CN103728405A - Research method of wood preservative migration rule in wooden children product - Google Patents
Research method of wood preservative migration rule in wooden children product Download PDFInfo
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Abstract
The invention discloses a research method of a wood preservative migration rule in a wooden children product. The research method comprises the following steps of (1) smashing a wood sample the surface layer thickness of which is 3mm into 2mm chips through a grinding instrument, and measuring the total content of each preservative in the sample; (2) measuring the migration volume of each preservative in the sample, adding a migration solution in the sample, adding an internal standard operation solution, and measuring by adopting a gas chromatography-tandem mass spectrum detection method; and (3) analyzing the result which is obtained under different experimental simulation conditions based on the measurement of the total content of each preservative and the migration volume to obtain the maximum migration rate and the migration rule of the wood preservative. The research method provided by the invention has the advantages that the research method provides the theoretical foundation for the experimental design of the migration rule of the ten wood preservatives, the manufacture of a positive standard sample is beneficial, and meanwhile, a condition that the research result of the migration rule is exact and reliable is guaranteed.
Description
Technical field
The present invention relates to the research method of antiseptic Transport in a kind of timber, particularly relate to a kind of research method for Wood children articles for use wood preservative Transport.
Background technology
Common Wood children articles for use have wooden toy, infanette etc. on the market.Due to the report of the poisonous event of Toys paint coat, at present a lot of producers declare its product " log ", " non-toxic paint ", give the impression of a kind of environment-protecting asepsis of consumer, yet the harm being brought by the wood preservative that wherein may exist are often ignored by people.For avoiding occurring ftractureing because making moist the situation such as mouldy, log timber and finished product generally all can pass through preservative treatment.Take wooden toy as example; within 3 years old, following infant is when playing; often can catch in its mouth or lick and lick; or toy is immersed in water; wood preservative can move in infants along with saliva, sweat or water like this; it is worked the mischief, as polystream aldehydes matter and pyrethrin 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.
For the Transport research of wood preservative, the work of carrying out both at home and abroad is at present considerably less, and the data that can find only relates to the waterborne preservatives such as CCA and pentachlorophenol, for sample be mainly soil and underground water.There are reports to the migratory behaviour of the materials such as plastifier, bis-phenol, aromatic amine, ultraviolet absorber in the packaging materials for food such as plastics for domestic and international researcher, but because the material object of product matrix, environment for use, research is all different, existing achievement in research can not directly be applied mechanically.
Compare with Transport, the polystream phenols detection method residual with the agriculture of chrysanthemum ester class report is relative more, for be mainly food, environmental sample etc.Complicated component due to wood sample, only adopt chromatography or chromatogram-single-stage mass spectrometry that enough selectivity and sensitivity may not be provided, and tandem mass spectrum has high selectivity and highly sensitive feature, can in complex matrices, to trace materials, carry out confirmatory analysis, comparatively suitable for studying the Transport of material as detection technique.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of easy and simple to handle, research method of wood preservative Transport in Wood children articles for use accurately and reliably.
In Wood children articles for use, a research method for wood preservative Transport, comprises the steps:
(1) the positive criteria sample that contains 10 kinds of wood preservatives by self-control, with the total content of every kind of antiseptic reality in gas chromatography-tandem mass spectrometry working sample;
(2) measure the migration amount of every kind of antiseptic in positive: with low speed cutting machine, cut wood sample top layer 3mm thickness, through beveller, be ground into and be less than 2mm wood chip, accurately take 2g sample in 50mL tool plug test tube, add migration solvent 40mL, described migration solvent is simulate saliva, simulated sweat or water, after 37 ℃, 100r/min Water Under are bathed vibration 1～10h, cross 200 μ m stainless steel screens, obtain migration solution; In described migration solution, add in 1mL and mark working solution, pH value is adjusted to 6, add 1mL acetic anhydride to carry out derivatization, operate about 1min and be 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, 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, after vortex 30s, adopt gas chromatography-tandem mass spectrum detection method to measure;
(3) for the handling characteristics of Wood children articles for use, by setting different experimental simulation conditions, mensuration based on to the total content of every kind of antiseptic in sample and migration amount, the result obtaining is gathered and analyzed, draw maximum mobility and the Transport of every kind of wood preservative in Wood children articles for use.
