CN102565207A - Measuring method for migration quantity of harmful organisms in toy - Google Patents
Measuring method for migration quantity of harmful organisms in toy Download PDFInfo
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- CN102565207A CN102565207A CN2010106098081A CN201010609808A CN102565207A CN 102565207 A CN102565207 A CN 102565207A CN 2010106098081 A CN2010106098081 A CN 2010106098081A CN 201010609808 A CN201010609808 A CN 201010609808A CN 102565207 A CN102565207 A CN 102565207A
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Abstract
The invention discloses a measuring method for the migration quantity of harmful organisms in a toy, comprising the following steps of: selecting a smooth part of a toy sample, cutting off a component to be measured, adding the component to be measured into deionized water at 20+/-2 DEG C, and carrying out vibration extraction; extracting the obtained extracting solution by using a Chroma bond Easy solid-phase extraction column, eluting by using ethyl acetate and collecting eluent; removing water in the eluent, filtering, and then, measuring through gas chromatography-mass spectrometry. The measuring method for the migration quantity of harmful organisms in the toy, provided by the invention, can be used for simultaneously detecting 10 harmful organisms in the toy and is high in recovery rate and precision and accurate in result.
Description
Technical field
The present invention relates to the assay method of harmful organic substance migration amount in a kind of toy.
Background technology
China is toys export big country at present, and nearly in the world 2/3rds toy is produced in China.Current, guarantee that the quality safety of toy product becomes the key of China's toy industry development undoubtedly.And be a key factor that influences the toy product quality safety by the chemical hazard that toxic and harmful substance causes.
10 kinds of organism such as styrene often are used in the production run of toy.Chang Zuowei organic solvents such as ethylene glycol monoethyl ether, cyclohexanone, isophorone, trimethylbenzene are used for the making of toy lacquer; Styrene is widely used in as monomer and makes polystyrene (PS), foamed styrene (EPS), acrylonitrile-butadiene-styrene terpolymer toy materials such as (ABS).Research shows that these materials have toxicity in various degree, and long-term contact meeting causes harm in various degree to each system of human body.For example according to European Union's " material and potpourri classification, packing and label rules " (CLP) and the database of Environmental Protection Agency (EPA) and authoritative organizations such as (IRAC) of international cancer research institution, styrene, nitrobenzene, isophorone are considered to potential human carcinogen; Ethylene glycol monoethyl ether, 2-methoxyacetic acid ethyl ester, 2-methylpropanol acetic acid esters, 2-ethoxy ethyl acetate, two (2-methoxy ethyls) ether then is considered to have the material of genotoxicity, and cyclohexanone and trimethylbenzene also have certain toxicity on inhalation and acute toxicity.If these materials remain in the toy product, will in the toy use, migrate in the human body through sweat, saliva etc., thereby health is worked the mischief.
Both at home and abroad for the study on determination method of organism migration amount in the product, related products mainly are aspects such as food contact material, textile, sheath at present.Common detection method mainly contains vapor-phase chromatography (GC), GC-MS (GC-MS), high performance liquid chromatography (HPLC), liquid chromatography-tandem mass spectrometry method (LC-MS/MS) and AAS etc., and the sample pre-treatments mode is mainly conventional directly immersion or machine, headspace sampling (HS), solvent extraction (SE), SPE (SPE) etc. are directly gone up in microwave condition immersion back.
Summary of the invention
It is high to the purpose of this invention is to provide a kind of recovery and precision, can detect the method for 10 kinds of harmful organic substance migration amounts in the toy simultaneously.
The assay method of harmful organic substance migration amount comprises the steps: in the toy provided by the present invention
Choose part smooth in the toy sample, cut out component to be measured, component to be measured adds deionized water down at 20 ℃ ± 2 ℃, and vibration is extracted;
The extract that obtains is used eluent ethyl acetate through Chroma bond Easy SPE column extracting, collects eluent;
Eluent dewaters, filters laggard promoting the circulation of qi phase chromatography-mass spectroscopy and measures.
The assay method of harmful organic substance migration amount in the toy of the present invention, wherein: the rotating speed that said vibration is extracted is 60r/min ± 5r/min, and extraction time is 60min.
The assay method of harmful organic substance migration amount in the toy of the present invention, wherein: the total surface area of said component to be measured is 20cm
2
The assay method of harmful organic substance migration amount can detect 10 kinds of harmful organic substances in the toy simultaneously in the toy of the present invention, and the recovery and precision are high, and the result is accurate.
Description of drawings
Fig. 1 is the typical chromatographic fractionation figure of 10 kinds of materials of full scan pattern.
Fig. 2 is for selecting the typical chromatographic fractionation figure of 10 kinds of materials of ion scan pattern.
Orochem C18 solid-phase extraction column was to the recovery chromatogram of 10 kinds of materials when Fig. 3 was methanol-eluted fractions.
Oasis HLB Cartridge solid-phase extraction column was to the recovery chromatogram of 10 kinds of materials when Fig. 4 was methanol-eluted fractions.
