DHBA, unit are as follows: mol；N is Avgadro constant, 6.02 × 1023；F1It is 2,
The yield of 3-DHBA or 2,5-DHBA, respectively 52% and 48%；S is acquisition gas overall flow rate, unit are as follows: cm3.min-1；T is to adopt
Collect time, unit min；α is extraction efficiency, unit %.By changing two-way N2Flow rate obtain the OH of various concentration
Number of free radical.Mega-Ray exposure can also individually be carried out and generate OH free radical, two-way N is closed when experiment2Input and all the way O2
Mega-Ray light source is opened in input, simulates available light condition.To avoid environmental exact details from interfering, snowmaking experiment is all made of same
Position element replaces2H or13The biomass combustion indicant of C is as research object.By certain density levoglucosan, para hydroxybenzene
Formic acid, vanillic acid and dehydroabietic acid isotopic label are added in ultrapure water, and manually snowmaker produces simulation snow core.By mould
Quasi- snow core is uniformly laid in sample disc, and laying depth about 5cm is placed in flow reactor, in different reaction time and
It reacts OH free radical with snow core, is protected from light, freezen protective, remains examination with computer；It is dense to change OH free radical
Degree repeats to test.
Further, it after the sample after reaction being melted, is tested immediately with UPLC-MSMS, obtains each biomass fuel
Concentration after the reaction of burning indicant, obtains its photochemical reaction rate, and then assess its stability.Each indicant is at a certain temperature
Second order reaction constant can use formulaIt calculates, in formula: A: the real-time concentration of indicant, unit are
ng.g-1；A0: the initial concentration of indicant, unit ng.g-1；k 2: second order reaction rate constant, unit cm3.molecule- 1.min-1；[OH]: OH number of free radical, unit molecule.cm-3；t: reaction time, unit min.It is obtained by calculation specific
At a temperature of second order reaction rate constant under the conditions of difference OH number of free radical, resulting second order reaction constant is averaging, is obtained
Generally applicable second order reaction constant mean under to specific temperature.
Further, it on the basis of laboratory obtains second order reaction constant mean under each indicant specific temperature, can use
FormulaThe initial settlement concentration of biomass combustion indicant in snow and ice is calculated, in formula: A 'o: refer to
Show the initial settlement concentration of object, unit ng.g-1；A ': the measured concentration of sample, unit ng.g are acquired-1；k 2: second order reaction
Rate constant, unit cm3.molecule-1.min-1；[OH]: superglacial OH number of free radical, unit molecule.cm-3；t: the time that snowfall to sample acquires, unit min.By this method obtain biomass combustion indicant in snow and ice just
Begin sedimentation concentration, can correct since biomass combustion indicant bring influences in OH free-radical oxidation snow.
The present invention devises a kind of for correcting the reaction unit of biomass combustion indicant concentration in snow ice, and establishes
Experimental method can be used for studying various burning and exhausting indicants under different OH number of free radical, reaction time, reaction temperature
Stability difference, and calculate its second order reaction constant；Calculate the initial settlement concentration of biomass combustion indicant in snow and ice,
Eliminating as much as influences since OH free radical can aoxidize biomass combustion indicant bring in snow, and to result according to reaction
Rate and stability test result are corrected, and then the application for biomass combustion indicant in snow ice chemical research field provides
It uses for reference, provides scientific basis to establish the quantitative relationship of atmospheric environment and snow ice record, expand the research model of snow ice chemical field
Farmland.
