CN117524345A - Urban VOCs source analysis method based on receptor mode - Google Patents
Urban VOCs source analysis method based on receptor mode Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental monitoring, and particularly relates to an urban VOCs source analysis method based on a receptor mode. The invention firstly aims at O of a target city 3 Generating precursor organic matters with larger contribution, monitoring, obtaining the VOCs pollution characteristics and change rules of a target city, identifying key species of the VOCs generated by the ozone of the target city, and determining pollution sources contributing to the VOCs in the atmosphere of the target city; on-line monitoring of pollution sources contributing to VOCs in the atmosphere of a target city, correction of on-line monitoring data by manual monitoring, quality control of the monitoring data, establishment of an atmospheric VOCs source component spectrum and a typical VOCs pollution source emission component spectrum database according to the obtained monitoring data, and finally source analysis of the VOCs of the city by adopting a CMB mode, so that the sources of main NMHCs species of the target city and the relative relation of the sources are clarifiedContribution. The invention not only provides a method for establishing the urban pollution source spectrum, but also improves the accuracy and reliability of the urban VOCs source analysis method by optimizing the traceability method.
Description
Technical Field
The invention belongs to the technical field of environmental monitoring, and particularly relates to an urban VOCs source analysis method based on a receptor mode.
Background
Volatile Organic Compounds (VOCs) are important precursors for secondary atmospheric pollution, the formation of photochemical smog in many urban areas may be caused by chemical reactions dominated by VOCs, so that monitoring of VOCs has been started in many countries and regions, but in many countries and regions, the representative VOCs are not completely identical for specific cities, so that the specific selection of which VOCs are used for tracing of pollution source analysis has great difficulty, in addition, online monitoring of VOCs is excessively relied on in the process of source analysis, and the accuracy of tracing results of pollution sources is low due to neglecting the deviation between online monitoring data and actual environmental atmosphere.
In addition, because the oxygen-containing compound has both a primary source and a secondary source, the contribution condition of various sources cannot be analyzed through a receptor model, the positive definite matrix factorization (PMF) is adopted for analysis at present, but the analysis is only carried out on the basis of the receptor model and on the basis of continuous data monitored on line, and the analysis is easier to realize, but the analysis on pollution sources is poorer, so the analysis on the pollution sources of the receptor model is carried out by generally selecting the species with chemical activity smaller than that of toluene in non-methane volatile organic compounds (NMHCs), and the possible sources and relative importance of the NMHCs in the atmosphere are qualitatively and quantitatively described. Chemical mass balance mode (CMB) is the use of mass conservation principles to quantitatively estimate the relative contribution of various pollution sources by distributing NMHCs concentrations in the actual ambient atmosphere to different emission sources.
However, the precondition for applying the CMB model is to be an active spectrum, however, since the emission source is difficult and costly to sample, and only a few carbon sources are sampled, the specific pollution source class required may not have source spectrum data, and the source spectrum composition differences for the specific emission source class are not known.
Disclosure of Invention
In order to solve the technical problems, the invention provides an urban VOCs source analysis method based on a receptor mode.
The invention provides a method for analyzing urban VOCs sources based on a receptor mode, which comprises the following steps:
(1) Establishing a target city VOCs pollution source spectrum;
(2) Selecting fitting species required in calculation of receptor model from the pollution source spectrum determined in (1), the selection principle comprising:
a. the identified species of each source of contamination and the dominant species of NMHCs in the ambient atmosphere;
b. species which are easy to detect, have weak chemical activity and good fingerprint tracing effect;
c. the basic assumption of mass balance is satisfied, the photochemical reaction of NMHCs species in 3-5 h does not influence the mass balance in the process of transmitting from a pollution source to a receptor, and the species with the atmospheric life not less than toluene is selected as the fitting species;
the mathematical expression of the receptor model is:
wherein Cik is the concentration of the ith chemical component in the kth environmental sample at the receptor site; aij is the mass fraction of the ith chemical component emitted by pollution source j, i.e. pollution source spectrum; sjk is the contribution rate of the contamination source j to the acceptor point sample k;
(3) Main VOCs characteristic species of various pollution sources in the target city are defined;
(4) Normalization treatment of pollution source spectrum: converting the concentration data of the pollution source spectrum into percentage content of the total fitting species;
(5) The contribution rate of each pollution source is calculated and determined by using a CMB method.
Preferably, the mathematical equation of the model is solved by using an effective variance least square method, and the formula is as follows:
where Veff, i is the weight of the effective variance, S j Is a source spectrum database, and the solution of the effective variance least square method contains the source contribution S j One item, S j Unknown, and therefore requires iterative operations.
Preferably, the source spectrum described in (1) is established using the following method:
step S1, O of target city 3 Generating precursor organic matters with larger contribution to monitor so as to grasp the pollution characteristics and change rules of VOCs in the target city, identifying key species of the VOCs generated by the ozone in the target city according to the pollution characteristics of the VOCs, and determining pollution sources contributing to the VOCs in the atmosphere in the target city;
step S2, carrying out on-line monitoring on pollution sources contributing to VOCs in the atmosphere of the target city determined in the step S1, and correcting on-line monitoring data by assisting with manual monitoring;
step S3, quality control is carried out on the online monitoring data of the VOCs obtained in the step S2;
and S4, establishing an atmospheric VOCs source component spectrum and a typical VOCs pollution source emission component spectrum database according to the VOCs monitoring data obtained in the step S3.
Preferably, in step S1, the pollution characteristic includes: concentration levels and species composition of VOCs, temporal profile of VOCs, and spatial profile of VOCs.
