CN103529155A - Method for measuring content of wood preservatives of wooden products for children - Google Patents
Method for measuring content of wood preservatives of wooden products for children Download PDFInfo
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Abstract
The invention provides a method for measuring the content of wood preservatives of wooden products for children. The method comprises the following steps: crushing a sample to be measured, performing ultrasonic extraction by using methanol, filtering, adding an interior label working solution into the filtrate, centrifuging, filtering the supernate by using a filtering membrane, and performing spin-steaming concentration; and adding a potassium carbonate solution into the concentrated liquid, shaking uniformly, adding acetic anhydride, performing derivatization, oscillating while deflating and allowing the derivatized concentrated liquid to pass through an Oasis hydrophile lipophile balance (HLB) solid phase extraction column; sequentially leaching by using deionized water, pumping all the water by using a vacuum pump and eluting by using ethyl acetate to obtain eluent; adding a proper amount of anhydrous sodium sulfate into the eluent and drying; and performing vortical oscillation and measuring by a gas chromatography-tandem mass spectrum method. The invention establishes the method for measuring the content of 10 wood preservatives of the wooden products for children based on solid phase extraction-gas chromatography-tandem mass spectrum, which has excellent selectivity and sensitivity on detection of target objects of wood samples with complex matrix.
Description
Technical field
The present invention relates to a kind of assay method of antiseptic content, particularly relate to the assay method of wood preservation agent content in a kind of Wood children articles for use.
Background technology
In life, Wood children articles for use are very general, and as the Wood children furniture such as infanette, wooden toy, Wood children tableware etc., almost each children can touch, and whether Wood children articles for use safety and children healthy closely related.Current a lot of producer declares its product " manufacture of pure natural log ", " health environment-friendly non-toxic paint " etc., gives the impression of a kind of health environment-friendly of consumer." yet log ", " without paint " are also not equal to absolute environmental protection, timber starting material and finished product generally all can pass through preservative treatment, and some wood preservative has stronger toxicity, as chlorophenols compound, chrysanthemum ester type compound etc., these materials can migrate in body through breathing, saliva or sweat in children's contact process, to its healthy formation serious harm, may teratogenesis, carcinogenic and cause gene mutation etc.European Union is at the toy harmonized stndard EN71-9 announcing, and relate to 10 kinds of wood preservatives carried out limiting the quantity of requirement in 10,11 herein, wherein minimum limiting the quantity of as 1mg/kg.
Relate at present in the detection method report of antiseptic in timber and woodwork, the timber products relating in the document that can find has wood furniture, cootle, cork, wooden toy etc. for red wine, and detection method is vapor-phase chromatography (GC-ECD) and gas chromatography-mass spectrography (GC-MS).Yet the material composition of wood sample is complicated, adopts existing gas chromatography or gas chromatography-mass spectrography that enough selectivity and sensitivity can not be provided sometimes, easily cause situations such as " false positives " or " being difficult to quantitatively " to occur.And tandem mass spectrum has high selectivity and highly sensitive feature, can in complex matrices, to trace materials, carry out confirmatory analysis.Even do not have gas chromatography-tandem mass spectrometry to detect the relevant report of wood preservative in Wood children articles for use both at home and abroad at present simultaneously.
Intend herein, based on organophosphorous pesticides-tandem mass spectrum (SPE-GC-MS/MS) technology, setting up 10 kinds of detection methods that wood preservative is accurate, sensitive, stable in Wood children articles for use.By wood sample pretreatment process is optimized, investigate in detail the impact of kinds of experiments parameter on result, and carry out the mensuration of method validation and actual sample, guarantee that the method can be applicable to the actual testing of antiseptic in Wood children articles for use.
Summary of the invention
The technical problem to be solved in the present invention is to provide the assay method of wood preservation agent content in a kind of accurate, sensitive, stable Wood children articles for use.
