CN114935618B - Non-target screening-based precise identification method for odor-causing substances - Google Patents
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Abstract
The invention provides a non-target screening-based odorizing substance precise identification method, which comprises the following specific steps: s1, sample pretreatment; s2, a non-target screening method; s3, sensory evaluation; s4, analyzing smell activity values; s5, comprehensive judgment and analysis; s6, determining key odor factors. The invention discloses a non-target screening coupling sensory evaluation, olfactory detection technology, odor activity value and comprehensive judgment analysis-based odor factor accurate identification method, which constructs an olfactory evaluation rule and a key odor substance evaluation system of odor, provides a new thought and a new method for solving the problem of 'smelling and failing to detect' in actual monitoring, and provides a technical method and application support for subsequent accurate tracing and control treatment of odor pollution.
Description
Technical Field
The invention provides a non-target screening-based precise identification method for odorizing substances, and belongs to the technical field of environmental monitoring.
Background
Malodor/off-flavors are typical disturbing people. In recent three years, the odor/peculiar smell complaint reporting amount of China exceeds 20 percent, which is inferior to the second place of noise. Complaints include various pollution sources of industry, agriculture, life and the like, wherein the industry sources also cover a plurality of industries such as chemical industry, rubber, plastics, medicines, coating, food processing and the like. In addition, off-flavors have the dual attributes of sensory and chemical contamination and can exist in environmental media such as air, water, soil, etc., with differences in the release characteristics, composition of matter, odor characteristics, and environmental impact of different types of sources. Therefore, how to accurately identify the odor substances and key odor causing factors is a core scientific problem of odor treatment, and is a symptom of lack of pertinence in current odor management and control.
The identification of the environmental peculiar smell substances mainly adopts the detection technology of volatile/semi-volatile organic compounds, wherein the gas chromatography-mass spectrometry technology is the most widely used method and is combined with a plurality of pretreatment technologies such as three-stage cold trap pre-concentration, thermal desorption, solid-phase microextraction, headspace, solvent absorption and the like. At present, the analysis technology of the environmental organic pollutants is mainly focused on the research of a target method of a certain or a certain type of pollutants, which means that a plurality of unknown pollutants cannot be identified, so that the detection result cannot comprehensively reflect the actual pollution condition, and the peculiar smell pollutants in the complex environment are mostly unknown, so that the target analysis method is not suitable for identifying the peculiar smell matters in the environment. Compared with target analysis, non-target screening refers to a method for total screening of pollutants contained in a sample by changing chromatographic analysis conditions, applying deconvolution technology and setting screening requirements and screening rules on the premise that a standard substance is not used and an analyte is not pre-selected, but the method is difficult to popularize and use in a full-scan mode of conventional mass spectrometry, and is mainly poor in spectrum matching degree of the analyte due to low sensitivity of the conventional mass spectrometry, matrix effect and co-flowing impurities.
Environmental malodor-causing factor identification methods include odor activity values (Odor Activity Value, OAV) and gas chromatography-olfactory detection techniques (Gas Chromatography-olfactor, GC-O). OAV is the ratio of odorant concentration to olfactory threshold and allows an exact assessment of the contribution of a single odorant component to the overall odor, but the method is based on the assumption that the overall odor profile is a simple sum of odorant attributes, whereas there are complex interactions of synergy, accumulation, antagonism, etc. among the actual odorant components in the overall odor contribution. GC-O can combine the separation capacity of gas chromatography with human olfaction, a technique to screen and evaluate the size of the contribution of odor-active substances from complex mixtures, but the important premise of this technique application is to select the appropriate pretreatment method and formulate the olfactory evaluation rules. The environment peculiar smell pollution condition is complex, peculiar smell components are various, a single method can not deal with the identification of odorizing substances in a complex environment, a plurality of technologies are required to be organically combined, and an evaluation route and a method system suitable for odorizing factors in the environment field are formulated, but no related research report exists at present.
Disclosure of Invention
Aiming at the problems and limitations of the traditional analysis technology in the analysis of the odor pollution, the invention provides an accurate analysis and identification method of the environmental odor pollutant, which combines a high-sensitivity instrument analysis and sensory evaluation method, comprehensively considers the factors influencing the odor effectiveness such as human olfactory perception, substance components and contents thereof, substance structure and odor characteristics, and the like, can effectively improve the identification rate of the odor-causing substance of the environmental odor pollution, and provides a powerful technical support for the diagnosis of the odor pollution event and the subsequent pollution treatment.
