CN112730575B - Resolving ambient air PM2.5Method for obtaining primary sulfate - Google Patents
Resolving ambient air PM2.5Method 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 129
- 239000012080 ambient air Substances 0.000 title claims abstract description 65
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 131
- 239000011593 sulfur Substances 0.000 claims abstract description 129
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000000203 mixture Substances 0.000 claims abstract description 111
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 46
- 239000001301 oxygen Substances 0.000 claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005516 engineering process Methods 0.000 claims abstract description 23
- 238000005194 fractionation Methods 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000002028 Biomass Substances 0.000 claims abstract description 9
- 238000001228 spectrum Methods 0.000 claims abstract description 9
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- 239000003245 coal Substances 0.000 claims abstract description 7
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 11
- 239000003344 environmental pollutant Substances 0.000 claims description 9
- 231100000719 pollutant Toxicity 0.000 claims description 9
- 230000008878 coupling Effects 0.000 claims description 8
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- 238000005859 coupling reaction Methods 0.000 claims description 8
- 238000013178 mathematical model Methods 0.000 claims description 3
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 2
- YALHCTUQSQRCSX-UHFFFAOYSA-N sulfane sulfuric acid Chemical compound S.OS(O)(=O)=O YALHCTUQSQRCSX-UHFFFAOYSA-N 0.000 claims description 2
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a method for analyzing the primary sulfate source in ambient air PM 2.5, which comprises the steps of firstly measuring the sulfur and oxygen isotope composition of sulfate in ambient air PM 2.5, the sulfur isotope composition of ambient air SO 2 and a pollution source sample, collecting biomass combustion, fire 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, then calculating the sulfur isotope composition of the primary sulfate in PM 2.5, and finally analyzing the source of the primary sulfate in ambient air PM 2.5 by utilizing a sulfur isotope technology. The invention calculates the sulfur isotope composition of the primary sulfate by utilizing the isotope fractionation effect and the mass balance model of the sulfur and oxygen isotopes, solves the problem 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 a primary sulfate source in ambient air PM 2.5, in particular to a method for tracing the primary sulfate source in ambient air PM 2.5 by utilizing a sulfur and oxygen isotope coupling technology.
Background
PM 2.5 is a particulate matter with the aerodynamic diameter smaller than or equal to 2.5 mu m, is extremely easy to attach pollutants such as water-soluble ions, carbon-containing components, heavy metals and the like, and the combined action of the various pollutants enhances the toxic action of PM 2.5 on human bodies, so that the exposure risk of the human bodies to lung cancer is increased, and the morbidity and mortality of cancers and respiratory diseases are increased. Ren Jiao et al (Ren Jiao, yin Shijie, guo Shufen, 2020. Seasonal pollution characteristics and source analysis of water-soluble ions in the atmosphere PM 2.5 of taiyuan, environmental science journal 40 (10), 1-11) compared the concentration of water-soluble ions in urban PM 2.5 in our country, found that SO 4 2-、NO3 -、NH4 + (collectively referred to as SNA) in PM 2.5 from 2015 to 2019 was the most predominant water-soluble ion, accounting for 26.80% -53.46% of PM 2.5, where SO 4 2- accounted for 27.64% -44.64% of SNA, and the source of SO 4 2- was clear to play an important role in effectively controlling pollution of PM 2.5. The current analysis method of water-soluble ion source in PM 2.5 mainly comprises an ion ratio method, correlation analysis and principal component analysis. Cheng Yuan et al (Cheng Yuan, wu Jianhui, bi Xiaohui, yang Jiamei, liu Baoshuang, dai Qili, li Pu, yu Jia, feng Yinan, 2019. Water-soluble ions are characteristic and source of pollution in atmospheric PM 2.5 of Wuhan, environmental science journal 39 (1), 189-196) research finds that the annual NO 3 -/SO4 2- ratio of Wuhan is 0.9, indicating that the stationary source contribution is relatively large, and principal component analysis finds that water-soluble ions in PM 2.5 of Wuhan are mainly derived from emissions of coal and motor vehicles, industrial production, dust and the like. Mu et al (Mu,L.,Zheng,L.,Liang,M.,Tian,M.,Li,X.,Jing,D.,2019.Characterization and source analysis of water-soluble ions in atmospheric particles in Jinzhong,China.Aerosol andAir QualityResearch 19(11),2396-2409) used principal component analysis to study the source of water-soluble ions in the particulate matter and found that the major factors affecting water-soluble ions in jin were secondary formation, coal combustion, biomass combustion, dust particles and industrial emissions.