Chroma bond Easy solid-phase extraction column was to the recovery chromatogram of 10 kinds of materials when Fig. 5 was methanol-eluted fractions.
Orochem C18 solid-phase extraction column was to the recovery chromatogram of 10 kinds of materials when Fig. 6 was eluent ethyl acetate.
Oasis HLB Cartridge solid-phase extraction column was to the recovery chromatogram of 10 kinds of materials when Fig. 7 was eluent ethyl acetate.
Chroma bond Easy solid-phase extraction column was to the recovery chromatogram of 10 kinds of materials when Fig. 8 was eluent ethyl acetate.
Embodiment
Sample pre-treatments:
Choose part comparatively smooth in the toy sample, cutting out total surface area is 20cm
2Component to be measured, be preferably the less shape of circle or corner angle, the thickness of selected portion is then also charged to its area of section in the total area greater than 1mm.Use antimagnetic type tweezer that the testing sample of well cutting is put into the 100mL conical flask.Add the 25mL deionized water down as the migration solvent at 20 ℃ (± 2 ℃), the jam-pack bottle stopper is positioned in the oscillator, 60r/min (± 5r/min) rotating speed extracts 60min down.The migration solution that obtains is passed through respectively through the Oasis of 5mL deionized water balance HLB Cartridge, Orochem C18 and Chroma bondEasy; Water in the extraction column is drained the back with methyl alcohol, ethyl acetate, 3 kinds of different eluting solvent wash-outs of methyl alcohol-ethyl acetate (volume ratio 1: 1); Wash-out 5 times; Each consumption is 1mL, and vacuum filtration eluent in extraction column all drips, and collects eluent.Eluent is dewatered, supplies behind the 0.45 μ m filtering with microporous membrane GC-MS to measure with anhydrous sodium sulfate.
The gas chromatography-mass spectrum condition determination:
Gas chromatography-mass spectrum is separated the actual conditions that is adopted, comprise that chromatographic column kind, temperature programme condition, sample introduction pattern, injector temperature etc. do not limit, the every method that can effectively separate 10 kinds of target substances all can.
What below provide is typical condition determination.
A. capillary chromatographic column: DB-624 quartz capillary column: 60m * 0.25mm i.d., 1.4 μ m, or equivalents;
B. temperature programme: initial temperature is 40 ℃, keeps rising to 120 ℃ with 5 ℃/min speed behind the 1min, rises to 150 ℃ with 3 ℃/min speed then, rises to 230 ℃ with 15 ℃/min speed, keeps 5min;
C. carrier gas: high-pure helium, flow velocity are 1.0mL/min;
D. injector temperature: 235 ℃; Sample introduction pattern: split sampling, split ratio 10: 1;
E. detecting device: mass selective detector (MSD); Mass scanning scope: 29m/z～140m/z;
G. interface temperature: 250 ℃;
H. ionization mode: EI; Ionizing energy: 70eV;
I. monitoring mode: SIM;
Shown in typical following Fig. 1 and 2 of chromatographic fractionation figure, 1. ethylene glycol monoethyl ethers among Fig. 1 and 2,2.2-methoxyacetic acid ethyl ester, 3.2-methylpropanol acetic acid esters, 4. styrene, 5.2-ethoxy ethyl acetate, 6. cyclohexanone, 7. pair (2-methoxy ethyl) ether, 8. trimethylbenzene, 9. nitrobenzene, 10. isophorone.
The characteristic ion of each material is as shown in the table:
Table 1.10 kind of material title and measure employed characteristic ion
| Title | CAS | Characteristic ion (band *'s is quota ion) |
| Ethylene glycol monoethyl ether | 110-80-5 | 31/45/59 * |
| 2-methoxyacetic acid ethyl ester | 110-49-6 | 43 */45/48 |
| 2-methylpropanol acetic acid esters | 70657-70-4 | 31/43/59 * |
| Styrene | 100-42-5 | 78/103/104 * |
| The 2-ethoxy ethyl acetate | 111-15-9 | 43 */59/72 |
| Cyclohexanone | 108-94-1 | 42/55 */98 |
| Two (2-methoxy ethyl) ether | 111-96-6 | 45/58/59 * |
| Trimethylbenzene | 108-67-8 | 105 */119/120 |
| Nitrobenzene | 98-95-3 | 51/77 */123 |
| Isophorone | 78-59-1 | 54/82 */138 |
The preparation of standard solution and standard working curve
Stock solution: the standard items 0.1g (being accurate to 1mg) that takes by weighing each material to the brown volumetric flask of 100ml, methanol constant volume, obtaining concentration is the standard inventory solution of 1000mg/L, places 4 ℃ to keep in Dark Place.
Working solution: it is an amount of to draw above standard inventory solution, is diluted to the working solution of desired concn with methyl alcohol, and for ethylene glycol monoethyl ether, the concentration range of working solution is 0.5mg/L～100mg/L.For 2-methylpropanol acetic acid esters and trimethylbenzene, the concentration range of working solution is 0.05mg/L～100mg/L.For all the other 7 kinds of materials, the concentration range of working solution is 0.1mg/L～100mg/L.Place 4 ℃ to keep in Dark Place, for use.
