CN109142325A - The uncertainty analysis model and its method for building up of ICP-MS method measurement capsule heavy metal - Google Patents
The uncertainty analysis model and its method for building up of ICP-MS method measurement capsule heavy metal Download PDFInfo
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Abstract
The present invention relates to the uncertainty analysis models and its method for building up of a kind of ICP-MS method measurement capsule heavy metal, belong to Inductively coupled plasma mass spectrometry method detection technique field.Method includes the following steps: data acquisition: design recovery test with the content of heavy metal element in ICP-MS method measurement gelatin hollow capsule recovery test, and collects data；Model foundation: according to contents of heavy metal elements calculation formula, analyzing uncertainty source, establish measurement model, evaluation and calculating uncertainty.The above method passes through design recovery test, resettle measurement model, evaluation and calculating uncertainty, the uncertainty analysis model of ICP-MS method measurement capsule heavy metal, it analyzes with each factor that can influence testing result in the measurement capsule content of beary metal test of ICP-MS method, the control to major influence factors can then be reinforced, to reduce the unstability of measurement, ensure the reliability of measurement result.
Description
Technical field
The present invention relates to Inductively coupled plasma mass spectrometry method detection technique fields, survey more particularly to a kind of ICP-MS method
Determine the uncertainty analysis model and its method for building up of capsule heavy metal.
Background technique
Gelatin hollow capsule is made of pharmagel, can accommodate various solids, liquid etc., is easy to swallow, and dissolve rapidly.
The drug control law regulation in China, the gelatin for capsule manufacture must not use industrial gelatine.But the illegal manufacturer in part makes in recent years
With industrial manufacturing of gelatin capsule for medicine, exceeded more than 90 times of chromium in part of product.Chromium is that one kind is harmful to the human body
Heavy metal element, especially Cr VI have damage liver, kidney poisonous effect." Chinese Pharmacopoeia (version in 2015) " two regulations,
Gelatin hollow capsule must not cross 2/1000000ths containing chromium.
The measuring method of chromium has " Chinese Pharmacopoeia (version in 2015) " four 0406 general rule atoms in gelatin hollow capsule at present
Absorptiometry and " Chinese Pharmacopoeia (version in 2015) " four 0412 inductively coupled plasma mass spectrometries.
But the relatively evaluation Atomic absorption point of the document due to evaluating chromium content in ICP-MS measurement gelatin hollow capsule at present
Light photometry is lacked, and the sample pretreatment process of this method and continuous mode are complex, and impacted factor is more, because
This, needs based on measurement System Analysis and Error Tracing &, uncertainty evaluation is carried out to measuring system, to reflect measurement result
Accuracy, to judge that the accuracy of testing result provides scientific basis.
Summary of the invention
Based on this, it is necessary in view of the above-mentioned problems, providing a kind of uncertainty point of ICP-MS method measurement capsule heavy metal
The method for building up of model is analysed, the uncertainty analysis model established using this method can will affect each of testing result
The control that factor is reinforced after being analyzed to major influence factors ensures measurement result to reduce the unstability of measurement
Reliability.
A kind of method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal, comprising the following steps:
Data acquisition: design recovery test, with heavy metal in ICP-MS method measurement gelatin hollow capsule recovery test
The content of element, and collect data；
Model foundation: it according to contents of heavy metal elements calculation formula, analyzes uncertainty source, establish measurement model, comment
Fixed and calculating uncertainty.
The present inventor divides ICP-MS method measurement capsule heavy metal test process on the basis of long term test experience
Think after analysis, the key step of the detection process includes sample weighing, treatments of the sample, dilution constant volume, instrument analysis etc..Wherein sample
The uncertainty of product digestion is the most complicated, selects different pretreatment modes such as micro-wave digestion and wet digestion, acquisition not really
Surely degree component is also different, therefore can be assessed by recovery test.
On this basis, the above method resettles measurement model by design recovery test, and evaluation and calculating are uncertain
Degree, ICP-MS method measure the uncertainty analysis model of capsule heavy metal, to the measurement capsule content of beary metal examination of ICP-MS method
Each factor that testing result can be influenced in testing is analyzed, and can then reinforce the control to major influence factors, to reduce
The unstability of measurement ensures the reliability of measurement result.