The invention provides a non-target screening-based method for accurately identifying odor-causing substances, which comprises the following specific steps:
s1, sample pretreatment
Based on the release mechanism (including substance decomposition rule, diffusion coefficient, etc.) of the peculiar smell substances in the gas, water and soil, a proper variety of pretreatment combination technologies are selected, and the extraction efficiency of peculiar smell pollutants is improved. For the atmosphere, the pretreatment method comprises a cold trap pre-concentration method, an adsorption tube method, an absorption liquid method, a headspace method and the like; for water, including headspace method, solid phase microextraction method, etc.; for soil, headspace method, solvent-assisted evaporation method, and the like are included.
S2, non-target screening method
The environmental peculiar smell substances contain a few inorganic compounds such as ammonia, hydrogen sulfide and the like, and most of the environmental peculiar smell substances contain elements such as sulfur, nitrogen, oxygen, chlorine, phosphorus, arsenic and the like, and functional groups such as carbonyl, aldehyde group, methanol group, ester group, amino group, ether group, carboxyl group, carbocarboxyl group and the like, so that aldehyde ketone, alcohol phenolic ester, carboxylic acid, amine, mercaptan, thioether and the like are formed. Based on the physicochemical properties of the peculiar smell substances, the pollution recognition analysis mode is established by combining the characteristics of low concentration of the peculiar smell substances, large polarity difference, common isomerism phenomenon and the like in the complex environment matrix.
Gas chromatography high resolution mass spectrometry-olfactory detection analysis conditions: the chromatographic column selects a 60m polar capillary column with weak polarity; the flow rate of carrier gas is 1-1.5 mL/min; heating to 30-280 deg.c at 5-10 deg.c/min and maintaining at the initial and final temperature for 5-10 min; the temperature of the sample inlet is not lower than 120 ℃. The GC effluents were separated in a mass spectrometer and sniffer in a 1:1 ratio, with the olfactory detector line temperature being 280 ℃. Ion source (EI) temperature 250 ℃; quadrupole temperature 280 ℃; the temperature of the electron transmission line is 300 ℃; the acquisition mode is full scanning; the mass number range is 30-450 amu; mass resolution 60000FWHM. Samples were qualitatively screened for non-targeting using Compound Discoverer 3.0 software and key parameters are shown in table 1. The quantitative use of internal standard method, semi quantitative toluene.
Table 1 non-target screening key parameters
S3, sensory evaluation
6-10 sniffers with qualification certificates and actual working experience exceeding 5 years are selected, sensory tests are carried out on peculiar smell samples for 4-5 times in one week, the odor characteristics of the samples to be tested are required to be mastered, the sniffers group discusses and determines the sensory odor attributes of the samples to be tested, and a description word list of compound odors is formed.
Sample analysis is carried out by utilizing a proper pretreatment technology and a gas chromatography high-resolution mass spectrum-olfaction detection technology, each sniffer utilizes a time-intensity method to evaluate the odor and the intensity of the sniffer effluent, the odor description requirement is clear and easy to understand, and the odor description word of each single substance can be defined after the discussion of sniffer groups and the comparison of the related literature reports by adopting a' borrowing and self-evident manner; the descriptors were evaluated according to the intensity "0 to 4" with "0" indicating no perceived odor and "4" indicating a strong perceived descriptive odor. The intensities were averaged after repeating the measurement 3 times for each sample, and a "detected substance-smell word-smell intensity" list was formed in order of the intensities from the higher ones.
And according to a list of detected substances, smell words and smell intensity, analyzing the relation between the compound smell and the detected substances by using a partial least squares regression method, and further analyzing the odor factor of the odorous gas.
S4, analyzing smell activity value
In combination with the reports of related documents in China, japan, europe and America and other countries, the smell threshold of the substances is searched, the smell activity value of each substance is calculated based on the quantitative and semi-quantitative results of the substances, and the main contribution factors of the peculiar smell of the sample under the condition of not considering the interaction among the smells are determined through analysis.
