CN112730575A - PM (particulate matter) capable of analyzing ambient air2.5Method for obtaining primary sulfate - Google Patents
PM (particulate matter) capable of analyzing ambient air2.5Method for obtaining primary sulfate Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 122
- 239000013618 particulate matter Substances 0.000 title claims description 69
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 131
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000011593 sulfur Substances 0.000 claims abstract description 129
- 239000000203 mixture Substances 0.000 claims abstract description 106
- 239000012080 ambient air Substances 0.000 claims abstract description 56
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 48
- 239000001301 oxygen Substances 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 43
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- 239000002028 Biomass Substances 0.000 claims abstract description 9
- 238000002485 combustion reaction Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 9
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- 238000001228 spectrum Methods 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 8
- 238000010168 coupling process Methods 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- 239000003344 environmental pollutant Substances 0.000 claims description 8
- 231100000719 pollutant Toxicity 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 7
- 238000013178 mathematical model Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004508 fractional distillation Methods 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 description 15
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 230000000155 isotopic effect Effects 0.000 description 3
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Abstract
The invention discloses a method for analyzing PM in ambient air2.5The method for determining the source of primary sulfate comprises determining the PM of the ambient air2.5Sulfur and oxygen isotope composition of sulfate, and ambient air SO2Collecting biomass combustion, coal and motor vehicle tail gas samples in a research area, analyzing the sulfur isotope composition, establishing a source characteristic spectrum of the sulfur isotope composition in the research area, and calculating to obtain PM2.5Sulfur isotope composition of primary sulfate, and finally analyzing PM in ambient air by using sulfur isotope technology2.5Source of primary sulfate. The method utilizes the isotope fractionation effect and the sulfur and oxygen isotope mass balance model to calculate the sulfur isotope composition of the primary sulfate, solves the problems that the primary sulfate and the secondary sulfate are difficult to separate and the sulfur isotope composition of the primary sulfate is difficult to directly measure, and provides a new idea for effectively controlling and identifying the pollution of the sulfate.
Description
Technical Field
The invention relates to a method for analyzing PM in ambient air2.5Method for preparing primary sulfate source, especially by coupling sulfur and oxygen isotopesTrace ambient air PM2.5The method for preparing the primary sulfate source.
Background
PM2.5Is a particulate matter with aerodynamic diameter less than or equal to 2.5 μm, is easy to adhere to water-soluble ions, carbon-containing components, heavy metals and other pollutants, and the combination effect of various pollutants enhances PM2.5The toxic effect on human body increases the exposure risk of human body facing lung cancer, and increases the morbidity and mortality of cancer and respiratory system diseases. Ren jiao (ren jiao, Yi Shi Jie, Guo Shufeng, 2020. Taiyuan City atmospheric PM2.5Seasonal pollution characteristics and source analysis of medium water-soluble ions, the environmental science bulletin 40(10),1-11) compares the PM of cities in China2.5The concentration of water-soluble ions was found to be PM between 2015 and 20192.5In SO4 2-、NO3 -、NH4 +(SNA is the most important water-soluble ion, and occupies PM2.5In a proportion of 26.80% -53.46%, wherein SO4 2-Accounts for 27.64% -44.64% of SNA, and specifies SO4 2-Source of (2) effectively controls PM2.5Plays an important role. Current PM2.5The method for analyzing the water-soluble ion source mainly comprises an ion ratio method, correlation analysis and principal component analysis. Chengyuan etc. (Chengyuan, Wujiahui, Bixiahui, Yanglaumei, Liubao, Dai, Li Pu, Yujia, Feng Ying factory, 2019 atmospheric PM of Wuhan City2.5The environmental science bulletin 39(1),189 and 196) finds the annual NO in Wuhan City3 -/SO4 2-The ratio is 0.9, which indicates that the fixed source contribution is relatively large, and the principal component analysis finds the PM in Wuhan City2.5The water-soluble ions mainly come from coal and motor vehicle emissions, industrial production, dust emission and the like. Mu et al (Mu, L, Zheng, L, Liang, M, Tian, M, Li, X, J, D, 2019, Characterization and source analysis of water-soluble ions in organic particles in Jinzhong, China, Aerosol and Water quality research 19(11),2396-Combustion, dust particles and industrial emissions.
