CN114935618A - Odor causing substance accurate identification method based on non-target screening - Google Patents
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Abstract
The invention provides a non-target screening-based method for accurately identifying odoriferous substances, which comprises the following specific steps of: s1, preprocessing a sample; s2, a non-target screening method; s3, sensory evaluation; s4, analyzing the odor activity value; s5, comprehensive judgment and analysis; and S6, determining a key odor-causing factor. The invention discloses an odor factor accurate identification method based on non-target screening coupled sensory evaluation, an olfactory detection technology, an odor activity value and comprehensive evaluation analysis, constructs an olfactory evaluation rule of odor gas and a key odorant evaluation system, provides a new thought and a new method for solving the problem of 'smelling, smelling and undetected' in actual monitoring, and provides a technical method and an application support for subsequent accurate tracing and control treatment of odor pollution.
Description
Technical Field
The invention provides a non-target screening-based method for accurately identifying an odor causing substance, and belongs to the technical field of environmental monitoring.
Background
Malodour/odour is typically disturbing pollution. In recent three years, the rate of the complaints of the offensive odor/peculiar smell in China is more than 20 percent, and the complaints are second to the noise. The complaint objects comprise various pollution sources of industry, agriculture, life and the like, wherein the industrial sources also comprise various industries of chemical industry, rubber, plastics, medicine, coating, food processing and the like. In addition, the odor has dual attributes of sensory pollution and chemical pollution, can exist in environmental media such as gas, water, soil and the like, and has differences in release characteristics, substance compositions, odor characteristics and environmental influences 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 also a symptom of lack of pertinence of odor management and control at present.
The identification of the environmental odor 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 used in combination with various pretreatment technologies such as three-stage cold trap preconcentration, thermal desorption, solid phase microextraction, headspace, solvent absorption and the like. At present, the analysis technology of the organic pollutants in the environment mainly focuses on the target method research of a certain pollutant or a certain class of pollutants, which means that many unknown pollutants cannot be identified, so that the detection result cannot comprehensively reflect the actual pollution condition, and most of the peculiar smell pollutants in the complex environment are unknown, so that the target analysis method is not suitable for identifying the peculiar smell substances in the environment. Compared with target analysis, non-target screening refers to a method for carrying out total screening on pollutants contained in a sample by changing chromatographic analysis conditions, applying deconvolution technology, setting screening requirements and screening rules on the premise of not using standard substances and not carrying out pre-selection on analytes, but the method is difficult to popularize and use in a full-scanning mode of a conventional mass spectrum, and the conventional mass spectrum is low in sensitivity and poor in matching degree of a spectrogram of the to-be-detected substance due to matrix effect and co-outflow impurities.
The environmental Odor factor identification method comprises an Odor Activity Value (OAV) and a Gas Chromatography-olfaction detection technology (GC-O). OAV is the ratio of odorant concentration to olfactory threshold, and can exactly evaluate the contribution of single odorant component to the overall odor, but the method is based on the assumption that the overall odor characteristics are simple addition of the attributes of each odorant, and the actual odor components have complex interactions such as synergy, accumulation, antagonism and the like in the overall odor contribution. GC-O can combine the separation capacity of gas chromatography with human smell to screen and evaluate the contribution of smell active substances from a complex mixture, but the important premise of the application of the technology is to select a proper pretreatment method and formulate a smell evaluation rule. The environmental odor pollution condition is complex, the odor components are various, a single method cannot cope with the odor substance identification of complex environment, several technologies need to be organically combined, and an evaluation route and a method system suitable for the odor factors in the environmental field are formulated, but no relevant research report exists at present.
Disclosure of Invention
The invention provides an accurate analysis and identification method for environmental odor pollutants, aiming at the problems and limitations of the traditional analysis technology in odor pollution analysis, the method combines a high-sensitivity instrument analysis and sensory evaluation method, comprehensively considers the factors influencing the odor efficacy such as human olfactory sensation, substance components and content thereof, substance structure and odor characteristics, and the like, can effectively improve the odor substance identification rate of environmental odor pollution, and provides powerful technical support for odor pollution event diagnosis and 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 and the like) of the odor substances in gas, water and soil, a plurality of proper pretreatment combination technologies are selected to improve the extraction efficiency of the odor pollutants. For the atmosphere, the pretreatment method comprises a cold trap preconcentration method, an adsorption tube method, an absorption liquid method, a headspace method and the like; for water, the headspace method, solid phase microextraction method and the like are included; for soil, the headspace method, solvent-assisted evaporation method, and the like are included.
