CN113687000A - Detection method for sulfur dioxide in ambient air and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of sulfur dioxide detection, and discloses a method for detecting sulfur dioxide in ambient air and application thereof, wherein the method comprises the following steps: detecting a plurality of groups of sulfur dioxide standard gas samples with known concentration by a gas chromatograph, and establishing a substance quantity fraction-peak height standard curve by taking the maximum value of the response value corresponding to sulfur dioxide as the peak height; detecting the gas sample to be detected by a gas chromatograph, taking the maximum value of the response value corresponding to the sulfur dioxide as the peak height, and substituting the peak height into the relational expression of the standard curve, so as to calculate the sulfur dioxide content in the gas sample to be detected; wherein the gas chromatograph is equipped with a flame photometric detector. The sampling method is simple, the sampling time is short, toxic and harmful reagents are not used, the detection method has good selectivity, the consistency of the detection result and the automatic monitoring result is good, the automatic analysis after sampling can be realized, and the method can be used for continuously and rapidly measuring the trace sulfur dioxide in the ambient air.
Description
Technical Field
The invention relates to the technical field of sulfur dioxide detection, in particular to a method for detecting sulfur dioxide in ambient air and application thereof.
Background
Sulfur dioxide is a colorless, irritating gas that is one of the most common and major pollutants in the atmosphere. Sulfur dioxide has strong chemical activity, can stimulate the respiratory tract of a human body, and causes diseases such as pneumonia and the like; various metals and carbonate building materials can be corroded, and the safety of buildings and machinery is harmed; can react with various dyes and pigments to cause the fading and the damage of clothes and artworks. In recent years, with the continuous and intensive research on the mechanism of formation of atmospheric pollution, sulfur dioxide is recognized as an important precursor for forming secondary pollution of the atmosphere. The sulfur dioxide in the atmosphere is mainly generated from the combustion process of sulfur-containing minerals and fossil fuels, and the natural processes of volcanic eruption, organic matter decay and the like. In order to reduce the influence of sulfur dioxide on production and life, the concentration of sulfur dioxide in ambient air is strictly controlled in China. With the continuous progress of ecological environment protection technology and the gradual implementation of measures, the concentration of sulfur dioxide in the ambient air shows a gradual decline trend.
The current standard detection method for sulfur dioxide in ambient air mainly comprises HJ482-2009 Formaldehyde absorption-Pararosaniline spectrophotometry (lower detection limit is 0.007 mg/m)3Lower limit of quantitation of 0.028mg/m3) HJ483-2009 tetrachloromercury salt absorption-pararosaniline spectrophotometry (lower limit of detection 0.005 mg/m)3Lower limit of quantitation of 0.020mg/m3) And the like. In the implementation process of the standard methods, the problems and the disadvantages of strong reagent toxicity, secondary pollution, complex preparation process, much interference in sample determination, long field sampling time and the like are also exposed.
Therefore, the invention provides a method for detecting sulfur dioxide in ambient air, which is convenient to operate, and application thereof.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for detecting sulfur dioxide in ambient air and application thereof.
The invention discloses a method for detecting sulfur dioxide in ambient air and application thereof, which are realized by the following technical scheme:
the first purpose of the invention is to provide a method for detecting sulfur dioxide in ambient air, which comprises the following steps:
presetting a plurality of groups of sulfur dioxide standard gas samples with known concentration, respectively detecting the sulfur dioxide standard gas samples by a gas chromatograph to obtain peak heights corresponding to sulfur dioxide in the plurality of groups of sulfur dioxide standard gas samples with known concentration, and establishing a substance quantity fraction-peak height standard curve; detecting the gas sample to be detected through a gas chromatograph to obtain the peak height corresponding to the sulfur dioxide in the gas sample to be detected, and substituting the peak height into the relation of the standard curve to calculate the content of the sulfur dioxide in the gas sample to be detected;
wherein the peak height refers to the maximum value of the response value corresponding to the sulfur dioxide; and before detecting the peak height, the standard gas sample or the gas sample to be detected is further subjected to the following pretreatment:
adsorbing a standard gas sample or a gas sample to be detected in a thermal desorption tube filled with Tenax, then desorbing the standard gas sample or the gas sample to be detected at 275-285 ℃ to obtain desorption gas, purging the desorbed gas into a container at-25 to-15 ℃ by inert gas or nitrogen, heating the container to 290-310 ℃ at the speed of 35-45 ℃/s to volatilize the desorbed gas, and introducing the volatilized gas into a gas chromatograph for detection; the gas chromatograph is equipped with a flame photometric detector.
