Quantitative method for rapidly evaluating risk ranking of potential chemical substances in consumer goods

Abstract

The invention discloses a quantitative method for rapidly evaluating risk ranking of potential chemical substances in consumer goods, which comprises the following steps: (1) based on headspace gas chromatography-orbitrap high-resolution mass spectrometry, accurately identifying potential chemical substances in consumer goods of one type in a non-targeted screening manner to form a list of potential substances in consumer goods of one type; (2) performing material risk assignment and scoring, performing quantitative scoring and sorting on the material risks identified in a non-targeted manner, and forming a sorting list of the material risks in the consumer goods; and (3) evaluating the high-risk substances according to the risk scores, comparing the contents of the high-risk substances in different products through a visual graph, and comparing the content distribution difference of the high-risk substances in different products through difference significance analysis. The quantitative method for rapidly evaluating the risk ranking of the potential chemical substances in the consumer goods has important significance in improving the inspection and supervision technical level of the consumer goods in China, reducing public events, improving the quality of the consumer goods in China and guaranteeing the health and safety of consumers.

Description

Technical Field

[0001] The present invention relates to a method for evaluating chemical substances in consumer products, and in particular to a quantitative method for quickly determining the risk ranking of potential chemical substances in consumer products. Background Art

[0002] With the development of technology and society, people have realized that the chemical risks of products do not only come from target substances (such as formaldehyde, plasticizers, polycyclic aromatic hydrocarbons, etc. that are restricted by regulations), but also from many potential unknown substances that have not yet been detected. Non-targeted screening based on chromatography and high-resolution mass spectrometry has become a world academic frontier and research hotspot in recent years. It is a screening method that comprehensively identifies chemical substances in samples based only on chromatography-mass spectrometry data without prior information on standards and samples, and is not limited to specific substances. Non-targeted screening methods are in line with national development policies and are an important technical means to implement the State Council's 2022 "Action Plan for the Control of New Pollutants" to identify new pollutants in products, solve public safety incidents caused by unknown hazardous substances in products such as toxic runways, toxic cars, toxic stationery, and toxic school uniforms, and protect the health and safety of consumers. It also plays an important role in comprehensively identifying the chemical composition of products and promoting product quality improvement.

[0003] A sample may detect hundreds of substances through non-targeted screening, and dozens of similar products may detect even more substances. There is currently no internationally recognized standard evaluation method for how to quickly determine the risk ranking of chemical substances and identify high-risk chemical substances from a large number of chemical substances. Although some methods for material risk ranking and evaluation have been reported at home and abroad, they are only applicable to research in specific professional fields within a small range, not to consumer products (light industrial products such as children's toys, textiles, and daily toiletries), and cannot achieve rapid quantitative ranking of material risks. The quality and safety of consumer products are closely related to people's health. Accurately identifying potential chemical substances in consumer products through non-targeted screening methods, quickly determining the risk ranking of potential chemical substances in consumer products through reliable evaluation methods, and determining high-risk chemical substances that need to be controlled first are of great significance to improving the technical level of consumer product inspection and supervision in my country, reducing the occurrence of public events, improving the quality of consumer products in my country, and protecting the health and safety of consumers. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a quantitative method for quickly determining the risk ranking of potential chemical substances in consumer products.

[0005] The present invention provides a quantitative method for quickly determining the risk ranking of potential chemical substances in consumer products, comprising the following steps:

[0006] (1) Based on headspace gas chromatography-orbitrap high-resolution mass spectrometry, accurately identify potential chemical substances in a class of consumer products by non-targeted screening, and form a list of potential substances in this class of consumer products;

[0007] (2) Material risk scoring: quantitatively scoring and ranking the risks of substances identified in non-targeted ways to form a ranked list of substance risks in this category of consumer products;

[0008] (3) Assess high-risk substances based on risk scores, compare the content of high-risk substances in different products through visual graphics, and compare the content distribution differences of high-risk substances in different products through significance analysis.