In Wood children articles for use, an assay method for wood preservation agent content, comprises the steps:
Testing sample is pulverized, with the ultrasonic extraction of methyl alcohol, filtered, in filtrate, add interior mark working solution, centrifugal, supernatant is concentrated by rotary evaporation after membrane filtration; To adding solution of potassium carbonate in concentrate, after shaking up, add acetic anhydride to carry out derivatization, the venting of vibration limit, limit, concentrate after derivatization is adopted after by Oasis HLB solid-phase extraction column successively deionized water drip washing, vacuum pump water is drained, obtained eluent after eluent ethyl acetate, in described eluent, add appropriate anhydrous sodium sulfate drying, after vortex vibration, adopt gas chromatography-tandem mass spectrum method, under many reactive ions monitoring pattern MRM, measure, internal standard method is carried out quantitatively.
The assay method of wood preservation agent content in Wood children articles for use of the present invention, wherein, described method detects the content of 10 kinds of antiseptics simultaneously, described antiseptic is 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,3,4 trichlorophenols, 2,3,4,6-tetrachlorophenol, lindane, cypermethrin, cyfloxylate, decis, pentachlorophenol and 2,4 chlorophenesic acids.
The assay method of wood preservation agent content in Wood children articles for use of the present invention, wherein said gas chromatography-tandem mass spectrum condition is:
Agilent HP-5MS chromatographic column: 30m * 0.25mm i.d., 0.25 μ m; 280 ℃ of injector temperatures; Flow rate of carrier gas is 1.0mL/min; Splitless injecting samples, sample size 2 μ L;
Adopt temperature programme method: 60 ℃ of initial temperatures, with 20 ℃/min, rise to 200 ℃, then with 10 ℃/min, rise to 280 ℃, keep 8min; Solvent delay 5min; 250 ℃ of transmission line temperature; 180 ℃ of ion source temperatures; EI ionizes mode, ionizing energy 70eV; Multiple-reaction monitoring mode is measured.
In Wood children articles for use of the present invention, the assay method of wood preservation agent content, comprises the steps:
Sample is ground into and is less than 2mm wood chip with beveller, accurately take 2g sample in 50mL tool plug test tube, with the ultrasonic extraction of methyl alcohol 2 times, each 20mL, extracts 15min; Filter and merging filtrate to centrifuge tube, add mark working solution in 1mL, centrifugal 5min under 4 ℃, 13000r/min condition is transferred in heart bottle after 0.45 μ m PTFE membrane filtration, 35 ℃, 170hpa backspin inspissation are reduced to 1～3mL; In concentrate, add 40mL0.1mol/L solution of potassium carbonate, add 1mL acetic anhydride to carry out derivatization after shaking up, the venting of vibration limit, limit, operates about 1min and is placed on shaking table vibration 10min; Solution after vibration is passed through to Oasis HLB solid-phase extraction column, then through the drip washing of 5mL deionized water, utilize vacuum pump that water is drained, finally use 10mL eluent ethyl acetate, collect eluent and add appropriate anhydrous sodium sulfate drying, residual moisture in eluent is removed in assurance, after vortex vibration 30s, adopts gas chromatography-tandem mass spectrum method to measure.
The assay method of wood preservation agent content in Wood children articles for use of the present invention, the compound method of wherein said interior mark working solution is as follows:
Accurately take 50mg2,3,4-trichlorophenol, in the brown volumetric flask of 100mL, is that 9:1 ethanol/glacial acetic acid solution is as solvent constant volume by volume ratio, being mixed with mass concentration is the interior mark storing solution of 500mg/L, and being then diluted to concentration is the interior mark working solution of 5mg/L.
The assay method of wood preservation agent content in Wood children articles for use of the present invention, wherein said Oasis HLB solid-phase extraction column need be in advance through the activation of 5mL methyl alcohol, 5mL deionized water balance.
The assay method of wood preservation agent content in Wood children articles for use of the present invention, wherein said method is for the quantitative limit of 10 kinds of different preservatives materials between 0.0025mg/kg～0.2mg/kg, and the range of linearity is 0.0025mg/kg～25mg/kg.
The assay method of wood preservation agent content in Wood children articles for use of the present invention, is characterized in that: described concentrated by rotary evaporation process temperature is 35 ℃, is 300hPa when pressure starts, and is transitioned into gradually 170hPa in the situation that not producing bumping.