Detailed description of the invention
Fig. 1 is the reaction unit schematic diagram for correcting biomass combustion indicant concentration in snow ice.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Drawings and examples, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
As shown in Figure 1, a kind of for correcting the reaction unit of biomass combustion indicant concentration in snow ice comprising first
Compress N in road2N is compressed on input port 1 and the second tunnel2Input port 3, to compress N2The corresponding flowmeter that pipeline is equipped with (does not show
Out), contain 30% (weight) H2O2Aqueous solution reagent bottle 2, OH free-radical generator 4, low pressure mercury lamp ultraviolet source 5, compression O2Input
Mouthfuls 6 and be compression O2Flowmeter (not shown), flowing reactive cavity 7, sample disc 8, the Mega-Ray of pipeline outfit are simulated too
Sunlight source 9, thermometer 11 and salicylic acid sampling head 13.N2Carrier gas as reaction process.The first via compresses N2By flowmeter into
Enter 30%H is housed2O2Aqueous solution reagent bottle 2 has H2O and H2O2Air-flow enter OH free-radical generator 4, H2O and H2O2In purple
Outside line 5 irradiates lower photodissociation and generates OH free radical；Compress N in the second tunnel2It is directly entered OH free-radical generator 4 by flowmeter, is pressed
Contracting oxygen O2 With the N for flowing through OH free-radical generator 42Enter flowing reaction cavity 7, N after mixing2And O2Ratio is according in air
The setting of the two ratio；N is compressed by adjusting the first via2N is compressed with the second tunnel2Flow velocity and ratio control the dense of OH free radical
Degree.OH free radical generating device is placed on laboratory normal temperature environment, facilitates parameter regulation, and flowing reactive cavity is placed on small-sized cold
In library (- 20 DEG C to -5 DEG C controllable), for cold storage wall there are dedicated experiment mouth, flowing reactive cavity 7 and OH free-radical generator 4 are logical
Cross piping connection；Flowing reactive cavity 7 is designed as opening ways, convenient for picking and placing sample；7 upper cover of flowing reactive cavity collects simultaneously
At Mega-Ray simulated solar light source 9, for simulating available light environment；8 size of sample disc about 40cm(long) × 30cm(wide)
× 10cm(is deep), sample laying depth is 5cm or so when experiment, and snow and ice is enable more fully to connect with OH free radical
Touching, the OH free radical irradiate 30%H by low pressure mercury lamp2O2The mode of (weight) aqueous solution is simulated too using Mega-Ray
The mode of sunlight source irradiation generates, and the two is selected according to whether changing OH number of free radical.Flowing reactive cavity 7 goes out
Mouth is docked by union 12 with salicylic acid sampling head 13, utilizes the chemical reaction of salicylic acid and OH free radical trapping OH free
Base obtains the concentration of OH free radical by the production quantity of the two reaction product indirectly.
When being tested using above-mentioned reaction unit, comprising the following steps: be two-way N2Certain flow rate is set, it will
Sampling head 13 equipped with sampling film (salicylic acid is dispersed on film) is connect by union 12 with flowing reactive cavity 7, with
React the OH free radical generated sufficiently with salicylic acid, the primary product of generation is 2,3-DHBA and 2,5-DHBA, reaction one
After the section time, sampling film is removed, is extracted with methanol, and filters, dry up, using gas-chromatography after Silylation, n-hexane constant volume
Mass spectrometer (GC-MS) analysis, the concentration (unit: molecule.cm of OH free radical-3) formula can be usedIt calculates, in formula: M1To react the 2,3-DHBA or 2,5-DHBA that detect on post-sampling film
The amount of substance, unit are as follows: mol；N is Avgadro constant, 6.02 × 1023；F1For 2,3-DHBA or 2, the yield of 5-DHBA,
Respectively 52% and 48%；S is acquisition gas overall flow rate, unit are as follows: cm3.min-1；T is acquisition time, unit min；α is to mention
Take efficiency, unit %.By changing two-way N2Ratio obtain the OH number of free radical of various concentration, using low pressure mercury lamp
Irradiate 30%H2O2Mega-Ray is closed when the mode of (weight) aqueous solution generates OH free radical.Mega-Ray can also individually be carried out
Exposure generates OH free radical, and two-way N is closed when experiment2Input and all the way O2Mega-Ray light source is opened in input, simulates natural light
Lines part.And corresponding concentration is measured by the method for abovementioned steps.To avoid environmental exact details from interfering, snowmaking experiment is all made of
Isotope substitution (2H or13C biomass combustion indicant) is as research object.By certain density levoglucosan, to hydroxyl
Yl benzoic acid, vanillic acid and dehydroabietic acid isotopic label are added in ultrapure water, and manually snowmaker produces simulation snow core.
Simulation snow core is uniformly laid in sample disc 8, laying depth about 5cm is placed in flow reactor 7, and when experiment utilized
Low pressure mercury lamp irradiates 30%H2O2(weight) aqueous solution generates OH free radical using the irradiation of Mega-Ray simulated solar light source.Choosing
It selects under specific OH number of free radical, carries out OH free radical and snow core under different reaction time and reaction temperature anti-
It answers, is protected from light, freezen protective, remains examination with computer；Change OH number of free radical, repeats the step.