S2 non-target screening method
Besides a few inorganic compounds such as ammonia and hydrogen sulfide, many environmental odor substances contain elements such as sulfur, nitrogen, oxygen, chlorine, phosphorus and arsenic, and functional groups such as carbonyl, aldehyde, methanol, ester, amino, ether, carboxyl and carbocarboxyl, and constitute compounds such as aldehyde ketone, alcohol phenol ester, carboxylic acid, amine, thiol and thioether. Based on the physicochemical properties of the odor substances, and the characteristics of low concentration, large polarity difference, common isomerization phenomenon and the like of the odor substances in the complex environment matrix, a pollution recognition analysis mode is established.
Gas chromatography high resolution mass spectrometry-olfaction detection analysis conditions: the chromatographic column is a capillary column with 60m polarity and weak polarity; the flow rate of the carrier gas is 1-1.5 mL/min; temperature programming is carried out for 30-280 ℃, the temperature rising speed is 5-10 ℃/min, and the temperature is kept for 5-10 min at the initial and termination temperatures; the temperature of the sample inlet is not lower than 120 ℃. The GC effluent was separated in a mass spectrometer and sniffer port at a ratio of 1: 1 with a olfactometer line temperature of 280 ℃. The ion source (EI) temperature was 250 ℃; the temperature of the quadrupole rods is 280 ℃; the temperature of the electron transmission line is 300 ℃; the acquisition mode is full scanning; the mass number ranges from 30 amu to 450 amu; mass resolution 60000 FWHM. Sample characterization non-targeted screening was performed using Compound discover 3.0 software, with key parameters as shown in table 1. Internal standard method was used for quantification, and the half-quantity was calculated as toluene.
TABLE 1 non-target screening Key parameters
S3, sensory evaluation
Selecting 6-10 sniffers with qualification certificates and actual working experience of more than 5 years, carrying out sensory test on the odor sample for 4-5 times within one week, requiring to be skilled in mastering the odor characteristics of the sample to be tested, and discussing and determining the sensory odor attribute of the sample to be tested by a sniffing group to form a descriptor list of compound odor.
The method comprises the following steps of carrying out sample analysis by using a proper pretreatment technology and a gas chromatography high-resolution mass spectrometry-olfaction detection technology, evaluating the odor and the intensity of the effluent of a sniffing port by using a time-intensity method by each sniffer, and determining odor descriptors of single substances after discussing by a sniffing group and comparing related literature reports by using a manner of 'object-by-object' with clear and understandable odor description requirements; the descriptors are evaluated according to the intensity of "0 to 4 grades", the "0 grade" means that no odor is sensed, and the "4 grade" means that descriptive odor is strongly sensed. The intensity of each sample was averaged after repeating the measurement 3 times, and a list of "detected substance-odor word-odor intensity" was formed in descending order of intensity.
And analyzing the relation between the compound odor and the detected substances by utilizing a partial least square regression method according to the list of the detected substances, odor words and odor intensity, and further analyzing the odor-causing factors of the odor gas.
S4 analysis of odor activity value
According to relevant literature reports of countries and regions of China, Japan, Europe and America and the like, the olfactory threshold value of the substance is searched, the odor activity value of each substance is calculated based on the quantitative and semi-quantitative results of the substance, and the main contribution factor of the peculiar smell of the sample under the condition of not considering the interaction among the odors is analyzed and determined.
S5, comprehensive judgment and analysis
And (3) determining the weight coefficient (shown in a formula 1) and the assignment standard (shown in a table 2) of each element by using a fuzzy mathematical analysis method and taking an olfactory threshold, a molecular structure, a detectable rate, a relative content and an odor attribute as screening factors. And calculating the comprehensive score of the odor substances, and determining a main odor substance list.
y＝0.3a+0.3b+0.2c+0.1d+0.1e (1)
In the formula, a represents an olfactory threshold, b represents a molecular structure, c represents a detectable rate, d represents a relative content, and e represents an odor attribute.
