CN112285252A - Chemical risk assessment method for wood preservative in wooden toy - Google Patents
Chemical risk assessment method for wood preservative in wooden toy Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000012502 risk assessment Methods 0.000 title claims abstract description 32
- 239000003171 wood protecting agent Substances 0.000 title claims abstract description 32
- 238000013508 migration Methods 0.000 claims abstract description 47
- 230000005012 migration Effects 0.000 claims abstract description 47
- 231100001223 noncarcinogenic Toxicity 0.000 claims abstract description 12
- 230000000711 cancerogenic effect Effects 0.000 claims abstract description 11
- 231100000315 carcinogenic Toxicity 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000005259 measurement Methods 0.000 claims abstract description 5
- 238000010835 comparative analysis Methods 0.000 claims abstract description 4
- 239000003755 preservative agent Substances 0.000 claims description 57
- 239000002023 wood Substances 0.000 claims description 34
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 claims description 31
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical group OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 30
- 210000003296 saliva Anatomy 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 230000002335 preservative effect Effects 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 231100000822 oral exposure Toxicity 0.000 claims description 17
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 230000009747 swallowing Effects 0.000 claims description 14
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- 206010028980 Neoplasm Diseases 0.000 claims description 12
- 201000011510 cancer Diseases 0.000 claims description 12
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 claims description 12
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N gamma-hexachlorocyclohexane Natural products ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 claims description 12
- 229960002809 lindane Drugs 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 208000005623 Carcinogenesis Diseases 0.000 claims description 8
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- 231100000504 carcinogenesis Toxicity 0.000 claims description 8
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 8
- 231100000628 reference dose Toxicity 0.000 claims description 7
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 claims description 6
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
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- 238000001914 filtration Methods 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000012086 standard solution Substances 0.000 claims description 5
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- 239000007789 gas Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000002552 multiple reaction monitoring Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000002354 daily effect Effects 0.000 description 12
- 230000037230 mobility Effects 0.000 description 10
- 238000011160 research Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
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- 239000000047 product Substances 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
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- 150000002989 phenols Chemical class 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 235000012631 food intake Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 231100001081 no carcinogenicity Toxicity 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a chemical risk assessment method of a wood preservative in a wooden toy, which comprises the following steps: (1) collecting a large number of wooden toy samples, detecting and screening the existence level of the wood preservative in the samples, and carrying out comparative analysis on the content of the wood preservative in the samples according to different sample categories; (2) selecting a sample with higher content of the wood preservative to perform migration quantity measurement; (3) determining a chemical substance oral contact exposure mode according to the use characteristics of the wooden toy sample, and calculating the exposure amount by applying an exposure model; (4) according to the chemical hazard of the substance, carcinogenic risk and non-carcinogenic risk assessment is carried out.
Description
Technical Field
The invention relates to the field of consumer product safety, in particular to a chemical risk assessment method for a wood preservative in a wooden toy.
Background
For infants in the natural development stage from 3 months to 3 years, the urge to chew, lick and swallow objects during their growth is a natural development stage, which diminishes after 3 years of age. This oral activity may result in the child ingesting residual chemicals within the toy. Wood preservatives, such as polychlorinated phenols and lindane, are used to protect against insects and fungi to increase the life of wooden toys. The preservative adding process generally adopts a physical treatment method, compounds are infiltrated into the wooden toy through pressure, and the wood has better permeability due to the porous characteristic of the wood, so that chemical substances in the material are easy to migrate. Polychlorinated phenol and lindane are highly toxic substances and are listed as priority pollutants by the European Union and the U.S. environmental protection agency, particularly, lindane and pentachlorophenol are listed as a class 1 carcinogen by the International cancer research organization, 2,4, 6-trichlorophenol is listed as a class 2B carcinogen, and the content of lindane and pentachlorophenol in the wooden toy is regulated by the European Union toy safety standard EN 71-9 to be not more than 2 mg/kg.
In recent years, people pay more attention to chemical hazards. Polychlorinated phenols and lindane have been found in a variety of environmental and food samples. For adults, skin contact, inhalation and food intake are the main routes to contact wood preservatives. Infants and children 3-36 months old have unique exposure routes due to their behavioral characteristics as distinct from adults, and oral ingestion of preservatives in wooden toys may be the primary route of contact when playing the toy. Since a considerable amount of preservative can migrate into the body in a short time, the exposure risk should be taken into account. However, at present, no chemical risk assessment research method aiming at exposure of wood preservatives in wooden toys exists at home and abroad. The development of the systematic research method has profound significance for evaluating the exposure risk of the wood preservative when the wood toy is contacted, promoting the establishment of limited standards of the wood preservative in the wood toy in China, monitoring the wood toy products, guaranteeing the personal safety of infants and children and the like.