In Wood children articles for use of the present invention, the assay method difference from prior art of wood preservation agent content is:
In Wood children articles for use of the present invention, the assay method of wood preservation agent content has been set up the method for simultaneously measuring 10 kinds of wood preservation agent contents in Wood children articles for use based on organophosphorous pesticides-tandem mass spectrum (SPE-GC-MS/MS); At methanol solvate, extract, acetic anhydride reagent is derivative, after Solid phase extraction, through HP-5MS chromatographic column (30m * 0.25mm * 0.25 μ m) separation, adopt tandem mass spectrum to detect under many reactive ions monitoring pattern (MRM), there is better selectivity and sensitivity, adopt internal standard method to carry out quantitatively, quantitative result is more accurate; Investigate the impact of kinds of experiments parameter for testing result, and carried out method validation; The method of the invention, for the detection of object in the wood sample of complex matrices, has good selectivity and sensitivity.
For the quantitative limit (LOQ) of different material between 0.0025mg/kg～0.2mg/kg, the range of linearity is 0.0025mg/kg～25mg/kg, basic, normal, high 3 average recovery rates that add level are between 85.2%～100.1%, withinday precision (N=6) is between 0.6%～9.1%, and day to day precision (N=6) scope is between 2.3%～7.2%.The method is applied to, in actual sample selective examination, find the residual of multiple wood preservative.
Below in conjunction with accompanying drawing, the assay method of wood preservation agent content in Wood children articles for use of the present invention is described further.
Accompanying drawing explanation
The typical chromatographic fractionation figure (2mg/L) of 10 kinds of antiseptics that the assay method that Fig. 1 is wood preservation agent content in employing Wood children articles for use of the present invention obtains;
Fig. 2 is the chromatogram contrast that in the method for the invention, 3 kinds of scan patterns are measured actual timber toy sample;
Fig. 3 is the comparison of different solvents to 10 kinds of wood preservative extraction effects in the method for the invention;
Fig. 4 is the comparison of different solid-phase extraction columns to 10 kinds of wood preservative effect of extracting in the method for the invention;
Fig. 5 is the comparison of different eluting solvents to 10 kinds of wood preservative elute effects in the method for the invention;
Fig. 6 is the MRM chromatogram of the method for the invention empty sample and mark-on sample (2mg/kg).
Embodiment
In Wood children articles for use, an assay method for wood preservation agent content, comprises the steps:
1. instrument and reagent
7890A gas chromatograph: U.S. Agilent company; The triple level Four bar of Quattro Micro mass spectrum: U.S. Waters company, join EI source; Solid-phase extraction device: U.S. Supelco company; NVC-2000 type Rotary Evaporators: Japanese Eyela company; P300H ultrasonic cleaner: German Elma company; SM2000 type cutting and grinding instrument: German Retsch company; Hydro-extractor: Japanese Hitachi company; Oasis HLB solid-phase extraction column (6mL, 200mg): U.S. Waters company.
Standard items: 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,3,4 trichlorophenols, 2,3,4,6-tetrachlorophenol, lindane, cypermethrin, cyfloxylate, decis are all purchased from Accustandard company, purity >=98%; Pentachlorophenol, 2,4 chlorophenesic acids are purchased from Dr.Ehrenstorfer company, purity >=99%; Permethrin is purchased from Fluka company, purity >=98%; Wherein, Permethrin, cypermethrin, cyfloxylate are the potpourri of isomeride.The deionized water of experimental water for preparing through Milli-Q cleaning system; Helium, argon gas (> 99.999%); Methyl alcohol, acetonitrile, ethyl acetate, acetone, methylene chloride, normal hexane (chromatographically pure, U.S. J.T.Baker company); Other reagent using in experiment is pure for analyzing.
2. the preparation of standard solution
Test substance: accurately take 10 kinds of each 50mg of antiseptic standard items in the brown volumetric flask of 50mL, with 9:1(v/v) ethanol/glacial acetic acid solution constant volume, being mixed with concentration is single mark storing solution of 1000mg/L, and 10 kinds of materials that the single mark of utilization storing solution configuration concentration is 50mg/L are mixed storing solution entirely.In experiment as required, available 9:1(v/v) ethanol/glacial acetic acid be diluted to the serial working solution of desired concn.