The research method of wood preservative Transport in Wood children articles for use of the present invention, total content and the migration amount of 10 kinds of antiseptic materials in wherein said method while working sample, and simulated conditions are carried out Transport research by experiment, described antiseptic is 2,4 chlorophenesic acids, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, lindane, pentachlorophenol, cypermethrin, cyfloxylate, Permethrin and decis.
The research method of wood preservative Transport in Wood children articles for use of the present invention, wherein step (3) specifically comprises the steps: for polystream aldehydes matter, preparation 5mg/kg and 10mg/kg positive criteria sample, for pyrethrin, prepare 50mg/kg and 100mg/kg positive, in different migration solvents, move 1～10h respectively, bath temperature is decided to be 37 ℃, the migration amount of each material of difference sampling and measuring under simulated experiment condition, result gathers mapping, intuitively migratory behaviour is analyzed; By 10 kinds of actual total contents of material in all positive are measured, calculate the ratio of migration numerical quantity and corresponding total numerical quantity, be the mobility of each material in 10h, wherein each material maximal value of mobility in 10h is maximum mobility, maximum mobility by each material in the positive of comparison different content in difference migration solvent, and compare with result before, finally draw the Transport of 10 kinds of wood preservatives.
The research method of wood preservative Transport in Wood children articles for use of the present invention, also comprise the preparation of positive, comprise the steps: blank wood sample to be ground into beveller the wood chip that is less than 2mm, take appropriate wood chip in tool plug round-bottomed flask, in a conical flask, add complete mixed standard solution, and adding 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 standing over night after shaking table vibration 2h, guarantee that antiseptic fully infiltrates into timber inside, then 35 ℃, the steaming of 170hPa backspin, revolve pressure in steaming process and be transitioned into gradually 170hPa by 300hPa, solvent slow evaporation is done near, nearly dry wood chip sample is laid on large surface plate, until solvent volatilizees completely, obtains positive.
The research method of wood preservative Transport in Wood children articles for use of the present invention, wherein said interior mark working solution is prepared from by the following method: take 50mg2,3,4-trichlorophenol is in the brown volumetric flask of 100mL, ethanol/glacial acetic acid solution the constant volume that is 9:1 by volume ratio, be mixed with the interior mark storing solution of 500mg/L, being then diluted to concentration is the interior mark working solution of 5mg/L.
The research method of wood preservative Transport in Wood children articles for use of the present invention, the preparation method of wherein said simulate saliva is prepared from by the following method: take respectively sodium chloride 4.5g, potassium chloride 0.3g, sodium sulphate 0.3g, ammonium chloride 0.4g, 90% lactic acid 3.0g, urea 0.2g, after mixing, with deionized water, be settled to 1000mL, pH ≈ 3;
Described simulated sweat is prepared from by the following method: take respectively sodium bicarbonate 4.2g, and sodium chloride 0.5g, sal tartari 0.2g, is settled to 1000mL with deionized water after mixing, pH ≈ 8.8.
The research method of wood preservative Transport in Wood children articles for use of the present invention, wherein step (1) specifically comprises the steps: sample to be crushed to and to be less than 2mm wood chip, accurately take 2g, with the ultrasonic extraction of methyl alcohol 2 times, each 20mL, extract 15min, filtration merging filtrate are to centrifuge tube, add mark working solution in 1mL, at 4 ℃, centrifugal 5min under 13000r/min condition, after 0.45 μ m PTFE membrane filtration, be transferred in heart bottle, 35 ℃, 170hpa backspin inspissation is reduced to 2mL, in concentrate, add 40mL0.1mol/L solution of potassium carbonate, after shaking up, add 1mL acetic anhydride to carry out derivatization, the venting of vibration limit, limit, operate about 1min and be placed on shaking table vibration 10min, by the solution after derivatization by activating through 5mL methyl alcohol in advance, the Oasis HLB solid-phase extraction column of 5mL deionized water balance, 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, after vortex 30s, adopt gas chromatography-tandem mass spectrum detection method to measure.