[0009] The quantitative method for quickly determining the risk ranking of potential chemical substances in consumer products described in the present invention, wherein the full score of the risk assignment score is 100 points, and the larger the score, the greater the risk of the substance in the product, and the more it should be focused on. The risk assignment score calculation method is: Risk score = D 检出频次 +A 平均峰面积 +H 物质危害性 .

[0010] D 检出频次 , the full score is set at 25 points. The substance with the highest detection frequency in a category of products is given a full score of 25 points, and the detection frequency of other substances accounts for A% of the highest detection frequency, then the score is 25×A%. For example, there are 30 samples in total, and a substance with the highest detection frequency in 20 samples is scored 25 points, and another substance detected in 4 samples is scored 25×(4 / 20)=25×20%=5 points.

[0011] A 平均峰面积 , the full score is set to 25 points, and all substances are sorted in descending order according to the average peak area of ​​the substances detected in a class of products (the average peak area of ​​the substance detected in all samples is taken as the average), with the highest peak area being 25 points and the lowest peak area being 0 points, evenly distributed. For example, among the 26 substances detected in total, the substance with the highest average peak area is 25 points, and the substance with the second highest average peak area is 24 points.

[0012] H 物质危害性 The full score is 50 points, according to the International Agency for Research on Cancer (IARC), Class 1 carcinogens are 50 points, Class 2 carcinogens are 45 points, and Class 3 carcinogens are 40 points. Substances on the EU REACH Regulation SVHC list of high concern substances are 40 points. Other substances are classified by toxicity prediction, referring to the Toxtree classification, Cramer III is 30 points (high toxicity), Cramer II is 20 points (moderate toxicity), Cramer I is 10 points (low toxicity), and substances that do not show any toxicity information are 5 points.

[0013] The quantitative method for quickly determining the risk ranking of potential chemical substances in consumer products of the present invention is different from the prior art in that:

[0014] How to quickly determine the risk ranking of chemical substances from a large number of chemical substances and identify high-risk chemical substances, there is currently no recognized standard evaluation method internationally. Although some methods for material risk assessment have been reported at home and abroad, they are only applicable to research in specific professional fields within a small range, not to the consumer products mentioned in the present invention, and cannot achieve rapid quantitative ranking of material risks. The present invention is aimed at a large number of chemical substances screened out of non-targeted screening in a class of consumer products. For the first time at home and abroad, a method for assessing the risk ranking of potential chemical substances in consumer products with clear quantitative scores is proposed. The detection frequency of the substance in the product, the average peak area (representing the content) of the substance in the product, and the harmfulness of the substance are comprehensively considered. Three important factors, 25, 25, and 50 points are set respectively and scientific and reasonable assignment rules that can be easily operated are innovatively proposed. The risk score is 100 points, and the risk of the substance in this type of product is ranked according to the risk score of all substances. The processing speed of the method of the present invention is also very fast, and it only takes 3 to 4 hours to quantitatively assess the risk ranking of 100 substances.

[0015] The quality and safety of consumer products are closely related to people's health. The potential chemical substances in consumer products can be accurately identified through non-targeted screening methods. The risk ranking of potential chemical substances in consumer products can be quickly determined through the present invention. High-risk substances that need to be controlled first can be evaluated based on the risk score. The content of high-risk substances in different products can be compared through visual graphics. The content distribution differences of high-risk substances in different products can be compared through difference significance analysis. This is of great significance for improving the technical level of consumer product inspection and supervision in my country, reducing the occurrence of public events, improving the quality of consumer products, and protecting the health and safety of consumers.

