CN102866223A - Method for determining benzene and methylbenzene residue in nail polish by utilizing headspace-gas-chromatography mass spectrometry - Google Patents

Abstract

The invention relates to a method for determining the benzene and methylbenzene residue in nail polish, in particular to a method for determining benzene and methylbenzene residue in nail polish by utilizing headspace-gas-chromatography mass spectrometry. The method is characterized by comprising the following steps of (1) processing a test sample; (2) adopting the headspace-gas-chromatography mass spectrometry to determine; (3) carrying out blank test; and (4) calculating and expressing a result. The determination method has following technical effects that the determination method of the benzene and methylbenzene residue in the nail polish is developed for the first time, and the technical blank is filled; an optimum condition for determining the benzene and methylbenzene in the nail polish by utilizing the headspace-gas-chromatography spectrometry is supplied; and the method also can be applied to other cosmetics.

Description

The method of benzene and Residual Toluene in head space-GC-MS mensuration nail polish

Technical field

The present invention relates to the assay method of benzene and Residual Toluene in a kind of nail polish, especially relate to a kind of method that benzene in the nail polish and toluene is quantitatively detected by head space-GC-MS.

Background technology

In recent years, along with the raising of living standards of the people, people are constantly surging to the demand of cosmetics, and China has become the world the 8th, Asia the 2nd large Cosmetic Market.Meanwhile, cosmetics safety has caused people's concern day by day, adds in the cosmetics, residual chemical substance has potential harm to the health of human body.

Benzene and benzene homologues are a series of chemical substances that contain phenyl ring, and benzene is the strong carcinogenic substance of generally acknowledging at present, and other several benzene homologues all have in various degree toxicity to human body.Clear in China's " cosmetics health standard " and " hygienic standards for cosmetics ", benzene is banned substance in the components of cosmetics.Stipulated also in European Union's 76/768 instruction that benzene is banned substance, toluene is that component limits the use of material in the nail polish product.

At present, the assay method of benzene and toluene mainly contains vapor-phase chromatography and GC-MS in the cosmetics.Industry standard SN/T 2933-2011 " detection method of methenyl choloride, benzene, phenixin, trichloronitromethane, nitrobenzene and dichlorotoleune in the cosmetics " has stipulated gas chromatography-mass spectrum and the headspace gas chromatography assay method of benzene in the cosmetics, but it is only applicable to toner, moistens newborn frost and toothpaste type cosmetics; Simultaneously the pertinent literature report is applied to the detection method of benzene and toluene in the cosmetics, also is not suitable for this class matrix of nail polish.

Chinese invention patent application (application number: 201010619377.7 applyings date: 2010-12-31) disclose the rapid assay methods of benzene in a kind of wrappage, toluene and dimethylbenzene organic contaminant, be comprised of following step: wrappage are cut into fragment, put into the sample bottle sealing; The SPME needle tubing is inserted in the sample bottle; The pushing handle bar makes fiber head stretch out the SPME needle tubing, and fiber head places the sample upper space, extraction time 2～30 minutes; Then the retraction fiber head withdraws from needle tubing from sample bottle; The SPME needle tubing is inserted GC instrument injection port; The pushing handle bar stretches out fiber head, and the thermal desorption sample advances chromatographic column; The retraction fiber head is removed the SPME needle tubing; Adopt chromatograph-mass spectrometer to detect, external standard method is quantitative, detects and is limited to 0.001mg/m ²

Chinese invention patent application (application number: 201110167694.4 applyings date: 2011-06-21) disclose a kind of method of measuring benzene and benzene homologues content in the hot melt adhesive.Select benzene, toluene, ethylbenzene, ortho-xylene and p-dimethylbenzene or meta-dimethylbenzene, as the standard items of benzene and benzene homologues, as the matrix correcting fluid, stepwise dilution becomes standard operation solution with glyceryl triacetate.Add the matrix correcting fluid after taking by weighing the hot melt adhesive sample, utilize the static headspace-GC-MS instrument that standard operation solution and sample are detected analysis.Carrying out at last Specification Curve of Increasing and result calculates.This patent has been exempted numerous and diverse sample pretreatment process, has eliminated volatile becomes branch to cause in the sample impact and interference.The method recovery of standard addition is between 95%～101%, and the average relative standard deviation is 3.04%～4.14%, good reproducibility.