Disclosure of Invention
The invention aims to provide a chemical risk assessment method for a wood preservative in a wooden toy.
The invention discloses a chemical risk assessment method of a wood preservative in a wooden toy, which comprises the following steps:
(1) collecting a large number of wooden toy samples, detecting and screening the existence level of the wood preservative in the samples, and carrying out comparative analysis on the content of the wood preservative in the samples according to different sample categories;
(2) selecting a sample with higher content of the wood preservative to perform migration quantity measurement;
(3) determining an oral exposure mode according to the use characteristics of the wooden sample, and calculating the exposure amount by applying an exposure model;
(4) according to the chemical hazard of the substance, carcinogenic risk and non-carcinogenic risk assessment is carried out.
The chemical risk assessment method for the wood preservative in the wooden toy comprises the following steps of preparing a wood preservative, wherein the wood preservative is 2, 4-dichlorophenol, 2,4, 5-trichlorophenol, 2,4, 6-trichlorophenol, 2,3,4, 6-tetrachlorophenol, lindane and pentachlorophenol.
The chemical risk assessment method for the wood preservative in the wooden toy comprises the following steps of (1) collecting 90 wooden toy samples, wherein the samples are divided into four categories of building blocks, puzzles, beads and teaching aids.
The invention provides a chemical risk assessment method for wood preservatives in a wooden toy, wherein the detection screening method for the wood preservatives in the step (1) comprises the following steps:
crushing the sample into wood chips with the particle size of less than 2mm by using a cutting and grinding instrument, accurately weighing 2g of the sample in a 50mL test tube with a plug, and ultrasonically extracting for 2 times by using methanol, wherein 20mL of the sample is extracted each time for 15 min; filtering and combining the filtrates into a centrifuge tube, adding 100 mu L of internal standard working solution, centrifuging for 5min at 4 ℃ and 10000rpm, filtering by a 0.45 mu m polytetrafluoroethylene filter membrane, transferring into a parallel evaporation bottle, evaporating and concentrating to 2mL at 40 ℃ and 100hpa, adding 40mL of 0.1mol/L potassium carbonate solution into the concentrated solution, shaking uniformly, adding 1mL of acetic anhydride for derivatization, discharging while oscillating, operating for about 1min, and then placing in a shaking table for oscillation for 10 min; and (3) activating the derivatized solution by using 5mL of methanol in advance, balancing an HLB (hydrophile-lipophile balance) solid-phase extraction column by using 5mL of deionized water, leaching by using 5mL of deionized water, draining water by using a vacuum pump, eluting by using 10mL of ethyl acetate, collecting eluent, adding anhydrous sodium sulfate for drying, performing vortex for 30s, and performing on-machine determination and analysis.
The invention provides a chemical risk assessment method for a wood preservative in a wooden toy, wherein the migration amount measuring method in the step (2) comprises the following steps:
the sample was crushed to pieces smaller than 2mm by a cutting and grinding machine, and 2g of the sample was placed in a 50mL stoppered test tube. Adding 40mL of simulated saliva into a test tube, and vibrating in a water bath at 37 ℃ at a speed of 100rpm/min for 10min-32h to obtain a migration solution; adding 50 mu L of internal standard solution into the migration solution, wherein the internal standard solution contains 1mg/L of 2,3, 4-trichlorophenol, and then adding 1mL of acetic anhydride for derivatization; discharging gas while oscillating, operating for about 1min, and oscillating for 10min on a shaking table; and (3) activating the derivatized solution by using 5mL of methanol in advance, balancing an HLB (hydrophile-lipophile balance) solid-phase extraction column by using 5mL of deionized water, leaching by using 5mL of deionized water, draining water by using a vacuum pump, eluting by using 10mL of ethyl acetate, collecting eluent, adding anhydrous sodium sulfate for drying, performing vortex for 30s, and performing on-machine determination and analysis.
The invention relates to a chemical risk assessment method for wood preservatives in a wooden toy, wherein the on-machine determination analysis conditions are as follows:
the chromatographic column is HP-5MS, 30m multiplied by 0.25mm multiplied by 0.25 mu m; the temperature of a sample inlet is 290 ℃; the carrier gas is helium, the purity is 99.9 percent, and the flow rate is 1.0 mL/min; no shunt sampling; sample introduction amount: 2 mu L of the solution; column box temperature program: heating at 20 deg.C/min from 60 deg.C to 200 deg.C, heating at 25 deg.C/min from 200 deg.C to 290 deg.C, and maintaining for 1 min;
the temperature of the transmission line is 290 ℃, and the temperature of the ion source is 300 ℃; the ionization mode is EI; ionization energy is 70 eV; multiple reaction monitoring mode.