Under the chromatographic condition of setting, standard operation solution is measured by concentration from low to high successively, be ordinate with the peak area of the chromatographic peak that obtains, the sample introduction concentration of each corresponding material is the horizontal ordinate mapping, the drawing standard working curve.
Typical linear equation is as shown in table 2:
The quantitative limit of the range of linearity, linear equation, related coefficient and the method for table 2.10 kind of material
As eluant, eluent, Oasis HLB Cartridge, Orochem C18 and Chroma bond Easy are to effect of extracting such as Fig. 3 to 8 of 10 kinds of materials with methyl alcohol or ethyl acetate.At first with extraction column with the activation of 5mL methyl alcohol (Chroma bond Easy post is without activation); The 5mL deionized water balance; Then with 25mL concentration be 10 kinds of material hybrid analog-digital simulation solution of 5mg/L through solid-phase extraction column, with methyl alcohol or eluent ethyl acetate 5 times, each 1mL; Collect eluent, supply GC-MS to measure.
The result shows, as eluant, eluent, Chromabond bond Easy solid-phase extraction column is relatively good to the recovery of 10 kinds of materials with methyl alcohol or ethyl acetate.
Methyl alcohol, ethyl acetate, 3 kinds of different eluting solvents of methyl alcohol-ethyl acetate (volume ratio 1: 1) are to the eluting power of 10 kinds of materials on Chromabond Easy solid-phase extraction column.According to elution curve, during as eluent, the recovery is best with ethyl acetate.Use the 1ml eluent ethyl acetate at every turn, can the test substance wash-out that be adsorbed on the solid-phase extraction column is complete through 5 times.
The recovery and precision
Every kind of material has been set 3 and has been added concentration; As stated above (with Chromabond Easy solid-phase extraction column; With ethyl acetate as eluent); Each is added concentration repeat 6 tests, between 81.0%～110.3%, RSD is between 1.7%～5.1% for the organic average recovery rate of difference for method.Interpolation concentration, the recovery and the relative standard deviation (RSD) of 10 kinds of materials measured the result and is summarized in table 3.
The different recovery and precision (n=6) of adding the concentration material in table 3. toy
The mensuration of actual toy sample: use this method, the 9 kinds of toy samples (comprising 3 kinds of plastic toy samples, 4 kinds of paster type toy samples, 2 kinds of balloon samples) that buy from market are carried out the mensuration of above-mentioned 10 kinds of organism migration amounts.10 kinds of materials all do not detect in these 9 kinds of toy samples.
Above embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (3)
1. the assay method of harmful organic substance migration amount in the toy comprises the steps:
Choose part smooth in the toy sample, cut out component to be measured, component to be measured adds deionized water down at 20 ℃ ± 2 ℃, and vibration is extracted;
The extract that obtains is used eluent ethyl acetate through Chroma bond Easy SPE column extracting, collects eluent;
Eluent dewaters, filters laggard promoting the circulation of qi phase chromatography-mass spectroscopy and measures.
2. method according to claim 1 is characterized in that: the rotating speed that said vibration is extracted is 60r/min ± 5r/min, and extraction time is 60min.
3. method according to claim 1 and 2 is characterized in that: the total surface area of said component to be measured is 20cm
2
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103149294A (en) * | 2013-02-22 | 2013-06-12 | 上海市金山区青少年活动中心 | Method for determining migration of organic matter in apple label based on GC-MS (Gas Chromatography-Mass Spectrometer) |
| 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 |
-
2010
- 2010-12-28 CN CN2010106098081A patent/CN102565207A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| EUROPEAN COMMITTEE FOR STANDARDIZATION: "《BS EN-71-10：2005 safety of toys — part 10: organic chemical compounds – sample preparation and extraction》", 12 January 2006 * |
| EUROPEAN COMMITTEE FOR STANDARDIZATION: "《BS EN-71-10：2005 safety of toys — part 10: organic chemical compounds – sample preparation and extraction》", 12 January 2006, article "Migration – Sampling and extraction" * |
| EUROPEAN COMMITTEE FOR STANDARDIZATION: "《BS EN-71-11：2005，safety of toys — part 11: organic chemical compounds - methods of analysis》", 22 November 2005 * |
| 马强等: "气相色谱-质谱法测定玩具中的4种阻燃剂", 《分析试验室》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103149294A (en) * | 2013-02-22 | 2013-06-12 | 上海市金山区青少年活动中心 | Method for determining migration of organic matter in apple label based on GC-MS (Gas Chromatography-Mass Spectrometer) |
| CN103149294B (en) * | 2013-02-22 | 2015-08-05 | 上海市金山区青少年活动中心 | Based on the apple label organism migration assay method of GC-MS |
| 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 |
| CN103728405B (en) * | 2013-12-24 | 2016-12-07 | 中国检验检疫科学研究院 | The research method of timber preservative Transport in a kind of Wood children articles for use |
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Application publication date: 20120711 |