Internal standard compound matter: accurately take 50mg2,3,4-trichlorophenol is in the brown volumetric flask of 100mL, with 9:1(v/v) ethanol/glacial acetic acid solution is as solvent constant volume, being mixed with mass concentration is the interior mark storing solution of 500mg/L, and being then diluted to concentration is the interior mark working solution of 5mg/L.
3. the making of positive
Blank wood sample is ground into the wood chip that is less than 2mm with beveller, take appropriate wood chip in tool plug round-bottomed flask, in a conical flask, add appropriate complete mixed standard solution, and add appropriate methyl alcohol dilution, the solution after assurance dilution is poured into can be by whole wood chip submergences in round-bottomed flask.Round-bottomed flask is placed in to hold over night after shaking table vibration 2h, to guarantee that antiseptic fully infiltrates into timber inside.Then under 35 ℃, 170hPa, (300hPa during beginning, is transitioned into 170hPa gradually, to avoid solution bumping; The speed declining as for pressure is as the criterion not produce bumping, and bumping can be not quicker, and conservative words speed can be slow.) revolve steaming, solvent slow evaporation is done near.Nearly dry wood chip sample is laid on teflon pallet or large surface plate, until solvent volatilizees completely, obtains positive.
4. sample pre-treatments
Sample is ground into and is less than 2mm wood chip with beveller, accurately take 2g sample in 50mL tool plug test tube, with the ultrasonic extraction of methyl alcohol 2 times, each 20mL, extracts 15min.Filtration merging filtrate are to centrifuge tube, add mark working solution in 1mL, centrifugal 5min under 4 ℃, 13000r/min condition, through 0.45 μ m PTFE(teflon) be transferred in heart bottle after membrane filtration, (300hPa during beginning under 35 ℃, 170hpa, be transitioned into gradually 170hPa, to avoid solution bumping) concentrated by rotary evaporation to 1～3mL.In concentrate, add 40mL0.1mol/L solution of potassium carbonate, add 1mL acetic anhydride to carry out derivatization after shaking up, the venting of vibration limit, limit, operates about 1min and is placed on shaking table vibration 10min.Solution after derivatization is passed through to shift to an earlier date the Oasis HLB solid-phase extraction column through the activation of 5mL methyl alcohol, 5mL deionized water balance, then through the drip washing of 5mL deionized water, utilize vacuum pump that water is drained, finally use 10mL eluent ethyl acetate, collect eluent and add appropriate anhydrous sodium sulfate drying, residual moisture in eluent is removed in assurance, after vortex vibration 30s, adopts gas chromatography-tandem mass spectrum method to measure.
5. chromatography-mass spectroscopy condition
Agilent HP-5MS chromatographic column (30m * 0.25mm i.d., 0.25 μ m); 280 ℃ of injector temperatures; Flow rate of carrier gas is 1.0mL/min; Splitless injecting samples, sample size 2 μ L; Temperature programme: 60 ℃ of initial temperatures, with 20 ℃/min, rise to 200 ℃, then with 10 ℃/min, rise to 280 ℃ (keeping 8min); Solvent delay 5min; 250 ℃ of transmission line temperature; 180 ℃ of ion source temperatures; EI ionizes mode, ionizing energy 70eV; Multiple-reaction monitoring (MRM) mode is measured.
Under above-mentioned condition, the retention time of each test substance, characteristic ion peer parameters are in Table 1.
The parameters such as the retention time of table 1 test substance, monitoring ion pair, the range of linearity, related coefficient
Note: for chlorophenols, the ion pair of monitoring is the ion that the ester after acetic anhydride derivatization produces.As corresponding in pentachlorophenol is pentachlorophenol acetic acid esters.
Under the GC conditions of setting, 10 kinds of wood preservatives reach good separated with internal standard compound, and belongings mass-energy is detected in 21min, the typical chromatographic fractionation figure of 10 kinds of materials is shown in Fig. 1, and wherein label 1-10 is followed successively by: 2,4-chlorophenesic acid, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, ISTD2,3,4-trichlorophenol, 2,3,4,6-tetrachlorophenol, lindane, pentachlorophenol, Permethrin, cyfloxylate, cypermethrin, decis.
