CN106324140A - Method for determining migratable Cr(III) and migratable Cr(VI) in toy material simultaneously - Google Patents
Method for determining migratable Cr(III) and migratable Cr(VI) in toy material simultaneously Download PDFInfo
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- CN106324140A CN106324140A CN201610756583.XA CN201610756583A CN106324140A CN 106324140 A CN106324140 A CN 106324140A CN 201610756583 A CN201610756583 A CN 201610756583A CN 106324140 A CN106324140 A CN 106324140A
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- trivalent chromium
- transportable
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Abstract
The invention discloses a method for determining migratable Cr(III) and migratable Cr(VI) in a toy material simultaneously. The method comprises the following steps: a sample is taken from a toy product and placed into a container, then a 0.065-0.075 mol/L hydrochloric acid solution 50 times the mass of the sample is added to the sample, mixed with the sample and uniformly shaken, and the pH value is regulated to 1.1-1.3; the container is sealed and placed in a water bath at 35-39 DEG C, oscillated at a constant temperature for 0.5-1.5 h, left to stand out of the sun for 0.5-1.5 h, filtered by an aqueous filter membrane with the pore diameter of 0.45 mu m and centrifuged at 4,500-5,500 r/min for 8-10 min; a buffer solution with pH of 7.0 and an ammonia-water solution with the pH of 0.7 are added to a centrifuged supernatant and uniformly mixed, the mixture is heated at 45-55 DEG C for 0.5-1.5 h for complexation, and then a liquid chromatography/tandem inductively coupled plasma mass spectrometer is adopted for detection and analysis. With adoption of the method, Cr(III) and Cr(VI) are separated through a liquid chromatographic system, the content of Cr is determined with ICP-MS (inductively coupled plasma mass spectrometry), an analysis effect can be guaranteed, a preprocessing operation process can be simplified, and detection demands of the new Toy Safety Directive of EU for the migration quantity of Cr(III) and Cr(VI) can be met completely.
Description
Technical field
The invention belongs to detection method technical field, particularly relate to one and measure transportable trivalent in toy material simultaneously
Chromium and chromic method.
Background technology
Chromium element in nature generally exists with trivalent chromium and two kinds of forms of Cr VI.Trivalent chromium is that humans and animals is necessary
Trace element, participate in multiple metabolic activity, and more difficult through cell membrane, toxicity is less.Cr VI is chromium element highest price state
Metal ion, be also the maximum existence form of chromium element each valence state toxic.Cr VI has the strongest bio-toxicity, to skin
Skin mucosa has stimulation, can cause dermatitis, eczema, and invade human body by digestive tract, respiratory tract and skin, have cause prominent
Change, carcinogenesis.Trivalent chromium and Cr VI under certain condition can inversion of phases mutually, but chromic toxicity is relative to Cr VI
For much lower, detection trivalent chromium and Cr VI, distinguishes the valence state of chromium element, has great importance the most simultaneously.
In view of trivalent chromium and the difference of Cr VI toxicity, in July, 2013, formally effective European Union's toy safety newly instructed
Harmonized stndard EN71-3 of 2009/48/EC, amount transportable to the Cr VI in toy material proposes the most harsh management and control and wants
Asking: be divided three classes by toy material, in the III class material that can scrape, Cr VI limitation is the highest not can exceed that 0.2mg/kg, at liquid
In body or II sticky type toy material, the highest limitation is that (i.e. limit value in sample extraction liquid is only 0.1 μ to 0.005mg/kg
g/L)；And chromic minimum limitation is respectively 460mg/kg and 9.4mg/kg in III class and II type toy material.
Therefore, in the face of complexity and the chromic ultralow limitation requirement of toy sample material, conventional utilization is wide
ICP method and ultraviolet spectrophotometry all can not meet European Union new toy because of respective limitation and instruct trivalent chromium and six
The testing requirement of valency chromium.
