CN110849782B - Method for quantifying BrC source based on EEM method - Google Patents
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Abstract
The invention discloses a method for quantifying BrC source based on EEM method, belonging to the field of data analysis. 1) Acquiring EEMs of different aerosol samples; different aerosol samples include BB, CB, VE, CE, low oxidation secondary aerosol, medium oxidation secondary aerosol, and high oxidation secondary aerosol; 2) fitting EEMs by using a PARAFAC model, and selecting chromophoric groups according to the residual error change trend of the model, wherein the selected chromophoric groups are C1, C2, C3, C4, C5, C6, C7 and C8; and (4) carrying out data processing to obtain contribution values of chromophores in different sources. The method for quantifying the BrC source based on the EEM method can calculate the contribution values of different sources of the atmospheric aerosol, is favorable for carrying out source analysis on the local atmospheric pollution of different emission source structures, effectively establishes an atmospheric emission source list and provides a decision basis for atmospheric pollution control.
Description
Technical Field
The invention belongs to the field of data analysis, and particularly relates to a method for quantifying a BrC source based on an EEM method.
Background
Chromophoric group materials in Brown Carbon (BrC) are organic materials in aerosols that absorb solar radiation and participate in photochemical reactions, and have been shown to form triplets and generate reactive oxygen species, with important potential contributions to the aging process of atmospheric aerosols. Atmospheric chromophoric groups are one of the considerations currently used to improve the "global model of environmental quality and impact of global climate".
Three-dimensional fluorescence spectroscopy (EEM) is an important instrumental analysis method for identifying chromophore, and has been widely used for a long time in the study of the type and source of water-soluble chromophore organic matter (CDOM). In recent years, the EEM method has also been frequently applied to the field of research on atmospheric aerosols, which is used to characterize the chemical composition of organic aerosols. It was found that Humoid (HULIS) in actual atmospheric particulates is the most predominant chromophore type in atmospheric aerosols. Proteins in bioaerosols can also be identified by the EEM method. Some studies have also applied the EEM method to the tracing of aerosol sources. For example, Yan and Kim have discovered using EEM and isotopic tracing that HULIS is primarily derived from emissions from biomass combustion and terrestrial biogas and particulates. A great deal of research has been directed to the EEM method for exploring the processes and mechanisms of atmospheric chemical reactions. For example, the chemical reaction process of carbonyl compounds and amine species to produce BrC, and the photolysis process of atmospheric chromophoric groups. The EEM method has become the most direct and effective method for researching the types, sources and atmospheric chemical processes of atmospheric chromophoric groups, and has great potential to be widely applied in the atmospheric field.
Currently, there is no systematic analysis of atmospheric aerosols for the differences in chromophores of different anthropogenic origin; even if different kinds of chromophore substances are resolved by parallel factor analysis (PARAFAC), the content change of the chromophore is still not obvious. Researches show that the relative content of chromophores in the urban atmospheric aerosol does not change greatly in different seasons; currently, there is no basis for determining the correspondence between the atmospheric chromophore and the source, which is one of the important reasons for limiting the application of the EEM method to determine the chromophore source. Although some efforts have been made, the chemical structures or species of different chromophores are still unknown, and this situation leads to that even if different chromophores are identified and their contents in the sample are obtained by the EEM method, the data results and phenomena cannot be well explained in most cases, which is also an important reason for limiting the EEM method to the research on the chemical transformation and formation mechanism of atmospheric chromophores.