The research method of wood preservative Transport in Wood children articles for use of the present invention, the chromatography-mass spectroscopy condition of wherein said gas chromatography-tandem mass spectrum detection method is: Agilent HP-5MS chromatographic column, specification is 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 ℃ and keep 8min; Solvent delay 5min; 250 ℃ of transmission line temperature; 180 ℃ of ion source temperatures; EI ionizes mode, ionizing energy 70eV, and MRM pattern is measured.
In Wood children articles for use of the present invention, the research method difference from prior art of wood preservative Transport is:
Organophosphorous pesticides-tandem mass spectrum (SPE-GC-MS/MS) detection technique of described method based on 10 kinds of wood preservatives in Wood children articles for use, propose a kind of assay method of new wood preservative migration amount, can measure 10 kinds of polystream phenols and chrysanthemum ester class antiseptic content and migration amount in sample simultaneously.Also have, (1) wood sample is taked specific sampling mode, so that migration experimental design more has theoretical foundation, is more conducive to the making of positive criteria sample simultaneously.By designing the anti-experiment that pushes away, wood preservative with simulate saliva by wood surface under internal migration long period condition, in the 3mm of timber top layer, wood preservation agent content is far longer than inside, while releasing thus actual generation migratory behaviour, mainly that wood preservative in the 3mm of timber top layer moves out, desirable top layer 3mm while therefore sampling.(2) setting of migration solution generation derivative reaction pH value, because the character of polystream phenols and chrysanthemum ester class wood preservative material differs widely, adopts gas Chromatographic Determination polystream aldehydes matter to need first in solution of potassium carbonate medium, carry out acetic anhydride derivatization.And after migration test completes, the medium of derivatization is simulate saliva, simulated sweat or water, this research method, by carefully optimizing, is determined the derivatization pH value for 10 kinds of wood preservative the bests by the recovery, finds that the change of this value has appreciable impact for whole result of study in research.
Handling characteristics for Wood children articles for use, by setting different experimental simulation conditions, mensuration based on to the total content of every kind of antiseptic in sample and migration amount, gathers and analyzes the result obtaining, and draws maximum mobility and the Transport of wood preservative in Wood children articles for use.
For 10 kinds of wood preservatives, the positive criteria sample of preparing different content, in migration solution, move 1～10h respectively, bath temperature is decided to be 37 ℃, the migration amount of each material of difference sampling and measuring under simulated experiment condition, result gathers mapping, can intuitively to migratory behaviour, analyze, and on affecting the factor of Transport, inquires into.By 10 kinds of actual total contents of material in above-mentioned all positive are measured, with all migration numerical quantities, make ratio with corresponding total numerical quantity, draw the mobility of each material in 10h.Wherein each material maximal value of mobility in 10h is maximum mobility, maximum mobility by each material in the positive of comparison different content in difference migration solution, and mutually confirm with result before, finally draw the Transport of 10 kinds of wood preservatives.
In Wood children articles for use of the present invention, the research method of wood preservative Transport, for the mensuration of object total amount in the wood sample of complex matrices and migration amount, has good selectivity and sensitivity, easy and simple to handle, successful.Transport experimental design for 10 kinds of wood preservatives more has theoretical foundation, is more conducive to the making of positive criteria sample, guarantees the result of study of Transport more accurately and reliably simultaneously.
Below in conjunction with accompanying drawing, the research method of wood preservative Transport in Wood children articles for use of the present invention is described further.