In one of the embodiments, in the data acquisition step, the ICP-MS method method for measuring includes:
The preparation of test solution: weighing gelatin hollow capsule sample m g, in a manner of micro-wave digestion or wet digestion into
Row pre-treatment, is settled to VmL, obtains test solution, and prepare placebo solution simultaneously, is settled to VmL；
The preparation of calibration curve solution: heavy metal standard items to be measured are taken, the standard solution of series of concentrations is configured；
Upper machine testing: the test solution, placebo solution and calibration curve solution are imported into ICP-MS detection, obtained
The heavy metal concentration C into test solution, heavy metal concentration C in placebo solution0；
Content of beary metal calculates: content of beary metal X is calculated according to the following formula,
In formula, X: the content of heavy metal in sample；C: the concentration of heavy metal in test solution；C0: placebo solution
The concentration of middle heavy metal；V: constant volume；M: weighed sample size；N: conversion multiple.
When the unit of above-mentioned X is mg/kg, the unit of C is μ g/L；C0Unit be μ g/L；The unit of V is mL；The unit of m
For g；Then n is 1000.
The specific steps that pre-treatment is carried out in a manner of micro-wave digestion in one of the embodiments, are as follows: weigh through
The sample of crushing is added standard items and carries out recovery of standard addition test in micro-wave diminishing pot, while doing blank control, and nitre is added
Acid, in 90-110 DEG C of pre- resolution 25-35min on graphite resolution instrument, after in being cleared up in microwave dissolver, after by micro-wave digestion
Tank, which is put, catches up with sour 1.5-2.5h on graphite resolution instrument, is rinsed with water and is transferred in centrifuge tube, constant volume；
The specific steps that pre-treatment is carried out in a manner of wet digestion are as follows: weigh the sample through crushing in digestion tube
In, standard items are added and carry out recovery of standard addition test, while doing blank control, nitric acid is added, in 80-100 on graphite resolution instrument
DEG C pre- resolution 25-35min, after be warming up to 125-145 DEG C of resolution 0.5-1.5h, 150-180 DEG C is continuously heating to later, up to disappearing
Solution is to 1~2mL, constant volume.
Pre-treatment is carried out in the above described manner, and there is preferable detection effect.
In one of the embodiments, in the preparation step of the calibration curve solution, the series of concentrations is 0-30 μ g/
L.It will test concentration control within the above range, preferable detection effect can be obtained.
The heavy metal is chromium in one of the embodiments, in the upper machine testing step, the ICP-MS detector bar
Part is as follows.
Chromium is detected with above-mentioned condition, there is preferable survey effect.
In one of the embodiments, in the model foundation step, the measurement model are as follows:
Y=f (X1,X2,X3,X4,X5,X6,X7)
In formula, Y:ICP-MS method measures the uncertainty of capsule heavy metal；X1: the uncertainty introduced using standard items；
X2: the uncertainty introduced using balance；X3: the uncertainty introduced using measurer；X4: it is introduced using ICP-MS uncertain
Degree；X5: the uncertainty that standard curve fit introduces；X6: the uncertainty that Specimen eliminating introduces；X7: reagent blank introduces not
Degree of certainty；
It is expressed as formula:
In formula, urel(X): the uncertainty of ICP-MS method measurement capsule heavy metal；urel(Cs): being introduced using standard items
Uncertainty；urel(m): the uncertainty introduced using balance；urel(V): the uncertainty introduced using measurer；urel(instrument):
The uncertainty introduced using ICP-MS；urel(C): the uncertainty that standard curve fit introduces；urel(pre-treatment): sample disappears
Solve the uncertainty introduced；urel(blank): the uncertainty that reagent blank introduces.
It with above-mentioned model analysis uncertainty, traces to the source with multifactor, is convenient for Comprehensive Assessment influence factor, deeply relatively divides
The advantages of analysing different resolution modes, being convenient for control key influence factor.The present inventor is by measuring a capsule huge sum of money to ICP-MS method
Belong to test process to be analyzed and found after being groped, the uncertainty of this experiment is mainly derived from above-mentioned aspect, with above-mentioned source
Uncertainty to ICP-MS method measurement capsule heavy metal test carry out analyzing evaluation, can comprehensively, objectively respond influence detection
As a result each factor.