Disclosure of Invention
The present invention is directed to overcome the above disadvantages of the prior art and to provide a method for quantifying BrC source based on the EEM method.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a method for quantifying BrC source based on EEM method includes the following steps:
1) acquiring EEMs of different aerosol samples;
the different aerosol samples comprise BB, CB, VE, CE, low-oxidation secondary aerosol, medium-oxidation secondary aerosol and high-oxidation secondary aerosol;
2) fitting EEMs by using a PARAFAC model, and selecting chromophoric groups according to the residual error change trend of the model, wherein the selected chromophoric groups are C1, C2, C3, C4, C5, C6, C7 and C8;
3) the contribution of the jth chromophoric group from the ith source is xij；
1-7, and 1-7 correspond to BB, CB, VE, CE, low-oxidation secondary aerosol, medium-oxidation secondary aerosol and high-oxidation secondary aerosol in sequence;
j-1-8, 1-8 correspond to C1, C2, C3, C4, C5, C6, C7, and C8, respectively;
BB. The sum of the contributions of the chromophoric groups C1-C8 in CB, VE, CE, low-oxidation secondary aerosol, medium-oxidation secondary aerosol and high-oxidation secondary aerosol is respectively represented as yC1’、yC2’、yC3’、yC4’、yC5’、yC6’、yC7' and yC8’；
The contribution of the individual chromophoric groups C1-C8 in a single sample of an atmospheric aerosol on-line is yC1、yC2、yC3、yC4、yC5、yC6、yC7、yC8；
The system of multiple linear regression equations can thus be listed as follows:
a1、b1、c1、d1、e1、f1、g1the value range of (1) is [ 0-1 ],
approaching zero, solving equation set (2) and solving a1、b1、c1、d1、e1、f1And g1A value of (d);
and taking the solved value as the fluorescence contribution of the atmospheric aerosol online sample at the source.
Further, the method also comprises unknown sources, wherein the fluorescence contribution of the online sample of the atmospheric aerosol from the unknown sources is 1- (a)1+b1+c1+d1+e1+f1+g1)。
Further, the atmospheric aerosol online samples are divided into a plurality of groups, each group is solved according to the step 3) to obtain a plurality of groups a1、b1、c1、d1、e1、f1、g1；
Taking the average value to obtain a, b, c, d, e, f and g as the fluorescence contribution of the atmospheric aerosol online sample at the source.
Further, the fluorescence contribution of the online sample of the atmospheric aerosol from unknown sources is 1- (a + b + c + d + e + f + g).
Further, EEMs of different aerosol samples are obtained in the step 1), and extraction liquid adopted when the chromophoric groups are extracted is water and methanol.
Further, the solution samples Abs tested in EEMs for obtaining different aerosol samples in step 1)250Less than 0.5.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for quantifying the BrC source based on the EEM method, on the premise that the content change of the chromophore is not obvious, the content change of different chromophores in different aerosol samples is calculated, and the content of different chromophores in different aerosol samples is demonstrated to be different, so that the EEM method is capable of distinguishing different chromophores and sample types, and the result plays a role in promoting the application of the EEM method in the field of aerosol research; the method for quantifying the BrC source based on the EEM method can calculate the contribution values of different sources of the atmospheric aerosol, is favorable for carrying out source analysis on the local atmospheric pollution of different emission source structures, effectively establishes an atmospheric emission source list and provides a decision basis for atmospheric pollution treatment.
Drawings
FIG. 1 is a graph comparing the error of the results of the C2-C15 model in PARAFAC analysis for the water soluble material and methanol soluble material of the primary, secondary and PM samples of example 1;
FIG. 2 is a graph of the contribution of each source in the atmospheric sample of example 1.
Wherein: BB is biomass combustion; CB is coal combustion; VE is motor vehicle emissions; CE is cooking emission; the low-oxidation secondary aerosol, the medium-oxidation secondary aerosol and the high-oxidation secondary aerosol respectively represent secondary aerosols with different oxidation degrees generated due to different precursors and different reaction conditions.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
1) Sample collection
To quantify the origin of BrC using the EEM method, a first step entails the collection of samples comprising: atmospheric samples (off-line or on-line) to be determined for each source contribution, Primary Organic Aerosol (POA) emission source samples, Secondary Organic Aerosol (SOA) emission source samples, and the like. The city aerosol sample used in the research is an atmospheric aerosol sample in a certain area obtained by an online monitoring system in a laboratory, and other emission source samples used in the research are BB, CB, VE, CE and secondary aerosol samples obtained offline. The online sample is obtained by an online system, and the online sample measurement system comprises the following components: the water-soluble PM is obtained by connecting a three-dimensional fluorescence spectrum analyzer with an aerosol atomizer (PILS) and a TOC analyzer by using a PTFE (polytetrafluoroethylene) tubule2.5Chromophoric group information of (1). Prior to TOC and EEM, the PILS liquid samples were passed through a liquid chromatograph specialized stainless steel sieve plate (0.45 μm pore size) to remove insoluble particles (including black carbon). A peristaltic pump is added into the system to enable the collected sample solution to enter an EEM flow cell cuvette through a PTFE (polytetrafluoroethylene) tubule, the peristaltic pump extracts once at regular time, and the sample is continuously extracted within a specified time range. In order to ensure the EEM stable detection, the peristaltic pump is controlled to stop working during the EEM detection, and no sample is injected into the EEM flow cell.
