A kind of micro-wave digestion-ICP-MS measures cosmetics mesoboric acid and boratory method
Technical field
The present invention relates to a kind of cosmetics mesoboric acid and borate content detecting method, especially related to a kind of employing micro-wave digestion-inductivity coupled plasma mass spectrometry (ICP-MS) detection technique and measure cosmetics mesoboric acid and borate Determination on content method.
Background technology
Along with the upgrading of the level of consumption, China's cosmetics industry keeps average annual rapid growth more than 15%, has become the cosmetics production and marketing big country in Asia second, the world the 7th, and the cosmetics safety problem also more and more causes global attention.In recent years, along with new synthesizing with newfound chemical substance continues to bring out, limit with the growth rate of material kind very fast.But accurately the growth of quantitative detecting method but can not adapt to the growth rate that limits with material, particularly still can not give qualification for limiting with the content of material of bringing from raw material.Both at home and abroad in Cosmetic Manufacture to limiting use and health of bringing thus and environmental impact with material, become the major issue that concerns people ' s health, social stability even influence international trade relations.China is to the deposit of cosmetic standard detection method, be only limited at present stipulate in " cosmetics health standard " and GB, the rower method less than five, 60 kind, can not satisfy the needs that cosmetics are imported and exported and domestic production sale safety is checked on far away, more can not satisfy the demand of developing new product and integrating with international cosmetics industry.
Boron is to exist with the form of boric acid and borate (borax) in cosmetics, and boric acid is monobasic weak acid, for colourless, odorless, transparent crystalline powder, is slightly soluble in cold water, raises with temperature, and its solubleness obviously increases.Borax, promptly sodium tetraborate is most important borate, is colourless transparent crystal, solubleness is very big in water, and along with its solubleness of rising of temperature increases.Boric acid and borate have the anti-corrosive antibacterial ability, are widely used in being added in liquid astringent, prickly-heat powder, talcum powder, oral-cavity article and the hair-waving product.But it has certain toxicity, can be percutaneous the surface of a wound absorb or suck and cause poisoning, cause feeling sick, erythema and amentia etc., therefore classified as and limit the use of material by China and European Union.Regulation in " the cosmetics health standard " of China 2007 editions, the maximum consumption of talcum powder mesoboric acid is 5%, is 0.1% in the dental health product, is the forbiddings of articles for children below 3%, three years old in the other products (take a shower and hair-waving product except).
Existing China has only announced cosmetics mesoboric acid and boratory azomethine-H spectrophotometry in " cosmetics health standard " 2007 editions, domestic does not still have the open national standard and an industry standard method of inspection of approving.The domestic document of delivering is very few, mainly is these three kinds of methods of azomethine-H spectrophotometry, curcumin spectrophotometric method and potentiometric titration, and operational processes complex steps, sensitivity are low, stable, the problem of poor reproducibility but all exist.At present, do not inquire the bibliographical information that relevant micro-wave digestion-ICP-MS detection technique is measured cosmetics mesoboric acid and borate content.
Summary of the invention
The operational processes complex steps, the sensitivity that have the existence of method determination method now are low, stable in order to overcome, the technological deficiency of poor reproducibility, the purpose of this invention is to provide a kind of micro-wave digestion-ICP-MS and measure cosmetics mesoboric acid and boratory method.This method has strong, highly sensitive, the characteristic of accurate as a result of specificity.
In order to realize above-mentioned purpose, the present invention adopts following technical scheme:
A kind of micro-wave digestion-ICP-MS measures cosmetics mesoboric acid and boratory method, and this method comprises the steps:
1. choose the about 0.5~1g of cosmetic sample, mixing places jar in the micro-wave digestion;
2. 1. adding 4mL nitric acid in the described cosmetic sample, the 1mL30% hydrogen peroxide makes the abundant submergence of sample, puts microwave digestion system and clears up;
3. after treating the counteracting tank cooling, water repeatedly washes solution in the 50mL volumetric flask on a small quantity, is settled to scale, mixing;
4. preparation standard solution: use boron standard inventory solution, it is 0 μ g/L that the nitric acid stepwise dilution with 2% becomes concentration, 5 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L, the boron standard solution of 200 μ g/L;
5. draw calibration curve: under the icp ms condition of work of setting, adopt the online interior mark of beryllium standard operation solution to add, the abundance of ions of boron element is measured in the positive quantitative analysis method of interior calibration, interior mark beryllium working concentration is 10 μ g/L, concentration with boron element is horizontal ordinate, abundance of ions with boron element is an ordinate, instrument computer automatic drafting boron element calibration curve;
6. the 5. 3. abundance of ions of boron element and interior mark beryllium element in the sample solution of method determination step set by step, according to the response that the ratio of mark response in marking response and expect in the actual measurement beryllium is proofreaied and correct boron element, the calibration curve of use gained calculates the boron content in the cosmetic sample;
7. the result is calculated as follows:
Cosmetics mesoboric acid and boratory content are with X
iExpression, calculate by formula (1):
In the formula:
X
i---the massfraction of cosmetics mesoboric acid and borate content, unit are mg/kg;
C
i---the concentration of tested element in the sample solution, unit is μ g/L;
C
I0---the concentration of tested element in the blank solution, unit is μ g/L;
V---constant volume in the sample solution, unit are mL;
The quality of m---sample, unit is g;
F---boron is scaled the coefficient of boric acid or borax, and the boric acid coefficient is 5.72, and the borax coefficient is 8.83.