Summary of the invention
The present invention is directed to existing detection technique, the deficiency of method existence, it is provided that one measures in toy material simultaneously and can move
The trivalent chromium moved and chromic method, this kind of method uses liquid chromatographic system to realize trivalent chromium and chromic separation, uses
ICP-MS measures chromium content, both can guarantee that analytical effect, and can simplify again pre-treatment operating process, is entirely capable of meeting the new toy of European Union
The detection instructing amount transportable to trivalent chromium and Cr VI needs.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: one measures simultaneously can in toy material
The trivalent chromium migrated and chromic method, the method step includes:
(1) according to toy material type difference, sample from finished toy；
(2) prepare sample solution: different by material type in toy sample, take the sample no less than 0.1g respectively, put
In container, in sample, then add the hydrochloric acid solution (simulated gastric fluid) of the 0.065-0.075mol/L of sample mass 50 times,
With sample mixed, shaking up, regulation pH value is to 1.1～1.3；
(3) by container closure, being placed in the water-bath of 35-39 DEG C, constant temperature oscillation 0.5-1.5 hour, then lucifuge stands
0.5-1.5 hour, with the water system membrane filtration that aperture is 0.45 μm, then 4500-5500r/min was centrifuged 8～10min (these steps
Transportable chromium element in rapid mainly extraction toy, extracting solution is through filtering and centrifugal, it is ensured that extracting solution does not contains particulate matter)；
(4) take the supernatant after being centrifuged, add buffer and the ammonia spirit of pH7.0 of pH7.0, after mix homogeneously, 45-
55 DEG C of heating carry out complex reaction for 0.5-1.5 hour, then carry out with liquid chromatography tandem icp ms
Detection is analyzed.
Measure transportable trivalent chromium and a kind of improvement of chromic method, step in toy material as the present invention simultaneously
Suddenly the sampling described in (1) is to use the mechanical system cut or scrape to obtain sample from the finished toy of sale, if obtain
Sample is the painting layer on toy, should be placed in the metallic screen that aperture is 0.5mm and screen；If sample be yarn fabric or its
His polymer, the sample of clip should be less than 6mm, to guarantee the extraction effect of sample solution.
Measure transportable trivalent chromium and a kind of improvement of chromic method, step in toy material as the present invention simultaneously
Suddenly (2) add hydrochloric acid solution with 0.07mol/L hydrochloric acid solution with the weight ratio of 1:50 according to sample, shake 1min, check mixing
The acidity of liquid, if containing a large amount of basic matterials in sample, then pH of mixed is much larger than 1.3, adjusts with 6mol/L hydrochloric acid solution
PH to 1.1～1.3；If sample neutral and alkali material is few, pH, again more than 1.3, adjusts pH to 1.1～1.3 with 2mol/L hydrochloric acid.
In the present invention, the collocation method of buffer is: be added to the water mix homogeneously by nitric acid and EDTA-disodium hydrate
Obtain the HNO of final concentration of 0.075M (mol/L)3With 0.6mM mmol/L) the mixed solution of EDTA, then regulate with ammonia
PH value is to 7.0 (being used herein as ammonia is to form acid salt buffer system with nitric acid)；The buffer of pH7.0 in step (4)
It is 8:1 with the volume ratio of the ammonia spirit of pH7.0.
The addition of step of the present invention (4) ammonia spirit is 1:1 with the volume ratio of the addition of supernatant；Add and supernatant
The isopyknic ammonia spirit of liquid is for the pH of neutralising extract (supernatant), and research shows, Cr VI and trivalent chromium are necessarily
Under the conditions of can inversion of phases mutually, between pH6.8--7.1, two kinds of valence states are the most stable；Add buffer, be on the one hand
In order to keep the stability of whole solution system pH, another effect is that the EDTA in buffer can be anti-with trivalent chromium generation complexation
Should, form the trivalent chromium complex existed with anionic form, to realize ion exchange column separation.
Step of the present invention (4) carries out detection with liquid chromatography tandem icp ms and analyzes, wherein liquid
Being configured that in 1L water of the flowing phase of phase chromatograph, adds 71% nitric acid of 5mL, then adjusts pH7.0 to obtain with 25% ammonia
0.075M NH4NO3 solution.
Liquid chromatograph of the present invention is Ultra Performance Liquid Chromatography instrument (Agilent company of the U.S.)；Inductive etc. from
Daughter mass spectrograph (PE company of the U.S.)；Refrigerated centrifuger (Thermo Fisher company of the U.S.)；Ultrapure water machine (U.S. Milli
Poreco company).
Liquid phase chromatogram condition described in invention is: chromatographic column: Agilent Bio-WAX (4.6mm × 50mm, 5 μm)；Post
Temperature: room temperature；Flowing phase: in 1L water, adds 71% nitric acid of 5mL, then adjusts the 0.075M of pH7.0 acquisition with 25% ammonia
NH4NO3Solution；The flow velocity of flowing phase: 0.6mL/min；Sample size: 100 μ L；Analysis time: 3min
Icp ms parameter of the present invention is: RF voltage: 1600W；Pattern: DRC；Reaction
Gas: methane；Reaction gas flow velocity: 1.2mL/min；Secondary air speed: 1.2L/min；Plasma argon flow velocity: 15L/min；Dwell
time:1000s；RPQ:0.7.