[0016] In conjunction with the accompanying drawings, a quantitative method for quickly determining the risk ranking of potential chemical substances in consumer products of the present invention is further described below by taking a children's floor mat product as an example. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is the total ion chromatogram superposition of 34 children's floor mat samples in the present invention;

[0018] Figure 2 The summary statistics of substances identified in the children's floor mats of the present invention (the size of the circle indicates the number of substances);

[0019] Figure 3 This is a qualitative example of α-methylstyrene in the present invention: (a) EI spectrum; (b) PCI spectrum; the annotation includes the measured mass, elemental composition and mass deviation from the theoretical mass, in ppm;

[0020] Figure 4 This is a risk scoring radar chart for 5 representative substances in the present invention;

[0021] Figure 5 Figure 3 is the peak area distribution of 14 high-risk substances in the floor mat products made of four materials in the present invention. Different letter bars of the same compound have significant differences (Tukey HSD, p≤0.05). DETAILED DESCRIPTION

[0022] 1. Chemicals and Materials

[0023] Standards of 14 high-risk substances were purchased from Alfa Aesar (Lancaster, UK) and Tokyo Chemical Industry (Tokyo, Japan) with a purity of >95%. A mixture of C7-C40 normal alkanes was purchased from Sigma-Aldrich (St. Louis, MO, USA). 34 children's floor mats were randomly purchased from shopping malls or e-commerce platforms in Beijing, China, including 3 EPE materials, 15 XPE materials, 5 PVC materials, and 11 EVA materials. Before analysis, the samples were placed in separate PE self-sealing bags to prevent cross contamination.

[0024] 2. Methods:

[0025] A quantitative method for quickly determining the risk ranking of potential chemical substances in consumer products comprises the following steps:

[0026] (1) Based on headspace gas chromatography-orbitrap high-resolution mass spectrometry, accurately identify potential chemical substances in a class of consumer products by non-targeted screening, and form a list of potential substances in this class of consumer products;

[0027] (2) Material risk scoring: quantitatively scoring and ranking the risks of substances identified in non-targeted ways to form a ranked list of substance risks in this category of consumer products;

[0028] (3) Assess high-risk substances based on risk scores, compare the content of high-risk substances in different products through visual graphics, and compare the content distribution differences of high-risk substances in different products through significance analysis.

[0029] 1. Sample preparation in step (1):

[0030] The children's floor mat samples were cut into small pieces less than 5 mm. Then, 1 gram of the sample was transferred to a 20 mL headspace bottle. It was immediately sealed with a metal screw cap equipped with a polytetrafluoroethylene / silicone septum and then placed in a headspace autosampler. The headspace incubation temperature was set to 80 ° C, the incubation time was set to 30 min, and the injector temperature was set to 90 ° C. Under this condition, the volatile components in the sample were released into the headspace, and then 1 mL of the headspace volume was injected into the gas chromatograph for analysis.

[0031] Before injection, a blank analysis was performed using a 20 mL headspace vial without sample to identify potential systemic or non-systemic contamination, such as the ion source, column, injection needle, rubber septum, etc. A blank was injected every three samples.

[0032] 2. Instrument parameters in step (1):

[0033] The analysis was performed using a Trace 1310 gas chromatography system equipped with a quadrupole-orbitrap mass spectrometer (Thermo Fisher Scientific, Germany) and a TriPlus RSH autosampler with headspace injection. Inlet temperature: 250°C. Splitless injection was used, the injection volume was 1 mL, the carrier gas was helium (purity 99.999%), and the flow rate was 1 mL / min. Separation was performed on a weakly polar HP-5MS column (30 m×0.25 mm×0.25 μm), with a temperature program of 40°C (hold for 1 min), 5°C / min to 160°C, and then 20°C / min to 250°C.

[0034] Full scan mass spectra were collected in the range of m / z 40 to 500. Each sample was analyzed in electron ionization (EI) and positive chemical ionization (PCI) modes. The EI ionization energy was 70 eV. The PCI reaction gas was methane with a flow rate of 1.5 mL / min. The mass spectrometer transfer line temperature was 250 °C. The ion source temperatures of EI and CI were 280 °C and 250 °C, respectively. The mass resolution was set to 60000 FWHM, and the total ion current (TIC) intensity threshold was set to 2 × 10 6 The maximum injection time was set to 200 ms and the mass tolerance window was set to ±5 ppm.