The uncertainty introduced using balance includes: that the calibration of balance introduces not in one of the embodiments,
Degree of certainty and the uncertainty for weighing repeatability introducing；
The uncertainty introduced using measurer includes: that the uncertainty that sample constant volume generates and standard curve draw
The uncertainty entered；The uncertainty that the sample constant volume generates includes: the uncertainty of the introducing of volumetric flask volume, determines
Hold the uncertainty of the uncertainty and temperature difference generation that generate to the mobility of scale；The standard curve introduces not true
Fixed degree includes: that the uncertainty that standard solution introduces and standard series prepare the uncertainty introduced.
The uncertainty introduced using Inductively coupled plasma mass spectrometry includes: instrument in one of the embodiments,
The uncertainty that the uncertainty and sample duplicate measurements that the calibration of device introduces introduce.
To uncertainty source it is further refinement and it is perfect, can more comprehensively, objectively respond influence testing result it is each
Kind factor.
Before being carried out in a manner of micro-wave digestion or wet digestion to gelatin hollow capsule sample in one of the embodiments,
Processing, respectively synthesizes the uncertainty under Microwave Digestion and wet digestion method, respectively obtains Microwave Digestion and wet
Synthesis relative standard uncertainty under method resolution method, and analyze and obtain the expanded uncertainty and wet digestion of Microwave Digestion
The expanded uncertainty of method.By above-mentioned analysis, more preferably suitable pretreatment mode can be selected according to result, to improve detection
As a result accuracy and reliability.
The invention also discloses the uncertainties point for the ICP-MS method measurement capsule heavy metal that above-mentioned method is established
Analyse model.
Compared with prior art, the invention has the following advantages:
The method for building up of the uncertainty analysis model of a kind of ICP-MS method measurement capsule heavy metal of the invention, by setting
Recovery test is counted, measurement model, evaluation and calculating uncertainty are resettled, ICP-MS method measures the uncertain of capsule heavy metal
Analysis model is spent, is divided with each factor that can influence testing result in the measurement capsule content of beary metal test of ICP-MS method
Analysis, can then reinforce the control to major influence factors, to reduce the unstability of measurement, ensure the reliable of measurement result
Property.
Detailed description of the invention
Fig. 1 is uncertainty source analysis Cause and Effect matrix in embodiment.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give presently preferred embodiments of the present invention.But the invention can be realized in many different forms, however it is not limited to this paper institute
The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more thorough
Comprehensively.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Instrument and reagent are as follows in following embodiment:
Instrument: icp ms Agilent ICP-MS 7800；Miniport ultrapure water machine；ETHOS
One microwave dissolver；(5-50) μ L/MZ34895 adjustable pipette；(20-200) μ L/NZ45999 adjustable pipette；(100-
1000) μ L/NZ53342 adjustable pipette；Graphite clears up instrument DS-360；Microwave dissolver.
Reagent: nitric acid；Hydrogen peroxide is excellent pure grade, GBW08614 chromium single element standard substance solution: 1000mg/L, China
Metering scientific research institute；Gelatin hollow capsule is provided by Guangzhou medicine company factory.Water is level-one water as defined in GB/T 6682.
Embodiment
A kind of uncertainty analysis model of ICP-MS method measurement capsule heavy metal (chromium), is established by the following method:
One, data acquisition.
1 measurement method.
The preparation of 1.1 test solutions.
1.1.1 micro-wave digestion.
The uniform gelatin hollow capsule sample 0.2500g through crushing is weighed in polytetrafluoroethylene (PTFE) inner canister, while doing two parts
5mL nitric acid is added in blank control, in 100 DEG C of pre- resolution 30min on graphite resolution instrument, after in being cleared up in microwave dissolver, terminate
Polytetrafluoroethylene (PTFE) inner canister is put afterwards and catches up with sour 2h on graphite resolution instrument, is rinsed and is transferred in 25mL centrifuge tube three times with level-one water, it is cold
But, constant volume, ICP-MS detection to be imported.
1.1.2 wet digestion.
The uniform gelatin hollow capsule sample 0.2500g through crushing is weighed in digestion tube, while doing two parts of blank controls,
10mL nitric acid is added, in 90 DEG C of pre- resolution 30min on graphite resolution instrument, after be warming up to 135 DEG C of resolution 1h, be continuously heating to later
160 DEG C, until resolution, to 1~2mL, cooling is settled to 25mL, ICP-MS detection to be imported with level-one water.
The preparation of 1.2 standard curves.