S5, comprehensive judgment and analysis
And determining the weight coefficient (shown in formula 1) and the assignment standard (shown in table 2) of each element by using a fuzzy mathematical analysis method and taking an olfactory threshold value, a molecular structure, a detection rate, relative content and smell attribute as screening factors. And calculating the comprehensive score of the peculiar smell substances, and determining a main peculiar smell substance list.
y＝0.3a+0.3b+0.2c+0.1d+0.1e (1)
Wherein a represents an olfactory threshold, b represents a molecular structure, c represents a detection rate, d represents a relative content, and e represents an odor attribute.
Table 2 criteria for assigning filter factors
* Number of malodorous atoms or radicals: group 4 to 7 elements such as phosphorus, arsenic, sulfur and antimony, and odorizing functional groups such as carbonyl, aldehyde, methanol, ester, amino, ether, carboxyl and carbocarboxyl groups
S6, determining key odor causing factors
Based on GC-O technology, odor activity values and comprehensive evaluation analysis, the key malodorous substances are determined in combination with the complex odor attributes of the sample.
The invention discloses a non-target screening coupling sensory evaluation, olfactory detection technology, odor activity value and comprehensive judgment analysis-based odor factor accurate identification method, which constructs an olfactory evaluation rule and a key odor substance evaluation system of odor, provides a new thought and a new method for solving the problem of 'smelling and failing to detect' in actual monitoring, and provides a technical method and application support for subsequent accurate tracing and control treatment of odor pollution.
Drawings
FIG. 1 is a flow chart of a method for accurately identifying malodorous substances based on non-target screening according to the present invention
Detailed Description
The rubber industry is an important industry of peculiar smell complaints, and the invention selects a rubber mixing procedure of a certain enterprise as an implementation case for description.
(1) Composite odor descriptor list
And selecting banburying process waste gas of a large tire product enterprise as a test object, wherein the enterprise has 6 banburying waste gas exhaust cylinders, and under the full-load working condition, each exhaust cylinder is used for collecting 3 samples in parallel, and the total number of the samples is 18.
6 sniffers with qualification certificates and actual working experience exceeding 5 years are selected, the 6 sniffers are ensured to participate in odor concentration experiments of banburying waste gas samples of the enterprise for more than 5 times in a week, the overall odor characteristics of the banburying waste gas samples are mastered, sensory odor attribute evaluation is carried out, compound odor descriptors of each sample are recorded, and a list of compound odor descriptors is shown in table 3.
TABLE 3 banburying waste gas composite odor descriptor list
(2) List of "detected substance-smell word-smell intensity
The 18 samples are qualitatively and manually detected by olfactory analysis by adopting a pretreatment technology of a three-stage cold trap pre-concentration and adsorption tube method and adopting a method combining gas chromatography high-resolution mass spectrum-olfactory detection technology, and specific condition parameters are as follows:
(1) three-stage cold trap pre-concentration condition
The temperature of the first-stage trap is minus 40 ℃, the preheating and analysis temperature is 20 ℃, the baking temperature is 130 ℃ and the baking time is 5min; the temperature of the secondary trap is-40 ℃, the analysis temperature is 150 ℃, the baking temperature is 150 ℃ and the baking time is 35min; the temperature of the three-stage trap is minus 180 ℃, the sample injection time is 3min, the baking time is 2min, and the baking temperature is 150 ℃.
(2) Thermal desorption conditions
The adsorption tube is a three-in-one combination (Carbopack C, carbopack B, carboxen 1000);
desorber tube parameters: the initial temperature is 40 ℃, the dry blowing temperature is 40 ℃, the desorption temperature is 280 ℃, the desorption time is 11min, and the cooling time is 0.3min; trap parameters: the initial temperature is-10 ℃, the desorption temperature is 280 ℃, and the desorption time is 3min;
isothermal zone parameters: the valve temperature is 260 ℃, the gas phase transmission line temperature is 260 ℃, and the water cooling transmission line temperature is 260 ℃.
(3) Gas chromatography conditions
Selecting DB-5MS by a chromatographic column; high-purity helium is used as carrier gas, and the constant flow is 1.0mL/min; the initial temperature of the column temperature box is 30 ℃, the temperature is kept for 5min, the heating rate is 7 ℃/min, the final temperature is 280 ℃, and the temperature is kept for 5min; the temperature of the sample inlet is 250 ℃, and the temperature of the transmission line is 300 ℃;
(4) high resolution mass spectrometry conditions
The ion source (EI) temperature is 250 ℃ and the quadrupole temperature is 280 ℃; the acquisition mode is full scanning; the mass number range is 30-450 amu; mass resolution 60000FWHM;
(5) olfactometer condition
The GC effluents were separated in a mass spectrometer and sniffer in a 1:1 ratio with an olfactory detector line temperature of 280℃and an ODP port temperature of 160 ℃.