Stable isotope techniques are being applied in the source resolution of atmospheric pollutants, sulfur isotope techniques have been used to estimate emissions factors, resolve atmospheric pollutant sources and the tracers of the conversions. Han et al (Han, ren Jie, chen Shanli, wang, shen Xiaoyu, wei Ying, guo Zhaobing, zhu Bin, 2018. Based on sulfur oxygen isotope studies on sulfate sources and oxidation pathways in suburban summer atmosphere in south Beijing, environmental science 39 (05), 2010-2014) found that in suburban summer atmosphere in south Beijing SO 4 2- was mainly derived from local coal and tail gas emissions by comparing the sulfur isotope composition (delta 34 S) of aerosol SO 4 2- and a possible source of pollution, the oxidation pathway of secondary SO 4 2- in aerosol was mainly homogeneous oxidation. Wei Ying et al (Wei Ying, guo Zhaobing, ge Xin, zhou Shengnan, jiang Wenjuan, dan Lei, chen Shu, 2015. Sulfur oxygen isotope labeled sulfate sources in Nanjing and North suburban atmosphere PM 2.5 environmental science 36 (04), 1182-1186) found that SO 4 2- in Nanjing and North suburban winter atmosphere was primarily affected by sulfur in the local coal and secondarily transmitted sulfur over long distances by aerosol versus delta 34 S values of the potential sources of pollution and backward trajectory analysis. Norman et al (Norman,A.-L.,Anlauf,K.,Hayden,K.,Thompson,B.,Brook,J.R.,Li,S.-M.,Bottenheim,J.,2006.Aerosol sulphate and its oxidation on the Pacific NW coast:S and O isotopes in PM2.5.Atmospheric Environment 40(15),2676-2689) studied the SO 4 2- on the North coast of the Pacific ocean and its oxidation using the sulfur and oxygen isotopes in PM 2.5 to determine the contribution of primary and secondary SO 4 2-. Norman et al (Norman,A.L.,Belzer,W.,Barrie,L.,2004.Insights into the biogenic contribution to total sulphate in aerosol and precipitation in the Fraser Valley afforded by isotopes of sulphur and oxygen.Journal of Geophysical Research:Atmospheres 109(D5)) analyzed the biological contributions of total SO 4 2- in Friedel-crafts valley aerosols and precipitation by isotopes of sulfur and oxygen, studied the delta 34 S of SO 4 2- particulate matter and industrial source emissions SO 2, and found that the delta 34 S value ranges from-1.6 to 9 per mill. Sinha et al (Sinha,B.W.,Hoppe,P.,Huth,J.,Foley,S.,Andreae,M.O.,2008.Sulfur isotope analyses of individual aerosol particles in the urban aerosol at a central European site(Mainz,Germany).Atmospheric Chemistry and Physics 8(23),7217-7238) studied the chemical composition and isotopic composition of the German Meijin secondary SO 4 2-, found that the isotopic composition is homogeneous and unaffected by the chemical composition, and that the contribution of heterogeneous oxidation to secondary SO 4 2- formation varies greatly from day to day, depending on meteorological conditions. At present, no literature report on the study of the sulfur isotope composition of primary SO 4 2- in ambient air PM 2.5 is known, and no report on the application of sulfur isotope technology to primary SO 4 2- source analysis is known.