Stable isotope technology is being applied to the source analysis of atmospheric pollutants, and sulfur isotope technology has been used for the estimation of emission factors, the analysis of atmospheric pollutant sources, and the conversion tracing. Han 29667, et al (Han , Niger, Chenolili, a beautiful gem of Wang, Shenjia rain, Weiying, Guzhuang ice, Zhubin, 2018. research on sulfate sources and oxidation pathways in summer atmosphere in North suburbs of Nanjing based on sulfur and oxygen isotopes environmental sciences 39(05),2010-4 2-And possibly the sulfur isotope composition (delta) of the source34S), finding SO in the atmosphere in summer of suburb of Nanjing4 2-Mainly from local coal and tail gas emission, secondary SO in aerosol4 2-The oxidation route of (2) is dominated by homogeneous oxidation. Weiying and so on (Weiying, Guo Zhao, Ge Xin, Zhu Dong, Jiang Wen Juan, Shi Lei, Chen Shu, 2015. Sulfur oxygen isotope tracing south Beijing suburb atmosphere PM2.5Source of sulfate environmental science 36(04),1182-34S value comparison and backward trajectory analysis show that SO is in the atmosphere in the suburb winter of Nanjing4 2-Primarily by sulfur in local coal, and secondarily by remote sulfur transport. Norman et al (Norman, A. -L., Anauf, K., Hayden, K., Thompson, B., Brook, J.R., Li, S. -M., Bottenheim, J.,2006.Aerosol sulfate and its oxidation on the Pacific NW coast: S and O isotopes in PM)2.5Atmospheric Environment 40(15),2676-2689) utilizing PM2.5Research on SO on North coast of Taiping ocean by using sulfur and oxygen isotopes4 2-And oxidation thereof, determination of primary and secondary SO4 2-The contribution of (c). Norman et al (Norman, A.L., Belzer, W., Barrie, L.,2004.insight into the biological distribution of total sulfur in aerosol and precipitation in the framework Valley after which by side isotopes of sulflures and oxyden. journal of geographic Research: atmosphers 109(D5)) analyzed Frazier river Valley aerosols and total SO in precipitation by isotopes of sulfur and oxygen4 2-The biological cause contribution of (1) to research SO4 2-Particulate matter and industrial source emission SO2Delta of34S, finding δ34S value range is-1.6 ‰About 9 per mill. Sinha et al (Sinha, B.W., Hoppe, P., Huth, J., Foley, S., Andrea, M.O.,2008.Sulfur isocopane analytes of inorganic aerogel particles in the urban aerogel at a central European site (Mainz, Germany) Atmospheric Chemistry and Physics 8(23),7217-4 2-The isotopic composition was found to be homogeneous, unaffected by the chemical composition, and the heterogeneous oxidation was found to be on secondary SO4 2-The contribution formed varies greatly from day to day, depending on meteorological conditions. No concern with respect to ambient air PM is currently seen2.5Primary SO4 2-The literature reports on the research on the sulfur isotope composition, and the application of the sulfur isotope technology to primary SO is not found4 2-Report of source resolution.
SO in particulate matter4 2-The source is complex, and the SO can be generated by primary discharge or secondary oxidation4 2-The sulfur isotope composition characteristics of the emission source are reserved, and secondary SO4 2-Delta of34S value and precursor SO2Delta of34S value and oxidation process dependent, secondary SO4 2-Delta of34The S value can be used to determine SO formation4 2-The oxidation pathway of (Norman, A. -L., Anauf, K., Hayden, K., Thompson, B., Brook, J.R., Li, S. -M., Bottenheim, J.,2006.Aerosol sulfate and its oxidation on the Pacific NW coast: S and O isotopes in PM)2.5Atmospheric Environment 40(15), 2676-2689). SO in particulate matter4 2-Delta of34S values are primary and secondary SO4 2-Delta of34Results of S value synthesis in order to more accurately resolve SO4 2-The primary and secondary SO is required4 2-Delta of34S value, sulfur isotope composition characteristics of pollution source, primary SO4 2-Delta of34Delta of S value and contamination Source34S value comparison to clarify SO4 2-Primary emission source information. Shi Lei et al (Shi Lei, Gu Ning, Jiang Wen Juan, Rui Mao Ling, Zeng gang, 2016. Nanjing area atmospheric PM2.5Potential pollutionEnvironmental science 37(01),22-27) researches show that coal ash, motor vehicle tail gas and biomass ash delta in Nanjing area34The S value ranges from 1.8 per thousand to 3.7 per thousand, from 4.6 per thousand to 9.7 per thousand and from 5.2 per thousand to 9.9 per thousand respectively, and the sulfur isotope of the coal ash is lighter. Because of the difference of sulfur isotope composition of each pollution source in different areas, in order to research SO once in a targeted way4 2-The source of (a) is required to establish a source profile of the composition of the sulfur isotopes in the region of investigation.