Accompanying drawing explanation
Fig. 1 is the MRM chromatogram of 10 kinds of wood preservative standard solution in the research method of wood preservative Transport in Wood children articles for use of the present invention; Identical with table 1 of the antiseptic kind that numbering represents;
Fig. 2 be in the research method of wood preservative Transport in Wood children articles for use of the present invention 10 kinds of wood preservatives by simulate saliva the experimental result schematic diagram to timber internal migration; Wherein, A:0～3mm; B:3～6mm; C: residue wood sample;
Fig. 3 is the schematic diagram of the relative recovery of 10 kinds of materials in different pH value Imitating salivas in the research method of wood preservative Transport in Wood children articles for use of the present invention;
Fig. 4 is the schematic diagram of the relative recovery of 10 kinds of materials in different pH value Imitating sweat in the research method of wood preservative Transport in Wood children articles for use of the present invention;
Fig. 5 is 10 kinds of wood preservatives migration results schematic diagram under 37 ℃ of conditions in the research method of wood preservative Transport in Wood children articles for use of the present invention.
Embodiment
A research method for wood preservative Transport in Wood children articles for use, is characterized in that: comprise the steps:
One, preliminary preparation
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); Solid-phase extraction device (U.S. Supelco company); NVC-2000 type Rotary Evaporators (Japanese Eyela company); SM2000 type cutting and grinding instrument (German Retsch company); TechCut4 low speed cutting machine, joins micro-rack saw sheet (U.S. Allied company); NTS-4000 water bath with thermostatic control oscillator (Japanese Eyela 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 system; Helium, argon gas (> 99.999%); The ethanol using in experiment, acetic acid, acetic anhydride are pure for analyzing, and other reagent is chromatographically pure.
2, the preparation of solution
Test substance: take 10 kinds of each 100mg of antiseptic standard items in the brown volumetric flask of 100mL, with 9:1(v/v) ethanol/glacial acetic acid solution constant volume, being mixed with concentration is single mark storing solution of 1000mg/L, utilizes the complete mixed storing solution that single mark storing solution configuration concentration is 100mg/L.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: take 50mg2,3,4-trichlorophenol is in the brown volumetric flask of 100mL, with 9:1(v/v) ethanol/glacial acetic acid solution constant volume, is mixed with the interior mark storing solution of 500mg/L, and being then diluted to concentration is the interior mark working solution of 5mg/L.
Simulate saliva: sodium chloride 4.5g, potassium chloride 0.3g, sodium sulphate 0.3g, ammonium chloride 0.4g, 90% lactic acid 3.0g, urea 0.2g, deionized water is settled to 1000mL, pH ≈ 3.Simulated sweat: sodium bicarbonate 4.2g, sodium chloride 0.5g, sal tartari 0.2g, deionized water is settled to 1000mL, pH ≈ 8.8.
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 standing over night after shaking table vibration 2h, to guarantee that antiseptic fully infiltrates into timber inside.Then at 35 ℃, 170hPa(, by 300hPa, be transitioned into gradually 170hPa, to avoid solution bumping) backspin steams, by solvent slow evaporation near dry.Nearly dry wood chip sample is laid on large surface plate, until solvent volatilizees completely, obtains positive.
Two, assay method
(1) total amount of every kind of antiseptic in working sample:
Sample is crushed to and is less than 2mm wood chip, accurately take 2g, 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 2mL.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, 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, after vortex 30s, upper machine is measured.
(2) the migration amount of every kind of antiseptic in working sample:
With low speed cutting machine, cut wood sample top layer 3mm thickness, through beveller, be ground into and be less than 2mm wood chip, accurately take 2g sample in 50mL tool plug test tube, add migration solvent 40mL, 37 ℃, the rear 200 μ m stainless steel screens of crossing of 100r/min Water Under bath vibration (1～10h), obtain migration solution.In migration solution, add in 1mL and mark working solution, pH value is adjusted to 6, add 1mL acetic anhydride to carry out derivatization, operate about 1min and be 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, 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, after vortex 30s, upper machine is measured.