The SO 4 2- in the particulate matter is complex in source, and can be generated by primary emission or secondary oxidation, the primary SO 4 2- maintains the sulfur isotope composition characteristics of the emission source, the delta 34 S value of the secondary SO 4 2- is related to the delta 34 S value of the precursor SO 2 and the oxidation process, the delta 34 S value of the secondary SO 4 2- can be used for determining that the delta 34 S value of the SO 4 2- in the particulate matter forming the oxidation pathway (Norman,A.-L.,Anlauf,K.,Hayden,K.,Thompson,B.,Brook,J.R.,Li,S.-M.,Bottenheim,J.,2006.Aerosol sulphate and its oxidation on the Pacific NW coast:S and O isotopes in PM2.5.Atmospheric Environment 40(15),2676-2689). of SO 4 2- is the result of the combined action of the delta 34 S values of the primary and secondary SO 4 2-, and in order to analyze the source of the SO 4 2- more accurately, the delta 34 S value of the primary and secondary SO 4 2- and the sulfur isotope composition characteristics of the pollution source are required to be obtained, and the delta 34 S value of the primary SO 4 2- is compared with the delta 34 S value of the pollution source to determine the primary emission source information of the SO 4 2-. Dan Lei et al (Dan Lei, guo Zhaobing, jiang Wenjuan, ruideas, zeng Gang, 2016. Nanjing 'S atmosphere PM 2.5 potential pollution source sulfur carbon isotope composition characteristics. Environmental science 37 (01), 22-27) research shows that Nanjing' S coal ash, motor vehicle tail gas and biomass ash delta 34 S values are respectively 1.8-3.7 per mill, 4.6-9.7 per mill and 5.2-9.9 per mill, and the sulfur isotopes of coal-fired ash are lighter. Because of the difference in the composition of the sulfur isotopes of each pollution source in different regions, in order to purposefully study the source of the primary SO 4 2-, a source profile of the sulfur isotope composition of the study region needs to be established.
Disclosure of Invention
The invention aims to provide a method for analyzing primary sulfate sources in ambient air PM 2.5, which utilizes a sulfur and oxygen isotope coupling technology to study sulfur isotope composition of primary SO 4 2- and primary source analysis; solves the problems that the primary SO 4 2- and the secondary SO 4 2- in the particles are difficult to separate and the sulfur isotope composition of the primary SO 4 2- is difficult to directly measure.
The invention provides a method for analyzing the source of primary sulfate in ambient air PM 2.5, which comprises the steps of firstly measuring the sulfur and oxygen isotope composition of sulfate in ambient air PM 2.5, the sulfur isotope composition of ambient air SO 2 and a pollution source sample, then calculating to obtain the sulfur isotope composition of the primary sulfate in PM 2.5, and finally analyzing the source of the primary sulfate in ambient air PM 2.5 by utilizing a sulfur isotope technology. The method comprises the following steps:
(1) Collecting samples of ambient air PM 2.5 and SO 2;
(2) Measuring the oxygen isotope composition of sulfate in PM 2.5;
(3) Determining the proportion of primary sulfate and secondary sulfate in PM 2.5 by using the determination result in the step (2) and using an oxygen isotope mass balance model;
(4) Measuring the sulfur isotope composition of SO 2, and calculating the sulfur isotope composition of the secondary sulfate by utilizing the isotope fractionation effect;
(5) Determining the sulfur isotope composition of sulfate in PM 2.5, and determining the sulfur isotope composition of primary sulfate in PM 2.5 by using a sulfur isotope mass balance model;
(6) Collecting biomass combustion, coal burning and motor vehicle tail gas samples, measuring sulfur isotope composition, and establishing a source characteristic spectrum of the sulfur isotope composition of a research area;
(7) The source of primary sulfate in ambient air PM 2.5 was resolved using sulfur isotope technology.
In the above technical solution, further additional technical features are as follows:
The sulfur isotope technology is a source for tracing primary pollutants by utilizing the sulfur isotope composition characteristics of pollutants in the ambient air.
The source of the primary sulfate resolved by the sulfur isotope technology is that the sulfur isotope composition of the primary sulfate in the ambient air PM 2.5 is calculated by utilizing the sulfur and oxygen isotope coupling technology and combining the isotope fractionation effect and the isotope mass balance model, and the source of the primary sulfate in the trace PM 2.5 is formed by utilizing the sulfur isotope composition.