Further, the peak height is measured by:
and introducing the volatilized gas obtained by pretreating the standard gas sample or the gas sample to be detected into a gas chromatograph, detecting the gas by a flame photometric detector equipped with the gas chromatograph to obtain a chromatographic spectrogram with a response value changing along with retention time, and selecting the maximum value of the response value at the retention time of 4.2-4.4 min as the peak height corresponding to sulfur dioxide in the standard gas sample and the gas sample to be detected.
Further, the standard curve is established by the following steps:
and (3) repeatedly measuring each sulfur dioxide standard gas sample with known concentration for 2 times, and calculating a linear relation between the square root of the average value h of the sulfur dioxide peak heights and the quantity fraction c of substances thereof by using a least square method to obtain the standard curve: c is 78.35. h0.5。
Further, the standard gas sample or the gas sample to be detected passes through the thermal desorption pipe at the flow rate of 150-250 mL/min for 5-20 min, so that the standard gas sample or the gas sample to be detected is adsorbed in the thermal desorption pipe.
Furthermore, the particle size of the Tenax filled in the thermal desorption tube is 0.32 mm-0.42 mm.
Further, the conditions of the peak height test are as follows:
the chromatographic conditions were as follows: the carrier gas is nitrogen with volume fraction of more than 99.999 percent, and the flow rate of the column is 2 mL/min;
the temperature of the flame photometric detector is 200 ℃, the fuel gas is hydrogen with the volume fraction of more than 99.999 percent, the flow rate is 50mL/min, the combustion-supporting gas is air, and the flow rate is 60 mL/min.
Further, the chromatographic column of the Gas chromatograph is a Gas Pro bonded silica gel porous layer open tubular column.
Further, air in the area to be detected is collected through an air sampler, and then the air in the air sampler is introduced into the thermal desorption pipe.
Furthermore, the sampling rate of the atmospheric sampler is 150-250 mL/min.
The second purpose of the invention is to provide the application of the detection method in detecting the content of sulfur dioxide in ambient air.
Compared with the prior art, the invention has the following beneficial effects:
the method adopts the thermal desorption gas chromatography to detect the trace sulfur dioxide in the ambient air, and compared with the standard detection method, the method has the advantages of simple sampling method, short sampling time, no use of toxic and harmful reagents, good detection method selectivity, equivalent detection limit to the standard method, good consistency of the detection result and the automatic monitoring result, realization of automatic analysis after sampling, and continuous and rapid determination of the trace sulfur dioxide in the ambient air.
The method comprises the steps of enabling a sulfur dioxide sample in ambient air to pass through a thermal desorption tube filled with TenaxTA to be adsorbed in the thermal desorption tube, enabling the sulfur dioxide sample to enter a gas chromatograph after being desorbed, detecting the sulfur dioxide sample by using a flame photometric detector, and quantifying by using a standard curve established by sulfur dioxide standard gas in nitrogen. According to the method, the linear range of sulfur dioxide is 47.0-960 nmol/mol, the quantitative repeatability is 5.6%, the detection limit is 3.1nmol/mol, the linear correlation coefficient r is 0.9983, and inorganic sulfides and other inorganic gas impurities do not interfere with detection. The analysis result of the method is compared with the trace sulfur dioxide monitoring result of the atmospheric automatic station for a long time, the linear correlation coefficient r between the analysis result and the trace sulfur dioxide monitoring result is 0.91, meanwhile, the analysis of variance of the two samples is carried out by using an F test method, and the monitoring value and the analysis value have no significant difference along the trend of time change.
Drawings
FIG. 1 is a graph of the linear measurement range of a standard curve according to the present invention;
FIG. 2 is a blank value detection chromatogram with nitrogen as a blank in accordance with the present invention;
FIG. 3 is an analytical chromatogram of an inorganic sulfur gas mixture according to the present invention;
FIG. 4 is a trend graph of monitored values versus analyzed values in accordance with the present invention;
FIG. 5 is a graph of adsorption time versus response value for the present invention;
FIG. 6 shows the temperature rise procedure and chromatogram of the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
It should be noted that, in the following examples:
the Tenax (poly 2, 6-diphenyl-p-phenylene ether) used is Tenax TA, and the particle size of the Tenax TA is 0.32 mm-0.42 mm.