The off-line sample is used for collecting atmospheric PM by an XT-1025 intelligent large-flow air particulate matter collector2.5The particles are sampled. PM (particulate matter)2.5After the sample settled down from the impact zone to a 20X 25in quartz fiber membrane (which had been heated to 450 ℃ in a muffle furnace for 45min and then held for 4h), the operation of the sampler was automatically stopped (the stop time was 06:30:00 as early as each day).
The method comprises the steps of using a mobile phone to shoot data (including rated working condition flow, actually measured standard condition flow, accumulated working condition volume, accumulated standard condition volume, humidity, air temperature, air pressure and back pressure) displayed on a panel and a stopwatch at any time, inserting a USB flash disk into a USB flash disk slot under an operation panel, clicking a green 'dump' button to guide the data into the USB flash disk, and pulling out the USB flash disk after the panel displays 'data export is completed'. And taking out the filter membrane after the data is exported, loosening the six snap spring buckles at the periphery of the mainframe box, lifting the cutter assembly from the front, supporting the cutter assembly by using a manual hook, and then performing filter membrane replacement operation. If precipitation weather occurs, the cutter assembly is not opened when the filter membrane is replaced, but the cutting head (four snap spring buckles) is taken down, and the filter membrane assembly is taken out from the upper part. Care was taken to wipe the instrument clean of water stains on the outside and inside. The filter membrane assembly taken out is put into a stainless steel basin prepared in advance, a layer of tinfoil is laid on the bottom of the stainless steel basin, and the surface of the filter membrane is covered by another layer of tinfoil to prevent pollution. And then putting the new filter membrane assembly into the sampler, fixing four corner nuts (excessive force is not applied on the premise of ensuring compaction, and sliding is prevented), putting down the cutter assembly, and setting sampling parameters. Setting the starting time to be 07:00:00 under the [ timing long termination mode ]; the flow rate is 1000L/min; the timing length is 23.5h, after the relevant parameters are set, the [ confirmation ] is selected, the sampler enters a state to be operated, and after the sampler operates for about 2min, the panel data is recorded again. The background sample collection mode is the same as that of the actual sample, but the background sample collection time is only 5 s.
And POA emission source samples and SOA emission source samples can be collected on the Teflon filter membrane by a four-channel sampler. All of the above samples, except the on-line sample, were stored in a-20 ℃ refrigerator prior to use.
2) Sample pretreatment
The offline sample pretreatment operation comprises the following steps: putting 2 filter membrane samples with the diameter of 9mm into a 12mL clean glass bottle (preheated at 450 ℃ for 4h), adding 6mL ultrapure water, carrying out ultrasonic extraction for 30min (or 15min), filtering through a 0.45-micrometer filter membrane (PTFE) to obtain a water-soluble organic matter extract, and waiting for ultraviolet-visible absorption spectrum scanning and EEM analysis. Since not all chromophore species are water soluble, methanol, a polar solvent, may extract the chromophore species with greater fluorescence intensity, and therefore methanol was chosen as the solvent for extraction in addition to water. The pretreatment step is the same, and the extraction liquid comprises water-soluble organic matters and water-insoluble organic matters. While the pre-treatment of the POA and SOA samples followed the off-line sample procedure. If the atmospheric sample is obtained by an online system, a continuous chromophoric group spectrogram with high time resolution can be obtained in one measurement period.
3) EEM analysis
The experimental conditions of the sample solution in the 10X 10mm quartz cell in the analysis and measurement of the three-dimensional fluorescence spectrometer are as follows: excitation wavelength range of 200-600nm, emission wavelength range250800nm, wavelength interval of 5nm, exposure time of 0.5s (excitation wavelength range of 200-600nm, emission wavelength range of on-line atmospheric sample measurement)250800nm, wavelength interval 2nm, exposure time 2s, time resolution and precision, etc., as the case may be). In order to prevent the saturation of the sample signal and to effectively reduce the effect of internal filtration in EEM assays, the sample should be diluted beforehand with the corresponding solvent and all solution samples Abs should be guaranteed250Less than 0.5. The EEMs of the background samples were finally recorded under the same operating conditions and subtracted from the EEMs of the samples.