[0035] 3. Data processing

[0036] Thermo Scientific TraceFinderTM 4.1 software was used to collect and process data in step (1). The high-resolution mass spectrum of the unknown substance was decomposed into pure spectra using the Deconvolution Plugin of TraceFinder software and compared with the standard spectra in the NIST 2014 library. The deconvolution parameters were set as follows: TIC intensity threshold, 2e6; mass error, ±5ppm; S / N, 3; RT window, 10 seconds.

[0037] In step (3), one-way analysis of variance (SPSS Inc., Chicago, USA) was used to conduct differential analysis on harmful substances in children's floor mats.

[0038] After blank subtraction, most compounds are first characterized using NIST library search index (SI), high resolution filtering (HRF), and retention index deviation ΔRI. The smaller the ΔRI, the more reliable the qualitative result. The molecular ion peak and molecular formula are determined by measuring PCI to distinguish interferences with similar scores or no retention index RI data. Finally, some isomers are distinguished by comparing the subtle differences in ion fragments and verified against chemical standards.

[0039] 4. Risk assessment scoring scheme in step (3):

[0040] The risk assignment score is to sort the non-target screening substances in a batch of products to quickly identify high-risk substances in such products. Formula (1) gives a method for calculating the risk assignment score of a substance based on the detection frequency, average peak area and hazard of the substance. The higher the score (out of 100 points), the higher the risk of the substance in the product category and the more attention it needs.

[0041] Risk Assignment Score = D 检出频次 +A 平均峰面积 +H 物质危害性 (1)

[0042] D 检出频次 , the full score is set at 25 points. The substance with the highest detection frequency in a category of products is given a full score of 25 points, and the detection frequency of other substances accounts for A% of the highest detection frequency, then the score is 25×A%. For example, there are 30 samples in total, and a substance with the highest detection frequency in 20 samples is scored 25 points, and another substance detected in 4 samples is scored 25×(4 / 20)=25×20%=5 points.

[0043] A 平均峰面积, the full score is set to 25 points, and all substances are sorted in descending order according to the average peak area of ​​the substances detected in a class of products (the average peak area of ​​the substance detected in all samples is taken as the average), with the highest peak area being 25 points and the lowest peak area being 0 points, evenly distributed. For example, among the 26 substances detected in total, the substance with the highest average peak area is 25 points, and the substance with the second highest average peak area is 24 points.

[0044] H 物质危害性 The full score is 50 points, according to the International Agency for Research on Cancer (IARC), Class 1 carcinogens are 50 points, Class 2 carcinogens are 45 points, and Class 3 carcinogens are 40 points. Substances on the EU REACH Regulation SVHC list of high concern substances are 40 points. Other substances are classified by toxicity prediction, referring to the Toxtree classification, Cramer III is 30 points (high toxicity), Cramer II is 20 points (moderate toxicity), Cramer I is 10 points (low toxicity), and substances that do not show any toxicity information are 5 points.

[0045] The visualization graphics in step (3) include using Origin to draw bubble classification maps and peak area distribution maps of high-risk substances, using Metaboanalyst to draw cluster heat maps, using EVern to draw Venn diagrams, and using SPSS one-way analysis of variance to perform difference analysis and significance analysis on harmful substances in children's floor mats.

[0046] 2. Results and Discussion

[0047] 1. Non-targeted screening of unknown volatiles

[0048] Figure 1 Overlay chromatograms of 34 children's floor mat samples are shown, representing samples of four materials: EPE, XPE, PVC, and EVA. As can be seen from the figure, many volatile components were detected in the children's floor mats. There are differences between products, with some chromatographic peaks being unique to a few products and some being common to many products. The chromatographic peak distributions of products made of the same material are roughly similar, but there are also individual differences.