The chromatographic column of the Gas chromatograph is a Gas Pro bonded silica gel porous layer open tubular column.
The thermal desorption apparatus used was a model TM300 thermal desorption apparatus from Pekin Elmer, USA.
The gas chromatograph used is 7890 gas chromatograph of Agilent company in America, is provided with a Flame Photometric Detector (FPD), and an instrument gas path system is passivated to meet the requirement of sulfide detection.
The used air sampler is a constant-flow air sampler of standard measuring science and technology limited in Sichuan, and the flow range of the constant-flow air sampler is (0-1) L/min.
The gas dilution device used is a gas dilution device of the American environmental corporation, the mass flow control range of the gas dilution device is (0.01-1.0) L/min, and the flow stability of the gas dilution device is +/-2%.
Example 1
The embodiment provides a method for detecting sulfur dioxide in ambient air, which comprises the following steps:
collecting a gas sample to be detected by an atmospheric sampler at a sampling rate of 200mL/min, then introducing the gas in the atmospheric sampler into a thermal desorption tube, and allowing the gas sample to be detected to pass through the thermal desorption tube filled with Tenax at a flow rate of 200mL/min for 10min to be adsorbed in the thermal desorption tube;
placing the thermal desorption tube absorbed with the gas sample to be detected in a thermal desorption instrument at 280 ℃ to separate the gas from the thermal desorption tube, blowing the separated gas into a desorption cold trap of the thermal desorption instrument at the temperature of minus 20 ℃ by nitrogen with the volume fraction of 99.999%, then heating the desorption cold trap to 300 ℃ at the speed of 40 ℃/s to volatilize the gas, introducing the volatilized gas into a gas chromatograph equipped with a flame photometric detector through a transmission pipeline at the temperature of 150 ℃, further determining the sulfur dioxide content in the desorbed gas through the flame photometric detector, and carrying out qualitative and quantitative analysis on the gas.
Wherein, the chromatographic column of the Gas chromatograph is a Gas Pro bonded silica gel porous layer open tubular column.
The conditions for the qualitative and quantitative analysis are as follows:
the chromatographic conditions were as follows: the carrier gas is nitrogen with volume fraction of more than 99.999 percent, and the flow rate of the column is 2 mL/min;
the temperature of the flame photometric detector is 200 ℃, the fuel gas is hydrogen, the flow rate is 50mL/min, the combustion-supporting gas is air, and the flow rate is 60 mL/min.
Example 2
The embodiment provides a method for detecting sulfur dioxide in ambient air, which comprises the following steps:
collecting a gas sample to be detected by an atmospheric sampler at the sampling rate of 150mL/min, then introducing the gas in the atmospheric sampler into a thermal desorption tube, and enabling the gas sample to be detected to pass through the thermal desorption tube filled with TenaxTA at the flow rate of 150mL/min for 20min so as to be adsorbed in the thermal desorption tube;
placing the thermal desorption tube absorbed with the gas sample to be detected in a 275 ℃ thermal desorption instrument, separating the gas from the thermal desorption tube, blowing the separated gas into a desorption cold trap of the thermal desorption instrument with the temperature of minus 25 ℃ by nitrogen with the volume fraction of 99.999%, then heating the temperature of the secondary desorption cold trap to 290 ℃ at the speed of 35 ℃/s, volatilizing the gas, introducing the volatilized gas into a gas chromatograph equipped with a flame photometric detector through a transmission pipeline with the temperature of 150 ℃, further determining the sulfur dioxide content in the desorbed gas through the flame photometric detector, and carrying out qualitative and quantitative analysis on the gas.
Wherein the particle size of the TenaxTA filled in the thermal desorption tube is 0.32 mm.
The chromatographic column of the Gas chromatograph is a Gas Pro bonded silica gel porous layer open tubular column.