TABLE 2 screening factor assignment criteria
* Number of odorous atoms or radicals: phosphorus, arsenic, sulfur, antimony and other elements of groups 4 to 7, and functional groups with odor such as carbonyl, aldehyde, carbinol, ester, amino, ether, carboxyl, carbocarboxyl and the like
S6, determination of key odor-causing factor
And determining the key odoriferous substances based on GC-O technology, odor activity values and comprehensive judgment analysis by combining the composite odor attributes of the samples.
The invention discloses an odor factor accurate identification method based on non-target screening coupled sensory evaluation, an olfactory detection technology, an odor activity value and comprehensive evaluation analysis, constructs an olfactory evaluation rule of odor gas and a key odorant evaluation system, provides a new thought and a new method for solving the problem of 'smelling, smelling and undetected' in actual monitoring, and provides a technical method and an application support for subsequent accurate tracing and control treatment of odor pollution.
Drawings
FIG. 1 is a flow chart of the method for accurately identifying odoriferous substances based on non-target screening according to the present invention
Detailed Description
The rubber industry is a key industry for foreign odor complaints, and the invention selects a rubber mixing process of a certain enterprise as an implementation case for description.
(1) List of complex odor descriptors
Selecting waste gas of an internal mixing process of a large tire product enterprise as a test object, wherein the enterprise has 6 internal mixing waste gas exhaust cylinders, and under the full-load working condition, each exhaust cylinder parallelly collects 3 samples, and the total number of the samples is 18.
Selecting 6 sniffers with qualification certificates and actual working experience of more than 5 years, ensuring that the 6 sniffers participate in more than 5 times of odor concentration experiments of the internal mixing waste gas sample of the enterprise in one week, skillfully mastering the overall odor characteristics of the internal mixing waste gas sample, evaluating sensory odor attributes, and recording compound odor descriptors of each sample, wherein the list of the compound odor descriptors is shown in Table 3.
TABLE 3 list of odor descriptors for compounding of waste gases
(2) List of "detected substance-odor word-odor intensity
The method comprises the following steps of performing qualitative and artificial olfactory discrimination analysis and detection on the 18 samples by using a pretreatment technology of a three-stage cold trap preconcentration and adsorption tube method and a method combining a gas chromatography high-resolution mass spectrum-olfactory detection technology, wherein specific condition parameters are as follows:
three-stage cold trap preconcentration condition
The temperature of the primary trap is-40 ℃, the preheating and analyzing temperature is 20 ℃, the baking temperature is 130 ℃, and the baking time is 5 min; the temperature of the secondary trap is-40 ℃, the analysis temperature is 150 ℃, the baking temperature is 150 ℃, and the baking time is 35 min; the temperature of the third-stage trap is-180 ℃, the sample introduction time is 3min, the baking time is 2min, and the baking temperature is 150 ℃.
② conditions of thermal desorption
The adsorption tubes are three-in-one combined type (carbon C, carbon B, carbon 1000);
desorption 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 0.3 min; trap parameters: the initial temperature is minus 10 ℃, the desorption temperature is 280 ℃, and the desorption time is 3 min;
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 taken as carrier gas, and the constant flow is 1.0 mL/min; the initial temperature of the column oven is 30 ℃, the column oven is kept for 5min, the heating rate is 7 ℃/min, the final temperature is 280 ℃, and the column oven is kept for 5 min; the temperature of the sample inlet is 250 ℃, and the temperature of the transmission line is 300 ℃;
high resolution mass spectrum condition
The temperature of an ion source (EI) is 250 ℃, and the temperature of a quadrupole rod is 280 ℃; the acquisition mode is full scanning; the mass number ranges from 30 amu to 450 amu; mass resolution 60000 FWHM;
condition of olfactometer
The GC effluent was separated in a mass spectrometer and sniffer port at a ratio of 1: 1 with olfactive detector line temperature of 280 ℃ and ODP port temperature of 160 ℃.