Wherein, chromatography-mass spectroscopy condition is specially:
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, and MRM pattern is measured.
(3) for the handling characteristics of Wood children articles for use, by setting different experimental simulation conditions, mensuration based on to the total content of every kind of antiseptic in sample and migration amount, the result obtaining is gathered and analyzed, draw maximum mobility and the Transport of wood preservative in Wood children articles for use.
Three, results and analysis
1, the total quantity measuring method of wood preservative
Based on SPE-GC-MS/MS technology, the present invention has set up the method for simultaneously measuring these 10 kinds of wood preservatives in Wood children articles for use.Result shows, method, for the detection of object in the wood sample of complex matrices, has good selectivity and sensitivity.Under chromatogram mass spectrum condition of the present invention, the typical chromatographic fractionation figure of 10 kinds of materials is shown in Fig. 1.
Blank sample in the present invention is that a kind of matrix is totally and not containing the beech of test substance.Take blank sample as matrix, by mark-on, test detectability, quantitative limit and the range of linearity that obtains each material.The chromatogram of each material and mass spectrum parameter are in Table 1.
The CAS of table 1 test substance, chromatographic retention, the range of linearity and mass spectrum parameter
* parent ion > quota ion (collision energy, eV).
2, wood sample sampling mode determines
The square build beech blank sample that to choose 3 length of sides be 3cm, be placed in 500mL beaker, add the complete mixed standard solution 50mL of 100mg/L, add appropriate simulate saliva and mix, by the whole submergences of wood sample (tiny weight that can be suitable or support are auxiliary), sealing.After 3 samples soak respectively 1h, 5h and 24h, take out, in fuming cupboard, standing over night is dried.For the sample that soaks 1h, adopt low speed cutting saw that 6 surfaces of sample are cut and obtained 3 groups of wood chips successively from outside to inside, wherein 0～3mm layer is A sample; 3～6mm layer is B sample; Inner residue timber is C sample.Soak the sample of 5h and 24h in like manner; According to the Determination of Gross of setting up, to obtain 9, treat that test sample carries out respectively the mensuration of 10 kinds of wood preservation agent contents, result is as shown in Figure 2.
As seen from Figure 2, along with the growth of soak time, in sample, the content integral body of wood preservative shows a rising trend.Wood preservative with saliva by wood surface to internal migration, the content in A sample is all far longer than B and C, even if soaking under the condition of 24h, also not infiltration is evenly completely in timber inside for material.It is more than 5 times that in A sample, content is B+C to pyrethrin, and polystream aldehydes matter reaches more than 32 times.And in actual migration experiment, what study is that wood preservative is moved to outside by timber inside with migration solution, by anti-pushing manipulation, can judge that actual migration material is out mainly in 3mm top layer, 3mm moves out with migration solution to the antiseptic material in the timber of inside center is more difficult.Therefore the sampling mode of this migration experiment is defined as sample thief surface 3mm layer; For ease of making the positive criteria sample of known content, and carry out the exploration of Transport, wood sample is got to surperficial 3mm layer and by beveller, pulverize.
Described in step (2), wood sample is taked specific sampling mode, so that migration experimental design more has theoretical foundation, is more conducive to the making of positive criteria sample simultaneously.By designing the anti-experiment that pushes away, wood preservative with migration solvent by wood surface under its internal migration long period condition, in the 3mm of timber top layer, wood preservation agent content is far longer than inside, while releasing thus actual generation migratory behaviour, mainly that wood preservative in the 3mm of timber top layer moves out, desirable top layer 3mm while therefore sampling.