The conditions for the qualitative and quantitative analysis are as follows:
the chromatographic conditions were as follows: the carrier gas is nitrogen with volume fraction of more than 99.999 percent, and the flow rate of the column is 2 mL/min;
the temperature of the flame photometric detector is 200 ℃, the fuel gas is hydrogen with the volume fraction of more than 99.999 percent, the flow rate is 50mL/min, the combustion-supporting gas is air, and the flow rate is 60 mL/min.
Example 3
The embodiment provides a method for detecting sulfur dioxide in ambient air, which comprises the following steps:
collecting a gas sample to be detected by an atmospheric sampler at a sampling rate of 250mL/min, then introducing the gas in the atmospheric sampler into a thermal desorption tube, and enabling the gas sample to be detected to pass through the thermal desorption tube filled with TenaxTA at a flow rate of 250mL/min for 5min so as to be adsorbed in the thermal desorption tube;
placing the thermal desorption tube absorbed with the gas sample to be detected in a thermal desorption instrument at 285 ℃, separating the gas from the thermal desorption tube, blowing the separated gas into a desorption cold trap of the thermal desorption instrument at-15 ℃ by nitrogen with the volume fraction of 99.999%, then heating the temperature of the secondary desorption cold trap to 310 ℃ at the speed of 45 ℃/s to volatilize the gas, introducing the volatilized gas into a gas chromatograph equipped with a flame photometric detector through a transmission pipeline with the temperature of 150 ℃, further determining the sulfur dioxide content in the desorbed gas through the flame photometric detector, and carrying out qualitative and quantitative analysis on the gas.
Wherein the particle size of the TenaxTA filled in the thermal desorption tube is 0.42 mm.
The chromatographic column of the Gas chromatograph is a Gas Pro bonded silica gel porous layer open tubular column.
The conditions for the qualitative and quantitative analysis are as follows:
the chromatographic conditions were as follows: the carrier gas is nitrogen with volume fraction of more than 99.999 percent, and the flow rate of the column is 2 mL/min;
the temperature of the flame photometric detector is 200 ℃, the fuel gas is hydrogen with the volume fraction of more than 99.999 percent, the flow rate is 50mL/min, the combustion-supporting gas is air, and the flow rate is 60 mL/min.
The standard curves in the above embodiments of the present invention are obtained by the following steps:
(1) preparation of Standard samples
Respectively decompressing sulfur dioxide gas series standard substances in nitrogen, namely gases with the sulfur dioxide content of 47.0, 97.5, 489 and 960nmol/mol, then introducing the gases into a gas diluting device, setting the gas flow rate to be 200mL/min, adsorbing for 10min by using an adsorption tube, and directly introducing into a thermal desorption instrument for determination.
The series of standard substances of sulfur dioxide gas in nitrogen used by the invention are from liquefied air (Shanghai) compressed gas, and the sulfur dioxide content is 47.0, 97.5, 489 and 960nmol/mol respectively.
(2) Standard curve
By repeating the measurement of each standard substance in the above-mentioned sulfur dioxide gas series of standard substances 2 times, a linear relationship between the square root of the average value h of the sulfur dioxide peak height and the quantity fraction c of the substance was calculated by the least square method, and the result is shown in fig. 1, and a standard curve was obtained as follows: c is 78.35. h0.5And the linear range of the standard curve is 47.0-960 nmol/mol, so that a standard curve corresponding to the mass fraction-peak height of the substance is obtained, and the mass fraction of the target compound substance is calculated according to the standard curve.
Experimental part
In order to verify the reliability of the detection results of the method of the present invention, the present invention performed the following experiments.
(I) repeatability of test results of the method of the invention
According to the invention, a gas standard substance with the sulfur dioxide content of 489nmol/mol is selected, 6 repeated analyses are carried out according to the analysis conditions in the example 1, and the results are shown in the table 1, wherein the relative standard deviation of the retention time is 0.1%, and the relative standard deviation of the peak area is 5.6%.
TABLE 1 repeatability of assay results
(II) Linear measuring range detected by the method of the invention
(1) Blank value detection and method detection limits
Analysis was performed under the analysis conditions in example 1 using high-purity nitrogen gas, and a chromatogram was obtained as shown in FIG. 2, with a peak-to-peak noise n of 0.00113 μ A.