The method for assessing the chemical risk of a wood preservative in a wooden toy according to the present invention, wherein the oral exposure in step (3) is classified into an exposure by swallowing and biting a material or a small part and an exposure by licking and transferring via saliva;
oral exposure by swallowing the bitten material or widget is calculated according to formula (1), and oral exposure by licking saliva migration is calculated according to formula (2);
Epartial=IngR×C×10-6/BW (1)
e in formula (1)partialBy swallowing daily chemical substances, μ g/kg BW-day, IngR is the intake rate, mg/d, C is the substance concentration, μ g/kg, BW is body weight kg;
Esaliva=R×ED/BW (2)
e in formula (2)salivaIs the intake by saliva migration,. mu.g/kg BW-day, R is the migration rate,. mu.g/min, ED is the age-related exposure time, min/d, BW is body weight, kg.
The invention relates to a chemical risk assessment method for wood preservatives in wooden toys, wherein the risk of non-carcinogenic chemical substances in the step (4) is described by adopting a risk quotient, and the formula is as follows:
wherein HQ is the hazard quotient for the non-carcinogenic chemical, E is the daily average exposure, and RfD is the reference dose for daily oral preservative exposure;
the risk assessment of carcinogenic chemicals is described by the lifetime probability of carcinogenesis, and the formula is as follows:
Cancer Risk=E×SF (4)
where Cancer Risk is the lifetime probability of carcinogenesis, SF is the carcinogenesis slope factor, and E is the daily average exposure.
The invention uses gas chromatography-tandem mass spectrometry to detect and analyze 6 wood preservatives in 90 collected wooden toy samples, and the detection rates of the 6 preservatives are respectively between 2.2 and 22.2 percent. The content of the preservative is 0.6-9.6 mg/kg. The detection rate and the content of the 2, 4-dichlorophenol and the 2,4, 6-trichlorophenol are high. Therefore, we further investigated the migration behavior of 2, 4-dichlorophenol, 2,4, 6-trichlorophenol from toys to human saliva. As a result, it was found that the maximum mobilities of 2, 4-dichlorophenol and 2,4, 6-trichlorophenol in 11 positive samples were 7.1% -20.3% and 11.1% -E24.8 percent. For children from 3 months to 36 months, the daily average exposure level of 2, 4-dichlorophenol in the wooden toy is between 2.7 pg/(kg-day) and 46.9 pg/(kg-day), and the daily average exposure level of 2,4, 6-trichlorophenol is between 3.6 pg/(kg-day) and 69.4 pg/(kg-day). The risk of exposure by saliva migration is greater than the risk of exposure of the oral swallow widget, with 2,4, 6-trichlorophenol being exposed to levels greater than 2, 4-dichlorophenol in both modes. The maximum risk factors of 2, 4-dichlorophenol and 2,4, 6-trichlorophenol are 1.9X 10-4And 1.2X 10-9. The results of the above studies indicate that, although wood preservatives are included in wooden toys, direct contact with these substances does not currently pose an unacceptable risk to children.
The invention discloses a chemical risk assessment method of a wood preservative in a wooden toy, which mainly aims to:
1) exploring the level of presence of polychlorinated phenol and lindane wood preservatives in wooden toys and the level of distribution in different kinds of wooden toys;
2) further investigating the migration behavior of the wood preservative in different toy samples to the human body;
3) oral exposure of wood preservatives to children and health risks in wooden toys were first assessed.
The chemical risk assessment method for the wood preservative in the wooden toy has the advantages of strong pertinence and high accuracy, is a research method with systematicness, effectiveness and strong operability, can be used for assessing risks generated by oral exposure of the preservative and other products or substances in the wooden toy, perfects a health risk assessment system for the wooden toy products, and provides basic data and technical support for formulating relevant limit standards.
The method for evaluating the chemical risk of wood preservative in wooden toy of the present invention is further described with reference to the accompanying drawings.
Drawings
FIG. 1 illustrates the presence of 6 wood preservatives in a wooden toy according to the invention;
FIG. 2 is a representation of the presence of preservatives in 4 types of toys according to the invention;
FIG. 3 is a graph showing the migration of preservatives at various times in the present invention;
FIG. 4 is a graph showing the mobilities of 2, 4-dichlorophenol and 2,4, 6-trichlorophenol in different samples according to the present invention.
Detailed Description
A chemical risk assessment method for wood preservatives in wooden toys comprises the following steps:
collecting a large number of wooden toy samples, detecting and screening the existence level of wood preservatives in the samples, and carrying out comparative analysis on the content of the wood preservatives in the samples according to different sample categories;
reagents and materials:
and (3) standard substance: 2, 4-dichlorophenol, 2,4, 5-trichlorophenol, 2,4, 6-trichlorophenol, 2,3,4, 6-tetrachlorophenol, lindane and 2,3, 4-trichlorophenol (internal standard) are all purchased from Accustandard company of America, and the purity is more than or equal to 98 percent; pentachlorophenol was purchased from Supelco, USA with a purity of 99% or more.