Disclosure of Invention
The invention aims to provide a method for analyzing PM in ambient air2.5Method for preparing primary sulfate source by researching primary SO by using sulfur and oxygen isotope coupling technology4 2-The sulfur isotope composition and the primary source analysis; solves the problems of primary and secondary SO in the particles4 2-Difficult separation and direct measurement of one-time SO4 2-The sulfur isotope composition of (a).
The invention provides a method for analyzing PM in ambient air2.5The method for determining the source of the primary sulfate is to measure the PM of the ambient air firstly2.5Sulfur and oxygen isotope composition of sulfate, and ambient air SO2And sulfur isotope composition of a pollution source sample, and then calculating to obtain PM2.5Sulfur isotope composition of primary sulfate, and finally analyzing PM in ambient air by using sulfur isotope technology2.5Source of primary sulfate. The method comprises the following steps:
(1) collecting PM in ambient air2.5And SO2A sample;
(2) measurement of PM2.5Oxygen isotope composition of sulfate salt;
(3) determining PM by using the measurement result in the step (2) and an oxygen isotope mass balance model2.5The proportion of the primary sulfate and the secondary sulfate;
(4) determination of SO2The sulfur isotope composition of the secondary sulfate is calculated by utilizing the isotope fractionation effect;
(5) measurement of PM2.5Sulfur isotope composition of sulfate salt, using sulfurIsotope mass balance model determination of PM2.5Sulfur isotope composition of primary sulfate;
(6) collecting samples of biomass combustion, coal and motor vehicle tail gas, measuring sulfur isotope composition, and establishing a source characteristic spectrum of the sulfur isotope composition in a research area;
(7) method for analyzing PM in ambient air by utilizing sulfur isotope technology2.5Source of primary sulfate.
In the above technical solution, further additional technical features are as follows:
the sulfur isotope technology is used for tracing the source of the primary pollutant by utilizing the sulfur isotope composition characteristics of the pollutant in the ambient air.
The method for analyzing the source of the primary sulfate by using the sulfur isotope technology is to calculate the PM of the ambient air by using the sulfur and oxygen isotope coupling technology and combining the isotope fractionation effect and the isotope mass balance model2.5The sulfur isotope composition of the primary sulfate is utilized to trace PM2.5Source of primary sulfate.
The sulfur and oxygen isotope coupling technology is to calculate PM by using an oxygen isotope mass balance model2.5The proportion of the primary sulfate and the secondary sulfate is combined with the sulfur isotope composition of the secondary sulfate obtained by utilizing the isotope fractionation effect, and finally the PM is calculated by utilizing a sulfur isotope mass balance model2.5Sulfur isotope composition of primary sulfate. The sulfur isotope composition of the primary sulfate can be calculated by the following mathematical model.
δ34SPM sulphate＝δ34Sprimary×(1-fsecondary)+δ34Ssecondary×fsecondary
δ18OPM sulphate＝δ18Oprimary×(1-fsecnodary)+δ18Osecondary×fseccondary
δ34Ssecondary＝α×(δ34SSO2+1000)–1000
In the formula (f)secnodary-ambient air PM2.5The proportion of secondary sulfate;
δ34SPM sulphate-ambient air PM2.5Sulfur isotope composition of sulfate salt,% o;
δ34Sprimary-ambient air PM2.5Sulfur isotope composition of the primary sulfate is per mill;
δ34Ssecondary-ambient air PM2.5Sulfur isotope composition of secondary sulfate is per mill;
δ18OPM sulphate-ambient air PM2.5Oxygen isotope composition of sulfate salt,% o;
δ18Oprimary-ambient air PM2.5Oxygen isotope composition of the primary sulfate is per mill;
δ18Osecondary-ambient air PM2.5Oxygen isotope composition of secondary sulfate;
δ34SSO2SO in ambient air2The composition of the sulfur isotope is per mill;
alpha-fractional distillation coefficient of sulfur isotope.