Preferably, in step S2, when the target city VOCs are monitored online, the arrangement of the sampling points and the number is according to the following:
(a) Selecting a place which fully represents urban pollution characteristics as a sampling point;
(b) Selecting open land in urban commercial area, wherein the included angle between the horizontal line of the sampling port and the height of surrounding buildings is not more than 30 degrees, no local pollution source exists around the monitoring points, the number and the adsorption capacity of the buildings are avoided, and the distance between the sampling points in the traffic dense area and the traffic main road is 100m;
(c) Determining the sampling height of VOCs according to different monitoring scheme relation objects, and keeping the sampling height at a breathing zone 1.5-2 m away from the ground when researching harm of the VOCs to human bodies; if the sampling height is continuous, the distance between the sampling height and the ground is 3-15 m; sampling of urban VOCs is performed on a roof, and even if the roof is used, the sampling port and the foundation ground are required to be kept at a relative height of more than 1.5m so as to reduce the influence from the ground;
(d) Setting conditions of all sampling points are consistent, so that the obtained monitoring data are comparable;
(e) The number of the sampling points is a benefit function corresponding to economic investment and precision requirements, and is comprehensively determined according to the size of a monitoring range, the spatial distribution characteristics of pollutants, population distribution and density, weather, topography, economic conditions and other factors;
(f) Sampling periods are tightly controlled at 9:00 am and 13:00 midday quasi-points.
Preferably, in step S3, an online VOCs monitoring system is established by using GC-MS/FID, and the reliability of online monitoring data is improved by the following conditions: qualitative and quantitative analysis, blank testing, instrument calibration, daily calibration, limit of detection, accuracy, retention time, internal standard response, correlation of isomers.
The qualitative and quantitative analysis is to calibrate an online GC-MS/FID system by adopting mixed standard gas, specifically to dilute 1ppm of multi-mixed standard gas into standard gas with the mixing ratio of 0.5-8 ppb;
FID detector, identifying target compound by comparing the retention time of target compound and standard gas, and obtaining standard curve by measuring five mixing ratios of 0.5, 1, 2,4, 8ppbv response, wherein the value of each mixing ratio takes the average value of 3-5 parallel measurements;
MS detector GC-MS analysis relies on mass spectra that identify the target compound by matching it to the spectra of known compounds in the database, in addition to retention time, quantification of unknown compounds using an internal standard curve method;
the blank test comprises an instrument blank test and a pipeline blank test, wherein the pipeline blank test comprises a standard sample pipeline blank test and an air sample pipeline blank test; the specific test method is as follows:
instrument blank experiment: setting the sampling volume of a sampling system to be 0, operating an instrument for analysis, and if the species is detected, indicating that the interior of the instrument is polluted or the carrier gas is impure, stopping sample analysis to maintain the instrument until the instrument is blank and has no response, and then carrying out subsequent analysis; pipeline blank experiment: connecting high-purity nitrogen to a standard gas sampling port and an air sampling port of the instrument, realizing pipeline blank measurement by injecting high-purity nitrogen, and measuring again after reaching balance after a period of time if the target compound is detected by the standard gas pipeline until the response of the target compound in the blank is eliminated or is lower than the detection limit of the instrument; if the air sample pipeline has species detection, the high-purity nitrogen is replaced for re-measurement or the pre-treatment equipment is heated for back blowing and then re-measurement is carried out.
The daily calibration is to ensure the stability of the GC-MS/FID system, 4ppbv of mixed standard gas is injected once a day, the time change of benzene response factors detected by MS and ethane response factors detected by FID in daily calibration is compared, and the response factors of benzene are corrected according to the environmental response of CFC-113, so that the response factors of the compounds are changed within a range of 20 percent.
The invention has the beneficial effects that:
(1) The accuracy of VOCs monitoring data obtained by the target city is remarkably improved by reasonably arranging the sampling number and the like of VOCs sampling sites of the target city and performing quality control on the online monitoring data through manual monitoring;
(2) By establishing the component spectrum of the VOCs pollution sources in the target city, the analysis result of the receptor analysis model is closer to the real situation, and the analysis of the VOCs pollution sources in the target city is successfully realized.
Drawings
FIG. 1 is a graph showing the dependence of ozone concentration on temperature for six substations in Jinan City;
FIG. 2 is a graph showing the correlation of ozone concentration with relative humidity;
FIG. 3 is a graph showing the dependence of ozone concentration on wind speed;
FIG. 4 is a schematic diagram of a city monitoring station, refinery, upwind, suburban O 3 -VOC-NOx sensitivity analysis results;
FIG. 5 is a graph showing contributions of different classes of VOCs in a municipal monitoring station sample to total VOCs concentration and OH consumption rate;
FIG. 6 is a graph showing the contribution of various classes of VOCs to total OFP in a market monitoring station, refinery, horse race site sample;
FIG. 7 shows the source and relative contribution of major NMHCs species in Jinan.
Detailed Description
The present invention will now be further described in connection with specific embodiments in order to enable those skilled in the art to better understand the invention.
The present invention will be described by taking source analysis of atmospheric VOCs in Jinan city as an example.