The chromium single element standard solution that 100 μ L concentration are 1000 μ g/mL is accurately drawn using pipettor, it is fixed with 1% nitric acid
It is dissolved in 10mL volumetric flask, the chromium standard reserving solution that concentration is 10 μ g/mL is made.Face the used time and accurately draws 1mL chromium with pipettor
Standard reserving solution is made among the chromium standard that concentration is 1 μ g/mL with 1% nitric acid constant volume in 10mL volumetric flask and uses liquid.Point
It Shi Yong not be filled in using 0 μ L of liquid, 10 μ L, 40 μ L, 100 μ L, 150 μ L, 200 μ L in 10mL tool among pipettor precision absorption chromium standard
In colorimetric cylinder, chromium concn is respectively 0 μ g/L, 1 μ g/L, 4 μ g/L, 10 μ g/L, 15 μ g/L, 20 μ in this serial chromium standard solution
g/L。
Machine testing on 1.3.
Above-mentioned test solution, placebo solution and calibration curve solution are imported into ICP-MS detection, obtain test sample
Heavy metal concentration C in solution, heavy metal concentration C in placebo solution0。
Upper machine testing condition is as shown in table 1.
1 ICP-MS work station instrument parameter of table
1.4 content of beary metal calculate.
The calculation formula of chromium content are as follows:
In formula, X: the content of chromium in sample, unit mg/kg；C: the concentration of chromium in digestive juice, unit μ g/L；C0: blank is molten
The concentration of chromium in liquid, unit μ g/L；V: constant volume, Unit/mL；M: weighed sample size, unit g.
Two, model foundation.
1, it analyzes, establish model.
Analysis continuous mode can be seen that the test of chromium in above-mentioned ICP-MS method measurement capsule, and key step includes
Sample weighing, treatments of the sample, dilution constant volume, instrument analysis etc..Wherein the uncertainty of treatments of the sample is the most complicated, and selection is different
Pretreatment mode such as micro-wave digestion and wet digestion, the partial uncertainty of acquisition is also different, therefore can pass through recycling
Rate is tested to assess.
Therefore, through analyzing, the uncertainty of this experiment is mainly derived from the following aspects: a, using standard items introducing
Uncertainty；B, the uncertainty introduced using balance；C, the uncertainty introduced using measurer；D, using inductive coupling etc. from
The uncertainty that sub- mass spectrograph introduces；E, the uncertainty that standard curve fit introduces；F, the uncertainty that Specimen eliminating introduces；
G, the uncertainty that reagent blank introduces.Uncertainty source analysis Cause and Effect matrix is as shown in Figure 1.
Establish following measurement model:
Y=f (X1,X2,X3,X4,X5,X6,X7)
In formula, Y:ICP-MS method measures the uncertainty of capsule heavy metal；X1: the uncertainty introduced using standard items；
X2: the uncertainty introduced using balance；X3: the uncertainty introduced using measurer；X4: it is introduced using ICP-MS uncertain
Degree；X5: the uncertainty that standard curve fit introduces；X6: the uncertainty that Specimen eliminating introduces；X7: reagent blank introduces not
Degree of certainty.It can be expressed as formula:
In formula, urel(X): the uncertainty of ICP-MS method measurement capsule heavy metal；urel(Cs): being introduced using standard items
Uncertainty；urel(m): the uncertainty introduced using balance；urel(V): the uncertainty introduced using measurer；urel(instrument):
The uncertainty introduced using ICP-MS；urel(C): the uncertainty that standard curve fit introduces；urel(pre-treatment): sample disappears
Solve the uncertainty introduced；urel(blank): the uncertainty that reagent blank introduces.
2, the evaluation of partial uncertainty.
2.1 uncertainties introduced using standard items.
The chromium single element standard solution (1000mg/L) used is measured, the expanded uncertainty that certificate provides is 2mg/L,
Fiducial probability is 95%, Coverage factor k=2.
Therefore, standard uncertainty are as follows: u (Cs)=2/2=1mg/L；Relative standard uncertainty are as follows: urel(Cs)=1/
1000=0.001.
2.2 uncertainties introduced using balance.
2.2.1 the uncertainty that the calibration of balance introduces.
Sample 0.5000g is weighed using the assay balance of a ten thousandth, the error of indication that balance calibration certificate provides is ±
0.00005g, obeys distributed rectangular, and Coverage factor isIt is converted into standard uncertainty are as follows:Relative standard uncertainty is uref(m)1=2.89=10-5/ 0.5=5.77 × 10-5。
2.2.2 the uncertainty that repeatability introduces is weighed.