The sulfur and oxygen isotope coupling technology calculates the proportion of primary sulfate and secondary sulfate in PM 2.5 by utilizing an oxygen isotope mass balance model, combines the sulfur isotope composition of the secondary sulfate obtained by utilizing an isotope fractionation effect, and finally calculates the sulfur isotope composition of the primary sulfate in PM 2.5 by utilizing a sulfur isotope mass balance model. 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
Wherein, f secnodary is the proportion of the secondary sulfate in the ambient air PM 2.5;
Delta 34SPM sulphate -sulfur isotope composition of sulfate in ambient air PM 2.5, mill;
Delta 34Sprimary -sulfur isotope composition of primary sulfate in ambient air PM 2.5, per mill;
Delta 34Ssecondary -sulfur isotope composition of secondary sulfate in ambient air PM 2.5, mill;
delta 18OPM sulphate -oxygen isotope composition of sulfate in ambient air PM 2.5, mill;
Delta 18Oprimary -oxygen isotope composition of primary sulfate in ambient air PM 2.5, per mill;
delta 18Osecondary -oxygen isotope composition of the secondary sulfate in ambient air PM 2.5, mill;
Delta 34SSO2 -sulfur isotope composition of SO 2 in ambient air, mill;
Alpha-fractionation coefficient of sulfur isotopes.
The source of the primary sulfate in the PM 2.5 is the source characteristic spectrum of comparing the calculated sulfur isotope composition of the primary sulfate in the PM 2.5 with the sulfur isotope composition of the research area, and the primary emission source of the sulfate in the PM 2.5 is defined.
The invention has the beneficial effects that: compared with the prior art, the method for analyzing the primary sulfate source in the ambient air PM 2.5 has the outstanding characteristics and remarkable progress that: (1) The novel method for analyzing the primary sulfate source in the ambient air PM 2.5 is provided, and the problems that the prior sulfate source is complex and the primary sulfate and the secondary sulfate are difficult to accurately identify are solved; (2) The isotope fractionation effect and the isotope mass balance model are applied to the determination of the sulfur isotope composition of the primary sulfate in PM 2.5, so that the blank of the current research is filled, and basic data is provided for the application of the isotope technology in the atmospheric science; (3) The sulfur and oxygen isotope coupling technology is applied to the source analysis of the primary pollutants in the ambient air PM 2.5, and a new idea is opened up for the application of the isotope technology in the field of environmental science.
Drawings
FIG. 1 is a schematic illustration of the process of the present invention.
FIG. 2 is a diagram of a filter sample processing procedure for the method of the present invention.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1:
The invention takes analysis of primary sulfate sources in ambient air PM 2.5 in 4 seasons of spring, summer, autumn and winter of Taiyuan as an example, and further detailed description of the specific implementation mode of the invention is made by using the examples with reference to the attached drawings, and the analysis is based on the fact that the analysis can be realized by a person skilled in the technical field. The present examples are intended to be illustrative of the present invention and are not intended to be limiting.
The method for analyzing the primary sulfate in the ambient air PM 2.5 is implemented by firstly measuring the sulfur and oxygen isotope composition of the sulfate in the ambient air PM 2.5, the sulfur isotope composition of the ambient air SO 2 and a pollution source sample, then calculating the sulfur isotope composition of the primary sulfate in the PM 2.5, and finally analyzing the source of the primary sulfate in the ambient air PM 2.5 by utilizing a sulfur isotope technology. The specific method comprises the following steps:
And step one, collecting environmental air and pollution source samples. And (3) collecting an ambient air sample: the sampling points are functional areas such as a Taiyuan commercial area, a residential area, an industrial area and the like; the sampling period is 4 seasons of spring, summer, autumn and winter which are not rainy, snowy and windy days; the sampling quantity is limited by meeting the composition test of sulfur and oxygen isotopes and representing the quality of the ambient air in Taiyuan city; the sampling time can be determined according to the cleanliness of local air, the detection limit of the isotope composition testing method and the sampling efficiency of the instrument, and the principle of meeting the requirement of component analysis is taken as the principle. And (3) pollution source sample collection: collecting biomass combustion particle samples of wheat straw, corn straw, mung bean straw, phoenix tree leaf, grape vine and sunflower straw in a research area, collecting a bottom ash sample of a coal-fired boiler dust remover, and collecting tail gas particle samples of a gasoline vehicle and a diesel vehicle. Sampling other requirements are implemented according to national sampling standards.