Example 1
The method for establishing the source component spectrum of the atmospheric VOCs in Jinan city comprises the following steps:
step S1, p Jinan O 3 Generating precursor organic matters with larger contribution to monitor so as to grasp the pollution characteristics and change rules of VOCs in Jinan, identify key species of VOCs generated by ozone in Jinan according to the pollution characteristics of the VOCs, and determine pollution sources contributing to the VOCs in the atmosphere in Jinan; the specific operation is as follows:
analysis of ozone Source
I. Influence of Meteorological factors on ozone Generation
The invention selects six points of a central urban city monitoring station sub-station, a suburb junction blue-flying technology school sub-station, an industrial area Jinan Baosheng sub-station, a cleaning comparison point horse-race sub-station, an industrial county Pinyin urban sub-station and an agricultural county Jiyang development area sub-station with representative urban city monitoring stations, subsuburbs, suburbs of urban-suburb junction blue-flying technology school sub-stations for carrying out correlation analysis of ozone and meteorological factors (wind speed, humidity, temperature and mixed height).
The detected correlation results of ozone, temperature, humidity and wind speed are shown in figures 1-3.
The graph of ozone dependence on temperature in fig. 1 shows: o of different sites 3 The concentrations all show a good positive correlation with the temperature, i.e. the higher the temperature, the more O 3 The higher the concentration, the correlation coefficient R for the six substations is between 0.60-0.73, because of O 3 Is produced by the photochemical reaction of primary pollutants such as VOCs, NOx and the like under the irradiation of sunlight, and the high temperature is favorable for the photochemical reaction, thereby leading to O 3 An increase is generated.
Wherein, the cleaning comparison point horse race substation has the best correlation, and the industrial county Pingyin urban substation has the worst correlation. The horse race sub-station is a cleaning control point, and is positioned at the mountain top of the horse race, the altitude is approximately 900m, the highest temperature during observation is 26.5 ℃, and the ozone concentration is 0.255mg/m at the highest 3 Significantly lower than other substations in urban areas. It can be seen that the increase in temperature significantly favors ozone generation, which is most readily generated at temperatures in the range of 30.+ -. 2 ℃.
The correlation diagram of ozone concentration and relative humidity in fig. 2 shows that the industrial area jinan baosheng substation, the industrial county Pingyun urban substation and the agricultural county jiyang development area substation have better correlation, and the correlation coefficients R are respectively 0.48, 0.44 and 0.45, so that the other substations have poorer correlation.
In the correlation diagram of the ozone concentration and the wind speed in fig. 3, the correlation of the central urban city monitoring station, the industrial county Pingyin urban area substation and the agricultural county Jiyang development area substation is better, the correlation coefficients R are respectively 0.35, 0.33 and 0.35, and the correlation of other substations is poorer.
In conclusion, the concentration of ozone in Jinan city is obviously influenced by meteorological factors, the temperature and ozone are better in correlation, the temperature rise is favorable for generating ozone, and the correlation of wind speed, relative humidity and ozone is poor. Therefore, screening ozone observation data of urban exceeding period, and carrying out probability analysis simultaneously with temperature, humidity and air pressure, the result shows that the temperature is above 30 ℃, the humidity is within 30% +/-10%, and the pressure is within 995kPa, so that high value of ozone is easy to occur.
Nonlinear response of ozone to precursor
Due to O 3 Is a secondary pollutant, and the concentration of the precursor VOCs and NOx can influence O 3 Thus determining O 3 The relationship with the precursor is established as O 3 One step of the control strategy is critical. Previous studies have shown that O 3 Not simply linear with VOCs and NOx, different zone O 3 The production of a different sensitivity to VOCs and NOx, otherwise known as O 3 The production is either VOCs controlled or NOx controlled.
At a plurality of O 3 In the generation sensitivity research method, an EKMA curve is adopted, the actual measurement average value of species except NOx and VOCs is taken as a constraint condition of a model, and considering that the feasibility of the control of the natural source VOCs is lower than that of the artificial source VOCs, isoprene in a scene is set to be a fixed value, and a sensitivity experiment is not carried out on the isoprene in the scene. The specific method comprises the following steps: assuming 30 emission scenarios of NOx and VOCs activities, for a total of 900 scenarios, simulating P under corresponding scenarios by using RACM2 mechanism O3 Thereby drawing P O3 An isoconcentration curve, in the scenario assumption, the study period is 10:00-18:00 per day.
The EKMA curves of the sites of the urban monitoring station, the refinery monitoring station, the upwind monitoring station and the suburban monitoring station are shown in the accompanying figures 4 (a-d), wherein the curves are net photochemical generation rate P of ozone O3 The gray line is the ridge line of the EKMA graph, the point of the area above the ridge line, O 3 Generating a control region belonging to VOCs; a point located in the area below the ridge line, O thereof 3 The formation is mainly affected by NOx.
From the graph a, the actual measurement value of the station is positioned at the left side of the ridge line, so that the position O of the monitoring station in Jinan city 3 The generation is in the VOCs control zone, which is the central urban area in the atanan city, which is a typical urban site.
The position of the black frame point in the b graph is an EKMA graph of a monitoring site of the oil refinery, and the position of the actual measured value of the site can be seen to be positioned at the left side of a ridge line, so that the O of the site of the oil refinery in the Jinan province 3 The generation is also in the VOCs control zone.
The graph c is an EKMA graph of an upwind monitoring station, the graph shows that the position of the actual measured value of the station is positioned on the right side of a ridge line, the concentration of VOCs of the point position is extremely low, the reduction of NOx level is not obvious, and the graph belongs to a NOx control area, so that the NOx of the point position is controlled to be relative to O 3 The reduction of the generated ozone has a certain ozone reducing effect.
d is a suburb monitoring station EKMA curve represented by the station of the university of great clearance city, and the position of the actual measurement value of the station is positioned at the left side of the ridge line and belongs to the VOCs control area, so that the NOx of the point is controlled to be relative to O 3 The reduction of the generated ozone has a certain ozone reducing effect.