The balance repeatability standard deviation 0.1mg that calibration certificate provides, obeys distributed rectangular, and Coverage factor isIt is converted into
Standard uncertainty are as follows:Relative standard uncertainty are as follows:
urel(m)2=5.77 × 10-5/ 0.5=1.15 × 10-4。
Therefore the relative standard uncertainty for using balance to introduce are as follows: urel(m)=1.29 × 10-4。
2.3 uncertainties introduced using measurer.
Mainly include standard solution and test solution are measured using measurer, constant volume when the uncertainty that introduces.
2.3.1 the uncertainty u that sample constant volume generatesrel(sample V).
2.3.1.1 the A class uncertainty of the introducing of volumetric flask volume.
According to " JJG 196-2006 often uses volumetric glass vertification regulation " pertinent regulations, at 20 DEG C, 25mLA level capacity bottle
Volume error is ± 0.03mL, is calculated by being uniformly distributed, and Coverage factor isThus the standard uncertainty introduced are as follows:
2.3.1.2 it is settled to the B class uncertainty that the mobility of scale generates.
As shown in table 2, by repeating to weigh 10 times, statistics obtains urel(sample V2)。
Table 2 duplicate measurements, 10 results
Relative standard uncertainty are as follows:
2.3.1.3 the A class uncertainty that temperature difference generates.
Ambient laboratory conditions are 20 DEG C ± 3 DEG C, and the coefficient of expansion of water volume is 2.1 × 10-4℃-1, glass volume it is swollen
Swollen coefficient is 2.5 × 10-5℃-1, therefore the volume change generated are as follows: Δ V=25 × (2.1 × 10-4-2.5×10-5) × 3=
0.0139mL, the uncertainty that temperature effect introduces are as follows:
The relative standard uncertainty for showing that sample constant volume generates: u is synthesized by above threerel(sample V)=8.01 ×
10-4。
2.3.2 the B class uncertainty u that standard curve introducesrel(mark).
2.3.2.1 the uncertainty u that standard solution introducesrel(making).
Standard reserving solution prepare in use 10mL volumetric flask constant volume, hybrid standard liquid prepare in, use (100-1000) μ L
Pipettor is drawn in the A level capacity bottle of standard stock solution 0.1mL to 10mL and constant volume, obtains the mark that chromium concn is C=10.00mg/L
Quasi- stock solution, continue draw standard reserving solution 0.1mL to 10mL A level capacity bottle in and constant volume, obtain chromium concn be C=
The standard solution of 0.10mg/L.
1. diluting the uncertainty of introducing: (20-200) μ L pipettor being used to draw chromium standard liquid 0.1mL, pipettor calibrating card
The error of indication that book provides is ± 1%, is converted into standard uncertainty are as follows:Relative standard
Uncertainty are as follows: urel(make1)=5.77 × 10-4/ 0.1=5.77 × 10-3。
2. the uncertainty that constant volume generates: the maximum tolerance of 10mLA level capacity bottle is respectively ± 0.020mL, by square
Shape distribution considers that standard uncertainty is respectively as follows:Relative standard uncertainty are as follows:
urel(make2)=0.0115/10=0.00115
3. the uncertainty that temperature fluctuation is introduced into: variation of ambient temperature ± 3 DEG C in experimentation, it is assumed that it is distributed rectangular,Coefficient of expansion α=2.1 × 10 of water-4℃-1, the coefficient of expansion of glass is 2.5 × 10-5℃-1, then 10mL volumetric flask by
The uncertainty that temperature effect introduces are as follows:Standard inventory
The relative uncertainty degree that liquid introduces:
2.3.2.2 standard series prepares the uncertainty u introducedrel(matching).
1mL chromium standard reserving solution is accurately drawn with pipettor, and with 1% nitric acid constant volume in 10mL volumetric flask, concentration is made
To use liquid among the chromium standard of 1 μ g/mL.It is drawn respectively using pipettor precision and uses 0 μ L of liquid, 40 μ L, 100 among chromium standard
μ L, 150 μ L, 200 μ L are settled to scale with 1% nitric acid in 10mL color-comparison tube, mix, this serial chromium standard solution
Middle chromium concn is respectively 0 μ g/L, 4 μ g/L, 10 μ g/L, 15 μ g/L, 20 μ g/L；1000 are pipetted from the standard solution of 10 μ g/L again
μ L obtains the chromium standard solution of 1 μ g/L into 10mL color-comparison tube.