Ambient air PM 2.5 (particulate matter having an aerodynamic diameter of less than 2.5 microns) and SO 2 collection: the sampling device is an improved standard large-volume sampler (TH-1000F) produced by Wuhan Tianhong instrument limited company. The sample of ambient air PM 2.5 is collected by a quartz fiber filter membrane, and the filter membrane is burned for 4.5 hours at 450 ℃ in a muffle furnace before sampling in order to avoid the influence of residual carbon and other impurities in the filter membrane. And collecting a SO 2 sample by using a glass fiber filter membrane soaked by alkali liquor.
And step two, preprocessing the collected ambient air PM 2.5、SO2 and the biomass combustion sample according to the flow shown in the figure 2. The specific process is as follows: taking 1/4 sample filter membranes, shearing, putting into a centrifuge tube, adding 50mL of deionized water, carrying out ultrasonic treatment at a constant temperature of 20 ℃ for 30min, centrifuging at 6000r/min for 10min, filtering the centrifuged solution by a filter head, finally adding 3mL of 1mol/L BaCl 2 solution, standing for 24h after full oscillation, carrying out suction filtration by an acetate filter membrane to obtain BaSO 4 precipitate, repeatedly cleaning the precipitate by deionized water, transferring the precipitate and the filter membrane together into a crucible, and burning for 2h at 850 ℃ in a muffle furnace to obtain pure BaSO 4 powder. In order to ensure the amount of the sample required by analysis and test, sulfur and oxygen isotopes form a test sample, and 1/4 of the film is used for pretreatment to obtain BaSO 4 powder. The Ai Shika method is adopted to convert sulfur in the coal-fired smoke dust and motor vehicle tail gas into BaSO 4. The sulfur, oxygen isotope composition in PM 2.5, SO 2, and sulfur isotope composition in the pollution source sample were tested using an isotope mass spectrometer. And establishing a source characteristic spectrum of the Taiyuan sulfur isotope composition by using the sulfur isotope compositions of the biomass combustion, the coal burning and the motor vehicle tail gas samples obtained through the tests.
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.
And thirdly, determining the proportion of primary and secondary sulfate in the PM 2.5 by utilizing an oxygen isotope mass balance model according to the oxygen isotope composition of sulfate in the PM 2.5 measured in the second step.
The expression of the oxygen isotope composition is delta 18O＝[(18O/16O) sample of /(18O/16O) Standard of -1 multiplied by 1000, wherein delta 18 O is the oxygen isotope composition, per mill, (18O/16O) sample of is the oxygen isotope ratio of the sample, and 18O/16O) Standard of is 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)
Wherein delta 18OPM sulphate refers to the oxygen isotope composition of SO 4 2- in the particulate matter, per mill; delta 18Oprimary refers to the oxygen isotope composition of primary SO 4 2-, calculated by formula (2); f secnodary denotes the proportion of secondary SO 4 2- in the particulate matter; delta 18Osecondary refers to the oxygen isotope composition of secondary SO 4 2-, per mill. The heterogeneous oxidation mechanism calculates the oxygen isotope value of the secondary SO 4 2- using formulas (3) and (4), and the in-phase oxidation mechanism calculates the oxygen isotope value of the secondary SO 4 2- using formulas (5) and (6).
δ18Oprimary＝0.06×δ18Ovapour+38‰ (2)
Delta 18Osecondary＝0.78×δ18Oliquid+12.0‰(Fe3+ and excess O 2) (3)
Delta 18Osecondary＝0.528×δ18Oliquid–3.4‰(H2O2 and HCl) (4)
δ18Osecondary＝0.69×δ18Oliquid+9.5‰(O3) (5)
δ18Osecondary＝0.84×δ18Oliquid+6.2‰(NO2) (6)
Wherein δ 18Ovapour is the oxygen isotope composition of water vapor, and δ 18Ovapour can be replaced by δ 18Oliquid because the coefficient of δ 18Ovapour in formula (2) is only 0.06; delta 18Oliquid is the oxygen isotope value in precipitation, per mill. Data for oxygen stable isotopes in Taiyuan precipitation were 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 the secondary sulfate.