[0049] A total of 71 volatile compounds were identified in 34 children's floor mats. The detailed information of all volatile compounds is listed in Table 1. A total of 43 compounds [M+H] + . Base peak ions of all substances [M] + and [M+H] + The mass deviations of the samples were all less than 5ppm. The ΔRI values ​​were all less than 50, and the ΔRI values ​​of 7 substances were marked as N / A because they had no retention index values ​​in the NIST spectral library for comparison. The bubble classification diagram of the 71 substances in the sample is shown in Figure 1. Figure 2As shown. Circles of different colors represent different substances in the sample. The size of the circle indicates the number of substances. The horizontal axis represents the 11 categories of 71 substances. The vertical axis represents the ratio of the number of substances detected to the total number of substances in the category. Figure 2 The types and quantities of substances detected in samples of different materials are shown, as well as a comparison between them.

[0050] Take the identification of α-methylstyrene as an example. Figure 3 As shown in a, the library search index of the unknown candidate peak is relatively close. α-methylstyrene has SI = 892, HRF value = 96.2376, ΔRI = 2. Figure 3 As shown in b, the deviation between the mass of all ion fragments in the EI spectrum and their theoretical mass is less than 1 ppm. Figure 3 The corresponding adduct ions [M+H] were found in the PCI spectrum of c + 119.08570 and [M+C2H5] + 147.11705, the exact mass deviations are 1.453ppm and 1.515ppm respectively, which shows Figure 3 m / z 118.07766 in b is the molecular ion peak.

[0051] Table 1 List of volatile chemicals identified in children's floor mats

[0052]

[0053]

[0054]

[0055] 2. Identify high-risk substances through risk assignment scoring

[0056] According to the risk assignment scoring scheme proposed in the present invention, the 71 substances identified were scored, and the detection frequency, average peak area, and substance hazard were scored separately. Finally, the total score was sorted from high to low to obtain the risk ranking list of substances in the products in Table 2. In this way, the risks of unknown substances screened in these products can be quickly determined. Taking α-methylstyrene in Table 2 as an example, it was detected in 8 samples, and its D 检出频次 The score is 6.25. The average peak area is 4170021, A 平均峰面积 The score is 21.6. It is a Class 2 carcinogen, H 物质危害性 The score is 45. Therefore, it is the substance with the highest risk score (72.85 points) among children's floor mats and is also the most risky substance.

[0057] In addition, toluene, ethylene glycol butyl ether, methyl isobutyl ketone, o- / m- / p-xylene, 1,2-dichlorobenzene, 2,6-di-tert-butyl-p-methylphenol and hexachloro-1,3-butadiene are listed as Category 2 or Category 3 carcinogens, and formamide and N-methylpyrrolidone are substances of high concern in the REACH regulation, among which formamide is listed as a Category 1B toxic substance for child reproduction by the European Chemicals Agency (ECHA). According to the toxicity prediction Toxtree classification, 1-decyne, 2,5-dichlorotoluene and 1,2-epoxydecane are classified as Cramer Class III highly toxic substances.

[0058] This scoring scheme can be understood as a three-dimensional radar chart, which selects five representative substances to draw Figure 4 As can be seen from the figure, the coordinate values ​​of the three axes jointly determine the area of ​​the triangle. The larger the area of ​​the triangle, the higher the risk score of the substance. The risk scoring method proposed in this paper is convenient and fast. It only takes 3 hours to complete the rapid risk scoring of 71 substances and screen out high-risk substances in 34 batches of samples.