3, the impact of migration pH
In the test of wood preservative total amount, need be at 0.1mol/L solution of potassium carbonate back warp acetic anhydride reagent derivatization for polystream aldehydes matter, and the medium of migration experiment is the migration solvents such as simulate saliva, simulated sweat or water, can be by directly carry out derivatization in migration solution, more for convenience after if migration experiment finishes.In 40mL simulate saliva, simulated sweat, solution of potassium carbonate, carry out respectively mark-on, regulate pH value to 2～9 of simulate saliva and sweat, then add acetic anhydride to carry out derivatization.The recovery of solution of potassium carbonate of take is 100% benchmark, obtains moving under different pH the relative recovery of 10 kinds of materials in solution.From Fig. 3 and Fig. 4, the recovery of 10 kinds of materials is moved pH to be affected obviously, and polystream aldehydes matter recovery under acid condition is very low, along with alkaline enhancing is more conducive to derivative reaction and obtains the higher recovery; Pyrethrin is comparatively stable under acidity and neutrallty condition, and under higher pH value, the recovery starts variation.Consider, select the pH value that migration experiment is finished to rear migration solution to be adjusted to 6, for all substances, all can guarantee the more satisfied recovery.
Described in step (2), move in solution and add in 1mL and mark after working solution, pH value is set as 6 and has decisive role for whole experimental result.Because the character of polystream phenols and chrysanthemum ester class wood preservative material differs widely, adopt gas Chromatographic Determination polystream aldehydes matter to need first in solution of potassium carbonate medium, carry out acetic anhydride derivatization.And after migration test completes, the medium of derivatization is simulate saliva, simulated sweat or water, this research method is by carefully optimizing, by the recovery, determine the derivatization pH value for 10 kinds of wood preservative the bests, in research, find that the change of this value has appreciable impact for whole Transport result of study.
4, simulation draws Transport and maximum mobility by experiment
For polystream aldehydes matter, preparation 5mg/kg and 10mg/kg positive, for pyrethrin, prepare 50mg/kg and 100mg/kg positive, in simulate saliva and sweat, move 1～10h respectively, bath temperature is decided to be 37 ℃ (human body temperature under regular service condition), the migration amount of each material of sampling and measuring under simulated experiment condition, the results are summarized in Fig. 5 respectively.It should be noted that, the detected level of decis, lower than its quantitative limit, is measured but still converse migration by linear equation, only for reference.
To the data analysis in Fig. 5, show that 10 kinds of materials mainly contain following Transport:
(1) migration 10h is in the time, and each substance rule is out not identical.With the growth of transit time, in sample, the migration amount integral body of polystream aldehydes matter shows a rising trend, and for example 2,4-chlorophenesic acid, the migration amount of the positive of 5mg/kg and 10mg/kg in saliva and perspiration all increases in time and increases.And the migration amount of pyrethrin increases in time and is substantially steady state (SS) in sample, as cyfloxylate.This may be because pyrethrin reaches balance within a short period of time in timber body and migration medium.
(2) the migration amount of the wood preservative that content is identical in sweat obviously will be higher than the migration amount in saliva.As 2,3,4,6-tetrachlorophenol, average migration amount is than high 9.1 times in saliva in sweat for 5mg/kg positive, and 10mg/kg positive is high 8.6 times.Yet for different material, this species diversity is not quite identical, for example migration amount is with almost equal in saliva in sweat for the 5mg/kg positive of lindane, and the migration amount of 10mg/kg positive in sweat is a little more than saliva.
(3), for polystream aldehydes matter, in identical migration medium, the high sample migration amount of wood preservation agent content is apparently higher than the low sample of content.As pentachlorophenol, 10mg/kg positive average migration amount in sweat is higher 2.9 times than 5mg/kg positive, and in saliva, gap is 2.5 times.The rule of pyrethrin in sweat is identical with polystream aldehydes matter, and in saliva, migration amount is subject to the impact of content of material in sample not fairly obvious.
By 10 kinds of actual total contents of material in above-mentioned all positive criteria samples are measured, with all migration numerical quantities, make ratio with corresponding total numerical quantity, draw the mobility of each material in 10h.Wherein each material maximal value of mobility in 10h is listed in table 2 and table 3.