Stock solutions of standard substances: accurately weighing 100mg of preservative standard substances respectively in a 100mL brown volumetric flask, fixing the volume by using a 9:1(v/v) ethanol/glacial acetic acid solution to prepare a single-standard stock solution with the concentration of 1000mg/L, and preparing a fully-mixed stock solution with the concentration of 100mg/L by using the single-standard stock solution. In the experiment, a series of working solutions diluted to the required concentration with 9:1(v/v) ethanol/glacial acetic acid can be used as required.
Internal standard substance: 50mg of 2,3, 4-trichlorophenol is accurately weighed into a 100mL brown volumetric flask, a 9:1(v/v) ethanol/glacial acetic acid solution is used as a solvent for constant volume to prepare an internal standard stock solution with the mass concentration of 500mg/L, and then the internal standard stock solution is diluted to an internal standard working solution with the concentration of 1 mg/L.
The simulated saliva was configured according to the European Union DIN53160-2010 standard.
Simulated saliva: 0.17g MgCl2·6H2O,0.15g CaCl2·6H2O,0.76g K2HPO4·2H2O,0.53g K2CO30.33g NaCI and 0.75g KCI, dissolving potassium and sodium salt in 900mL deionized water, adding calcium and magnesium salt, dissolving completely, and adding 1%Adjusting the pH value of the hydrochloric acid aqueous solution to 6.8 +/-0.1, and then using deionized water to fix the volume to 1L. The product is preserved in dark, and the pH value before use is ensured to be approximately equal to 6.8 +/-0.1.
Thermo Fisher TSQ-8000Evo triple quadrupole GC-MS (Thermo Fisher Co., USA); CF16RXII centrifuge (Hitachi, japan); SM2000 cutting mill (Retsch, germany); solid phase extraction devices (Supelco, usa); oasis HLB solid phase extraction column (6ml, 0.2g, Waters); ultrasonic cleaner model P300H (Elma, germany); an NTS-4000 constant temperature water bath shaker, EYEL4 shaker (Japanese eye); sync core parallel evaporator (BUCHUI, switzerland).
90 wooden toys of different brands were randomly collected from various supermarkets and markets in Beijing. These samples were kept in individually sealed packages prior to analysis to avoid cross-contamination.
The sample processing method comprises the following steps:
the sample was crushed with a cutting grinder into chips of less than 2 mm. The method is used for measuring the residual quantity and migration quantity of the preservative in the sample.
Sample treatment at the time of residue measurement: accurately weighing 2g of sample in a 50mL test tube with a plug, and performing ultrasonic extraction for 15min by using methanol for 2 times, wherein each time is 20 mL. Filtering and combining the filtrates into a centrifuge tube, adding 100 μ L of internal standard working solution, centrifuging at 4 deg.C and 10000rpm for 5min, filtering with 0.45 μm PTFE (polytetrafluoroethylene) filter membrane, transferring into a parallel evaporation bottle, and evaporating and concentrating at 40 deg.C and 100hpa to about 2 mL. Adding 40mL of 0.1mol/L potassium carbonate solution into the concentrated solution, shaking uniformly, adding 1mL of acetic anhydride for derivatization, discharging gas while shaking, operating for about 1min, and then placing in a shaking table for shaking for 10 min. Activating the derivatized solution by using 5mL of methanol in advance, balancing an HLB solid-phase extraction column by using 5mL of deionized water, leaching by using 5mL of deionized water, draining water by using a vacuum pump, eluting by using 10mL of ethyl acetate, collecting eluent, adding a proper amount of anhydrous sodium sulfate for drying, performing vortex for 30s, and performing on-machine determination.
Analysis conditions were as follows:
the chromatographic column was HP-5MS (30 m.times.0.25 mm.times.0.25 μm); the temperature of a sample inlet is 290 ℃; the carrier gas is helium, the purity is 99.9 percent, and the flow rate is 1.0 mL/min; no shunt sampling; sample introduction amount: 2 mu L of the solution; column box temperature program: the temperature is raised from 60 ℃ to 200 ℃ at 20 ℃/min, and then from 200 ℃ to 290 ℃ at 25 ℃/min, and the temperature is maintained for 1 min.
The temperature of the transmission line is 290 ℃, and the temperature of the ion source is 300 ℃; the ionization mode is EI; ionization energy is 70 eV; multiple reaction monitoring mode.