The PM is traced by utilizing the sulfur isotope composition2.5The source of the primary sulfate is the PM obtained by comparative calculation2.5The sulfur isotope composition of the primary sulfate and the source characteristic spectrum of the sulfur isotope composition in the research area are determined, and the PM is determined2.5A primary source of sulfate emissions.
The invention has the beneficial effects that: the invention provides a PM analyzing environment air2.5Compared with the prior art, the method for preparing the primary sulfate source has the outstanding characteristics and remarkable progress that: (1) provides a new analysis environment air PM2.5The method for detecting the primary sulfate source overcomes the problems that the existing sulfate source is complex and the primary sulfate and the secondary sulfate are difficult to accurately identify; (2) application of isotope fractionation effect and isotope mass balance model to PM2.5The determination of the sulfur isotope composition of the primary sulfate fills the gap of the current research, and is an isotope technologyProviding basic data in the application of atmospheric science; (3) applying sulfur and oxygen isotope coupling technology to PM in ambient air2.5In the source analysis of the primary pollutant, a new idea is opened up for the application of isotope technology in the field of environmental science.
Drawings
FIG. 1 is a schematic diagram of a route for carrying out the process of the present invention.
FIG. 2 is a diagram of a filter sample treatment program according to the method of the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
the invention uses environmental air PM in spring, summer, autumn and winter of Taiyuan city in 4 seasons2.5The primary sulfate source is analyzed as an example, and the embodiment of the present invention is further described in detail by way of examples in conjunction with the accompanying drawings, so that those skilled in the art can realize the invention. The present embodiment is a detailed description of the present invention, and does not limit the present invention in any way.
The invention provides a method for analyzing PM in ambient air2.5The method of primary sulfate in the first place comprises measuring PM of ambient air2.5Sulfur and oxygen isotope composition of sulfate, and ambient air SO2And sulfur isotope composition of a pollution source sample, and then calculating to obtain PM2.5Sulfur isotope composition of primary sulfate, and finally analyzing PM in ambient air by using sulfur isotope technology2.5Source of primary sulfate. The specific method comprises the following steps:
step one, collecting environmental air and pollution source samples. Collecting an ambient air sample: the sampling point locations are functional areas such as commercial areas, residential areas, industrial areas and the like of the Taiyuan city; the sampling period is 4 seasons of spring, summer, autumn and winter in a non-snowy and windy day; the sampling quantity is limited by meeting the test of sulfur and oxygen isotope composition and representing the quality of environmental air in Taiyuan; the sampling time can be determined according to the cleanliness of local air, the detection limit of the isotope composition testing method used and the sampling efficiency of the instrument, and the principle is that the requirements of component analysis can be met. Collecting a pollution source sample: the method comprises the steps of collecting biomass combustion particle samples of wheat straws, corn straws, mung bean straws, Chinese parasol tree leaves, grape vines and sunflower straws in a research area, collecting bottom ash samples of a coal-fired boiler dust remover, and collecting tail gas particle samples of gasoline vehicles and diesel vehicles. Sampling and other requirements are implemented according to national sampling specifications.
Ambient air PM2.5(particulate matter having an aerodynamic diameter of less than 2.5 microns) and SO2Collecting: sampling is carried out for 7 days in succession in 4 seasons of spring, summer, autumn and winter respectively, and an improved standard large-volume sampler (TH-1000F) produced by Wuhan sky rainbow instruments GmbH is selected as a sampling device. Collecting PM of ambient air by using quartz fiber filter membrane2.5For the samples, in order to avoid the influence of residual carbon and other impurities in the filter membrane, the filter membrane is burned for 4.5 hours in a muffle furnace at 450 ℃ before sampling. Collecting SO with glass fiber filter membrane soaked in alkali liquor2And (3) sampling.