It is provided according to " JJG 646-2006 pipettor vertification regulation ", capacity is permitted when 1mL adjustable pipette draws 1000 μ L
Perhaps error is ± 1%, and capacity franchise includes volume calibration, personnel's reading, by being uniformly distributed, then partial uncertainty are as follows:
Again according to regulation, measurement reproducibility is ± 0.5% when 1mL adjustable pipette draws 1000 μ L, by being uniformly distributed, then
Partial uncertainty are as follows:
Bring synthetic standards are uncertain when then 1mL adjustable pipette draws 1000 μ L are as follows:
Relative standard uncertainty are as follows: urel(V1)=
0.00644。
Same Fa Ke get prepares the standard uncertainty that standard series process uses pipettor, see the table below 3:
3 pipettor relative standard uncertainty of table
In standard series process for preparation, 5 A grades of 10mL volumetric flasks have been used, have calibrated the uncertainty introduced are as follows:
5 merging:
The uncertainty that temperature fluctuation is introduced into: variation of ambient temperature ± 3 DEG C in experimentation, it is assumed that it is distributed rectangular,Coefficient of expansion α=2.1 × 10 of water–4℃-1, the coefficient of expansion of glass is 2.5 × 10-5℃-1, then 10mL volumetric flask by
Temperature effect introduce uncertainty be
Therefore the relative standard uncertainty introduced when the use of A grades of 10mL volumetric flask constant volume amounts being 10mL are as follows:
Then standard solution prepare and dilution in measuring device calibration introduce uncertain urel(mark) are as follows:
It synthesizes and is using the relative standard uncertainty that measurer introduces
2.4 uncertainties introduced using icp ms.
2.4.1 instrument calibration introduce uncertainty:
The expanded uncertainty for the measurement result that calibration certificate provides is 1.2%, Coverage factor k=2, then marks relatively
Quasi- uncertainty are as follows: urel(school)=0.012/2=0.006.
2.4.2 the A class uncertainty u that sample duplicate measurements introducesrel(weight):
To same sample solution duplicate measurements 5 times, it the results are shown in Table 4.
4 repeated measuring results of table
It is indicated with very poor, therefore:
Therefore the relative standard uncertainty that synthesis is introduced using icp ms are as follows:
The standard uncertainty that 2.5 fitting operations curves introduce.
Using the Cr standard solution of 6 concentration, each concentration measures three times respectively, the results are shown in Table 5.
The signal response and concentration of 5 Cr standard solution of table
Using linear least squares fit standard curve, equation of linear regression A=aC+b is obtained, asks dense by standard curve
The standard uncertainty u (C) generated when spending is calculated according to following formula:
In formula: u (C) is that the uncertainty introduced when C is sought in matched curve；S is standard deviation,
P is the measurement number of test solution, p=3；N is the measurement total degree of standard solution, n=18；C is test sample
The concentration of chromium in solution, C=6.62 μ g/L；For the measurement average value of chromium concn in standard solution；AiFor the signal of standard solution
Response；A is the slope of equation of linear regression, a=6746.1；B is the intercept of equation of linear regression, b=-633.92；It is related
Coefficient r=0.9996.Data in table are substituted into above formula, acquire standard uncertainty u (C)=0.0560 μ g/L, then relative standard
Uncertainty are as follows: urel(C)=0.0560/6.62=0.00846.
The uncertainty that 2.6 Specimen eliminatings introduce.
Not exclusively or element loss, pollution and digestion solution loss etc. in digestion process due to Specimen eliminating, it therefore introduces certain
Uncertainty, this uncertainty can be assessed by mark-on reclaims test.
In this experiment, micro-wave digestion and wet digestion have done mark-on reclaims test three times respectively, and the mark-on of micro-wave digestion returns
Yield is respectively 96.6%, 101% and 95.9%, the recovery of standard addition of wet digestion is respectively 94.8%, 97.8%,
97.2%.It is indicated with very poor,R: very poor；C: very poor coefficient.Therefore sample micro-wave digestion process is introduced and is not known
Degree: urel(micro-)=0.0174；Wet digestion process introduces uncertainty: urel(wet)=0.0102.
The uncertainty that 2.7 reagent blanks introduce.
The reagent that this experiment uses is excellent pure grade.Therefore, the results change that chromium content is measured after deduction blank is small, therefore recognizes
It is negligible for the influence of generation.
3, relative standard uncertainty is synthesized.