Advantages of the present invention and beneficial effect:
1. the method for the present invention have convenient and swift, interference less, qualitative accurately, detection limit low (can as little as 50ng/L) etc. excellent
Point, is entirely capable of meeting the detection demand that transportable trivalent chromium and Cr VI are limited the quantity by European Union's new toy instruction.
2. the present invention overcomes tradition " to use wide ICP method and ultraviolet spectrophotometry all because of respective limitation
And European Union new toy can not be met and instruct trivalent chromium and chromic testing requirement " defect；Because while ultraviolet spectrometry light
Degree method is a kind of chromic method of commonplace indirect determination of using, but but cannot measure trivalent chromium；ICP method can only
Realize the quantitative analysis of chromium element, trivalent chromium and Cr VI can not be distinguished, it is therefore necessary to and separation means combination, first not
Separate with the chromium of form, more successively to the upper detection of spectrum (mass spectrum).Method in the present invention, it is simply that use liquid phase systems to exist
Realize trivalent chromium and chromic separation on anion-exchange column, Cr VI pH more than 6.8 time with anion CrO42-Form
Exist, trivalent chromium and EDTA complexation, form chelate anion [Cr (III)-EDTA]1-, two kinds of ion pairs are in anion exchange
Retention time on post is different, and chromic anion the most out, after the reservation of chromic ion is higher out, then uses ICP-
MS detects Cr52Ion, thus realize trivalent chromium and chromic measure simultaneously.
Accompanying drawing explanation
Fig. 1 is to measure transportable trivalent chromium and chromic analyzing detecting method flow process in toy material of the present invention simultaneously
Figure.
Fig. 2 is to measure transportable trivalent chromium and chromic separation chromatography figure in toy material of the present invention simultaneously.
Fig. 3 is that the trivalent chromium in standard working solution of the present invention is measured, according to concentration and the peak area recorded, drafting
Standard curve.
Fig. 4 is that the Cr VI in standard working solution of the present invention is measured, according to concentration and the peak area recorded, drafting
Standard curve.
Detailed description of the invention
Below with reference to specific embodiment, the present invention and beneficial effect thereof are described in further detail, but, this
Bright detailed description of the invention is not limited thereto.
1, reagent and instrument
1.1 reagent used: it is pure that 30% hydrochloric acid is analytical pure, 71% nitric acid, 25% ammonia is top grade；Diethylamine tetrem
Acid disodium salt dihydrate is chromatographically pure；Cr (III) 1000 μ g/mL, Cr (VI) 1000 μ g/mL standard solution is coloured purchased from country
Metal and electronic material Institute of Analysis.
Configuration buffer solution: in 1L water, adds 0.2233g Na2EDTA salt, is uniformly mixed, and adds
71% nitric acid of 5mL, then pH value determination, adjust pH7.0 with 25% ammonia.
The configuration of flowing phase: in 1L water, adds 71% nitric acid of 5mL, then adjusts pH7.0 with 25% ammonia.
1.2 instruments used: Ultra Performance Liquid Chromatography instrument (Agilent company of the U.S.)；Inductivity coupled plasma mass spectrometry
Instrument (PE company of the U.S.)；Refrigerated centrifuger (Thermo Fisher company of the U.S.)；(U.S. Milli Poreco is public for ultrapure water machine
Department).
2, in toy material transportable trivalent chromium and chromic while assay method (flow chart is as shown in Figure 1)
The pre-treatment (extraction of transportable chromium element) of 2.1 toy sample
Taking commercially available child's down toy, in toy sample, the clip textile material no less than 0.1g, is divided into not
All samples being smaller in size than 6mm under the situation of pressurized.If experimental sample is not commaterial or color, it is necessary to from every kind
The quality detection part no less than 0.1g is taken off on different materials.Weigh the sample of 0.1～0.11g, be placed in triangular flask, then
In sample, add the hydrochloric acid solution (simulated gastric fluid) of the 0.07mol/L of sample mass 50 times, with sample mixed, shake up, regulation
PH value is to 1.1～1.3；Being closed by triangular flask, be placed in 37 DEG C of water-baths, constant temperature oscillation extracts 1 hour, and then to stand 1 little for lucifuge
Time, with 0.45 μm water system membrane filtration, then 5000r/min is centrifuged 10min；Take the supernatant 1mL after being centrifuged, add pH7.0
The ammonia spirit 1mL of buffer 8mL and 0.07mol/L, mix homogeneously, 50 DEG C of heating in water bath carry out complex reaction for 1 hour, so
Carry out detection with liquid chromatography tandem icp ms afterwards to analyze.