Conclusion: organophosphorous pesticides-tandem mass spectrum that the present invention sets up (SPE-GC-MS/MS) method, can measure 10 kinds of wood preservatives in Wood children articles for use simultaneously.Pretreatment and instrument condition have carefully been optimized in experiment, have carried out method validation, finally 12 kinds of actual samples are detected.Result shows, the method can effectively be got rid of the interference of complicated wood sample matrix, and testing result is accurate, sensitive, stable, can be used for the actual testing of 10 kinds of antiseptics in Wood children articles for use.
MS/MS method is set up as follows: first, under Scan pattern, each material is scanned, sweep limit 40m/z is to 400m/z, selected signal strong and have higher specific charge as parent ion.Then, adopt Daughter scan pattern to carry out second order ms analysis, daughter ion is optimized to selection, determine quota ion and auxiliary qualitative ion.By optimizing the mass spectrum parameters such as lens voltage, collision energy, mass resolution, make the parent ion of wood preservative and the ion pair intensity of feature fragmention generation reach maximum.
23 kinds of different modes of embodiment are on detecting the impact of effect
We adopt the mass spectrographic Scan pattern of triple level Four bars, SIM pattern (selecting ion scan pattern) and MRM pattern to measure respectively certain a actual wooden toy sample (positive detecting while detecting actual sample, not carrying out any reference material or internal standard compound adds), the results are shown in Figure 2.In the visible wood sample of chromatogram under Scan pattern, material composition is complicated.When adopting single-stage mass spectrum SIM pattern, cyfloxylate (label 8) and cypermethrin (label 9) that part material particularly has isomeride are still subject to matrix interference impact, can not provide enough selectivity on the one hand, cause may occurring situations such as " false positives " or " being difficult to quantitatively " when qualitative, can not provide enough sensitivity on the one hand.And while adopting MRM pattern, the situation of matrix interference is obviously improved, selectivity obviously improves, and it is qualitative, quantitatively more accurate to make, and sensitivity simultaneously also obtains raising.
The optimization of embodiment 3 Pretreatments
1, extract the selection of solvent
The absolute recovery that extracts every kind of material in positive of take is index, methyl alcohol, methyl alcohol/glacial acetic acid (9:1 have been investigated respectively, v/v), ethyl acetate, the extraction effect of 4 kinds of extracts of acetonitrile to wood preservative, timber positive (the 5mg/kg that with 4 kinds of extracts, 2g is contained to 10 kinds of wood preservatives respectively, be equivalent to machine concentration 1mg/L) ultrasonic extraction, concentrated, derivative, the Solid-Phase Extraction and the upper machine that carry out under the same terms are measured.Contrast with standard solution, the recovery obtaining is shown in Fig. 3.Result shows, the extraction effect of 4 kinds of solvents has marked difference, the extraction effect of ethyl acetate the poorest (recovery < 65%) wherein, methyl alcohol/glacial acetic acid extraction effect of acetonitrile and 9:1 is placed in the middle, the recovery the highest (> 74%) of antiseptic while using methyl alcohol as extract, and repeatability is also relatively better, and (RSD≤12.4%, n=4), therefore selected methyl alcohol is as the extraction solvent of this method.
2, the selection of solid-phase extraction column
10 kinds of antiseptics after derivatization proceed to organic phase through Solid-Phase Extraction by water, 7 kinds of solid-phase extraction column ENVI-Chrom P(6mL have been investigated altogether, 250mg, U.S. Supelco company), Sep-park C18, Oasis HLB Cartridge(6mL, 200mg, U.S. Waters company), Bond Elut PLEXA(6mL, 200mg, U.S. Agilent company), Bond Elut C18(3mL, 200mg, U.S. Agilent company), Chromabond Easy, Chromabond HR-P(6mL, 200mg, Germany MN company) effect of extracting to 10 kinds of materials.First by 5mL methyl alcohol activation for extraction column, 5mL deionized water balance, then the mixed solution after derivatization is passed through respectively to 7 kinds of solid-phase extraction columns, after 5mL water wash, use 10mL eluent ethyl acetate, eluent is dry rear for Instrument measuring.Take the recovery as index, the peak area that the extraction column that in result, the recovery is the highest is obtained to material is defined as 100%, the peak area of other extraction column calculates in contrast relative percentage and the difference (see figure 4) between them is compared in mapping, and in Fig. 4, label 1-7 is followed successively by Supelclean ENVI-Chrom P, Sep-park C18, Bond Elut PLEXA, Chromabond Easy, Oasis HLB, Chromabond HR-P, Bond Elut C18.