(6) Non-target screening conditions
The signal-to-noise ratio is more than 3, the sample blank ratio is more than 10, the mass deviation is < +/-5 ppm, the response intensity is more than or equal to 100,000, the high-resolution filter is set to 97%, the delta R.T. is less than or equal to 10, the index threshold is more than or equal to 750, and the database is a NIST spectrum library.
Each sniffer evaluates the smell and intensity of the sniffer effluent by using a time-intensity method, and the smell description adopts a way of "borrowing from things", and the smell description words of single substances are defined after the discussion of sniffer groups and the comparison of related literature reports; the descriptors were evaluated according to the intensity of "0 to 4" with "0" indicating no perceived odor and "4" indicating a strong perceived descriptive odor. The intensities were averaged after repeating the measurement 3 times for each sample, and a "detected substance-smell word-smell intensity" list was formed in order of the intensities from the higher ones. And analyzing the relation between the compound smell and the detected substances based on a 'detected substance-smell word-smell intensity' list by using a partial least square regression method, and further analyzing the odor causing factors of the peculiar smell. The list of "detected substance-smell word-smell intensity" is shown in table 4, and the analysis result of the partial least squares regression method is shown in table 5.
TABLE 4 list of "detected substance-smell word-smell intensity" for banburying exhaust gas
TABLE 5 partial least squares regression results for banburying exhaust gas samples
(3) Odor activity value of each substance in banburying waste gas
Based on a quantitative method, related literature reports of countries and regions such as China, japan, europe and America are combined, the smell threshold of the substance is searched, the smell activity value (OAV) of each detected substance is calculated, and a related calculation formula is shown as a formula (2).
In the formula, OAV i The odor activity value of the i-th substance is dimensionless; c (C) i Mg/m is the average concentration of the i-th substance 3 ；OT i The sniff threshold of the i-th substance, mg/m 3 。
Based on the method, substances with OAV value larger than or equal to 1 are used as main contribution factors of the peculiar smell of the sample, and the odor activity value calculation result is shown in Table 6.
TABLE 6 odor major contributor to banburying exhaust gas samples
(4) Comprehensive evaluation and analysis of banburying waste gas
And determining the weight coefficient (formula 1) and the assignment standard (table 1) of each element by using a fuzzy mathematical analysis method and taking the olfactory threshold, the molecular structure, the detection rate, the relative content and the smell attribute as screening factors. And calculating the comprehensive score of the peculiar smell substances, and screening the peculiar smell substances with the score of more than 1.5 as a main peculiar smell substance list, as shown in table 7.
TABLE 7 comprehensive evaluation and analysis list of banburying waste gas
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(5) Key malodor-causing substances
TABLE 8 Table of key malodorous substances in banburying exhaust gas
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Based on GC-O technology, odor activity value and comprehensive evaluation analysis, and combined with the composite odor attribute of the odor gas, determining the key odor-causing substances of the odor gas, and finally obtaining the key odor-causing substances of 49 banburying waste gases including alcohols, acids, esters, aldehydes, ketones, benzene series, alkane olefins and other compounds.