Step two, collecting the PM of the ambient air2.5、SO2And the biomass combustion sample are pretreated according to the flow shown in the attached figure 2. The specific process is as follows: 1/4 sample filter membranes are taken, cut into pieces and put into a centrifuge tube, 50mL deionized water is added, ultrasonic treatment is carried out for 30min at the constant temperature of 20 ℃, then centrifugation is carried out for 10min at 6000r/min, then the centrifuged solution is filtered by a filter head, and finally 3mL of 1mol/L BaCl is added2Fully oscillating the solution, standing for 24h, and performing suction filtration by using an acetate fiber filter membrane to obtain BaSO4Precipitating, repeatedly cleaning the precipitate with deionized water, transferring the precipitate and the filter membrane to a crucible, and burning at 850 deg.C in a muffle furnace for 2 hr to obtain pure BaSO4And (3) powder. In order to ensure the sample amount required by the analysis and test, the sulfur and oxygen isotope composition test samples are respectively pretreated by 1/4 films to obtain BaSO4And (3) powder. Converting sulfur in coal-fired flue dust and motor vehicle exhaust into BaSO by adopting the Askaka method4. Testing PM with isotope mass spectrometer2.5Sulfur, oxygen isotope composition, SO2And sulfur isotope composition in the contamination source sample. The sulfur isotope composition of the biomass combustion, fire coal and motor vehicle tail gas samples obtained by testing is utilized to establishSource profile of original market sulfur isotope composition.
The pretreatment method of the sample and the test analysis method of the sulfur and oxygen isotope composition in the steps are the prior art, are mature, and have good reproducibility of the analysis result.
Step three, according to the PM measured in the step two2.5Oxygen isotope composition of sulfate, and determination of PM by using oxygen isotope mass balance model2.5The ratio of primary and secondary sulfates.
The oxygen isotope composition is expressed as delta18O＝[(18O/16O)Sample (I)/(18O/16O)Standard of merit－1]X 1000, where delta18O is oxygen isotope composition,% O%18O/16O)Sample (I)Is the oxygen isotope ratio of the sample (b) ((b))18O/16O)Standard of meritIs the standard oxygen isotope ratio.
The mathematical model in the above steps of the invention is as follows:
δ18OPM sulphate＝δ18Oprimary×(1-fsecnodary)+δ18Osecondary×fseccondary (1)
in the formula, delta18OPM sulphateRefers to SO in the particulate matter4 2-Oxygen isotope composition,% o; delta18OprimaryMeans SO at one time4 2-The oxygen isotope composition per mill is calculated by a formula (2); f. ofsecnodaryRefers to secondary SO in particulate matter4 2-The proportion of the components is calculated; delta18OsecondaryMeaning secondary SO4 2-The oxygen isotope composition is per mill. Heterogeneous oxidation mechanism Secondary SO is calculated using equations (3) and (4)4 2-Oxygen isotope value of (1), in-phase oxidation mechanism, secondary SO calculated using equations (5) and (6)4 2-Oxygen isotope value of (a).
δ18Oprimary＝0.06×δ18Ovapour+38‰ (2)
δ18Osecondary＝0.78×δ18Oliquid+12.0‰(Fe3+And an excess of O2) (3)
δ18Osecondary＝0.528×δ18Oliquid–3.4‰(H2O2And HCl) (4)
δ18Osecondary＝0.69×δ18Oliquid+9.5‰(O3) (5)
δ18Osecondary＝0.84×δ18Oliquid+6.2‰(NO2) (6)
In the formula, delta18OvapourIs the oxygen isotope composition of water vapor, o is due to delta in formula (2)18OvapourThe coefficient of (d) is only 0.06, so δ can be used18OliquidSubstitution of delta18OvapourCalculating; delta18OliquidIs used for reducing the oxygen isotope value in water by per thousand. Data for oxygen stable isotopes in Tamagaldi are derived from GNIP (http:// www.iaea.org /).
The above method has been applied to estimate the ratio of primary and secondary sulfates in particulate matter, discussing the oxidation mechanism of secondary sulfates.
Step four, according to the SO measured in the step two2Sulfur isotope composition of (1), using SO2Oxidation to SO4 2-The sulfur isotope composition of the secondary sulfate was calculated.