III. Identification of key species of VOCs generated by ozone in Jinan City
According to the results of the research on the degradation of volatile organic compounds by Atkinson and Arey, and by combining the OH reaction constants of the volatile organic compounds at room temperature, the OH consumption rate calculation is respectively carried out on all online data (measured by VOC online monitoring equipment) acquired from urban monitoring stations, marquee and refineries in 2019 in month 6 (relatively strong photochemical reaction in month 6).
OH free radical reactivity analysis of VOCs at municipal monitoring station
Figure 5 shows the contributions of several volatile organics (alkanes, alkenes, aromatics, alkynes, and OVOCs) from the market monitoring stations to total VOCs concentration and total OH consumption rate.
The volume concentration of VOCs at the market monitoring station ranges from 10.30ppb to 83.79ppb, wherein the alkane is the highest in proportion, the average contribution value is 47%, the contributions of the olefin, the acetylene, the aromatic hydrocarbon and the OVOCs are 14%, 1%, 8% and 30%, respectively, the corresponding alkane OH consumption rate is 17%, and the OH consumption rates of the olefin, the acetylene, the aromatic hydrocarbon and the OVOCs are 73% and 0%, 10% and 1%, respectively. It follows that the volume concentration of alkane is relatively high, but due to k of the vast majority of alkane OH The reaction constant is small, the chemical activity is weak, and the contribution to the accumulated total amount of the OH consumption rate is small; and the volume concentration of olefin species k is only 14% of the total VOCs OH The reaction constant is large, the chemical activity is strong, and the total contribution is7 cumulative consumption rate; the proportion of the aromatic hydrocarbon contribution to OH consumption is approximately equal to the proportion of the aromatic hydrocarbon contribution to the volume concentration of VOCs. The on-line VOC monitoring equipment can measure limited OVOCs species, and for higher-activity OVOCs species such as formaldehyde, acetaldehyde, etc., the equipment can not carry out analysis monitoring well. The total concentration of the OVOCs measured by the VOC on-line monitoring equipment in the site of the city monitoring station is mostly contributed by the less active acetone (average concentration 7.57 ppb), so that the OVOCs concentration of this site, although relatively high, contributes very little to the total OH consumption rate.
Since the OH reaction rate constant of olefins is relatively high, even if the total VOCs volume concentration is not large, it is possible to form a high OH consumption rate if the olefin concentration is high, and thus effective control of olefins is an important means of reducing the OH consumption rate of the atmosphere at the site.
Since olefins have the greatest effect on the chemical activity of VOCs in the atmosphere of the site, further analysis of the main active components in the olefins is performed below. Table 1 lists the VOCs species names with the average OH consumption rate of the Jinan province top 10 and their relative contributions to the total OH consumption rate.
TABLE 1 VOCs species at top 10 of the OH reactivity ranking of the monitoring stations in the market and their contribution values
It can be seen that isoprene is the species with the highest rate of OH consumption among all olefins, mainly due to the k of isoprene OH The reaction constant is far higher than that of other olefins, however, isoprene is mainly discharged by natural sources such as trees and the like, artificial sources can also have a certain contribution to isoprene in the atmosphere, vegetation discharge of isoprene is mainly influenced by factors such as temperature, humidity, tree species and the like, and controlling the artificial source discharge can not necessarily effectively reduce the concentration of isoprene and the contribution of the isoprene to the OH consumption rate.
Analysis of the activity of anthropogenic olefins shows that the average contribution of n-butene, cis-2-pentene, cis-2-butene and propylene to the OH consumption rate is relatively large; in urban areas, unsaturated olefins such as n-butene, cis-2-pentene, cis-2-butene, propylene and the like mainly come from motor vehicle exhaust and other fixed combustion sources, the components have relatively small variation, and the contribution to the OH consumption rate of the olefins is relatively stable, which indicates that the n-butene, cis-2-pentene, cis-2-butene, propylene are the most common olefin components in the urban environment atmosphere and are also important components for the OH consumption rate of olefin VOCs.
Also, from the average results, 10 species contributed over 70% of the OH reactivity of VOCs at Jinan, where the largest contribution was isoprene, n-butene, cis-2-butene, and cis-2-pentene, respectively, each of which contributed over 5% of the OH reactivity of the total VOCs. Of the top 10 species, only isopentane was an alkane species, and no aromatic and OVOCs species, indicating that other VOCs species than olefins contributed little to the OH reactivity of the atmosphere in the atactic urban environment. If the OH consumption rate of the environmental atmosphere in the Jinan city is controlled, the olefinic species should be mainly controlled.
OH free radical reactivity analysis of refinery VOCs
Table 2 lists the names of VOCs species with the top 10 of the refinery average OH consumption rates and their relative contributions to the total OH consumption rate.