Chinese invention patent application (application number: 201110168277.1 applyings date: 2011-06-22) disclose a kind of method of measuring benzene and benzene homologues content in the essence spice for cigarette.Comprise the preparation of interior mark matrix correcting fluid, standard operation solution and sample, utilize the static headspace-GC-MS instrument that standard operation solution and sample are detected analysis, carry out as a result calculating behind the Specification Curve of Increasing.This patent has been exempted numerous and diverse sample pretreatment process, has eliminated impact and interference that the analysis on volatile composition in the sample causes, reduces the error of being brought by pre-treating method reappearance and instrument precision problem.The chromatographic condition that adopts all separates better 5 kinds of target compounds and interior mark chromatographic peak, and detection limit is at 0.91 μ g/kg～1.82 μ g/kg, and recovery of standard addition is 94%～103%, and the average relative standard deviation is 3.9%～4.9%.

Chinese invention patent application (application number: 201110168336.5 applyings date: 2011-06-22) disclose a kind of method of measuring benzene and benzene homologues content in the smoke aqueous gel.Comprise the preparation of interior mark matrix correcting fluid, standard operation solution and sample solution, the steps such as Static Headspace gas phase chromatograph mass spectrum analysis, Specification Curve of Increasing and as a result calculating.Detection method after improving and optimizing have simple to operate accurate, highly sensitive, the recovery is high and the advantage such as good reproducibility.The method utilizes fluorobenzene as interior mark, and inner mark method ration detects, and effectively reduces the error of bringing because of preparation of samples process, different applied sample amount or instrument precision etc.; The chromatographic condition that adopts makes the degree of separation of 5 kinds of target compounds and interior mark chromatographic peak better, and has preferably linear dependence.Detection limit is between 0.40 μ g/kg～0.84 μ g/kg, and quantitative limit is at 21.32 μ g/kg～2.79 μ g/kg, and recovery of standard addition is 95%～101%, and the average relative standard deviation is 0.91%～2.46%.

Summary of the invention

In order to solve the difficult problem that benzene and Residual Toluene detect in the existing nail polish, the purpose of this invention is to provide a kind of utilize head space-GC-MS accurately, the detection method of benzene and Residual Toluene in sensitive, the easy nail polish.

In order to realize above-mentioned purpose, the present invention has adopted following technical scheme:

The method of benzene and Residual Toluene is characterized in that the method comprises the steps: in head space-GC-MS mensuration nail polish

1) sample pretreating: take by weighing 1.0 g samples in 10 mL volumetric flasks, be settled to 10 mL with dimethyl formamide, the vortex mixing is got 1.0 mL, measures for head space-gas chromatography mass spectrometer;

2) measure: adopt head space-GC-MS, wherein:

The head space condition is: holding temperature is 60 ℃, and temperature retention time is 600 s, and the sample introduction needle temperature is 65 ℃, and oscillator speed is 500 rpm;

GC conditions is: chromatographic column is DB-WAX, 30 m * 0.25 mm * 0.25 μ m, Temperature Programmed Processes is 35 ℃ and keeps 5 min, is warming up to 230 ℃ with the programming rate of 30 ℃/min, keeps 3 min, input mode is split sampling, split ratio is 20:1, and injector temperature is 200 ℃, and sample size is 500 mL, carrier gas is helium, and flow velocity is 1.0 mL/min;

The mass spectrum condition is: the ionization mode is electron bombardment ionization source, and bombarding energy is 70 ev, and ion source temperature is 230 ℃, and interface temperature is 280 ℃, and detecting pattern is for selecting ion monitoring;

3) blank test

Except not adding the sample, all undertaken by the said determination step;

4) result calculates and statement

By formula (1) calculates benzene or toluene level in the sample:

………………………（1）

In the formula:

Benzene or toluene level in X-sample, unit is every kilogram of milligram;

C-obtained the concentration of benzene in the sample liquid or toluene by standard working curve, unit is every milliliter of microgram;

V-sample liquid final volume, unit are milliliter;

The sample size of m-final samples liquid representative, unit is gram.