Condition for non-target screening
The signal to noise ratio is larger than 3, the sample blank ratio is larger than 10, the mass deviation is less than +/-5 ppm, the response intensity is larger than or equal to 100,000, the high-resolution filter is set to be 97 percent, the delta R.T. is smaller than or equal to 10, the index threshold value is larger than or equal to 750, and a NIST spectrum library is selected for Database.
Each sniffer respectively evaluates the odor and the intensity of the effluent of the sniffing port by using a time-intensity method, the odor description adopts a mode of 'object by object' and defines the odor descriptor of a single substance after the discussion of a sniffing group and the comparison of related literature reports; each descriptor is evaluated according to the intensity of 0-4 grade, wherein the 0 grade is that no odor is sensed, and the 4 grade is that the descriptive odor is strongly sensed. The intensity of each sample was averaged after repeating the measurement 3 times, and a list of "detected substance-odor word-odor intensity" was formed in descending order of intensity. And analyzing the relation between the compound odor and the detected substances by utilizing a partial least squares regression method based on a list of the detected substances, odor words and odor intensity, and further analyzing the odor-causing factors of the odor gas. The list of "detected substance-odor word-odor intensity" is shown in table 4, and the analysis results by partial least squares regression are shown in table 5.
TABLE 4 list of "detected substances-odor words-odor intensity" of mixing exhaust gases
TABLE 5 partial least squares regression results for internal mixing exhaust samples
(3) Odor activity value of each substance in banburying waste gas
Based on a quantitative method, related literature reports of China, Japan, Europe, America and other countries and regions are combined, a smell threshold of a substance is searched, and the Odor Activity Value (OAV) of each detected substance is calculated, wherein a related calculation formula is shown as a formula (2).
In the formula, OAV i Is the i-th speciesQualitative odor activity value, dimensionless; c i Is the average concentration of the i-th substance in mg/m 3 ；OT i The olfactory threshold of the ith substance is mg/m 3 。
Based on the method, substances with OAV values of more than or equal to 1 are used as main contributing factors of the peculiar smell of the sample, and the calculation results of the smell activity value are shown in a table 6.
TABLE 6 Main contribution factor of odor of internal mixing waste gas samples
(4) Comprehensive judgment and analysis of banburying waste gas
And (3) 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 odor attribute as screening factors. And calculating the comprehensive score of the odor substances, and screening the odor substances with the score of more than 1.5 as a main odor substance list as shown in Table 7.
TABLE 7 comprehensive evaluation and analysis list of waste gas from banburying
(5) Key odoriferous substances
TABLE 8 list of key odoriferous substances in the waste gas from internal mixing
Based on GC-O technology, odor activity value and comprehensive judgment and analysis, the key odoriferous substances of the odoriferous gas are determined by combining the compound odor attribute of the odoriferous gas, and finally the key odoriferous substances of 49 banburying waste gases including alcohols, acids, esters, aldehydes, ketones, benzene series, alkane olefins and other compounds are obtained.