TABLE 2 VOCs species and contribution values from refinery OH reactivity top 10
Refinery sites are typical industrial park sites with higher concentration of VOCs compared to urban atmospheric environment, ranging from 9.17ppb to 805.6ppb by volume. Wherein the concentration of alkane is the highest, the average contribution value is 57%, and the contributions of olefin, acetylene, aromatic hydrocarbon and OVOCs are respectively 9%,12%, 10% and 12%. The corresponding alkane OH consumption rate is 20%, the OH consumption rate of olefin, acetylene, aromatic hydrocarbon and OVOCs is 45% and 1%, 15% and 19%, respectively, and the volume concentration of olefin species k accounting for only 9% of the total VOCs OH The reaction constant is large, the chemical activity is strong, and the accumulated consumption rate of OH is 45% in total. The alkyne measured by the VOCs on-line monitoring equipment is acetylene only, and the OH reaction rate constant k of acetylene OH Very low, so that the concentration contribution of 12% alkyne is only 1% contribution to the OH consumption rate. The proportion of the aromatic hydrocarbon contribution to OH consumption is approximately equal to the proportion of the aromatic hydrocarbon contribution to the volume concentration of VOCs. The higher concentrations of the OVOCs species measured by the VOC on-line monitoring equipment in the refinery site include n-hexanal, 2-butanone, acetone and propanal, which have higher OH reactivity and lower acetone reactivity with 2-butanone, and the site concentration contribution is 12% of the OVOCs contribution to the total OH consumption rate is 19%.
On average, 10 species contributed over 60% of the OH reactivity of refinery VOCs, with the largest contribution being isoprene, n-hexanal, isobutylene and propylene, respectively, each of which contributed over 5% of the OH reactivity of the total VOCs. Of the top 10 species, there are 7 olefin species, which shows the importance of the olefin contribution to OH reactivity in the refinery atmosphere. If the OH reactivity of the refinery is controlled, the olefinic species should be controlled primarily.
OH free radical reactivity analysis of horse race VOCs
The volleyball station VOCs range in volume concentration from 4.19ppb to 48.93 ppb. Wherein the alkane accounts for the highest proportion, the average contribution value is 45%, the contributions of the alkene, the acetylene, the aromatic hydrocarbon and the OVOCs are respectively 11%, 9%, 8% and 26%, the corresponding OH consumption rate of the alkane is 11%, the OH consumption rate of the alkene, the acetylene, the aromatic hydrocarbon and the OVOCs is respectively 39% and 1%, 10% and 38%, and the total OH consumption rate of the alkene species with the volume concentration of only 11% of the total VOCs is approximately 40%. The alkyne measured by the VOCs on-line monitoring equipment is acetylene only, and the OH reaction rate constant k of acetylene OH Extremely low, thus a concentration contribution of 9% alkyne pairsThe contribution of the OH consumption rate is only 1%. The proportion of the aromatic hydrocarbon contribution to OH consumption is approximately equal to the proportion of the aromatic hydrocarbon contribution to the volume concentration of VOCs. Unlike the city monitoring station sites where higher concentrations of the OVOCs in run Ma Ling sites included acetone, n-hexanal, 2-butanone and propanal, where the OH reactivity of n-hexanal and propanal was higher and the reactivity of acetone with 2-butanone was lower, the OVOCs species of the site contributed much more to the total OH consumption rate than the city monitoring station sites, and the concentration of the sites contributed 38% to the total OH consumption rate for 26% of the OVOCs. The VOCs species names with average OH consumption rate of the horse race station top 10 and their relative contributions to the total OH consumption rate are shown in table 3.
TABLE 3 VOCs species and contribution values from the top 10 OH reactivity ranks at the horse race site
On average, 10 species contributed over 70% of the OH reactivity of the horse race site VOCs, with the largest contribution being n-hexanal, isoprene, ethylene, propionaldehyde and cis 2-butene, respectively, and the OH reactivity contribution of the 5 species relative to the total VOCs was over 5%, with the top 10 species, olefins, OVOCs and aromatics species.
Ozone generation potential analysis of different VOCs species
The OFP calculation was performed on all on-line data collected from the city monitoring station, the horse race, and the refinery, month 2019, in combination with the MIR constants for each volatile organic compound.
The average value of each VOCs species in environmental samples collected by the monitoring station, the oil refinery and the horse race in Jinan city is used for representing the pollution condition of the VOCs in the atmosphere of the station, the average value of each species is used for calculating the OFP composition condition of the VOCs in different categories, the results are shown as a-c in figure 6, and the VOCs species and the contribution values of the VOCs in the top 10 positions of the OFP ranking of each station are shown in tables 4-6 respectively.
Table 4 Top 10 VOCs species and contribution values of the monitoring stations OFP in the market
In the above table, OFP is the generation of O 3 Is a ppb by volume concentration.
The table shows that the OFP cumulative value of the Jinan city monitoring station is 89.31ppb O 3 Wherein the olefin contribution is highest, 48%, the components with the largest contribution in the olefin are n-butene, and secondly isoprene and ethylene, respectively, which have calculated OPF contributions to total VOCs of 12.49%, 11% and 4.82%, respectively, the OFP contribution of aromatic species to total VOCs of about 24%, and the most contributing species in the aromatic species are m/p-xylene and toluene, respectively, which have contributions of 3.49% and 3.29%, respectively. Alkane and OVOCs contributed relatively little to the OFP of the station, 20% and 8%, respectively, as can be seen if O to the station 3 Control is exercised and olefins will be the subject of major management.
TABLE 5 VOCs species and contribution values for the top 10 refinery OFP ranks
The data in the table show that the station had an OFP cumulative value of 162.14ppb O 3 Wherein the contribution of aromatic hydrocarbon is up to 31%, and the most contributing species of aromatic hydrocarbon species are m/p-xylene and toluene, respectively, and the contributions of these two species are dividedThe OFP contribution of the olefinic species to the total VOCs was about 26%, the most contributing component in the olefins was isoprene, and next propylene and ethylene, respectively, which contributed 5.01%, 4.97% and 4.20% to the OPF calculated for the total VOCs, respectively, at 10.29% and 6.91%, respectively. The alkane and OVOCs have relatively equivalent total OFP contribution rates of 22% and 19% to the station, respectively, and it is seen that the simultaneous control of olefins and aromatics will result in O 3 The reduction of the formation has a better effect.