[0059] In order to visualize and compare the contents of high-risk substances in children's floor mats made of different materials, the peak areas of 14 substances detected in 34 samples are shown in Figure 2. Figure 5 As shown. It can be seen that the content of formamide in EVA and XPE mats is relatively high, which may be due to the use of azodicarbonamide, a foaming agent, in the manufacturing process, which produces formamide when heated. In addition to formamide, the content of α-methylstyrene and toluene in EVA mats is also high, and the risk scores of these two substances are in the top three. Most high-risk substances are found in PVC mats, including high concentrations of toluene, ethylene glycol butyl ether, 1-decyne, 4-methylpentanone and n-methylpyrrolidone. In contrast, the content of 14 high-risk substances in XPE and EPE mats is relatively low, among which EPE has the lowest content, only 1,2-epoxydecane, and almost no others. XPE and EPE are both polyethylene foams, but the foaming methods are different. It is obvious that the chemical hazard of physically foamed polyethylene (EPE) is less than that of chemically foamed polyethylene (XPE). According to the difference significance analysis with Tukey HSD, there are significant differences in the concentration levels of these substances in products made of different materials. In general, in terms of volatile hazards, EPE floor mats are relatively safe, EVA and PVC have relatively high chemical risks (although PVC floor mats are expensive and more comfortable), and XPE is in the middle.

[0060] Table 2 Risk ranking list of substances in children's floor mats

[0061]

[0062]

[0063] Conclusion

[0064] In the present invention, 71 volatile substances were identified from children's floor mats using headspace gas chromatography-orbitrap high-resolution mass spectrometry. The proposed risk assignment scoring method ranks the risks of substances in the form of quantitative assignment scores to quickly identify high-risk substances in products. The combination of non-targeted screening and risk assignment scoring can quickly identify unknown hazards in products and identify high-risk substances that need to be focused on, which is of great significance for government agencies to carry out risk monitoring and effective control, and promote product quality improvement and children's health protection.

[0065] The embodiments described above are merely descriptions of preferred implementation modes of the present invention and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A quantitative method for rapidly assessing the risk ranking of potential chemical substances in consumer products, comprising the following steps: (1) Based on headspace gas chromatography-orbitrap high-resolution mass spectrometry, accurately identify potential chemical substances in a class of consumer products by non-targeted screening, and form a list of potential substances in this class of consumer products; (2) Material risk scoring: quantitatively scoring and ranking the risks of substances identified in non-targeted ways to form a ranked list of substance risks in this category of consumer products; (3) Assess high-risk substances based on risk scores, compare the content of high-risk substances in different products through visual graphics, and compare the content distribution differences of high-risk substances in different products through significance analysis.

2. The quantitative method for rapidly assessing the risk ranking of potential chemical substances in consumer products according to claim 1, characterized in that: The maximum score for the risk assignment score is 100 points. The higher the score, the greater the risk of the substance in this type of product, and the more it should be controlled. The risk assignment score is calculated using the following formula: Risk score = D 检出频次 +A 平均峰面积 +H 物质危害性 .

3. The quantitative method for rapidly assessing the risk ranking of potential chemical substances in consumer products according to claim 2, characterized in that: D 检出频次 , the full score is set at 25 points; the substance with the highest detection frequency in a category of products takes a full score of 25 points, and the percentage of the detection frequency of other substances in the highest detection frequency is A%, then the score is 25×A%.

4. The quantitative method for rapidly assessing the risk ranking of potential chemical substances in consumer products according to claim 2, characterized in that: A 平均峰面积 , the full score was set at 25 points, and all substances were sorted in descending order according to the average peak area of ​​substances detected in a class of products, with the highest peak area being 25 points and the lowest peak area being 0 points, with an even distribution.

5. The quantitative method for rapidly assessing the risk ranking of potential chemical substances in consumer products according to claim 2, characterized in that: H 物质危害性 The full score is 50 points, based on the Class 1 carcinogens identified by the International Agency for Research on Cancer (IARC) with 50 points, Class 2 carcinogens with 45 points, and Class 3 carcinogens with 40 points; substances on the SVHC list of very high concern under the EU REACH Regulation with 40 points; other substances are classified by toxicity prediction, with reference to the Toxtree classification, Cramer III with 30 points, highly toxic, Cramer II with 20 points, moderately toxic, Cramer I with 10 points, low toxicity, and substances that do not show any toxicity information with 5 points.

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