Synthesis relative standard uncertainty under 3.1 Microwave Digestions.
When currently processed mode is micro-wave digestion, ICP-MS method measures the analysis on Uncertainty column of chromium in gelatin hollow capsule
Table is as shown in table 6, and each uncertain component is irrelevant, the relative standard uncertainty of measurement result synthesis are as follows:
Result For Determination of Chromium Content is 0.331mg/kg, combined standard uncertainty in gelatin hollow capsule are as follows:
u(X1)=0.0134mg/kg.
Each partial uncertainty list of 6 Microwave Digestion of table
Synthesis relative standard uncertainty under 3.2 wet digestion methods.
When currently processed mode is wet digestion, ICP-MS method measures the analysis on Uncertainty column of chromium in gelatin hollow capsule
Table such as table 7, each uncertain component is irrelevant, the relative standard uncertainty of measurement result synthesis are as follows:
Result For Determination of Chromium Content is 0.331mg/kg, combined standard uncertainty in gelatin hollow capsule are as follows:
u(X2)=0.0125mg/kg.
Each partial uncertainty list of 7 wet digestion method of table
3.3 expanded uncertainties and measurement result indicate.
3.3.1 the expanded uncertainty under Microwave Digestion.
Assuming that measurement result meets normal distribution, Coverage factor k=2 is selected when fiducial probability is 95%, then microwave disappears
It solves under pretreatment mode, the expanded uncertainty of Result For Determination of Chromium Content in gelatin hollow capsule are as follows:
U(XIt is micro-)=2 × 0.0134=0.027, measurement result are represented by 0.331 ± 0.027mg/kg.
Expanded uncertainty under 3.32 wet digestion methods.
Assuming that measurement result meets normal distribution, Coverage factor k=2 is selected when fiducial probability is 95%, then microwave disappears
It solves under pretreatment mode, the expanded uncertainty of Result For Determination of Chromium Content in gelatin hollow capsule are as follows:
U(XIt is wet)=2 × 0.0125=0.025, measurement result are represented by 0.331 ± 0.025mg/kg.
4 results.
The analysis on Uncertainty of the uncertainty analysis model of capsule heavy metal (chromium) is measured by above-mentioned ICP-MS method
As a result as can be seen that the uncertainty influence factor sequence that this experiment influences measurement result is to use ICP-MS > using measurer >
Specimen eliminating > standard curve fit > uses balance using standard items >.
Wherein, the uncertainty introduced using balance is minimum, can be ignored substantially；It is introduced using measurer uncertain
Degree is maximum, it is seen that reasonable employment pipettor and selection dilute of crucial importance step by step；Secondly, increasing Duplicate Samples measures number, protect
The stabilization of measurement reproducibility is held, periodic maintenance instrument verifies the uncertainty of also ICP-MS capable of reducing using during carrying out；Sample
The uncertainty that resolution introduces also should not be underestimated: where wet digestion and the pretreatment mode of micro-wave digestion are to sample measurements
Significant difference it is little, can be according to the suitable resolution mode of experiment actual needs selection；Furthermore according to machine concentration on sample
It selects suitable curve ranges, selection proper storage, have accuracy and precision of the card standard items to sample test in validity period
It spends extremely important.
Therefore, it with chromium content in ICP-MS method measurement gelatin hollow capsule, needs to reinforce to above-mentioned major influence factors
Control, reduces the unstability of measurement, ensures the reliability of measurement result.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal, which is characterized in that including
Following steps:
Data acquisition: design recovery test, with heavy metal element in ICP-MS method measurement gelatin hollow capsule recovery test
Content, and collect data；
Model foundation: according to contents of heavy metal elements calculation formula, analyzing uncertainty source, establish measurement model, evaluation and
Calculate uncertainty.
2. the method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal according to claim 1,
It is characterized in that, in the data acquisition step, the ICP-MS method method for measuring includes:
The preparation of test solution: gelatin hollow capsule sample m g is weighed, before carrying out in a manner of micro-wave digestion or wet digestion
Processing, is settled to VmL, obtains test solution, and prepare placebo solution simultaneously, be settled to VmL；
The preparation of calibration curve solution: heavy metal standard items to be measured are taken, the standard solution of series of concentrations is configured；
Upper machine testing: the test solution, placebo solution and calibration curve solution are imported into ICP-MS detection, supplied
Heavy metal concentration C in test sample solution, heavy metal concentration C in placebo solution0；
Content of beary metal calculates: content of beary metal X is calculated according to the following formula,
In formula, X: the content of heavy metal in sample；C: the concentration of heavy metal in test solution；C0: a huge sum of money in placebo solution
The concentration of category；V: constant volume；M: weighed sample size；N: conversion multiple.