After sample after reacting under different OH number of free radical is melted respectively, is tested, obtained with UPLC-MSMS immediately
Take concentration after the reaction of each biomass combustion indicant.The second order reaction constant of each indicant at a certain temperature can use formula = -k 2 [OH] t It calculates, in formula: A: the real-time concentration of indicant, unit ng.g-1；A0: indicant it is initial
Concentration, unit ng.g-1；k 2: second order reaction rate constant, unit cm3.molecule-1.min-1；[OH]: OH free radical is dense
Degree, unit molecule.cm-3；t: reaction time, unit min.Specific temperature difference OH number of free radical item is obtained by calculation
Second order reaction rate constant under part is averaging resulting second order reaction constant, obtains generally applicable two under specific temperature
Order reaction constant mean。
It further, can on the basis of laboratory obtains the second order reaction constant mean under each indicant different temperatures
Use formulaCalculate the initial settlement concentration of biomass combustion indicant in snow and ice, in formula::
The initial settlement concentration of indicant, unit ng.g-1；A ': the measured concentration of sample, unit ng.g are acquired-1；k 2: second level is anti-
Answer rate constant, unit cm3.molecule-1.min-1；[OH]: superglacial OH number of free radical, unit molecule.cm-3；t: the time that snowfall to sample acquires, unit min.Biomass combustion indicant in snow and ice is obtained by this method
Initial settlement concentration can be corrected since biomass combustion indicant bring influences in OH free-radical oxidation snow.
Wherein in order to make flowing reactive cavity quickly reach balance with environment temperature, reaction cavity main body is good by thermal conductivity
Red copper material is made；Mega-Ray analog light source shelling machine is antifog material, prevents fogging under low temperature from influencing penetrating light intensity.
In addition, reactor wall covers Teflon film, enhance the reactionlessness of inside cavity.
The present invention is described in detail above by specific and preferred embodiment, but those skilled in the art should be bright
White, the present invention is not limit to that embodiments describe above, all within the spirits and principles of the present invention, made any modification,
Equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of for correcting the reaction unit of biomass combustion indicant concentration in snow ice comprising the first via compresses N2Input
N is compressed on mouth (1) and the second tunnel2Input port (3), to compress N2Corresponding flowmeter that pipeline is equipped with contains 30% H2O2It is water-soluble
Liquid reagent bottle (2), OH free-radical generator (4), low pressure mercury lamp ultraviolet source (5), compression O2Input port (6) is compression O2Pipeline
The flowmeter of outfit, flowing reactive cavity (7), sample disc (8), Mega-Ray simulated solar light source (9), for measuring reaction when
The thermometer (11) and salicylic acid sampling head (13) of specific temperature, it is characterised in that:
The first via compresses N2Entered by flowmeter and contains 30%H2O2Aqueous solution reagent bottle (2) has H2O and H2O2Air-flow enter
N is compressed on OH free-radical generator (4), the second tunnel2OH free-radical generator (4), H are directly entered by flowmeter2O and H2O2?
Photodissociation generates OH free radical under the irradiation of the low pressure mercury lamp ultraviolet source (5) of OH free-radical generator (4)；Compressed oxygen O2 With stream
N through OH free-radical generator (4)2Enter flowing reaction cavity (7) after mixing；OH free-radical generator (4) is placed in room temperature ring
Border, flowing reactive cavity (7) are placed in miniature cold storage, and there are experiment mouth, flowing reactive cavity (7) and OH free radicals for cold storage wall
Generator (4) passes through the piping connection across experiment mouth；Flowing reactive cavity (7) is designed as opening ways, and upper cover is integrated
Mega-Ray simulated solar light source (9), for simulating available light environment；
Snow and ice to be measured is laid with when experiment in sample disc (8), generates OH free radical using OH free-radical generator (4), this
When close Mega-Ray simulated solar light source (9), or individually carry out Mega-Ray exposure generate OH free radical, close two at this time
Road N2Input and all the way O2Mega-Ray light source is opened in input, simulates available light condition；Make snow and ice fully with OH from
By base contact or sufficiently reception Mega-Ray analog light source irradiation, the snow and ice sufficiently reacted with OH free radical is saved, stream
It is docked by union (12) with salicylic acid sampling head (13) outlet of dynamic reaction cavity (7)；Salicylic acid sampling head after reaction
(13) sampling film is connected to the concentration of gas chromatography-mass spectrometry measurement OH free radical after treatment, and by different OH
After the snow and ice processing saved after being reacted under number of free radical, it is put into ultra performance liquid chromatography mass spectrometer and tests each life
Concentration after the reaction of substance combustion indicant；
Concentration after the reaction of each biomass combustion indicant is obtained, is calculated under the conditions of specific temperature difference OH number of free radical
Second order reaction rate constant, to resulting second order reaction constant be averaging, obtain second order reaction constant mean under specific temperature,
Using the second order reaction constant mean, the initial settlement concentration of biomass combustion indicant in natural environment snow ice is calculated, from
And correct the concentration of biomass combustion indicant in snow ice under natural environment；Wherein,
The second order reaction constant of each indicant at a certain temperaturek 2It is calculated using following formula:
(1)
In formula: A: the real-time concentration of indicant, unit ng.g-1；A0: the initial concentration of indicant, unit ng.g-1；k 2: two
Order reaction rate constant, unit cm3.molecule-1.min-1；[OH]: OH number of free radical, unit molecule.cm-3；t:
Reaction time, unit min；
The initial settlement concentration of biomass combustion indicant in natural environment snow ice is calculated using following formula:
(2)
In formula:: the initial settlement concentration of indicant, unit ng.g in natural environment glacier-1；A ': in natural environment glacier
The measured concentration of indicant, unit ng.g-1；: the second order reaction rate constant mean value under specific temperature, unit
cm3.molecule-1.min-1；[OH]: superglacial OH number of free radical, unit molecule.cm-3；t: snowfall to sample is adopted
The time of collection, unit min.