From the results of view, each extraction column all has stronger stick effect to 10 kinds of materials, and therefore the best results of Oasis HLB post chooses it as test extraction column.
3, the selection of eluting solvent
Keep other experiment condition constant, investigated methyl alcohol, acetone, normal hexane, methylene chloride and the elute effect of 5 kinds of different eluting solvents of ethyl acetate to 10 kinds of antiseptics on Oasis HLB solid-phase extraction column.Each 2mL, wash-out 7 times, the machine on each 2mL eluent of collecting is measured, and is judged that the elute effect of ethyl acetate is best by each material elution curve obtaining, and volume is decided to be 10mL and can guarantees 10 kinds of material wash-outs complete.Fig. 5 is the contrast of 5 kinds of eluting solvent volumes elute effect while being 10mL, and the eluting solvent peak area that the recovery is the highest is defined as 100%, and the peak area of other eluting solvent calculates relative percentage in contrast.As seen from the figure, methyl alcohol and acetone are poor to the eluting power of 10 kinds of materials, and normal hexane is poor to pyrethrin eluting power, and the elute effect of ethyl acetate is relatively best.Therefore, method is finally chosen 10mL ethyl acetate as eluting solvent.
4, the selection of derivatization condition
Keep other experiment condition constant, to the volume of derivatization medium (0.1mol/L solution of potassium carbonate) investigated respectively 10,15,20,25,30,35,40,45,50mL, and compare its recovery, finally choose the solution of potassium carbonate that adds 40mL0.1mol/L.
To the volume of derivatization reagent acetic anhydride investigate respectively 0.2,0.4,0.6,0.8,1.0mL, and its recovery of comparison, when discovery use amount 0.6mL is above, the recovery is not significantly increased, the volume of acetic anhydride is decided to be 1.0mL the most at last, and slightly excessive acetic anhydride can guarantee that chlorophenols is by abundant derivatization.
The many wood qualities that do not identify of Wood children articles for use of selling on the market at present, part is designated pine, beech, lotus wood, birch, in experimentation, we take wooden toy sample as main, choose the toy sample of 10 parts of various materials, carry out respectively sample blank experiment.All kinds of wood samples are under this method extraction and condition determination, and impurity disturbs few, and the mensuration of target compound is had no significant effect.Finally choose a kind of matrix wherein the most totally and not containing the beech of test substance as blank sample for the making of positive and the mensuration of the recovery.
Mark-on in the extract of blank wood sample, obtains the range of linearity of each material, and related coefficient is all greater than 0.9993, specifically in Table 1.
By the standard reserving solution 9:1(v/v of test substance) ethanol/glacial acetic acid be diluted to 0.001～50mg/L, take blank wood sample as matrix, carry out the mark-on experiment of low concentration level, obtain the detectability (LOD of each material, S/N > 3) and quantitative limit (LOQ, S/N > 10).The scope of determining each material detectability is 0.001mg/kg～0.05mg/kg, and the scope of each material quantitative limit is 0.0025mg/kg～0.2mg/kg.Can see, each material quantitative limit obtaining far below limiting the quantity of of stipulating in the toy safety standard EN 71-9 of European Union (in 10 kinds of materials 2,4-chlorophenesic acid, 2,4, limiting the quantity of as 5mg/kg of 6-trichlorophenol, 2,3,4, limiting the quantity of as 1mg/kg of 6-tetrachlorophenol, the limiting the quantity of as 2mg/kg of pentachlorophenol, lindane, 2,4,5-trichlorophenol, Permethrin, cyfloxylate, cypermethrin, limiting the quantity of of decis are 10mg/kg).