Table 6 VOCs species and contribution values from the top 10 of the horse race OFP rank
The table shows that the station had an OFP cumulative value of 34.74ppb O 3 Wherein the OVOCs species contribute the highest OFP calculated for total VOCs, about 38%, the most contributing species of the OVOCs species are n-hexanal and propanal, respectively, the contributions of these two species are 15.42% and 6.28%, respectively, the contribution of the olefin is 28%, and the most contributing components of the olefin are ethylene and cis 2-butene, respectively, which contribute 10.55% and 3.88% to the OPF calculated for total VOCs. Alkane and aromatic hydrocarbons contribute relatively little to the OFP of the station, 12% and 21%, respectively, mainly because the horse race station is a background station in the atanan city, no obvious artificial source is discharged, and the concentration of various VOCs species is relatively uniform.
Step S2, carrying out on-line monitoring on pollution sources contributing to VOCs in the Jinan atmosphere determined in the step S1, and correcting on-line monitoring data by assisting with manual monitoring; the specific operation is as follows:
(1) Establishing sampling points of VOCs in Jinan city and carrying out online monitoring on the sampling points;
the region of Jinan city is wide, the east-west exhibition is quite different, the industrial layout is not uniformly distributed, and the urban development is also uneven. Therefore, in order to cover the regional research background of different development levels in winter and summer, the selected research object covers the urban areas in south China, nutmeg, positive, long-distance, flat yin and the like.
(a) On-line sampling site: the Jinan city station (mountain road 183), jinan city refinery, jinan city upwind horse race;
(b) Offline sampling site: an Jinan real station (mountain road 183), jinan city construction university, jiyang district environmental monitoring station of Jinan city, jinan city long Qing district Qilu industrial university;
(c) Reinforced observation gridding sampling site
According to the spatial distribution characteristics of CO in the Jinan city of 2018, the method is used for treating the important pollution areas in urban areas and the counties in peripheral areas
Setting VOCs sampling points;
(d) Sampling time
According to weather forecast, the grid sampling work in the whole market range is completed twice under the condition of no obvious precipitation in the last day of 9 in 2018 and 1 in 2019.
Sampling periods are tightly controlled at 9:00 am and 13:00 midday quasi-points because: at 9 am, when the traffic early peak is finished, sampling the higher level state representing the urban VOCs as much as possible; and secondly, the solar altitude is lower at 9 am, solar radiation is weak, the influence of photochemical reaction on the freshly discharged VOCs is relatively small, the 13:00 in noon is one of the time periods when solar illumination is sufficient, and the concentration of the VOCs reflects the sum of residual after photochemical reaction and fresh emission in noon. The daily change characteristic sample collection time developed at the conditional place is from 6:00 am to 22:00 night quasi-point for sampling.
Step S3, quality control is carried out on the online monitoring data of the VOCs obtained in the step S2; the specific operation is as follows:
and performing quality control on the online monitoring data of VOCs: an online VOCs monitoring system is established by using GC-MS/FID, and quality control is performed on online VOCs monitoring sites through blank experiments, instrument calibration, daily calibration, detection limits, precision, retention time, internal standard response and isomer analysis.
The qualitative and quantitative analysis is to calibrate an online GC-MS/FID system by adopting mixed standard gas, in particular to dilute 1ppm of multi-mixed standard gas into standard gas with the mixing ratio of 0.5-8 ppb;
FID detector, identifying target compound by comparing the retention time of target compound and standard gas, and obtaining standard curve by measuring five mixing ratios of 0.5, 1, 2,4, 8ppbv response, wherein the value of each mixing ratio takes the average value of 3-5 parallel measurements;
MS detector GC-MS analysis relies on mass spectra that identify the target compound by matching it to the spectra of known compounds in the database, in addition to retention time, quantification of unknown compounds using an internal standard curve method;
the blank test comprises an instrument blank test and a pipeline blank test, wherein the pipeline blank test comprises a standard sample pipeline blank test and an air sample pipeline blank test; the specific test method is as follows:
instrument blank experiment: setting the sampling volume of a sampling system to be 0, operating an instrument for analysis, and if the species is detected, indicating that the interior of the instrument is polluted or the carrier gas is impure, stopping sample analysis to maintain the instrument until the instrument is blank and has no response, and then carrying out subsequent analysis; pipeline blank experiment: connecting high-purity nitrogen to a standard gas sampling port and an air sampling port of the instrument, realizing pipeline blank measurement by injecting high-purity nitrogen, and measuring again after reaching balance after a period of time if the target compound is detected by the standard gas pipeline until the response of the target compound in the blank is eliminated or is lower than the detection limit of the instrument; if the air sample pipeline has species detection, the high-purity nitrogen is replaced for re-measurement or the pre-treatment equipment is heated for back blowing and then re-measurement is carried out.
The daily calibration is to ensure the stability of the GC-MS/FID system, 4ppbv of mixed standard gas is injected once a day, the time change of benzene response factors detected by MS and ethane response factors detected by FID in daily calibration is compared, and the response factors of benzene are corrected according to the environmental response of CFC-113, so that the response factors of the compounds are changed within a range of 20 percent.
According to the measurement results of the present invention, the following conditions for quality control are recommended: the detection limit is in the range of 0.01 to 0.32 ppb; the precision (the proximity of repeated measurement, RSD) is 0.24% -8.88%; the retention time drift is: FID is less than or equal to 0.2 minutes, MS is less than or equal to 0.1 minutes; the daily calibration recovery rate is 80% -120%; the response change of the internal standard is less than or equal to 40 percent; the correlation coefficient of the isomer is more than or equal to 0.8.