2.2 preparation standard working solution
The preparation of standard reserving solution (M1): take the Cr (III) and Cr (VI) standard solution (Cr (III) and Cr of 0.5mL respectively
(VI) in standard solution, the concentration of Cr (III) and Cr (VI) is respectively 1000mg/L), with buffer solution constant volume to 50mL, 50 DEG C
Heating 1h.
The preparation of dilution standard storing solution (M2): take trivalent chromium and the Cr VI M1 storing solution of 0.5mL respectively, by flowing phase
It is diluted to 50mL, is M2.
The preparation of standard working solution: take M2 solution, being diluted to the concentration of Cr (III) and Cr (VI) with buffer respectively is
0.1 μ g/L, 0.2 μ g/L, 0.4 μ g/L, 0.8 μ g/L, 1.0 μ g/L, i.e. obtain the standard working solution of variable concentrations.
2.3 liquid chromatography tandem icp mses measure (HPLC-ICP-MS)
A liquid phase chromatogram condition:
Chromatographic column: Agilent Bio-WAX (4.6mm × 50mm, 5 μm).
Column temperature: room temperature
Flowing phase: 0.075M NH4NO3Solution (in 1L water, adds 71% nitric acid of 5mL, then adjusts with 25% ammonia
pH7.0)
Flow velocity: 0.6mL/min
Sample size: 100 μ L
Analysis time: 3min
B icp ms parameter
RF voltage: 1600W；Pattern: DRC；Reaction gas: methane；Reaction gas flow velocity: 1.2mL/min；Secondary air speed:
1.2L/min；Plasma argon flow velocity: 15L/min；Dwell time:1000s；RPQ:0.7
2.4 transportable chromium constituent content computational methods and detection limit
Respectively the trivalent chromium in standard working solution and Cr VI are measured, according to concentration and the peak area recorded, paint
Standard curve processed, respectively obtains trivalent chromium and chromic standard curve, respectively shown in Fig. 3 and Fig. 4；
Peak area according to component to be measured each in the liquid chromatogram that sample solution records and the standard curve of correspondence thereof, meter
Calculating the concentration of each composition to be measured in sample solution, in sample, the content of determinand is calculated according to following computing formula, knot
Fruit retains 3 position effective digitals.
The computing formula of transportable chromium constituent content in toy:
In formula:
Transportable constituent content, mg/kg in C toy；
F sample liquid extension rate；
The volume of V inspection sample measuring liquid, mL；
C1The content of element, mg in sample liquid (or after dilution)；
C0The content of element, mg in blank solution；
M sample quality, g.
The calculating of detection limit:
The tested component least concentration that can detect in the sample is referred to as detecting limit, typically detection limit is defined as signal to noise ratio
(S/N) concentration during 3:1, computing formula is:
In formula:
D detects limit
Q sample size
Atlas analysis (is typically obtained) by S/N--signal to noise ratio by software workstation
In the present invention, configuration concentration is the trivalent chromium of 0.05 μ g/L, Cr VI mixed standard solution, detects through instrument,
The chromatogram obtained is analyzed by software workstation, and signal to noise ratio S/N is 3.25, therefore calculates detection and be limited to 50ng/L.
2.5 testing result
It is calculated the content of composition to be measured in down toy sample according to step 2.4, as shown in the table, toy difference material
In 3 subsamples that material splits, trivalent chromium content all meets the limitation requirement of European Union toys standard EN71-3 (2013), Cr VI
All do not detect.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out suitable change and amendment.Therefore, the invention is not limited in detailed description of the invention disclosed and described above, to this
Some modifications and changes of invention should also be as falling in the scope of the claims of the present invention.Although additionally, this specification
In employ some specific terms, but these terms are merely for convenience of description, and the present invention does not constitute any restriction.
Claims (9)
1. one kind measures transportable trivalent chromium and chromic method in toy material simultaneously, it is characterised in that the method walks
Suddenly include:
(1) according to toy material type difference, sample from finished toy；
(2) prepare sample solution: different by material type in toy sample, take the sample no less than 0.1g respectively, be placed in appearance
In device, in sample, then add the hydrochloric acid solution of the 0.065-0.075mol/L of sample mass 50 times, with sample mixed, shake
Even, regulation pH value is to 1.1～1.3；
(3) by container closure, being placed in the water-bath of 35-39 DEG C, constant temperature oscillation 0.5-1.5 hour, then lucifuge stands 0.5-1.5
Hour, with the water system membrane filtration that aperture is 0.45 μm, then 4500-5500r/min is centrifuged 8～10min；
(4) take the supernatant after being centrifuged, add buffer and the ammonia spirit of pH7.0 of pH7.0, after mix homogeneously, 45-55 DEG C
Heat 0.5-1.5 hour and carry out complex reaction, then detect with liquid chromatography tandem icp ms
Analyze.