The expression of the sulfur isotope composition is delta34S＝[(34S/32S)Sample (I)/(34S/32S)Standard of merit－1]X 1000, where delta34S is the composition of sulfur isotope ‰: (34S/32S)Sample (I)Is the sulfur isotope ratio of the sample (C:34S/32S)standard of meritStandard sulfur isotope ratios. The isotopic fractionation coefficient (α) characterizes the relative differences in isotopic composition between substances caused by fractionation. Alpha is defined as the quotient of the ratio of the contents of two isotopes in one compound and the corresponding ratio of the other compound.The precursor SO can be obtained by definition2And the sulfur isotope composition of the product secondary sulfate. The mathematical model in the above steps of the invention is as follows:
δ34Ssecondary＝α×(δ34SSO2+1000)–1000 (8)
in the formula, delta34SsecondaryIs the sulfur isotope composition of the secondary sulfate,% o; alpha is the fractional distillation coefficient of the isotope and is obtained by consulting the literature.
Step five, testing the obtained PM according to the step two2.5Determining the sulfur isotope composition of the sulfate, the proportion of the secondary sulfate calculated in the third step, the sulfur isotope composition of the secondary sulfate calculated in the fourth step, and determining the PM by using a sulfur isotope mass balance model2.5Sulfur isotope composition of primary sulfate.
Due to PM2.5The primary and secondary sulfates are difficult to separate, so that the sulfur isotope composition of the primary sulfate cannot be directly tested by using an instrument. The steps of the invention utilize the sulfur isotope mass balance principle to obtain the sulfur isotope composition of the primary sulfate through calculation, thereby providing basic data for the application of isotope technology in atmospheric science. Due to the PM of the ambient air2.5The sulfates in (1) include primary and secondary sulfates, thus ambient air PM2.5Middle-enriched34S capacity equal to primary and secondary sulfate enrichment34Linear summation of S capabilities. Therefore, the PM of the ambient air can be calculated by the following sulfur isotope mass balance model2.5Sulfur isotope composition of primary sulfate:
δ34SPM sulphate＝δ34Sprimary×(1-fsecondary)+δ34Ssecondary×fsecondary (7)
in the formula, delta34SPM sulphateRefers to SO in the particulate matter4 2-The composition of the sulfur isotope is per mill; delta34SprimaryMeans SO at one time4 2-The composition of sulfur isotope is per mill.
Step six, comparing and calculatingTo PM2.5The source characteristic spectrum of the sulfur isotope composition of the primary sulfate and the sulfur isotope composition of Tao Yuan City obtained in the second step is discussed to the PM2.5A primary source of sulfate emissions.
At present, the existing literature utilizes a sulfur isotope technology to resolve the source of sulfate in particulate matters and discusses the oxidation mechanism of secondary sulfate, and no technology of sulfur isotope technology to resolve PM in ambient air is found2.5Source of primary sulfate. Researches find that the sulfur isotope composition of the sulfate directly discharged by pollution sources has difference, so that the sulfur isotope composition can be used as a good marker for PM (particulate matter) in ambient air2.5In the first analysis of the source of sulfate. However, the primary sulfate is difficult to separate from the secondary sulfate, so that the sulfur isotope composition of the primary sulfate cannot be directly tested.
The steps of the invention are to obtain the environmental air PM in 4 seasons of spring, summer, autumn and winter through the model2.5Comparing the sulfur isotope composition of the primary sulfate with the sulfur isotope characteristic spectrum of the pollution source in the research area, and judging PM2.5The sulfur isotope composition of the primary sulfate is in the range of coal-fired smoke dust, motor vehicle tail gas or sulfur isotope composition of sulfate discharged by biomass combustion, thereby determining PM2.5The primary sulfate mainly comes from which kind of pollution source. The result can determine the main source of primary sulfate in 4 seasons of spring, summer, autumn and winter, so that the emission of the primary sulfate can be controlled in a targeted manner by taking measures in different seasons, and the PM of the environmental air in the Taiyuan city can be further effectively controlled2.5The pollution of sulfate reduces the harm to the health of human body.