And step four, calculating the sulfur isotope composition of the secondary sulfate by utilizing the isotope fractionation effect of SO 4 2- generated by oxidizing SO 2 according to the sulfur isotope composition of SO 2 measured in the step two.
The expression of the composition of the sulfur isotopes is delta 34S＝[(34S/32S) sample of /(34S/32S) Standard of -1 x 1000, wherein delta 34 S is the composition of the sulfur isotopes, per mill, (34S/32S) sample of is the ratio of the sulfur isotopes of the sample, (34S/32S) Standard of is the ratio of the standard sulfur isotopes. The relative difference in the composition of the isotopes between the substances caused by the fractionation is characterized by the isotope fractionation coefficient (alpha) is defined as the quotient of the ratio of the two isotopic contents in a certain compound to the corresponding ratio of the other compound.
δ34Ssecondary＝α×(δ34SSO2+1000)–1000 (8)
Wherein delta 34Ssecondary is sulfur isotope composition of the secondary sulfate, per mill; alpha is the fractionation coefficient of the isotope, and is obtained by reference.
And fifthly, determining the sulfur isotope composition of the primary sulfate in the PM 2.5 by using a sulfur isotope mass balance model according to the sulfur isotope composition of the sulfate in the PM 2.5 obtained by the test in the step two, the proportion of the secondary sulfate obtained by the calculation in the step three and the sulfur isotope composition of the secondary sulfate obtained by the calculation in the step four.
Since primary and secondary sulfates in PM 2.5 are more difficult to separate, the sulfur isotope composition of the primary sulfate cannot be directly tested by an instrument. The method utilizes the sulfur isotope mass balance principle to obtain the sulfur isotope composition of the primary sulfate through calculation, and provides basic data for the application of the isotope technology in the atmospheric science. Since the sulfate in ambient air PM 2.5 includes both primary and secondary sulfate, the capacity of ambient air PM 2.5 to enrich 34 S is equal to the linear sum of the capacities of primary and secondary sulfate enrichment 34 S. The sulfur isotope composition of the primary sulfate in ambient air PM 2.5 can be calculated from the following sulfur isotope mass balance model:
δ34SPM sulphate＝δ34Sprimary×(1-fsecondary)+δ34Ssecondary×fsecondary (7)
Wherein delta 34SPM sulphate refers to the sulfur isotope composition of SO 4 2- in the particulate matter, per mill; delta 34Sprimary refers to the sulfur isotope composition of primary SO 4 2-, per mill.
And step six, comparing the calculated sulfur isotope composition of the primary sulfate in the PM 2.5 with the source characteristic spectrum of the sulfur isotope composition of the Taiyuan market obtained in the step two, and discussing the primary emission source of the sulfate in the PM 2.5.
At present, the sulfur isotope technology is used for analyzing the source of sulfate in the particulate matters and discussing the oxidation mechanism of the secondary sulfate, and the sulfur isotope technology is not used for analyzing the source of primary sulfate in the ambient air PM 2.5. The study finds that the sulfur isotope composition of the sulfate directly discharged by the pollution source is different, so the sulfur isotope composition can be used as a good marker for source analysis of primary sulfate in the ambient air PM 2.5. 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 method comprises the steps of comparing the sulfur isotope composition of the primary sulfate in the PM 2.5 in 4 seasons of the ambient air of spring, summer, autumn and winter obtained through the model with the sulfur isotope characteristic spectrum of a pollution source in a research area, judging whether the sulfur isotope composition of the primary sulfate in the PM 2.5 is in the sulfur isotope composition range of sulfate discharged by coal-fired smoke dust, motor vehicle tail gas or biomass combustion, and determining which pollution source the primary sulfate in the PM 2.5 mainly comes from. The result can determine which pollution source is the main source of the primary sulfate in 4 seasons of spring, summer, autumn and winter, so that measures can be taken in different seasons to control the emission of the primary sulfate in a targeted manner, further the pollution of the sulfate in the ambient air PM 2.5 in Taiyuan city is effectively controlled, and the harm to the human health is reduced.