4) PARAFAC data processing
To demonstrate whether the EEM method can distinguish between different samples, the EEM data analyzed therefore includes EEM data for all different types of samples (atmospheric PM samples, POA samples, SOA samples), both water soluble and water insoluble. Referring to fig. 1, fig. 1 is a comparison of the error of C2-C15 model results of water soluble and methanol soluble species of primary, secondary and west ampere PM samples in a PARAFAC analysis in which a PARAFAC model of 8 components (C1-C8) was selected based on EEM morphological characteristics of the various components and residual error variation trends of the model.
5) Multiple linear regression
Previous studies have not systematically analyzed whether the chromophoric groups in different anthropogenic aerosols are different. In the research, PM samples of BB, CB, VE and CE in a certain area and secondary aerosol samples with different oxidation degrees formed by different precursors are selected as research objects. Since the relative amounts of different types of chromophoric groups in samples from different sources may be different, the relative amounts of the individual chromophoric groups C1-C8 in different sources can be determined as shown in the following table. Each column in Table 1 represents the contribution of a single chromophore in x1-x7 (actually 5 sources), and each row represents the contribution of C1-C8 chromophores in a single source. The specific contribution is measured by the EEM and PARAFAC methods described in steps 3) and 4).
TABLE 1 relative contribution of C1-C8 in different sources
BB, CB, VE, CE, a low-oxidation (Less Oxygenated) secondary aerosol, a medium-oxidation (Moderate Oxygenated) secondary aerosol, and a high-oxidation (high Oxygenated) secondary aerosol have been set as x1、x2、x3、x4、x5、x6And x7. The sum of the contributions of the various chromophoric groups (C1-C8) from the seven emission sources mentioned above is denoted yC1’、yC2’、yC3’、yC4’、yC5’、yC6’、yC7’、yC8', and the contribution of each chromophore (C1-C8) in a single sample of an in-line aerosol at a location is denoted as yC1、yC2、yC3、yC4、yC5、yC6、yC7、yC8Thereby listing the matrix (1). By a1-g1Respectively represent x1-x6Corresponding coefficient variables, a multiple linear regression equation (2) can be derived.
Find a1-g1Is the main objective of the present multiple linear regression equation, which represents the contribution of each emission source (BB, CB, VE, CE, low oxidation secondary aerosol, medium oxidation secondary aerosol, and high oxidation secondary aerosol) to the atmospheric PM sample, respectively.
Now the error is counted as yCn-yCn'; the squared deviation is Abs (y)Cn-yCn’)2(ii) a If the error (%) is a positive value and the absolute value thereof is larger than the allowable SD, the error (%) is set to A, if the error (%) is a positive value and the absolute value thereof is smaller than the allowable SD, the error (%) is set to B, if the error (%) is a negative value and the absolute value thereof is smaller than the allowable SD, the error (%) is set to C, if the error (%) is a negative value and the absolute value thereof is larger than the allowable SD, the error (%) is set to D, and the deviation is counted as A2+1*B2+1*C2+2*D2. In addition, the dispersion (negative penalty), the square of dispersion (negative penalty) taking the spectral error into account and the like of the chromophoric groups C1-C8 in the atmospheric sample are calculated for the consideration of numerical optimization. From the multiple linear regression equation (2), let yCn-yCn' approach to zero, in a particular algorithm so that
Approaching zero. The planning and solving operation is as follows: "set target":
a cell; "to": a minimum value; "by changing the variable cell": a-g value cells; "compliance constraint": a-g value of 0-1&The unknown component is more than or equal to 0; checking "make the unconstrained variable a non-negative number"; "selection solution method": pure linear programming; "solve for". Solving to obtain a of a first group of samples1-g1The value is obtained.
Because the atmospheric aerosol online samples in a certain area are 532 groups (2018/12/3110: 00-2019/1/2213:00), the operation is recorded by using a macro and calculation operation is continued, and 532 groups of a-g values (a-g) can be obtained1-g1、a2-g2、……a532-g532)(532×7)，ai-giRepresents BB, CB,The seven sources of VE, CE, low-oxidation secondary aerosol, medium-oxidation secondary aerosol and high-oxidation secondary aerosol respectively account for the fluorescence contribution of the ith sienna atmospheric aerosol online sample.
