CN105954250A - Novel method for measuring arsenic in urine - Google Patents
Novel method for measuring arsenic in urine Download PDFInfo
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- CN105954250A CN105954250A CN201610525065.7A CN201610525065A CN105954250A CN 105954250 A CN105954250 A CN 105954250A CN 201610525065 A CN201610525065 A CN 201610525065A CN 105954250 A CN105954250 A CN 105954250A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
- G01N21/6404—Atomic fluorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
Abstract
The invention discloses a novel method for measuring arsenic in urine. The method is characterized in that arsenic in urine is quantitatively measured with a wet digestion-hydride generation-atomic fluorescence spectrometry method through an AFS-230E type dual-channel atomic fluorophotometer instrument. An optimal instrument condition is adopted, the digestive fluid composition is optimized, and a digestive instrument and the digestive utensil are used in the experimental operation processes of sample pretreatment, standard curve drawing, sample determination and the like, so that the concentration and using amount of a reagent are lowered, the operation process and treatment time of the sample pretreatment are shortened effectively, the sample detection range is widened, the detection limit is lowered, and the method is suitable for measuring low arsenic, medium arsenic and high arsenic in urine and is suitable for detecting arsenic in a large batch of urine samples. Compared with the prior art, the novel method has the advantages of high precision, high sensitivity, high accuracy, high reliability, easiness, convenience, rapidness, low interference, wide linear range, high practicability, low cost and the like.
Description
Technical field
The present invention relates to a kind of measure the novel method of arsenic in urine, belong to atomic fluorescence spectrophotometer method
Measure the technical field of arsenic in urine.
Background technology
In urine, arsenic horizontal direct reaction arsenic is in the absorbtivity of individual level, and it can be near with quantitative predication
The phase individual absorbtivity to arsenic is that Recent Research is individual contacts most reliable index to arsenic, also by
The biological indicator contacted as main arsenic.By amount to arsenic contact individual to different industries with
In urine, the relation research of each form arsenic and total arsenic amount shows, in urine, arsenic level is detection and evaluates duty
The important indicator of industry arsenic contact；China occurs in that more high arsenic endemicity lesion in recent years, high
The urine sample arsenic content of the biggest ratio of arsenic area crowd is higher, needs to carry out long-term monitoring, i.e.
Also it is as endemic arsenic poisoning detection and one of the leading indicator evaluated.By to arsenic in urine
Measure the important technology that analysis is prevention and control arseniasis to ensure, then carry out the detection work of arsenic in urine
Especially seem important.
The method of detection urine arsenic has a variety of, as 1. arsenic speckle detection method, 2. spectrophotomelric assay method,
3. Catalytic Polarographic detection method, 4. Atomic Absorption detection method, 5. Hydride generation-atomic fluorescence spectrometry light
Spectrum detection method (HG-AFS), 6. inductively coupled plasma detection method, 7. multiple techniques (HPLC
Being combined with ICP-AES, ICP-MS, HPLC Yu HG-AFS is combined) etc., the most 1.-4. plant
Method or to there is reaction interference, precision the highest, or have that sensitivity is low, solvent toxicity big,
Or there is complex operation, time length, pollute big, or have that lowest detectable limit is higher, equipment is held high
6., 7. as carrying out the latest development method of the analyses such as chemical form the defect such as expensive, although,
But have that equipment price is expensive, common laboratory does not possesses equally, economy and practicality relatively low
Defect.Therefore, for existing widely used and promote urine arsenic detection method, should possess through
Several big factors such as Ji property, the suitability, accuracy, and the up-to-date health industry that existing China concludes
Standard is WS/T 474-2015 " the mensuration hydride-generation atomic fluorescence method of arsenic in urine ",
It uses HG-AFS, has the most well confirmed this point.