Content of preservative in the wooden toy:
because the sample contains a trace amount of wood preservative, a high-sensitivity gas chromatography tandem mass spectrometry (GC-MS/MS) method is adopted. The optimized parameters of the process are shown in table 1. The limit of quantitation (LOQ) of 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, 2,4, 5-trichlorophenol, 2,3,4, 6-tetrachlorophenol, lindane was 0.25. mu.g/kg, and the limit of quantitation (LOQ) of pentachlorophenol was 0.5. mu.g/kg.
Table 1 mass spectral parameters of wood preservatives
The screening results of 6 preservatives in 90 wooden toys are shown in figure 1, and the results show that 6 substances are detected to different degrees, wherein 2, 4-dichlorophenol and 2,4, 6-trichlorophenol have higher detection frequencies, and the detection frequencies are 22.2% (20/90) and 21.1% (19/90), respectively. Their toxicity and risk should be taken into account. In particular, 2,4, 6-trichlorophenol has been classified as a possible class 2B human carcinogen. The detection frequencies of the substances 2,4, 5-trichlorophenol, 2,3,4, 6-tetrachlorophenol, lindane and pentachlorophenol were 7.8% (7/90), 4.4% (4/90), 2.2% (2/90) and 2.2% (2/90), respectively. The detected content ranges of the 6 substances are respectively 0.7-9.4 mug/kg, 0.8-9.6 mug/kg, 0.8-2.5 mug/kg, 0.6-1.1 mug/kg, 0.6-1.2 mug/kg and 0.9-1.6 mug/kg. The detection averages were 3.7, 4.4, 1.3, 0.8, 0.9, and 1.3. mu.g/kg, respectively.
To further investigate the distribution level of preservatives in different types of toys, samples were classified into 4 types: the toy building block (n is 33), the jigsaw puzzle (n is 20), the bead string toy (n is 18) and the teaching aid (n is 19). As can be seen from FIG. 2, 4-dichlorophenol and 2,4, 6-trichlorophenol were detected at high rates in various samples. The highest detection rate of 2, 4-dichlorophenol in the teaching aid is 26.3%, and the highest detection rate of 2,4, 6-trichlorophenol in the jigsaw puzzle is 35%. 2,4, 5-trichlorophenol was also detected in the class 4 samples. In addition, 2,3,4, 6-tetrachlorophenol, lindane and pentachlorophenol were also present in individual samples. The results show that the distribution of the preservative in different kinds of toys is different.
Secondly, selecting a sample with high content of wood preservative to perform migration volume determination;
sample treatment at the time of migration measurement: a2 g sample was placed in a 50mL stoppered tube. Simulated saliva (40mL) was added to the tube and shaken at 100rpm/min in a 37 ℃ water bath for 10min-32h to give a migration solution. Then, 50. mu.L of an internal standard solution (1mg/L of 2,3, 4-trichlorophenol) was added to the migration solution. Then adding 1mL of acetic anhydride for derivatization, vibrating while deflating, operating for about 1min, and then placing in a shaking table for 10min for vibration. And (3) activating the derivatized solution by using 5mL of methanol in advance, balancing an HLB (hydrophile-lipophile balance) solid-phase extraction column by using 5mL of deionized water, leaching by using 5mL of deionized water, draining water by using a vacuum pump, eluting by using 10mL of ethyl acetate, collecting eluent, adding anhydrous sodium sulfate for drying, performing vortex for 30s, and performing on-machine determination and analysis.
Migration of wood preservative in saliva:
according to the existence of the preservative in the wooden toy, a migration test is further carried out, the migration situation of the children in saliva is simulated when the mouth of the children is contacted with the sample, and the migration situation of the children in the saliva is researched. 11 samples with higher contents of 2, 4-dichlorophenol and 2,4, 6-trichlorophenol are selected from the 90 samples for research. The migration time range is 10min-32 h. As can be seen from fig. 3, the migration of the preservative increases gradually with time, reaching equilibrium. Sample 8 showed maximum transport of 0.8 and 1.4. mu.g/kg for 2, 4-dichlorophenol and 2,4, 6-trichlorophenol, respectively. It is noted that in some samples, migration was detected even when the preservative was exposed for 10 min.
The migration ability of the preservative is expressed by mobility, and calculated with reference to formula (5):
wherein MR is the mobility of the preservative from the wooden toy to simulated saliva, csimulantIs the concentration of preservative in simulated saliva (. mu.g/mL), vsimulantIs the volume of simulated saliva (mL), csampleIs the content of preservative in the sample (. mu.g/g), msampleIs the sample mass (g).