By in blank sample, every kind of antiseptic being set respectively to basic, normal, high 3 different interpolation levels, obtain the recovery scope of each material between 85.2%～100.1%, withinday precision (N=6) is less than 9.1%, and average is 3.1%.Day to day precision (N=6) scope is between 2.3%～7.2%.Concrete data are in Table 2.The MRM chromatogram of blank sample and mark-on sample (2mg/kg) is shown in Fig. 6, and in Fig. 6, A is MRM blank sample chromatogram; B is MRM mark-on sample chromatogram figure (2mg/kg).
The recovery of table 210 kind of antiseptic, detectability, quantitative limit, repeated data
Note: the interpolation concentration of each material respectively is, low concentration: 0.01,0.01,0.01,0.01,0.05,0.01,0.05,0.1,0.1, concentration in 0.2mg/kg.: 2.5,2.5,5,0.5,1,1,5,5,5,5mg/kg. high concentration: 5,5,10,1,2,2,10,10,10,10mg/kg
The mensuration of embodiment 5 actual samples
Application this method, measures totally to the 12 sections of wooden toy samples that collect from the market.Found that, at least detect a kind of wood preservative in 7 sections of toy samples, wherein have 3 sections of toy samples to detect and surpass 4 kinds of antiseptics, all the other 5 sections of toys detect.From test substance angle, 9 kinds of wood preservatives have been detected altogether.Wherein cypermethrin, cyfloxylate and decis nearly all detect in 7 sections of toys, can infer, they are more often used in the preservative treatment of wooden toy product.Specifically can be in Table 3.
The testing result (S1:Sample1) of the actual wooden toy sample of table 3.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that those of ordinary skills make technical scheme of the present invention, all should fall in the definite protection domain of the claims in the present invention book.
Claims (8)
1. an assay method for wood preservation agent content in Wood children articles for use, is characterized in that: comprise the steps:
Testing sample is pulverized, with the ultrasonic extraction of methyl alcohol, filtered, in filtrate, add interior mark working solution, centrifugal, supernatant is concentrated by rotary evaporation after membrane filtration; To adding solution of potassium carbonate in concentrate, after shaking up, add acetic anhydride to carry out derivatization, the venting of vibration limit, limit, concentrate after derivatization is adopted after by Oasis HLB solid-phase extraction column successively deionized water drip washing, vacuum pump water is drained, obtained eluent after eluent ethyl acetate, in described eluent, add appropriate anhydrous sodium sulfate drying, after vortex vibration, adopt gas chromatography-tandem mass spectrum method, under many reactive ions monitoring pattern MRM, measure, internal standard method is carried out quantitatively.
2. the assay method of wood preservation agent content in Wood children articles for use according to claim 1, is characterized in that: described method detects the content of 10 kinds of antiseptics simultaneously, and described antiseptic is 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,3,4 trichlorophenols, 2,3,4,6-tetrachlorophenol, lindane, cypermethrin, cyfloxylate, decis, pentachlorophenol and 2,4 chlorophenesic acids.
3. the assay method of wood preservation agent content in Wood children articles for use according to claim 1, is characterized in that: described gas chromatography-tandem mass spectrum condition is:
Agilent HP-5MS chromatographic column: 30m * 0.25mm i.d., 0.25 μ m; 280 ℃ of injector temperatures; Flow rate of carrier gas is 1.0mL/min; Splitless injecting samples, sample size 2 μ L;
Adopt temperature programme method: 60 ℃ of initial temperatures, with 20 ℃/min, rise to 200 ℃, then with 10 ℃/min, rise to 280 ℃, keep 8min; Solvent delay 5min; 250 ℃ of transmission line temperature; 180 ℃ of ion source temperatures; EI ionizes mode, ionizing energy 70eV; Multiple-reaction monitoring mode MRM measures.