Data in table, it is minimum that the maximum mobility of pyrethrin in 10h is nearly all less than in 1%, 100mg/kg positive the mobility of decis in saliva, only has 0.1%.The mobility of polystream aldehydes matter is obviously high a lot, all more than 3%, individual other as in 10mg/ kg sample 2,4, the maximum mobility of 6-trichlorophenol in sweat even can reach 69%.There is so significant difference, may be relevant with the dissolubility of two class materials in aqueous solution, polystream aldehydes matter is generally slightly soluble in water, if solubleness in pentachlorophenol water is 14mg/L, 2,4, in 6-trichlorophenol water, solubleness is 0.8g/L, and pyrethrin is all insoluble in water, as Permethrin solubleness in water is less than 0.03mg/L, water-soluble hardly under decis normal temperature.
This also can corroborate each other with other experimental result obtaining herein.In Fig. 2, wood preservative is through saliva to wood sample internal penetration, and in the B sample obtaining and C sample, pyrethrin content will be apparently higher than polystream aldehydes matter.Pyrethrin easily through saliva to timber internal penetration, be not easy on the contrary in actual use accordingly to move in human body through saliva, polystream aldehydes matter is easier in saliva migrates to human body.In Fig. 5, polystream aldehydes matter, because solubleness in water is better, with the growth of transit time, is migrated in solution by timber inside gradually, therefore shows a rising trend.And pyrethrin is insoluble in water, increase in time migration amount and be not also significantly increased, may be in timber body and migration medium, to reach balance within a short period of time.
The initial content of polystream aldehydes matter and the maximum mobility in migration medium in table 2 positive
The initial content of pyrethrin and the maximum mobility in migration medium in table 3 positive
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. a research method for wood preservative Transport in Wood children articles for use, is characterized in that: comprise the steps:
(1) the positive criteria sample that contains 10 kinds of wood preservatives by self-control, with the total content of every kind of antiseptic reality in gas chromatography-tandem mass spectrometry working sample;
(2) measure the migration amount of every kind of antiseptic in positive: with low speed cutting machine, cut wood sample top layer 3mm thickness, through beveller, be ground into and be less than 2mm wood chip, accurately take 2g sample in 50mL tool plug test tube, add migration solvent 40mL, described migration solvent is simulate saliva, simulated sweat or water, after 37 ℃, 100r/min Water Under are bathed vibration 1～10h, cross 200 μ m stainless steel screens, obtain migration solution; In described migration solution, add in 1mL and mark working solution, pH value is adjusted to 6, add 1mL acetic anhydride to carry out derivatization, operate about 1min and be 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, 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, after vortex 30s, adopt gas chromatography-tandem mass spectrum detection method to measure;
(3) for the handling characteristics of Wood children articles for use, by setting different experimental simulation conditions, mensuration based on to the total content of every kind of antiseptic in sample and migration amount, the result obtaining is gathered and analyzed, draw maximum mobility and the Transport of every kind of wood preservative in Wood children articles for use.
2. the research method of wood preservative Transport in Wood children articles for use according to claim 1, it is characterized in that: total content and the migration amount of 10 kinds of antiseptic materials in described method while working sample, and simulated conditions are carried out Transport research by experiment, described antiseptic is 2,4 chlorophenesic acids, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, lindane, pentachlorophenol, cypermethrin, cyfloxylate, Permethrin and decis.
3. the research method of wood preservative Transport in Wood children articles for use according to claim 1 and 2, it is characterized in that: step (3) specifically comprises the steps: for polystream aldehydes matter, preparation 5mg/kg and 10mg/kg positive criteria sample, for pyrethrin, prepare 50mg/kg and 100mg/kg positive, in different migration solvents, move 1～10h respectively, bath temperature is decided to be 37 ℃, the migration amount of each material of difference sampling and measuring under simulated experiment condition, result gathers mapping, intuitively migratory behaviour is analyzed; By 10 kinds of actual total contents of material in all positive are measured, calculate the ratio of migration numerical quantity and corresponding total numerical quantity, be the mobility of each material in 10h, wherein each material maximal value of mobility in 10h is maximum mobility, maximum mobility by each material in the positive of comparison different content in difference migration solvent, and compare with result before, finally draw the Transport of 10 kinds of wood preservatives.