Figure 4 shows the maximum mobility of 2, 4-dichlorophenol and 2,4, 6-trichlorophenol from the wooden toy to the simulated saliva migration equilibrium of the 11 samples described above. The mobility ranges of 2, 4-dichlorophenol and 2,4, 6-trichlorophenol in different samples were 7.1-20.3% and 11.1-24.8%, respectively, and the average mobility was 12.4% and 16.2%, respectively. When 2, 4-dichlorophenol and 2,4, 6-trichlorophenol were present simultaneously in the sample, the mobility of 2,4, 6-trichlorophenol was slightly higher than that of 2, 4-dichlorophenol. The water solubility of 2, 4-dichlorophenol is 4.5g/L and the water solubility of 2,4, 6-trichlorophenol is 0.8g/L, which is understood to mean that the mobility of 2, 4-dichlorophenol is higher than that of 2,4, 6-trichlorophenol, but in practice the opposite result is obtained. It follows that the mobility of the preservative is not only related to the water solubility, but may also be related to the composition of the saliva and the microstructural properties of the wood sample.
Thirdly, determining an oral exposure mode according to the use characteristics of the wooden sample, and calculating the exposure amount by using an exposure model;
exposure evaluation:
the exposure evaluation refers to the process of measuring and estimating the exposure quantity, the exposure frequency, the exposure duration, the exposure route and the like when a human body is exposed to a certain chemical substance. Oral exposure is one of the primary modes of exposure, resulting from oral swallowing of small parts or biting materials and oral licking of saliva equilibrium. The oral exposure by swallowing the bitten material or small parts is calculated according to equation (1), and the oral exposure resulting from saliva balance in the mouth is calculated according to equation (2).
Epartial=IngR×C×10-6/BW (1)
E in formula (1)partialThe daily intake of chemicals by swallowing (. mu.g/kg BW-day), IngR is the intake rate (mg/d), C is the concentration of the substance (. mu.g/kg), and BW is the body weight (kg).
Esaliva=R×ED/BW (2)
E in formula (2)salivaIs intake balanced by saliva (. mu.g/kg BW-day), R is migration rate (. mu.g/min), ED is exposure time per age (min/d), BW is body weight (kg).
Exposure evaluation results:
to accurately assess the effect of preservative exposure on children, exposure assessments were performed on two common scenes of oral exposure of children from 3 months to 3 years old (3 months to 12 months, 1 to 2 years old, 2 to 3 years old), i.e., exposure by swallowing bitten material or widgets and by licking saliva migration. According to the research result of national institute of public health and environment in the Netherlands, the mass of the toy bitten or scraped off by teeth every day is 8mg/d, the time for the children to orally lick saliva is 9.9, 22.4 and 26min/d respectively according to the research of Guney et al, Canada geological mining center, and the time from 3 months to 3 years old, and the migration rate R is obtained by multiplying the unit migration amount by the mass of the sample and dividing by the migration time. Referring to the U.S. EPA data, children at different stages weigh 8.3, 11.4 and 13.8kg, respectively.
The daily exposure of the child to the preservative via the toy was calculated using equations (1) and (2) and the results are shown in table 2. The average daily exposure level of 2, 4-dichlorophenol taken by children by swallowing bitten material or small parts is 2.7-4.5pg/(kg day), and the maximum exposure level of children at 3-12 months of age is 8.1pg/(kg day). The average exposure amount of 2,4, 6-trichlorophenol in children of 3-12 months old is 3.6-6.0 pg/(kg-day), and the maximum exposure amount is 9.2 pg/(kg-day). This result is consistent with the tendency of children 3-12 months old to bite the toy easily.
In contrast, children of 12-24 months of age were exposed to an average of 28.5-46.9 pg/(kg-day) of 2, 4-dichlorophenol per day and 62.9 pg/(kg-day) of 2, 4-dichlorophenol maximal exposure via the salivary migration pathway. The average exposure level of the 2,4, 6-trichlorophenol is 42.2-69.4pg/(kg day), and the maximum exposure level of the children at 12-24 months of age is 108.7pg/(kg day). The results indicate that the contribution of the salivary migration pathway to exposure is greater than the swallowing bite material or widget pathway.
TABLE 2 Children oral exposure results (pg/[ kg. day ])
And fourthly, carrying out carcinogenic risk and non-carcinogenic risk assessment according to the chemical hazard of the substances.
And (3) risk assessment:
the purpose of risk characterization is to determine whether a risk exists and to quantitatively describe the level of risk. There are two methods described: a description of the risk of non-carcinogenicity and a description of the risk of carcinogenicity.
The risk of non-carcinogenic chemicals is described using risk quotient values, and the formula is as follows:
where HQ is the hazard quotient for non-carcinogenic chemicals, E is the daily average exposure, and RfD is the reference dose for daily oral preservative exposure. The United states environmental protection agency comprehensive Risk information System (IRIS) toxicology assessment recommends that 2, 4-dichlorophenol has an RfD value of 3 μ g/(kg day).