As optimized technical scheme, the 2. middle microwave digestion system of described step is cleared up program and is made of following two steps:
Step |
Power (W) |
Heating-up time (min) |
Temperature (℃) |
Retention time (min) |
Step1 |
1600 |
5 |
120 |
2 |
Step2 |
1600 |
9 |
195 |
30. |
As optimized technical scheme, described step is the concrete steps of middle preparation standard solution 4.: accurately draw 1.0mL boron standard inventory solution in the plastics volumetric flask of 100mL, be settled to scale with the dilution of 2% salpeter solution, be mixed with the standard operation solution that is equivalent to every milliliter 10 μ g boron earlier.Draw boron standard operation liquid 0,50,200,500,2000 μ L respectively in 100mL plastics volumetric flask, be settled to scale with 5% salpeter solution, solution concentration is equivalent to every liter 0,5 in the volumetric flask, 20,50,100,200 μ g boron.
As optimized technical scheme, described step 5. in the condition of work of icp ms as follows:
Project |
Running parameter |
Plasma jet |
18L/min |
The assist gas flow |
1.8L/min |
The refrigerating gas flow |
0.17L/min |
Carrier gas flux |
0.96L/min |
Sampling depth |
7.5mm |
Plasma RF power |
1.4kw |
Sample introduction stabilization time |
20s |
One-level is extracted lens |
-2V |
Secondary extracts lens |
-171V |
Three grades of extraction lens |
-200V |
The corner lens |
-220V |
Pump speed | 4rpm |
Count |
|
1 |
Scanning times |
30 |
Multiplicity |
5 |
Measuring Time |
0.43s. |
As optimized technical scheme, container is plastic containers in the described assay method, and spends the night through 20% nitric acid dousing.Because boron has very strong memory effect in the testing process, should thoroughly clean instrument sample introduction and atomization system before detecting.
Among the present invention with cosmetic sample through nitric acid, behind the hydrogen peroxide micro-wave digestion, organism is decomposed, sample solution is imported icp ms (ICP-MS) atomizer, be written into the high temperature high-frequency plasma by argon gas, ionization takes place, produce ion, enter mass spectrometer after the ion focus, the characteristic ion abundance of boron element and online interior mark beryllium element in the test sample solution, the characteristic ion abundance of boron element is directly proportional with the content of boron element, according to surveying mark response and the response of expecting that the interior ratio of marking response is proofreaied and correct boron element in the beryllium, calibration directrix curve method is carried out quantitative measurement in adopting, calculate the content of boron element in the cosmetics, obtain boric acid and boratory content by reduction coefficient again.
The present invention has overcome the defective of prior art, it is strong to have set up a kind of specificity, highly sensitive, the result is accurate, adopt the method for micro-wave digestion-icp ms (ICP-MS) technical measurement cosmetics mesoboric acid and borate content, make pre-treatment more easy, fast, fully, the recovery improves greatly, component to be measured is vulnerable to pollution not, be difficult for loss, and adopt the ICP-MS spectral line simple, detecting pattern is flexible, simple operating steps, the accuracy height, detection limit is low, various interference are few, detect lower bound and reach 2.0mg/kg, the recovery is 94.3%~102.6%, relative standard deviation≤2.5%, be enough to satisfy the minimum requirements of the current international practice, be applicable to the detection of cosmetics safety health project.
The present invention has filled up the technological gap of domestic micro-wave digestion-inductivity coupled plasma mass spectrometry technology in cosmetics mesoboric acid and borate detection; harmful material detection technique new standard that limits the use of has the meaning that weighs very much the people in the cosmetics for formulating; to protection human body health, promote China's cosmetics industry sound development and foreign trade promotion to have very realistic meanings simultaneously.