(2) Blank value detection
The limit of detection D of the analytical method was calculated as follows:
in the formula, c is the mass fraction of sulfur dioxide in the low-concentration gas standard substance (47.0nmol/mol), and h is the average value of peak heights (0.766 μ A).
(III) interference test of other gases on detection method of the invention
The invention is carried out by Agilent 7890 gas chromatograph equipped with flame photometric detector, which responds to sulfur-containing compounds only, and common gas impurities such as CO and CO2Methane CH4And so on, are unresponsive. According to the invention, the inorganic sulfur mixed gas standard substance is directly subjected to sample injection analysis, the result is shown in figure 3 and table 2, the separation degree of each adjacent component is greater than 1.5, and the measurement of sulfur dioxide is not interfered.
TABLE 2 analysis results of inorganic sulfur mixture gas
Wherein the inorganic sulfur mixed gas standard substance is from Chinese test technology research institute, and comprises hydrogen sulfide (H)2S) 5. mu. mol/mol, Carbon Oxysulfide (COS) 20. mu. mol/mol, carbon disulfide (CS)2) 10. mu. mol/mol, sulfur dioxide (SO)2)20μmol/mol。
(IV) comparing with monitoring results of automatic atmospheric stations
The air near an atmospheric automatic station was sampled and analyzed 13 times within 63 days by thermal desorption gas chromatography and compared with the results of the contemporaneous monitoring of the automatic station, as shown in table 3:
TABLE 3 comparison of monitor values to assay values
The trend of the monitored and analyzed values over time is shown in fig. 4.
The monitoring values c in Table 3 are shown by the least square methodMAnd the check value cAPerforming regression analysis to obtain a fitting curve of cM＝0.6463×cA-0.76, correlation coefficient r ═ 0.91; performing double-sample variance analysis on the two samples by using an F test method, wherein F is 1.74, and searching an F distribution table to obtain F0.05(12,12) is 2.69, and F is 1.74<F0.05, which shows that the monitored value and the analyzed value have no significant difference along the time change trend.
(V) Effect of adsorption time on test results
The present invention selects different adsorption times, and performs the sulfur dioxide gas standard substance whose analyte amount fraction is 97.5nmol/mol according to the analysis conditions of example 1, and obtains a relationship between the adsorption time t and the detector response peak height h as shown in fig. 5.
It can be seen from fig. 5 that the adsorption time and the detector response are logarithmically related for the same concentration of the sulfur dioxide gas sample. Considering factors such as total analysis time, standard gas consumption and the like, the adsorption time selected by the method is 10 min.
It should be noted that the detection method or principle not specifically described in the present invention belongs to the prior art, and those skilled in the art should understand that the instruments used in the above embodiments of the present invention are as follows.
The Gas chromatograph adopted by the invention is a 7890 type Gas chromatograph, and is provided with a Flame Photometric Detector (FPD), Agilent company in America is provided with a Gas Pro bonded silica gel porous layer open tubular column, the inner diameter is 0.32mm, the length is 30m, and an instrument Gas path system is subjected to passivation treatment to meet the requirement of sulfide detection; through tests and optimization, the retention time of sulfur dioxide can be shortened to be within 5min by selecting a chromatographic temperature rising program as shown in figure 6.
TM300 thermal desorption apparatus, Pekin Elmer, usa;
a stainless steel thermal desorption tube, the diameter of which is 6.35mm (1/4 inches), the length of which is 88.9mm (3.5 inches), and 0.2g of poly 2, 6-diphenyl-1, 4-phenylate (Tenax TA, the particle diameter is 0.32 mm-0.42 mm, 60-80 meshes) is filled in the stainless steel thermal desorption tube;
the constant-current air sampler is a Sichuan standard measurement science and technology limited company, and the flow range is 0-1L/min.