The risk of carcinogenic chemicals is described by the lifetime probability of carcinogenesis, which is given by the formula:
Cancer Risk=E×SF (4)
wherein, the Cancer Risk is the lifetime probability of carcinogenesis, the SF is the carcinogenic slope factor, and the United states environmental protection agency comprehensive Risk information System (IRIS) toxicology data suggests that the SF of 2,4, 6-trichlorophenol is 1.1 × 10-2(kg·d)/mg。
And (4) risk evaluation result:
the non-carcinogenic hazard quotient of 2, 4-dichlorophenol and the carcinogenic risk of 2,4, 6-trichlorophenol were calculated using (3) and (4), and the results are shown in Table 3. The average hazard quotient range of the 2, 4-dichlorophenol is 8.1 multiplied by 10-6~1.4×10-4Maximum value of 1.9X 10-4. The hazards caused by saliva migration exposure are greater in both oral exposure routes. The us EPA considers a hazard quotient value of 1.0 to be an acceptable threshold below which no clinical adverse effects are observed in experimental animals. In this study, the hazard quotient for both pathways was below 1. This result indicates that the exposed receptor is unlikely to experience an adverse non-carcinogenic risk as expected.
One part per million human cancer risk (10) with reference to the US EPA guidelines for risk assessment-6) Is considered to be an acceptable threshold. The qualitative description of the risk of cancer is given by the very low risk ≦ 10-6) Low risk (10)-6-10-4) Moderate risk (not less than 10)-4-10-3) High risk (10)-3-10-1) And very high risk (not less than 10)-1). For 2,4, 6-trichlorophenol, the average cancer risk was 4.0X 10-11To 7.6X 10-10The maximum cancer risk is 1.2X 10-9. Less than 10-6The result of (a) is at a safety risk level. Thus, oral exposure does not pose an unacceptable risk to children. Saliva migration shows a higher risk of cancer than swallowing the bitten material or small parts.
TABLE 3 Exposure Risk of Wood preservatives in wooden toys
And (4) conclusion:
the content of 6 wood preservatives in 90 wooden toys is screened, and the detection rate of 2, 4-dichlorophenol and 2,4, 6-trichlorophenol is higher than that of other preservatives. Therefore, migration tests were performed on both preservatives to investigate their migration behavior and migration rate from the sample to saliva. Daily exposure assessment results show that the contribution to exposure via the salivary migration pathway is greater than the material or widget pathway via swallowing and biting. The maximum hazard quotient of 2, 4-dichlorophenol is 1.9 x 10-42,4, 6-trichlorophenol has a maximum cancer risk value of 1.2X 10-9. According to the current contact level of childrenThese preservatives do not pose an unacceptable risk to children. It is noteworthy that the risk increases if the residual amount of these preservatives in the wooden toy increases. There remains a need for more preventive and supervised measures in the production and use of wooden toys to minimize the health risks to children.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (8)
1. A chemical risk assessment method for wood preservatives in wooden toys is characterized by comprising the following steps: the method comprises the following steps:
(1) collecting a large number of wooden toy samples, detecting and screening the existence level of the wood preservative in the samples, and carrying out comparative analysis on the content of the wood preservative in the samples according to different sample categories;
(2) selecting a sample with higher content of the wood preservative to perform migration quantity measurement;
(3) determining two oral exposure modes according to the use characteristics of the wooden sample, and calculating the exposure amount by using an exposure model;
(4) according to the chemical hazard of the substance, carcinogenic risk and non-carcinogenic risk assessment is carried out.
2. A chemical risk assessment method of wood preservatives in wooden toys as claimed in claim 1, characterized in that: the wood preservative is 2, 4-dichlorophenol, 2,4, 5-trichlorophenol, 2,4, 6-trichlorophenol, 2,3,4, 6-tetrachlorophenol, lindane and pentachlorophenol.
3. A chemical risk assessment method of wood preservatives in wooden toys as claimed in claim 2, characterized in that: the number of the wooden toy samples collected in the step (1) is 90, and the sample categories are divided into four categories of building blocks, puzzles, beads and teaching aids.