4. the assay method of wood preservation agent content in Wood children articles for use according to claim 1, is characterized in that: comprise the steps:
Sample is ground into and is less than 2mm wood chip with beveller, accurately take 2g sample in 50mL tool plug test tube, with the ultrasonic extraction of methyl alcohol 2 times, each 20mL, extracts 15min; Filter and merging filtrate to centrifuge tube, add mark working solution in 1mL, centrifugal 5min under 4 ℃, 13000r/min condition is transferred in heart bottle after 0.45 μ m PTFE membrane filtration, 35 ℃, 170hpa backspin inspissation are reduced to 1～3mL; In concentrate, add 40mL0.1mol/L solution of potassium carbonate, add 1mL acetic anhydride to carry out derivatization after shaking up, the venting of vibration limit, limit, operates about 1min and is placed on shaking table vibration 10min; Solution after vibration is passed through to Oasis HLB solid-phase extraction column, then through the drip washing of 5mL deionized water, utilize vacuum pump that water is drained, finally use 10mL eluent ethyl acetate, collect eluent and add appropriate anhydrous sodium sulfate drying, residual moisture in eluent is removed in assurance, after vortex vibration 30s, adopts gas chromatography-tandem mass spectrum method to measure.
5. according to the assay method of wood preservation agent content in the Wood children articles for use described in claim 3 or 4, it is characterized in that: the compound method of described interior mark working solution is as follows:
Accurately take 50mg2,3,4-trichlorophenol, in the brown volumetric flask of 100mL, is that 9:1 ethanol/glacial acetic acid solution is as solvent constant volume by volume ratio, being mixed with mass concentration is the interior mark storing solution of 500mg/L, and being then diluted to concentration is the interior mark working solution of 5mg/L.
6. the assay method of wood preservation agent content in Wood children articles for use according to claim 5, is characterized in that: described Oasis HLB solid-phase extraction column need be in advance through the activation of 5mL methyl alcohol, 5mL deionized water balance.
7. the assay method of wood preservation agent content in Wood children articles for use according to claim 1, it is characterized in that: described method is for the quantitative limit of 10 kinds of different preservatives materials between 0.0025mg/kg～0.2mg/kg, and the range of linearity is 0.0025mg/kg～25mg/kg.
8. the assay method of wood preservation agent content in Wood children articles for use according to claim 4, is characterized in that: described concentrated by rotary evaporation process temperature is 35 ℃, is 300hPa when pressure starts, and is transitioned into gradually 170hPa in the situation that not producing bumping.
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| CN106645448A (en) * | 2016-09-28 | 2017-05-10 | 广州纤维产品检测研究院 | Separation detection method of phenol compounds in textiles |
| CN107870215A (en) * | 2017-11-28 | 2018-04-03 | 广东省测试分析研究所（中国广州分析测试中心） | The gas chromatography combined with mass spectrometry analysis method of potassium cinnamate content in a kind of measure food |
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| CN103852533A (en) * | 2014-03-26 | 2014-06-11 | 昆山洛丹伦生物科技有限公司 | Detecting method for pentachlorophenol in plastic component of electronic element |
| CN105842376A (en) * | 2016-04-27 | 2016-08-10 | 江苏德旺化工工业有限公司 | Method for detecting polychlorobiphenyl in dye |
| CN105842376B (en) * | 2016-04-27 | 2018-02-09 | 江苏德旺化工工业有限公司 | The detection method of polystream phenol in a kind of dyestuff |
| CN106645448A (en) * | 2016-09-28 | 2017-05-10 | 广州纤维产品检测研究院 | Separation detection method of phenol compounds in textiles |
| CN106645448B (en) * | 2016-09-28 | 2019-11-29 | 广州纤维产品检测研究院 | The method for separating and detecting of phenol compound in textile |
| CN107870215A (en) * | 2017-11-28 | 2018-04-03 | 广东省测试分析研究所（中国广州分析测试中心） | The gas chromatography combined with mass spectrometry analysis method of potassium cinnamate content in a kind of measure food |
| CN108693262A (en) * | 2018-04-13 | 2018-10-23 | 佛山市梅雨科技有限公司 | A kind of assay method of Determination of Preservatives in Cosmetics |
| CN110568104A (en) * | 2019-09-24 | 2019-12-13 | 杭州市质量技术监督检测院 | Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware |
| CN110699418A (en) * | 2019-11-14 | 2020-01-17 | 浙江星博生物科技股份有限公司 | Detection method based on GC-MS sperm counting and application |
| CN112285252A (en) * | 2020-10-30 | 2021-01-29 | 中国检验检疫科学研究院 | Chemical risk assessment method for wood preservative in wooden toy |
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