4. the research method of wood preservative Transport in Wood children articles for use according to claim 3, it is characterized in that: also comprise the preparation of positive, comprise the steps: blank wood sample to be ground into beveller the wood chip that is less than 2mm, take appropriate wood chip in tool plug round-bottomed flask, in a conical flask, add complete mixed standard solution, and adding 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 standing over night after shaking table vibration 2h, guarantee that antiseptic fully infiltrates into timber inside, then 35 ℃, the steaming of 170hPa backspin, revolve pressure in steaming process and be transitioned into gradually 170hPa by 300hPa, solvent slow evaporation is done near, nearly dry wood chip sample is laid on large surface plate, until solvent volatilizees completely, obtains positive.
5. the research method of wood preservative Transport in Wood children articles for use according to claim 4, it is characterized in that: described interior mark working solution is prepared from by the following method: take 50mg2,3,4-trichlorophenol is in the brown volumetric flask of 100mL, ethanol/glacial acetic acid solution the constant volume that is 9:1 by volume ratio, be mixed with the interior mark storing solution of 500mg/L, being then diluted to concentration is the interior mark working solution of 5mg/L.
6. the research method of wood preservative Transport in Wood children articles for use according to claim 5, is characterized in that:
The preparation method of described simulate saliva is prepared from by the following method: take respectively sodium chloride 4.5g, and potassium chloride 0.3g, sodium sulphate 0.3g, ammonium chloride 0.4g, 90% lactic acid 3.0g, urea 0.2g, is settled to 1000mL with deionized water after mixing, pH ≈ 3;
Described simulated sweat is prepared from by the following method: take respectively sodium bicarbonate 4.2g, and sodium chloride 0.5g, sal tartari 0.2g, is settled to 1000mL with deionized water after mixing, pH ≈ 8.8.
7. the research method of wood preservative Transport in Wood children articles for use according to claim 1, it is characterized in that: step (1) specifically comprises the steps: sample to be crushed to and to be less than 2mm wood chip, accurately take 2g, with the ultrasonic extraction of methyl alcohol 2 times, each 20mL, extract 15min, filtration merging filtrate are to centrifuge tube, add mark working solution in 1mL, at 4 ℃, centrifugal 5min under 13000r/min condition, after 0.45 μ m PTFE membrane filtration, be transferred in heart bottle, 35 ℃, 170hpa backspin inspissation is reduced to 2mL, in concentrate, add 40mL0.1mol/L solution of potassium carbonate, after shaking up, add 1mL acetic anhydride to carry out derivatization, the venting of vibration limit, limit, operate about 1min and be placed on shaking table vibration 10min, by the solution after derivatization by activating through 5mL methyl alcohol in advance, the Oasis HLB solid-phase extraction column of 5mL deionized water balance, 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, after vortex 30s, adopt gas chromatography-tandem mass spectrum detection method to measure.
8. the research method of wood preservative Transport in Wood children articles for use according to claim 1, it is characterized in that: the chromatography-mass spectroscopy condition of described gas chromatography-tandem mass spectrum detection method is: Agilent HP-5MS chromatographic column, specification is 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 ℃ and keep 8min; Solvent delay 5min; 250 ℃ of transmission line temperature; 180 ℃ of ion source temperatures; EI ionizes mode, ionizing energy 70eV, and MRM pattern is measured.
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| CN107525913A (en) * | 2017-08-18 | 2017-12-29 | 张承军 | The detection means and detection method that phosphate plasticizer migrates from fabric to skin |
| CN109187782A (en) * | 2018-09-03 | 2019-01-11 | 必维申优质量技术服务江苏有限公司 | The novel detection method of chlorophenol in textile |
| 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 |
| 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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