And S4, establishing an atmospheric VOCs source component spectrum and a typical VOCs pollution source emission component spectrum database according to the VOCs monitoring data obtained in the step S3.
Example 2
Selecting 26 species of acetylene, propane, n-butane, isopentane, n-pentane, 2-dimethylbutane, cyclopentane, 2, 3-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexane, methylcyclopentane, 2, 4-dimethylpentane, benzene, cyclohexane, 2-methylhexane, 3-methylhexane, n-heptane, toluene, 2-methylheptane, 3-methylheptane, n-octane, tetrachloroethylene, n-nonane, n-decane and undecane as basic fitting species from the pollution sources determined in S1 based on the receptor pattern; estimating errors in the environmental data and the source component spectrum, and checking the results;
NMHCs was source resolved using the following model:
wherein Cik is the concentration of the ith chemical component in the kth environmental sample at the receptor site; aij is the mass fraction of the ith chemical component emitted by pollution source j, i.e. the source spectrum; sjk is the contribution rate of the contamination source j to the acceptor point sample k.
The equation is solved by adopting the effective variance least square method, and the equation is shown as follows:
where Veff, i is the weight of the effective variance, the solution of the effective variance least squares method contains the active contribution S j One item, S j Unknown, and therefore requires iterative operations.
With mean value of point samplesThe standard deviation is taken as a representative, and the ambient air concentration and the uncertainty of the ambient air concentration representing the point sample are brought into the CMB model for calculation, and the diagnostic parameters output by the model are within acceptable ranges from the output result. R is R 2 Between 0.75 and 1.00 χ 2 The analysis results are within 4.0, and the M% range is 66.23-118.43%, so that the analysis results of the model can better reflect the actual conditions of the environment atmosphere.
The result shows that the tail gas of the motor vehicle is the most important source of NMHCs in the atmosphere of Jinan city, the proportion change range is 16.87-58.82 percent, the average value is 31.40 percent, the urban traffic is larger, and the proportion of the tail gas of the motor vehicle is relatively higher; the paint and the solvent volatilize to be another important NMHCs source except the automobile exhaust emission, the average contribution of Jinan city is 25.20+/-9.26%, the contribution range of industrial sources is 12.90+/-5.09%, the proportion of the industrial sources in suburbs is larger, the emission and diffusion information of the sources is captured according to online continuous observation, and the contribution value of the industrial sources can reach 23.45% at the maximum; the concentration level of C5-C7 and aromatic hydrocarbon of solvent products of pharmaceutical pollution sources is high, the average contribution of the solvent products is as high as 9.4%, the relative contribution range of oil refining is (0.81-12.80%), the aromatic hydrocarbon and C2-C5 alkane in VOCs discharged by oil refineries in Jinan province are majority, and the contribution of individual sample petroleum refining emission sources can reach 12.8%.
FIG. 7 illustrates the sources of the major NMHCs species in Jinan and their constitution, and in summary, the C2 component comes from an incomplete combustion process, with the proportion of volatile sources increasing with increasing carbon number.
The C2 component ethane, acetylene and ethylene in China mainly come from the tail gas emission of motor vehicles, most isopentane comes from the gasoline volatilization of motor vehicles, about half of benzene and toluene come from the emission of motor vehicles, and the contribution of motor vehicle tail gas to other NMHCs is relatively large.
The largest contribution of acetylene and isopentane in the emission of the motor vehicle is 78.70+/-4.55% and 76.49+/-4.93% respectively, which respectively indicate incomplete combustion and volatilization of oil gas, and the contribution of alkane and aromatic hydrocarbon above C4 is second largest source of automobile exhaust gas in the use process of the paint and the solvent, especially the aromatic hydrocarbon component, and the proportion of the paint and the solvent is increased.
As mentioned above, the contribution of industrial sources to total NMHCs is not significant, but the industrial sources are diverse and diverse in species, with relatively large contributions of n-hexane and benzene being 19.87 ±13.07% and 13.63±8.78%, respectively, and some pharmaceutical enterprises also contribute to the xylenes component of the urban atmosphere.
The method of the invention realizes more accurate and sensitive tracing and analysis of the VOCs in Jinan province, and defines the source and the relative contribution of main NMHCs species in Jinan province.
The above is only taken as an example of Jinan city, the method of the invention can also be applied to VOCs source analysis in other cities, and the key of the invention is the determination of source spectrum, which is also the difficult problem to be solved by the invention.
Claims (8)
1. The urban VOCs source analysis method based on the receptor mode is characterized by comprising the following steps of:
(1) Establishing a target city VOCs pollution source spectrum;
(2) Selecting fitting species required in calculation of receptor model from the pollution source spectrum determined in (1), the selection principle comprising:
a. the identified species of each source of contamination and the dominant species of NMHCs in the ambient atmosphere;
b. species which are easy to detect, have weak chemical activity and good fingerprint tracing effect;
c. the basic assumption of mass balance is satisfied, the photochemical reaction of NMHCs species in 3-5 h does not influence the mass balance in the process of transmitting from a pollution source to a receptor, and the species with the atmospheric life not less than toluene is selected as the fitting species;
the mathematical expression of the receptor model is:
wherein Cik is the concentration of the ith chemical component in the kth environmental sample at the receptor site; aij is the mass fraction of the ith chemical component emitted by pollution source j, i.e. pollution source spectrum; sjk is the contribution rate of the contamination source j to the acceptor point sample k;
(3) Main VOCs characteristic species of various pollution sources in the target city are defined;
(4) Normalization treatment of pollution source spectrum: converting the concentration data of the pollution source spectrum into percentage content of the total fitting species;
(5) The contribution rate of each pollution source is calculated and determined by using a CMB method.