4. A chemical risk assessment method of wood preservatives in wooden toys as claimed in claim 3, characterized in that: the detection and screening method for the wood preservative in the step (1) comprises the following steps:
crushing the sample into wood chips with the particle size of less than 2mm by using a cutting and grinding instrument, accurately weighing 2g of the sample in a 50mL test tube with a plug, and ultrasonically extracting for 2 times by using methanol, wherein 20mL of the sample is extracted each time for 15 min; filtering and combining the filtrates into a centrifuge tube, adding 100 mu L of internal standard working solution, centrifuging for 5min at 4 ℃ and 10000rpm, filtering by a 0.45 mu m polytetrafluoroethylene filter membrane, transferring into a parallel evaporation bottle, evaporating and concentrating to 2mL at 40 ℃ and 100hpa, adding 40mL of 0.1mol/L potassium carbonate solution into the concentrated solution, shaking uniformly, adding 1mL of acetic anhydride for derivatization, discharging while oscillating, operating for about 1min, and then placing in a shaking table for oscillation for 10 min; and (3) passing the derivatized solution through an HLB solid-phase extraction column which is activated by 5mL of methanol and balanced by 5mL of deionized water in advance, leaching by 5mL of deionized water, draining water by using a vacuum pump, eluting by using 10mL of ethyl acetate, collecting eluent, adding anhydrous sodium sulfate for drying, swirling for 30s, and then performing on-machine determination and analysis.
5. A chemical risk assessment method of wood preservatives in wooden toys as claimed in claim 3, characterized in that: the migration amount measuring method in the step (2) comprises the following steps:
the sample was crushed to pieces smaller than 2mm by a cutting and grinding machine, and 2g of the sample was placed in a 50mL stoppered test tube. Adding 40mL of simulated saliva into a test tube, and vibrating in a water bath at 37 ℃ at a speed of 100rpm/min for 10min-32h to obtain a migration solution; adding 50 mu L of internal standard solution into the migration solution, wherein the internal standard solution contains 1mg/L of 2,3, 4-trichlorophenol, and then adding 1mL of acetic anhydride for derivatization; discharging gas while oscillating, operating for about 1min, and oscillating for 10min on a shaking table; and (3) passing the derivatized solution through an HLB solid-phase extraction column which is activated by 5mL of methanol and balanced by 5mL of deionized water in advance, leaching by 5mL of deionized water, draining water by using a vacuum pump, eluting by using 10mL of ethyl acetate, collecting eluent, adding anhydrous sodium sulfate for drying, swirling for 30s, and then performing on-machine determination and analysis.
6. A chemical risk assessment method of wood preservatives in wooden toys according to claim 4 or 5, characterized in that: the on-machine determination analysis conditions are as follows:
the chromatographic column is HP-5MS, 30m multiplied by 0.25mm multiplied by 0.25 mu m; the temperature of a sample inlet is 290 ℃; the carrier gas is helium, the purity is 99.9 percent, and the flow rate is 1.0 mL/min; no shunt sampling; sample introduction amount: 2 mu L of the solution; column box temperature program: heating at 20 deg.C/min from 60 deg.C to 200 deg.C, heating at 25 deg.C/min from 200 deg.C to 290 deg.C, and maintaining for 1 min;
the temperature of the transmission line is 290 ℃, and the temperature of the ion source is 300 ℃; the ionization mode is EI; ionization energy is 70 eV; multiple reaction monitoring mode.
7. The method for chemical risk assessment of wood preservatives in wooden toys as claimed in claim 6, wherein:
the transoral exposure mode in the step (3) can be divided into the exposure generated by swallowing the bitten material or small parts and licking the transsalivary migration;
oral exposure by swallowing the bitten material or widget is calculated according to formula (1), and oral exposure by licking saliva migration is calculated according to formula (2);
Epartial=IngR×C×10-6/BW (1)
e in formula (1)partialBy swallowing daily chemical substances, μ g/kg BW-day, IngR is the intake rate, mg/d, C is the substance concentration, μ g/kg, BW is body weight kg;
Esaliva=R×ED/BW (2)
e in formula (2)salivaIs the intake by saliva migration,. mu.g/kg BW-day, R is the migration rate,. mu.g/min, ED is the age-related exposure time, min/d, BW is body weight, kg.
8. The method for chemical risk assessment of wood preservatives in wooden toys as claimed in claim 7, wherein: the risk of the non-carcinogenic chemical substance in the step (4) is described by using a risk quotient, and the formula is as follows:
wherein HQ is the hazard quotient for the non-carcinogenic chemical, E is the daily average exposure, and RfD is the reference dose for daily oral preservative exposure;
the risk assessment of carcinogenic chemicals is described by the lifetime probability of carcinogenesis, and the formula is as follows:
Cancer Risk=E×SF (4)
where Cancer Risk is the lifetime probability of carcinogenesis, SF is the carcinogenesis slope factor, and E is the daily average exposure.
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CN103529155A (en) * | 2013-09-27 | 2014-01-22 | 中国检验检疫科学研究院 | Method for measuring content of wood preservatives of wooden products for children |
CN103728405A (en) * | 2013-12-24 | 2014-04-16 | 中国检验检疫科学研究院 | Research method of wood preservative migration rule in wooden children product |
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CN103728405A (en) * | 2013-12-24 | 2014-04-16 | 中国检验检疫科学研究院 | Research method of wood preservative migration rule in wooden children product |
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