It is stated that the values of a-g denote x1-x7The current h value (i.e., the contribution of the unknown component) represents 1-SUM(a-g)A new set of data (532 x 8) is obtained. Then, the average values of a-h are respectively obtained (for example, the average value of a for representing BB is calculated according to the following formula (a obtained from the atmospheric sample 1 + a obtained from the atmospheric sample 2 + a obtained from the sample … + a obtained from the sample 532)/532), and the average value can represent the contributions of different sources of the atmospheric aerosol online sample in a certain area, so as to obtain the conclusion, referring to FIG. 2, FIG. 2 is a graph of the contributions of all the sources in the atmospheric sample in example 1, and BB accounts for 18%; CB accounts for 45%; VE accounts for 0.3%; CE accounts for 27%; SOAs (including Less Oxygenated, Moderate Oxygenated, Highly Oxygenated) account for 0.5% and unknown constituents account for 9.2%.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. A method for quantifying BrC source based on EEM method is characterized by comprising the following steps:
1) acquiring EEMs of different aerosol samples;
the different aerosol samples comprise BB, CB, VE, CE, low-oxidation secondary aerosol, medium-oxidation secondary aerosol and high-oxidation secondary aerosol;
2) fitting EEMs by using a PARAFAC model, and selecting chromophoric groups according to the residual error change trend of the model, wherein the selected chromophoric groups are C1, C2, C3, C4, C5, C6, C7 and C8;
3) the contribution of the jth chromophoric group from the ith source is xijContribution xijMeasured by the EEM and PARAFAC methods;
1-7, and 1-7 correspond to BB, CB, VE, CE, low-oxidation secondary aerosol, medium-oxidation secondary aerosol and high-oxidation secondary aerosol in sequence;
j-1-8, 1-8 correspond to C1, C2, C3, C4, C5, C6, C7, and C8, respectively;
BB. The sum of the contributions of the chromophoric groups C1-C8 in CB, VE, CE, low-oxidation secondary aerosol, medium-oxidation secondary aerosol and high-oxidation secondary aerosol is respectively represented as yC1’、yC2’、yC3’、yC4’、yC5’、yC6’、yC7' and yC8’；
The contribution of the individual chromophoric groups C1-C8 in a single sample of an atmospheric aerosol on-line is yC1、yC2、yC3、yC4、yC5、yC6、yC7、yC8；
Thus, the following set of multiple linear regression equations may be listed:
a1、b1、c1、d1、e1、f1、g1the value range of (1) is [ 0-1 ],
approaching zero, solving equation set (2) and solving a1、b1、c1、d1、e1、f1And g1A value of (d); will solve out a1、b1、c1、d1、e1、f1、g1The value of (a) is taken as the fluorescence contribution of the atmospheric aerosol online sample given to the atmospheric aerosol online sample at each emission source.
2. The method for quantifying BrC source based on EEM method according to claim 1, further comprising unknown source, wherein the fluorescence contribution of the online sample of atmospheric aerosol from unknown source is 1- (a)1+b1+c1+d1+e1+f1+g1)。
3. The method for quantifying BrC source based on EEM method according to claim 1, wherein the atmospheric aerosol online samples are in groups, each group is solved according to step 3) to obtain groups a1、b1、c1、d1、e1、f1、g1；
And taking the average value of the values to obtain a, b, c, d, e, f and g, and respectively using the a, b, c, d, e, f and g as the fluorescence contribution of the atmospheric aerosol online sample to the atmospheric aerosol online sample at each emission source.
4. The method for quantifying BrC source based on EEM method according to claim 3, further comprising unknown source, wherein the fluorescence contribution of the online sample of atmospheric aerosol from unknown source is 1- (a + b + c + d + e + f + g).
5. The method of claim 1, wherein the EEMs of different aerosol samples are obtained in step 1), and the extraction solution used for extracting chromophoric groups is water and methanol.
6. The method for quantifying BrC source based on EEM method of claim 1, wherein the step 1) of obtaining the Abs of the solution samples tested in EEMs of different aerosol samples250Less than 0.5.
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