A gas dilution device, Environment corporation, USA, the mass flow control range is 0.01-1.0L/min, and the flow stability is +/-2%;
the method comprises the steps of enabling a sulfur dioxide sample in ambient air to pass through a thermal desorption tube filled with TenaxTA, adsorbing for 10min at the flow rate of 200mL/min, desorbing at 300 ℃, then enabling the sample to enter a gas chromatograph, detecting by using a flame photometric detector, and establishing a standard curve by using sulfur dioxide standard gas in nitrogen for quantification. According to the method, the linear range of sulfur dioxide is 47.0-960 nmol/mol, the quantitative repeatability is 5.6%, the detection limit is 3.1nmol/mol, the linear correlation coefficient r is 0.9983, and inorganic sulfides and other inorganic gas impurities do not interfere with detection. The analysis result of the method is compared with the trace sulfur dioxide monitoring result of the atmospheric automatic station for a long time, the linear correlation coefficient r between the analysis result and the trace sulfur dioxide monitoring result is 0.91, meanwhile, the analysis of variance of the two samples is carried out by using an F test method, and the monitoring value and the analysis value have no significant difference along the trend of time change.
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A method for detecting sulfur dioxide in ambient air is characterized by comprising the following steps:
presetting a plurality of groups of sulfur dioxide standard gas samples with known concentration, respectively detecting the sulfur dioxide standard gas samples by a gas chromatograph to obtain peak heights corresponding to sulfur dioxide in the plurality of groups of sulfur dioxide standard gas samples with known concentration, and establishing a substance quantity fraction-peak height standard curve;
detecting the gas sample to be detected through a gas chromatograph to obtain the peak height corresponding to the sulfur dioxide in the gas sample to be detected, and substituting the peak height into the relation of the standard curve to calculate the content of the sulfur dioxide in the gas sample to be detected;
wherein the peak height refers to the maximum value of the response value corresponding to the sulfur dioxide; and before detecting the peak height, the standard gas sample or the gas sample to be detected is further subjected to the following pretreatment:
adsorbing a standard gas sample or a gas sample to be detected in a thermal desorption tube filled with Tenax, then desorbing the standard gas sample or the gas sample to be detected at 275-285 ℃ to obtain desorption gas, purging the desorbed gas into a container at-25 to-15 ℃ by inert gas or nitrogen, heating the container to 290-310 ℃ at the speed of 35-45 ℃/s to volatilize the desorbed gas, and introducing the volatilized gas into a gas chromatograph for detection; the gas chromatograph is equipped with a flame photometric detector.
2. The method of claim 1, wherein the peak height is measured by:
and introducing the volatilized gas obtained by pretreating the standard gas sample or the gas sample to be detected into a gas chromatograph, detecting the gas by a flame photometric detector equipped with the gas chromatograph to obtain a chromatographic spectrogram with a response value changing along with retention time, and selecting the maximum value of the response value at the retention time corresponding to sulfur dioxide as the peak height corresponding to the sulfur dioxide in the standard gas sample or the gas sample to be detected.
3. The method of claim 1, wherein the standard curve is established by the steps of:
and (3) repeatedly measuring each sulfur dioxide standard gas sample with known concentration for 2 times, and calculating a linear relation between the square root of the average value h of the sulfur dioxide peak heights and the quantity fraction c of substances thereof by using a least square method to obtain the standard curve:
c＝78.35·h0.5。
4. the method according to claim 1, wherein the standard gas sample or the gas sample to be detected is passed through the thermal desorption tube at a flow rate of 150-250 mL/min for 5-20 min, so that the standard gas sample or the gas sample to be detected is adsorbed in the thermal desorption tube.
5. The method for detecting sulfur dioxide in ambient air according to claim 1, wherein the particle size of the Tenax filled in the thermal desorption tube is 0.32mm to 0.42 mm.
6. The method for detecting sulfur dioxide in ambient air as claimed in claim 1, wherein said peak height test condition is:
the chromatographic conditions were as follows: the carrier gas is nitrogen with volume fraction of more than 99.999 percent, and the flow rate of the column is 2 mL/min;
the temperature of the flame photometric detector is 200 ℃, the fuel gas is hydrogen, the flow rate is 50mL/min, the combustion-supporting gas is air, and the flow rate is 60 mL/min.
7. The method according to claim 1, wherein the chromatographic column of the Gas chromatograph is a Gas Pro bonded silica gel porous open tubular column.
8. The method as claimed in claim 1, wherein the air in the area to be detected is collected by an atmospheric sampling device, and then the gas in the atmospheric sampling device is introduced into the thermal desorption tube.
9. The method as claimed in claim 8, wherein the sampling rate of the atmospheric sampling device is 150-250 mL/min.
10. Use of a method according to any one of claims 1 to 9 for detecting the sulphur dioxide content of ambient air.
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