As preferably, above-mentioned selection ion monitoring condition is as follows:

The compound title	Monitor ion
		Benzene	*78，77，52， 51
Toluene	*91，92，65， 51

Wherein, what be with " * " is quota ion, and all the other are qualitative ion.

Assay method of the present invention adopts head space-GC-MS to measure benzene and Residual Toluene in the nail polish, and method is easy, quick, accurate, reliable, and detectability, the recovery and precision all meet the requirements.

Assay method of the present invention has following technique effect:

1) develops first the assay method of benzene and Residual Toluene in the nail polish, filled up technological gap;

2) provide head space-GC-MS to measure the optimal conditions of benzene and toluene in the nail polish;

3) this method also can be applicable to other kind cosmetics.

Description of drawings

Fig. 1 is benzene and toluene standard solution chromatogram, benzene: 0.1 ug/mL; Toluene: 0.2 ug/mL.

Fig. 2 is that the head space holding temperature is on the impact of measured object response.

Fig. 3 is that the head space equilibration time is on the impact of measured object response.

Embodiment

For further specifying the present invention, specify with the following Examples:

1, reagent and material

1.1 dimethyl formamide (DMF): chromatographically pure;

1.2 standard items: benzene (CAS:71-43-2); Toluene (CAS:108-88-3);

1.3 standard reserving solution: take by weighing respectively 0.02 g, 0.04 g benzene, toluene standard items and be settled to 10 mL with DMF to be made into benzene concentration be that 2.0 mg/mL, toluene concentration are the standard reserving solution of 4.0 mg/mL, deposit in 4 ℃ of refrigerators;

1.4 standard operation liquid: as required, standard reserving solution is diluted to the standard operation solution of debita spissitudo with DMF.

2, instrument and equipment

2.1 head space-gas chromatography mass spectrometer;

2.2 vortex oscillator.

3, determination step

3.1 sample pre-treatments

Take by weighing 1.0 g samples in 10 mL volumetric flasks, be settled to 10 mL with dimethyl formamide, the vortex mixing is got 1.0 mL, measures for head space-gas chromatography mass spectrometer;

3.2 measure

3.2.1 head space-gaschromatographic mass spectrometry condition

Because test condition depends on employed instrument, therefore can not provide the general parameter of stratographic analysis.It is suitable adopting following operating conditions to be proved to be test.

⑴ head space condition

A) holding temperature is 60 ℃;

B) temperature retention time is 600 s;

C) the sample introduction needle temperature is 65 ℃;

D) oscillator speed is 500 rpm.

⑵ GC conditions

A) chromatographic column: DB-WAX, 30 m(length) * 0.25 mm (internal diameter) * 0.25 μ m(thickness);

B) column temperature: 35 ℃ (5 min) 30 ℃/min230 ℃ (3 min);

C) input mode: split sampling, split ratio 20:1;

D) sample size: 500 mL;

E) injector temperature: 200 ℃;

F) carrier gas and flow velocity: helium, 1.0 mL/min.

⑶ mass spectrum condition

A) ionization mode: electron bombardment ionization source (EI), bombarding energy 70 ev;

B) ion source temperature: 230 ℃;

C) makings interface temperature: 280 ℃;

D) detecting pattern: select ion monitoring (SIM), condition sees Table 1.

Table 1 is selected the ion monitoring condition

The compound title	Monitor ion
		Benzene	*78，77，52， 51
Toluene	*91，92，65， 51

What be with " * " is quota ion, and all the other are qualitative ion.

3.2.2 blank test

Except not adding the sample, all undertaken by above-mentioned steps.

4, the result calculates and statement

By formula (1) calculates benzene or toluene level in the sample:

………………………（1）

In the formula:

Benzene or toluene level in X-sample, unit is every kilogram (mg/kg) of milligram;

C-obtained the concentration of benzene in the sample liquid or toluene by standard working curve, unit is every milliliter of microgram (μ g/mL);

V-sample liquid final volume, unit are milliliter (mL);

The sample size of m-final samples liquid representative, unit is gram (g).

5, the linear relationship of method and detection limit

5.1 linear relationship

Under the determined experiment condition of this method, get series of standards solution, with the selection quasi-molecular ions area (Y-axis) of benzene or toluene corresponding concentration (X-axis) is mapped.The result shows, benzene concentration is good in 0.04 ~ 1.0 μ g/mL scope internal linear, and related coefficient is 0.9998; Toluene concentration is good in 0.10 ~ 2.5 μ g/mL scope internal linear, and related coefficient is 0.9998.