3. the method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal according to claim 2,
It is characterized in that, the specific steps for carrying out pre-treatment in a manner of micro-wave digestion are as follows: weigh the sample through crushing in microwave
In counteracting tank, standard items are added and carry out recovery of standard addition test, while doing blank control, nitric acid is added, on graphite resolution instrument
90-110 DEG C of pre- resolution 25-35min, after in being cleared up in microwave dissolver, after micro-wave diminishing pot is put on graphite resolution instrument
Sour 1.5-2.5h is caught up with, be rinsed with water and is transferred in centrifuge tube, constant volume；
The specific steps that pre-treatment is carried out in a manner of wet digestion are as follows: weigh the sample through crushing in digestion tube, add
Enter standard items and carry out recovery of standard addition test, while doing blank control, nitric acid is added, disappears in advance in 80-100 DEG C on graphite resolution instrument
Solve 25-35min, after be warming up to 125-145 DEG C of resolution 0.5-1.5h, 150-180 DEG C is continuously heating to later, until clearing up to 1
~2mL, constant volume.
4. the method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal according to claim 2,
It is characterized in that, the series of concentrations is 0-30 μ g/L in the preparation step of the calibration curve solution.
5. the method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal according to claim 2,
It is characterized in that, the heavy metal is chromium, in the upper machine testing step, the ICP-MS testing conditions are as follows.
6. the uncertainty analysis model of ICP-MS method measurement capsule heavy metal according to claim 1-5 is built
Cube method, which is characterized in that in the model foundation step, the measurement model are as follows:
Y=f (X1,X2,X3,X4,X5,X6,X7)
In formula, Y:ICP-MS method measures the uncertainty of capsule heavy metal；X1: the uncertainty introduced using standard items；X2: make
The uncertainty introduced with balance；X3: the uncertainty introduced using measurer；X4: the uncertainty introduced using ICP-MS；X5:
The uncertainty that standard curve fit introduces；X6: the uncertainty that Specimen eliminating introduces；X7: reagent blank introduces uncertain
Degree；
It is expressed as formula:
In formula, urel(X): the uncertainty of ICP-MS method measurement capsule heavy metal；urel(Cs): being introduced using standard items not true
Fixed degree；urel(m): the uncertainty introduced using balance；urel(V): the uncertainty introduced using measurer；urel(instrument): it uses
The uncertainty that ICP-MS is introduced；urel(C): the uncertainty that standard curve fit introduces；urel(pre-treatment): Specimen eliminating draws
The uncertainty entered；urel(blank): the uncertainty that reagent blank introduces.
7. the method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal according to claim 6,
It is characterized in that, uncertainty and weighing that the calibration that the uncertainty introduced using balance includes: balance introduces repeat
Property introduce uncertainty；
The uncertainty introduced using measurer includes: that the uncertainty that sample constant volume generates and standard curve introduce
Uncertainty；The uncertainty that the sample constant volume generates includes: the uncertainty of the introducing of volumetric flask volume, is settled to
The uncertainty that the uncertainty and temperature difference that the mobility of scale generates generate；The uncertainty that the standard curve introduces
It include: the uncertainty that standard solution introduces and the uncertainty that standard series preparation introduces.
8. the method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal according to claim 6,
It is characterized in that, the calibration that the uncertainty introduced using Inductively coupled plasma mass spectrometry includes: instrument introduces not
The uncertainty that degree of certainty and sample duplicate measurements introduce.
9. the method for building up of the uncertainty analysis model of ICP-MS method measurement capsule heavy metal according to claim 7,
It is characterized in that, pre-treatment is carried out to gelatin hollow capsule sample in a manner of micro-wave digestion or wet digestion, respectively to microwave
Uncertainty under resolution method and wet digestion method is synthesized, and the synthesis under Microwave Digestion and wet digestion method is respectively obtained
Relative standard uncertainty, and the extension for analyzing the expanded uncertainty and wet digestion method that obtain Microwave Digestion is uncertain
Degree.
10. the uncertainty for the ICP-MS method measurement capsule heavy metal that the described in any item methods of claim 1-9 are established
Analysis model.
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