Transportable trivalent chromium and chromic method in the toy material of mensuration simultaneously the most according to claim 1, it is special
Levying and be, the sampling described in step (1) is to use the mechanical system cut or scrape to obtain sample from the finished toy of sale,
If the sample obtained is the painting layer on toy, should be placed in the metallic screen that aperture is 0.5mm and screen；If sample is for spinning
Fabric or other polymer, the sample of clip should be less than 6mm.
Transportable trivalent chromium and chromic method in the toy material of mensuration simultaneously the most according to claim 1, it is special
Levying and be, step (2) adds hydrochloric acid solution with 0.07mol/L hydrochloric acid solution with the weight ratio of 1:50 according to sample, shakes 1min,
Checking the acidity of mixed liquor, if containing a large amount of basic matterials in sample, then pH of mixed is much larger than 1.3, molten with 6mol/L hydrochloric acid
Liquid adjusts pH to 1.1～1.3；If sample neutral and alkali material is few, pH again more than 1.3, with 2mol/L hydrochloric acid adjust pH to 1.1～
1.3。
Transportable trivalent chromium and chromic method in the toy material of mensuration simultaneously the most according to claim 1, it is special
Levying and be, the collocation method of the buffer described in step (4) is: be added to the water mixed by nitric acid and EDTA-disodium hydrate
Close the HNO uniformly obtaining final concentration of 0.075M3With the mixed solution of the EDTA of 0.6mM, then arrive with ammonia regulation pH value
7.0。
Transportable trivalent chromium and chromic method in the toy material of mensuration simultaneously the most according to claim 1, it is special
Levying and be, in step (4), the volume ratio of the ammonia spirit of the buffer of pH7.0 and pH7.0 is 8:1.
Transportable trivalent chromium and chromic method in the toy material of mensuration simultaneously the most according to claim 1, it is special
Levying and be, in step (4), the addition of ammonia spirit is 1:1 with the volume ratio of the addition of supernatant.
Transportable trivalent chromium and chromic method in the toy material of mensuration simultaneously the most according to claim 1, it is special
Levying and be, step (4) carries out detection with liquid chromatography tandem icp ms and analyzes, wherein liquid chromatograph
Flowing is mutually: in 1L water, adds 71% nitric acid of 5mL, then adjusts the 0.075M NH of pH7.0 acquisition with 25% ammonia4NO3Molten
Liquid.
Transportable trivalent chromium and chromic method in the toy material of mensuration simultaneously the most according to claim 1, it is special
Levying and be, described liquid phase chromatogram condition is: chromatographic column: Agilent Bio-WAX (4.6mm × 50mm, 5 μm)；Column temperature: room
Temperature；The flow velocity of flowing phase: 0.6mL/min；Sample size: 100 μ L；Analysis time: 3min.
Transportable trivalent chromium and chromic method in the toy material of mensuration simultaneously the most according to claim 1, it is special
Levying and be, described icp ms parameter is: RF voltage: 1600W；Pattern: DRC；Reaction gas: methane；
Reaction gas flow velocity: 1.2mL/min；Secondary air speed: 1.2L/min；Plasma argon flow velocity: 15L/min；Dwell time:
1000s；RPQ:0.7.
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| CN107576742A (en) * | 2017-09-22 | 2018-01-12 | 广东中测食品化妆品安全评价中心有限公司 | The detection method of trivalent chromium in a kind of health food |
| CN110296949A (en) * | 2018-03-22 | 2019-10-01 | 京东方科技集团股份有限公司 | A method of content of 6-valence Cr ions in measurement electronic apparatus material |
| CN110658319A (en) * | 2019-10-17 | 2020-01-07 | 绍兴市三合检测技术有限公司 | Method for detecting heavy metals in water |
| CN114047306A (en) * | 2021-08-20 | 2022-02-15 | 大连产品质量检验检测研究院有限公司 | Pretreatment mode and detection method for hexavalent chromium and trivalent chromium in food |
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| CN114047306A (en) * | 2021-08-20 | 2022-02-15 | 大连产品质量检验检测研究院有限公司 | Pretreatment mode and detection method for hexavalent chromium and trivalent chromium in food |
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