2. it is according to claim 1 for correcting the reaction unit of biomass combustion indicant concentration in snow ice, it flows through
Dynamic reaction cavity (7) N2And O2Ratio is set according to ratio both in air.
3. it is according to claim 1 for correcting the reaction unit of biomass combustion indicant concentration in snow ice, it is small-sized cold
The temperature regulating range in library is -20 DEG C to -5 DEG C.
4. according to claim 1 for correcting the reaction unit of biomass combustion indicant concentration in snow ice, sample disc
(8) having a size of 40cm × 30cm × 10cm, snow and ice laying depth is 5cm when experiment.
5. it is according to claim 1 for correcting the reaction unit of biomass combustion indicant concentration in snow ice, pass through tune
The whole first via compresses N2N is compressed with the second tunnel2Flow velocity change the concentration of the OH free radical generated under this mode.
6. a kind of side using biomass combustion indicant concentration in the correction snow ice of reaction unit described in one of claim 1-5
Method, comprising the following steps:
(1) two-way N is closed2Input and all the way O2Mega-Ray light source is opened in input, is two-way N2Certain flow velocity is set；Or
Close two-way N2Input and all the way O2Mega-Ray light source is opened in input, simulates available light condition；
(2) salicylic acid on the sampling film in salicylic acid sampling head (13) and OH radical reaction, generating primary product is 2,3-
DHBA and 2,5-DHBA removes sampling film after the two is sufficiently reacted, and is extracted with methanol, and filters, dries up, Silylation, just
It is analyzed after hexane constant volume with gas chromatography-mass spectrometry, obtains the concentration of OH free radical；
(3) change two-way N2Flow rate obtain the OH free radical of various concentration, and measured and corresponded to by the method for step (2)
Concentration；
(4) certain density levoglucosan, P-hydroxybenzoic acid, vanillic acid or dehydroabietic acid isotopic label are added
In ultrapure water, manually snowmaker produces snow ice, uses2H or13The biomass combustion indicant that C isotope replaces is as research
Object, which incorporates in snow ice, forms snow and ice；
(5) snow and ice is uniformly laid in sample disc (8), is placed in flowing reactive cavity (7), selected in specific OH
Under number of free radical, react OH free radical with snow and ice, after reaction
The sample is protected from light, freezen protective, remains the test of ultra performance liquid chromatography mass spectrometer；
(6) change OH number of free radical, repeat step (5)；
(7) it after melting the sample that step (6) obtain respectively, is tested immediately with ultra performance liquid chromatography mass spectrometer,
Concentration after the reaction of each biomass combustion indicant is obtained, it is free that specific temperature difference OH is calculated using the formula (1)
Second order reaction constant under base concentration conditions is averaging resulting second order reaction constant, obtains generally applicable under specific temperature
Second order reaction constant mean；
(8) it on the basis of obtaining the second order reaction constant mean under each indicant specific temperature, is calculated using the formula (2)
The initial settlement concentration of biomass combustion indicant in natural environment snow ice.
7. the method for biomass combustion indicant concentration, the concentration of OH free radical in correction snow ice according to claim 6
Calculation formula are as follows:(3),
In formula: [OH] represents the concentration of OH free radical, unit are as follows: molecule.cm-3；M1To be detected on reaction post-sampling film
2,3-DHBA or 2, the amount of the substance of 5-DHBA, unit are as follows: mol；N is Avgadro constant, and value is 6.02 × 1023；
F1For 2,3-DHBA or 2, the yield of 5-DHBA, respectively 52% and 48%；S is acquisition gas overall flow rate, unit are as follows: cm3.min-1；T is acquisition time, unit min；α is extraction efficiency.
8. the method for biomass combustion indicant concentration, flowing reactive cavity (7) in correction snow ice according to claim 6
Main body is made of the good red copper material of thermal conductivity.
9. the method for biomass combustion indicant concentration, Mega-Ray simulated light in correction snow ice according to claim 6
Source (9) shelling machine is antifog material.
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