Claims (5)
1. The method for accurately identifying the odorizing substances based on non-target screening is characterized by comprising the following specific steps of:
s1, sample pretreatment
Based on the release mechanism of the peculiar smell substances in the gas, water and soil, a plurality of proper pretreatment combination technologies are selected, so that the extraction efficiency of peculiar smell pollutants is improved;
s2, non-target screening method
Based on the physicochemical properties of the peculiar smell substances, the pollution recognition analysis mode is established by combining the common characteristics of low concentration, large polarity difference and isomerism of the peculiar smell substances in the complex environment matrix;
high-resolution mass spectrum-olfactory detection analysis of gas chromatography; sample characterization non-targeted screening was performed using Compound Discoverer 3.0 software; quantitatively using an internal standard method, wherein semi-quantitatively is calculated by toluene;
s3, sensory evaluation
6-10 sniffers are selected, sensory tests are carried out on the odor samples for 4-5 times within one week, the odor characteristics of the gas samples to be tested are required to be mastered, the sniffers group discusses and determines the sensory odor attributes of the samples to be tested, and a description word list of compound odors is formed;
sample analysis is carried out by utilizing a proper pretreatment technology and a gas chromatography high-resolution mass spectrum-olfaction detection technology, each sniffer evaluates the odor and the intensity of the sniffer effluent by utilizing a time-intensity method, and after the discussion of sniffer groups and the comparison of related literature reports, the odor descriptor of each single substance is defined; each descriptor is evaluated according to the intensity of 0 to 4, wherein 0 is no smell perceived, and 4 is strong smell perceived; repeating the measurement of each sample for 3 times, taking an average value of the intensities, and forming a list of 'detected substances-smell words-smell intensities' according to the order of the intensities from large to small;
according to the list of detected substances, smell words and smell intensity, analyzing the relation between the compound smell and the detected substances by using a partial least squares regression method, and further analyzing the odor factor of the odor sample;
s4, analyzing smell activity value
Searching an olfactory threshold of the substances, combining quantitative and semi-quantitative results, calculating odor activity values of the substances, and analyzing and determining main contribution factors of the odor of the sample under the condition of not considering interaction among the odors;
s5, comprehensive judgment and analysis
And (3) determining weight coefficients and assignment standards of all elements by using a fuzzy mathematical analysis method and taking an olfactory threshold, a molecular structure, a detection rate, relative content and smell attributes as screening factors, calculating comprehensive scores of the peculiar smell substances, and determining a main peculiar smell substance list:
y＝0.3a+0.3b+0.2c+0.1d+0.1e (1)
wherein a represents an olfactory threshold, b represents a molecular structure, c represents a detection rate, d represents a relative content, and e represents an odor attribute;
s6, determining key odor causing factors
Based on GC-O technology, odor activity values and comprehensive evaluation analysis, the key malodorous substances are determined in combination with the complex odor attributes of the sample.
2. The method for accurately identifying the odorizing substances based on the non-target screening according to claim 1, wherein in the step S1, for the atmosphere, a pretreatment method comprises a cold trap pre-concentration method, an adsorption tube method, an absorption liquid method and a headspace method; for water, including headspace method, solid phase microextraction method; for soil, headspace method, solvent assisted evaporation method are included.
3. The method for accurately identifying the odorizing substances based on the non-target screening according to claim 1, wherein in the S2, the odorizing substances comprise sulfur, nitrogen, oxygen, chlorine, phosphorus and arsenic elements, and carbonyl, aldehyde, methanol, ester, amino, ether, carboxyl and carbocarboxyl functional groups, so as to form aldehyde ketone, alcohol phenolic ester, carboxylic acid, amine, mercaptan and thioether compounds.
4. The method for accurately identifying the odorizing substances based on the non-target screening according to claim 1, wherein in the step S2, the analysis conditions of gas chromatography high-resolution mass spectrometry-olfaction detection are as follows: the chromatographic column selects a 60m polar capillary column with weak polarity; the flow rate of carrier gas is 1-1.5 mL/min; heating to 30-280 deg.c at 5-10 deg.c/min and maintaining at the initial and final temperature for 5-10 min; the temperature of the sample inlet is not lower than 120 ℃; separating GC effluent in a mass spectrum detector and a sniffing port according to the proportion of 1:1, wherein the temperature of a pipeline of the sniffing detector is 280 ℃; the temperature of the ion source is 250 ℃; quadrupole temperature 280 ℃; the temperature of the electron transmission line is 300 ℃; the acquisition mode is full scanning; the mass number range is 30-450 amu; mass resolution 60000FWHM.
5. The method for accurately identifying the odoriferous substances based on non-target screening according to claim 1, wherein in the step S2, the non-target screening is carried out, and key parameters are as follows: the signal-to-noise ratio is more than 3; the blank ratio of the sample is more than 10; mass deviation is < + -5 ppm; response intensity is not less than 100,000; the high resolution filter was set to 97%; the retention index is less than or equal to 10; the index threshold value is more than or equal to 750; the database is a NIST spectrum library.
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| CN105891433A (en) * | 2015-12-29 | 2016-08-24 | 北京师范大学 | Method for identifying underground water type drinking water source particular pollutants |
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