Description of drawings
Fig. 1 is the calibration curve of boron, and B is the boron concentration of standard solution among the figure, and I is the abundance of ions of boron element,
I=48712.8+11830×B,r=0.9999。
Fig. 2 is the abundance of ions figure of 200 μ g/L concentration boron.
Embodiment
1. use instrument and instrument condition
1.1 use instrument: icp ms (ICP-MS), model: VARIAN 820MS.
1.2 the instrument condition of work sees Table 2..
2. use reagent:
2.1 it is pure that agents useful for same is top grade, experimental water is the one-level water that meets regulation among the GB/T 6682.
2.2 nitric acid (ρ 1.42g/mL); Hydrogen peroxide (30% aqueous solution).
2.3 boron standard inventory solution: with national standard reagent (GBW), concentration is 1000 μ g/mL.
2.4 beryllium standard inventory solution: with national standard reagent (GBW), concentration is 1000 μ g/mL.
2.5 boron standard operation liquid: accurately draw 1.0mL boron standard inventory solution (GBW) in the volumetric flask of 100mL, be settled to scale with the dilution of 5% salpeter solution, this standard inventory solution is equivalent to every milliliter 10 μ g boron.
3. Specimen eliminating
Take by weighing about 0.5~1.0g sample (being accurate to 0.001g), place jar in the micro-wave digestion, add 4.0mL nitric acid (look the decision of Specimen eliminating complexity and whether need soak placement), and then add hydrogen peroxide 1.0mL, make the abundant submergence of sample.Put microwave digestion system and clear up, clear up program and see Table 1.
Table 1. micro-wave digestion device is cleared up program
Step |
Power (W) |
Heating-up time (min) |
Temperature (℃) |
Retention time (min) |
??Step1 |
??1600 |
??5 |
??120 |
?2 |
??Step2 |
??1600 |
??9 |
??195 |
??30 |
After treating the counteracting tank cooling, water repeatedly washes solution in the 50mL volumetric flask on a small quantity, is settled to scale, mixing.
4. calibration curve is drawn
Draw boron standard operation liquid 0,50,200,500,2000 μ L respectively in the 100mL volumetric flask, be settled to scale with 2% salpeter solution, solution concentration is equivalent to every liter 0,5 in the volumetric flask, 20,50,100,200 μ g boron.
Series standard solution imported in the instrument atomization system transfer to top condition measure.Concentration with boron element is horizontal ordinate, is ordinate instrument computer automatic drafting typical curve with the abundance of ions of boron element.
5. sample determination
Under table 2. condition, will measure in sample solution and the reagent blank liquid importing instrument atomization system.
The operating condition reference of table 2. instrument
Project |
Running parameter |
Plasma jet |
??18L/min |
The assist gas flow |
??1.8L/min |
The refrigerating gas flow |
??0.17L/min |
Carrier gas flux |
??0.96L/min |
Sampling depth |
??7.5mm |
Plasma RF power |
??1.4kw |
Sample introduction stabilization time |
??20s |
One-level is extracted lens |
??-2V |
Secondary extracts lens |
??-171V |
Three grades of extraction lens |
??-200V |
The corner lens |
??-220V |
Pump speed |
??4rpm |
Count |
??1 |
Scanning times |
??30 |
Multiplicity |
??5 |
Measuring Time |
??0.43s |
The intensity rate of boron element and internal standard element and working curve are relatively obtained boron content in the cosmetic sample.Converse cosmetics mesoboric acid and boratory content by computing formula as a result again.
The result is calculated as follows:
Cosmetics mesoboric acid and boratory content are with X
iExpression, calculate by formula (1):
In the formula:
X
i---the massfraction of cosmetics mesoboric acid and borate content, unit are every kilogram of milligram, mg/kg;
C
i---the concentration of tested element in the sample solution, unit is every liter of a microgram, μ g/L;
C
I0---the concentration of tested element in the blank solution, unit is every liter of a microgram, μ g/L;
V---constant volume in the sample solution, unit are milliliter, mL;
The quality of m---sample, unit is gram, g;
F---boron is scaled the coefficient of boric acid or borax, and the boric acid coefficient is 5.72, and the borax coefficient is 8.83.
Result of calculation keeps three position effective digitals.
It is 2.00mg/kg that cosmetics mesoboric acid of the present invention and borate detect lower bound, by white class cosmetic sample recovery of standard addition is tested, the recovery is 94.3%~102.6%, relative standard deviation≤2.5%, meet the requirement of GB/T27404-2008, prove the feasibility of above-mentioned detection method.The inventive method satisfies the minimum requirements of the current international practice, is applicable to the detection of cosmetics safety health project.