Claims (5)
1. PM (particulate matter) capable of analyzing ambient air2.5The method for preparing the primary sulfate source is characterized by comprising the following steps: firstly, collecting PM of ambient air2.5And SO2Sample, analysis of PM2.5Sulfur, oxygen isotope composition and SO of sulfate salt2Sulfur isotope group ofCollecting biomass combustion, coal burning and motor vehicle tail gas samples in a research area, analyzing sulfur isotope composition, establishing a source characteristic spectrum of the sulfur isotope composition in the research area, and calculating PM of ambient air by utilizing a sulfur and oxygen isotope coupling technology and combining an isotope fractionation effect and an isotope mass balance model2.5Sulfur isotope composition of primary sulfate, and finally PM comparison2.5The sulfur isotope composition of the primary sulfate and the source characteristic spectrum of the sulfur isotope composition in the research area define the primary emission source of the sulfate.
2. Resolving ambient air PM according to claim 12.5The method for preparing the primary sulfate source is characterized by comprising the following steps: the method comprises the following steps:
(1) collecting PM in ambient air2.5And SO2A sample;
(2) measurement of PM2.5Oxygen isotope composition of sulfate salt;
(3) determining PM by using the measurement result in the step (2) and an oxygen isotope mass balance model2.5The proportion of the primary sulfate and the secondary sulfate;
(4) determination of SO2The sulfur isotope composition of the secondary sulfate is calculated by utilizing the isotope fractionation effect;
(5) measurement of PM2.5Sulfur isotope composition of sulfate, determining PM by using sulfur isotope mass balance model2.5Sulfur isotope composition of primary sulfate;
(6) collecting samples of biomass combustion, coal and motor vehicle tail gas, measuring sulfur isotope composition, and establishing a source characteristic spectrum of the sulfur isotope composition in a research area;
(7) method for analyzing PM in ambient air by utilizing sulfur isotope technology2.5Source of primary sulfate.
3. Resolving ambient air PM according to claim 22.5The method for preparing the primary sulfate source is characterized by comprising the following steps: the sulfur isotope technology utilizes the sulfur isotope composition of pollutants in the ambient airThe signature tracks the source of the primary contaminant.
4. Resolving ambient air PM according to claim 32.5The method for preparing the primary sulfate source is characterized by comprising the following steps: the method comprises the following specific steps of: calculating PM of ambient air by utilizing sulfur and oxygen isotope coupling technology and combining isotope fractionation effect and isotope mass balance model2.5The sulfur isotope composition of the primary sulfate is utilized to trace PM2.5Source of primary sulfate.
5. Resolving ambient air PM according to claim 42.5The method for preparing the primary sulfate source is characterized by comprising the following steps: the sulfur and oxygen isotope coupling technology is to calculate PM by using an oxygen isotope mass balance model2.5The proportion of the primary sulfate and the secondary sulfate is combined with the sulfur isotope composition of the secondary sulfate obtained by utilizing the isotope fractionation effect, and finally, a sulfur isotope mass balance model is used for calculating PM2.5Sulfur isotope composition of primary sulfate; the sulfur isotope composition of the primary sulfate is calculated by the following mathematical model:
δ 34SPMsulphate = δ 34Sprimary × (1-f secondary) + δ 34Ssecondary × f secondary
δ 18OPMsulphate = δ 18Oprimary × (1-f secnodary) + δ 18Osecondary × f seccondary
δ 34Ssecondary = α×(δ 34SSO2 + 1000) – 1000
in the formula (I), the compound is shown in the specification,f secnodary-ambient air PM2.5The proportion of secondary sulfate;
δ 34SPMsulphate-ambient air PM2.5Sulfur isotope composition of sulfate salt,% o;
δ 34Sprimary-ambient air PM2.5Sulfur isotope composition of the primary sulfate is per mill;
δ 34Ssecondary-ambient air PM2.5Sulfur isotope composition of secondary sulfate is per mill;
δ 18OPMsulphate-ambient air PM2.5Oxygen isotope composition of sulfate salt,% o;
δ 18Oprimary-ambient air PM2.5Oxygen isotope composition of the primary sulfate is per mill;
δ 18Osecondary-ambient air PM2.5Oxygen isotope composition of secondary sulfate;
δ 34SSO2SO in ambient air2The composition of the sulfur isotope is per mill;
alpha-fractional distillation coefficient of sulfur isotope.
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