2. The method for resolving sources of urban VOCs based on receptor model according to claim 1, wherein the source spectrum in (1) is established by the following method:
step S1, O of target city 3 Generating precursor organic matters with larger contribution to monitor so as to grasp the pollution characteristics and change rules of VOCs in the target city, identifying key species of the VOCs generated by the ozone in the target city according to the pollution characteristics of the VOCs, and determining pollution sources contributing to the VOCs in the atmosphere in the target city;
step S2, carrying out on-line monitoring on pollution sources contributing to VOCs in the atmosphere of the target city determined in the step S1, and correcting on-line monitoring data by assisting with manual monitoring;
step S3, quality control is carried out on the online monitoring data of the VOCs obtained in the step S2;
and S4, establishing an atmospheric VOCs source component spectrum and a typical VOCs pollution source emission component spectrum database according to the VOCs monitoring data obtained in the step S3.
3. The method for resolving urban VOCs sources based on receptor model according to claim 2, wherein in step S1, the pollution characteristic comprises: concentration levels and species composition of VOCs, temporal profile of VOCs, and spatial profile of VOCs.
4. The method for analyzing urban VOCs sources based on receptor mode according to claim 2, wherein in step S2, when the target urban VOCs are monitored on line, the arrangement of sampling points and numbers is based on the following:
(a) Selecting a place which fully represents urban pollution characteristics as a sampling point;
(b) Selecting open land in urban commercial area, wherein the included angle between the horizontal line of the sampling port and the height of surrounding buildings is not more than 30 degrees, no local pollution source exists around the monitoring points, the number and the adsorption capacity of the buildings are avoided, and the distance between the sampling points in the traffic dense area and the traffic main road is 100m;
(c) Determining the sampling height of VOCs according to different monitoring scheme relation objects, and keeping the sampling height at a breathing zone 1.5-2 m away from the ground when researching harm of the VOCs to human bodies; if the sampling height is continuous, the distance between the sampling height and the ground is 3-15 m; sampling of urban VOCs is performed on a roof, and even if the roof is on the roof, the sampling port and the foundation ground are required to be kept at a relative height of more than 1.5m so as to reduce the influence from the ground;
(d) Setting conditions of all sampling points are consistent, so that the obtained monitoring data are comparable;
(e) The number of the sampling points is a benefit function corresponding to economic investment and precision requirements, and is comprehensively determined according to the size of a monitoring range, the spatial distribution characteristics of pollutants, population distribution and density, weather, topography, economic conditions and other factors;
(f) Sampling periods are tightly controlled at 9:00 am and 13:00 midday quasi-points.
5. The method for analyzing urban VOCs sources based on receptor model according to claim 2, wherein in step S3, an online VOCs monitoring system is established by GC-MS/FID, and the reliability of online monitoring data is improved by the following conditions: qualitative and quantitative analysis, blank testing, instrument calibration, daily calibration, limit of detection, accuracy, retention time, internal standard response, correlation of isomers.
6. The method for analyzing urban VOCs source based on receptor mode according to claim 5, wherein the qualitative and quantitative analysis is to calibrate an on-line GC-MS/FID system by using mixed standard gas, in particular to dilute 1ppm of multi-mixed standard gas into standard gas with a mixing ratio of 0.5-8 ppb;
FID detector, identifying target compound by comparing the retention time of target compound and standard gas, and obtaining standard curve by measuring five mixing ratios of 0.5, 1, 2,4, 8ppbv response, wherein the value of each mixing ratio takes the average value of 3-5 parallel measurements;
MS detector GC-MS analysis relies on the mass spectrum of a target compound identified by matching it to the spectra of known compounds in a database, in addition to retention time, using an internal standard curve method to quantify unknown compounds.
7. The method for analyzing urban VOCs source based on receptor mode according to claim 5, wherein the blank test comprises an instrument blank test and a pipeline blank test, wherein the pipeline blank test comprises a standard sample pipeline blank test and an air sample pipeline blank test; the specific test method is as follows:
instrument blank experiment: setting the sampling volume of a sampling system to be 0, operating an instrument for analysis, and if the species is detected, indicating that the interior of the instrument is polluted or the carrier gas is impure, stopping sample analysis to maintain the instrument until the instrument is blank and has no response, and then carrying out subsequent analysis; pipeline blank experiment: connecting high-purity nitrogen to a standard gas sampling port and an air sampling port of the instrument, realizing pipeline blank measurement by injecting high-purity nitrogen, and measuring again after reaching balance after a period of time if the target compound is detected by the standard gas pipeline until the response of the target compound in the blank is eliminated or is lower than the detection limit of the instrument; if the air sample pipeline has species detection, the high-purity nitrogen is replaced for re-measurement or the pre-treatment equipment is heated for back blowing and then re-measurement is carried out.
8. The method according to claim 5, wherein the daily calibration is performed to ensure the stability of the GC-MS/FID system by injecting 4ppbv of mixed standard gas once a day, comparing the time variation of the response factors of benzene detected by MS and ethane detected by FID during daily calibration, and correcting the response factors of benzene according to the environmental response of CFC-113, so that the response factors of these compounds are varied within 20%.
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