5.2 detection limit

The inventive method detects for benzene in the nail polish and is limited to 0.4 mg/kg, and toluene detects and is limited to 1.0 mg/kg.

6, the recovery of method and precision

The experiment of this method recovery has been set three and has been added concentration, by the determined experiment condition of this method, each is added concentration carry out 6 experiments, and the recovery and precision the results are shown in Table 2.

The interpolation recovery experiment of benzene and toluene in table 2 nail polish

7, conclusion

Comprehensive above-mentioned situation, all technicals such as the recovery of the inventive method, detection limit and precision all meet the requirements, and method is applied to the nail polish sample detection, and reappearance is good.The method of inspection that the present invention sets up is easy and simple to handle, the result is accurate, can be used for the detection of benzene and toluene in the nail polish.

Emphasis of the present invention is optimized following experiment condition:

1. the selection of solvent

Water, ethyl acetate and dimethyl formamide have been investigated as the solvent effect.Water can not dissolve nail polish, though ethyl acetate can dissolve nail polish, is better than dimethyl formamide with the dissolubility of benzene and toluene, causes easily that reappearance is relatively poor as a result.Adopt the best results of dimethyl formamide.

2. the optimization of head space condition

2.1 temperature

Investigated the impact of different temperatures (35 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃) for benzene and toluene response, as shown in Figure 2.Along with the rising of temperature, response increases.But show on the chromatogram, the impurity peaks response also increases thereupon.Under the condition that satisfies the detection limit requirement, select 60 ℃ of holding temperatures as this method.

2.2 equilibration time

Under 60 ℃ of holding temperatures, oscillator speed 500rpm condition, investigated the impact of head space equilibration time for the measured object response, as shown in Figure 3.The equilibration time scope is in 300 s ~ 1200 s the time, and along with the increase of equilibration time, response there is no marked change, illustrates under this condition, and the equilibration time of 300 s is enough to make measured object to reach balance in gas-liquid two-phase.

Claims (2)

1. the method for benzene and Residual Toluene in head space-GC-MS mensuration nail polish is characterized in that the method comprises the steps:

1) sample pretreating: take by weighing 1.0 g samples in 10 mL volumetric flasks, be settled to 10 mL with dimethyl formamide, the vortex mixing is got 1.0 mL, measures for head space-gas chromatography mass spectrometer;

2) measure: adopt head space-GC-MS, wherein:

The head space condition is: holding temperature is 60 ℃, and temperature retention time is 600 s, and the sample introduction needle temperature is 65 ℃, and oscillator speed is 500 rpm;

GC conditions is: chromatographic column is DB-WAX, 30 m * 0.25 mm * 0.25 μ m, Temperature Programmed Processes is 35 ℃ and keeps 5 min, is warming up to 230 ℃ with the programming rate of 30 ℃/min, keeps 3 min, input mode is split sampling, split ratio is 20:1, and injector temperature is 200 ℃, and sample size is 500 mL, carrier gas is helium, and flow velocity is 1.0 mL/min;

The mass spectrum condition is: the ionization mode is electron bombardment ionization source, and bombarding energy is 70 ev, and ion source temperature is 230 ℃, and interface temperature is 280 ℃, and detecting pattern is for selecting ion monitoring;

Blank test

Except not adding the sample, all undertaken by the said determination step;

4) result calculates and statement

By formula (1) calculates benzene or toluene level in the sample:

………………………（1）

In the formula:

Benzene or toluene level in X-sample, unit is every kilogram of milligram;

C-obtained the concentration of benzene in the sample liquid or toluene by standard working curve, unit is every milliliter of microgram;

V-sample liquid final volume, unit are milliliter;

The sample size of m-final samples liquid representative, unit is gram.

2. head space according to claim 1-GC-MS is measured the method for benzene and Residual Toluene in the nail polish, it is characterized in that selecting the ion monitoring condition as follows:

The compound title Monitor ion Benzene *78，77，52， 51 Toluene *91，92，65， 51

Wherein, what be with " * " is quota ion, and all the other are qualitative ion.

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