Claims (4)
1. A method for resolving a primary sulfate source in ambient air PM 2.5, characterized by: firstly, collecting samples of ambient air PM 2.5 and SO 2, analyzing sulfur and oxygen isotope compositions of sulfate in PM 2.5 and sulfur isotope compositions of SO 2, collecting samples of biomass combustion, coal burning and motor vehicle tail gas in a research area, analyzing the sulfur isotope compositions, establishing a source characteristic spectrum of the sulfur isotope compositions in the research area, calculating the sulfur isotope compositions of primary sulfate in ambient air PM 2.5 by utilizing a sulfur and oxygen isotope coupling technology and combining an isotope fractionation effect and an isotope mass balance model, and finally comparing the sulfur isotope compositions of primary sulfate in PM 2.5 with a source characteristic spectrum of the sulfur isotope compositions in the research area to determine a primary emission source of sulfate;
the method for analyzing the primary sulfate source in the ambient air PM 2.5 comprises the following steps:
(1) Collecting samples of ambient air PM 2.5 and SO 2;
(2) Measuring the oxygen isotope composition of sulfate in PM 2.5;
(3) Determining the proportion of primary sulfate and secondary sulfate in PM 2.5 by using the determination result in the step (2) and using an oxygen isotope mass balance model;
(4) Measuring the sulfur isotope composition of SO 2, and calculating the sulfur isotope composition of the secondary sulfate by utilizing the isotope fractionation effect;
(5) The sulfur isotope composition of sulfate in PM 2.5 is determined, and the sulfur isotope composition of primary sulfate in PM 2.5 is determined by using a sulfur isotope mass balance model and 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
Wherein, f secnodary is the proportion of the secondary sulfate in the ambient air PM 2.5;
Delta 34SPM sulphate -sulfur isotope composition of sulfate in ambient air PM 2.5, mill;
Delta 34Sprimary -sulfur isotope composition of primary sulfate in ambient air PM 2.5, per mill;
Delta 34Ssecondary -sulfur isotope composition of secondary sulfate in ambient air PM 2.5, mill;
delta 18OPM sulphate -oxygen isotope composition of sulfate in ambient air PM 2.5, mill;
Delta 18Oprimary -oxygen isotope composition of primary sulfate in ambient air PM 2.5, per mill;
delta 18Osecondary -oxygen isotope composition of the secondary sulfate in ambient air PM 2.5, mill;
Delta 34SSO2 -sulfur isotope composition of SO 2 in ambient air, mill;
alpha-fractionation coefficient of sulfur isotopes;
(6) Collecting biomass combustion, coal burning and motor vehicle tail gas samples, measuring sulfur isotope composition, and establishing a source characteristic spectrum of the sulfur isotope composition of a research area;
(7) The source of primary sulfate in ambient air PM 2.5 was resolved using sulfur isotope technology.
2. The method of resolving a primary sulfate source in ambient air PM 2.5 as claimed in claim 1, wherein: the sulfur isotope technology is a source for tracing primary pollutants by utilizing the sulfur isotope composition characteristics of pollutants in the ambient air.
3. The method of resolving a primary sulfate source in ambient air PM 2.5 as claimed in claim 2, wherein: the specific steps of utilizing sulfur isotope technology are: the sulfur isotope composition of the primary sulfate in the ambient air PM 2.5 is calculated by utilizing a sulfur and oxygen isotope coupling technology and combining an isotope fractionation effect and an isotope mass balance model, and the source of the primary sulfate in the PM 2.5 is tracked by utilizing the sulfur isotope composition.