Claims (5)
1. A method for accurately identifying odor causing substances based on non-target screening is characterized by comprising the following specific steps:
s1 sample pretreatment
Based on the release mechanism of the odor substances in gas, water and soil, a plurality of proper pretreatment combination technologies are selected to improve the extraction efficiency of the odor pollutants;
s2 non-target screening method
Based on the physical and chemical properties of the odor substances, the pollution identification and analysis mode is established by combining the common characteristics of low concentration, large polarity difference and isomerization of the odor substances in the complex environment matrix;
gas chromatography high resolution mass spectrometry-olfaction detection analysis; sample characterization non-targeted screening was performed using Compound discover 3.0 software; quantitatively using an internal standard method, and measuring the semiquantitative amount by toluene;
s3, sensory evaluation
Selecting 6-10 sniffers, carrying out sensory test on the odor sample for 4-5 times within one week, requiring to be skilled in mastering the odor characteristics of the gas sample to be tested, discussing by a sniffing group and determining the sensory odor attribute of the sample to be tested to form a descriptor list of compound odor;
carrying out sample analysis by using a proper pretreatment technology and a gas chromatography high-resolution mass spectrometry-olfaction detection technology, evaluating the odor and the intensity of the effluent of the sniffing port by each sniffer by using a time-intensity method, and determining odor descriptors of each single substance after discussion by a sniffing group and comparison of related literature reports; evaluating each descriptor according to the intensity of 0-4 grade, wherein the 0 grade is that no odor is sensed, and the 4 grade is that description odor is strongly sensed; after each sample is repeatedly measured for 3 times, the strength is averaged, and a list of 'detected substance-odor word-odor strength' is formed according to the sequence of strength from large to small;
according to the list of 'detected substance-odor word-odor intensity', analyzing the relation between the compound odor and the detected substance by using a partial least square regression method, and further analyzing the odor-causing factor of the odor sample;
s4 analysis of odor activity value
Searching olfactory thresholds of the substances, calculating the odor activity value of each substance by combining quantitative and semi-quantitative results, and analyzing and determining main contribution factors of the peculiar smell of the sample under the condition of not considering the interaction among the odors;
s5, comprehensive judgment and analysis
Determining each element weight coefficient and assignment standard by applying a fuzzy mathematical analysis method and taking an olfactory threshold, a molecular structure, a detectable rate, a relative content and an odor attribute as screening factors, calculating an odor substance comprehensive score, and determining a main odor 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 detectable rate, d represents a relative content, and e represents an odor attribute;
s6, determination of key odor-causing factor
And determining the key odoriferous substances based on GC-O technology, odor activity values and comprehensive judgment analysis by combining the composite odor attributes of the samples.
2. The method for accurately identifying the odoriferous substance based on the non-target screening as claimed in claim 1, wherein in S1, the pretreatment method for the atmosphere comprises a cold trap preconcentration method, an adsorption tube method, an absorption liquid method, a headspace method; for water, a headspace method and a solid phase microextraction method are included; for soil, a headspace method, a solvent-assisted evaporation method are included.
3. The method for accurately identifying odor causing substances based on non-target screening as claimed in claim 1, wherein in S2, the odor causing substances include, in addition to ammonia and hydrogen sulfide, compounds containing sulfur, nitrogen, oxygen, chlorine, phosphorus, arsenic, and carbonyl, aldehyde, methanol, ester, amino, ether, carboxyl, and carbocarboxyl functional groups, which constitute aldone, alcoholic phenol ester, carboxylic acid, amine, thiol, and thioether compounds.
4. The method for accurately identifying the odor causing substance based on the non-target screening of claim 1, wherein in S2, the analysis conditions of gas chromatography high resolution mass spectrometry-olfaction detection are as follows: the chromatographic column is a capillary column with 60m polarity and weak polarity; the flow rate of the carrier gas is 1-1.5 mL/min; temperature programming is carried out for 30-280 ℃, the temperature rising speed is 5-10 ℃/min, and the temperature is kept for 5-10 min at the initial and termination temperatures; the temperature of a 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 ion source temperature is 250 ℃; the temperature of the quadrupole rods is 280 ℃; the temperature of the electron transmission line is 300 ℃; the acquisition mode is full scanning; the mass number ranges from 30 amu to 450 amu; mass resolution 60000 FWHM.
5. The method for accurately identifying the odor causing substance based on non-target screening according to claim 1, wherein in S2, the non-target screening, key parameters: the signal-to-noise ratio is more than 3; the blank ratio of the sample is more than 10; the mass deviation is less than +/-5 ppm; the response strength is more than or equal to 100,000; the high resolution filter was set to 97%; the retention index is less than or equal to 10; the index threshold is more than or equal to 750; the database is NIST spectral library.
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| CN115561365A (en) * | 2022-10-31 | 2023-01-03 | 广州市花都自来水有限公司 | Method and system for detecting peculiar smell substances in tap water |
| CN116068095A (en) * | 2023-03-22 | 2023-05-05 | 远东正大检验集团有限公司 | Down feather odor testing method |
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| CN116068095A (en) * | 2023-03-22 | 2023-05-05 | 远东正大检验集团有限公司 | Down feather odor testing method |
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