4. A method of resolving a primary sulfate source in ambient air PM 2.5 as claimed in claim 3, wherein: the sulfur and oxygen isotope coupling technology calculates the proportion of primary sulfate and secondary sulfate in PM 2.5 by using an oxygen isotope mass balance model, combines the sulfur isotope composition of the secondary sulfate obtained by using an isotope fractionation effect, and finally calculates the sulfur isotope composition of the primary sulfate in PM 2.5 by using a sulfur isotope mass balance model.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4891067A (en) * | 1988-05-13 | 1990-01-02 | Kennecott Utah Copper Corporation | Processes for the treatment of smelter flue dust |
| CN201077764Y (en) * | 2007-07-12 | 2008-06-25 | 核工业北京地质研究院 | Reactor for conversing sulfide/sulphates into SO2 |
| CN103134851A (en) * | 2011-11-23 | 2013-06-05 | 中国石油化工股份有限公司 | Direct measuring apparatus and measuring method for hydrogen sulfide content and sulfur isotope in natural gas |
| CN106018195A (en) * | 2016-05-23 | 2016-10-12 | 太原理工大学 | Method for estimating concentration of secondary organic carbon in particulate matters in environment air |
| GB2551127A (en) * | 2016-06-06 | 2017-12-13 | Thermo Fisher Scient (Bremen) Gmbh | Apparatus and method for static gas mass spectrometry |
| CN110057725A (en) * | 2019-05-14 | 2019-07-26 | 华北电力大学 | A kind of sulfate origin analysis method in Atmospheric particulates based on sulfur isotope |
| CN111272917A (en) * | 2020-03-30 | 2020-06-12 | 中国科学院地质与地球物理研究所 | Element isotope analysis system and method for analyzing sulfur isotope in trace sulfate sample and application thereof |
| CN111368401A (en) * | 2020-02-20 | 2020-07-03 | 南开大学 | Tracing method and device for pollution source and storage medium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10890592B2 (en) * | 2015-11-04 | 2021-01-12 | Metabolon, Inc. | Automated sample quality assessment |
-
2020
- 2020-12-18 CN CN202011505557.2A patent/CN112730575B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4891067A (en) * | 1988-05-13 | 1990-01-02 | Kennecott Utah Copper Corporation | Processes for the treatment of smelter flue dust |
| CN201077764Y (en) * | 2007-07-12 | 2008-06-25 | 核工业北京地质研究院 | Reactor for conversing sulfide/sulphates into SO2 |
| CN103134851A (en) * | 2011-11-23 | 2013-06-05 | 中国石油化工股份有限公司 | Direct measuring apparatus and measuring method for hydrogen sulfide content and sulfur isotope in natural gas |
| CN106018195A (en) * | 2016-05-23 | 2016-10-12 | 太原理工大学 | Method for estimating concentration of secondary organic carbon in particulate matters in environment air |
| GB2551127A (en) * | 2016-06-06 | 2017-12-13 | Thermo Fisher Scient (Bremen) Gmbh | Apparatus and method for static gas mass spectrometry |
| CN110057725A (en) * | 2019-05-14 | 2019-07-26 | 华北电力大学 | A kind of sulfate origin analysis method in Atmospheric particulates based on sulfur isotope |
| CN111368401A (en) * | 2020-02-20 | 2020-07-03 | 南开大学 | Tracing method and device for pollution source and storage medium |
| CN111272917A (en) * | 2020-03-30 | 2020-06-12 | 中国科学院地质与地球物理研究所 | Element isotope analysis system and method for analyzing sulfur isotope in trace sulfate sample and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| Aerosol sulphate and its oxidation on the Pacific NW coast: S and O isotopes in PM2.5;Ann-Lise Norman;Atmospheric Environment;第40卷;第2676–2689页 * |
| Roles of Sulfur Oxidation Pathways in the Variability in Stable Sulfur Isotopic Composition of Sulfate Aerosols at an Urban Site in Beijing, China;Mei-Yi Fan et al.;Environmental Science & Technology Letters;第7卷;第883-888页 * |
| 北京市大气细颗粒物PM_(2.5)的来源研究;朱先磊等;环境科学研究(第5期);第3-7页 * |
| 基于多种源解析技术的合肥市环境空气PM2.5来源解析;耿天召等;合肥工业大学学报（自然科学版）;20200630;第43卷(第6期);第830-838页 * |
| 基于硫氧同位素研究南京北郊夏季大气中硫酸盐来源及氧化途径;韩珣等;环境科学;第39卷(第5期);第2011-2013页 * |
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