WS/T 474-2015 standard is applicable to Endemic Arsenism Areas and divides and prevention effect
Judging, lowest detection is limited to 0.5 μ g/L, and measurement range is 0-40 μ g/L.But this method is behaviour
During work, exist Sample pretreatment sampling amount consumption big, sour many, use equipment many, operation
Loaded down with trivial details, generation acid mist easily causes the shortcomings such as environmental pollution more.Xiao Juntao " is using AFS-230E
Type atomic fluorescence spectrophotometer measures the arsenic in urine " (hereinafter referred to as document 1) (up-to-date medicine in the world
Information digest 2016,16 (4)) one disclosed herein with AFS-230E type atom fluorescent luminosity
Meter, uses wet digesting-HG-AFS to be measured arsenic in urine, and urine sample is equally through nitric acid-high chlorine
After acid digestion, under conditions of acidity, add thiourea and ascorbic acid solution 5 valency arsenic are reduced to
Trivalent arsenic, generates hydride under potassium borohydride effect, argon brings in quartz atomizer
Being decomposed into atomic state arsenic, the transmitting light at as hollow cathode lamp excites lower generation atomic fluorescence, its
Fluorescence intensity is directly proportional to the arsenic concentration in sample under rigid condition, with standard series ratio
More quantitative.The method, compared with WS/T 474-2015 standard method, simplifies sample treatment
Step, have adjusted the addition of arsenic standard solution in standard curve preparation process, and to instrument
Operating condition is partially adjusted, and optimizes the detection method of HG-AFS further.Result shows
The method minimal detectable concentration is 0.076 μ g/L, the scope 0-40 μ g/L of mensuration, relatively marks
Quasi-deviation is all below 3.86%, and recovery of standard addition is 90%-102%.The method still suffers from sample
Pre-treatment reagent consumption is many, loaded down with trivial details, and easily evaporates dry when digestion, affects the accuracy of result
And the good sample of pre-treatment needs the defects such as transfer.
Therefore, " in urine, the mensuration hydride of arsenic occurs to optimize existing WS/T 474-2015
Atomic fluorescence method " method, it is to the further lifting of arsenic determination techniques in urine, is to widen detection
Scope, simplification pre-treatment, reduction cost, a kind of new technique of shortening operating time, be for not
In the individual amount to arsenic contact of the same trade and lesion crowd urine, arsenic provides quick, economic, practical
Urine arsenic detection method, is this area worker one of Main way of being devoted to research.
Summary of the invention
During this research worker is by working in the study on prevention carrying out endemic arsenic poisoning for a long time, right
Urine arsenic detection method is studied for a long period of time, has invented one and can measure arsenic in urine, again economy
Efficiently and the result that measured can meet industry analysis deviation requirement measure the new side of arsenic in urine
Method.The method have easy and simple to handle, good stability, highly sensitive, interference less, the range of linearity
The feature such as wide, sample pre-treatments simple, low cost, environmental pollution are little, overcomes working standard
With the deficiency measuring urine arsenic technology in document.
The present invention adopts the following technical scheme that
A kind of measure the novel method of arsenic in urine, comprise the following steps:
1) instrumentation condition: AFS-230E dual channel atomic fluorescence photometers, photomultiplier tube
Negative high voltage is 280V, lamp current 50mA, auxiliary cathode current 25mA, atom height of instrument 8mm,
Carrier gas flux 400mL/min, shield gas flow amount 900mL/min, calm the anger flow 0.2MPa；2%
Solution of potassium borohydride, 5% hydrochloric acid solution；
2) sample pre-treatments: taking 1.0mL urine sample and put in 10.0mL digestion vessel, addition disappears
Change liquid 1.0mL, mixing, then digestion vessel are placed on the digestion instrument that temperature is 200 DEG C and disappear
Changing 40～60 minutes, be about 0.2ml to volume, liquid level is tranquil, in digestion vessel yellow or
Significantly white gas disappears, and liquid is colourless or pale yellow transparent state, standby；
3) preparation of standard curve: take 6 10.0mL and digest vessel, be separately added into 0.00,
0.10,0.30,0.50,0.70,1.00mL concentration be the arsenic standard working solution of 0.1 μ g/L,
Respectively add 1.0mL normal person and mix urine, add Digestive system 1.0mL, mixing, put
Digest 40～60 minutes on the digestion instrument that temperature is 200 DEG C, be about 0.2mL to volume, molten
Liquid is colourless or faint yellow, adds 5% thiourea-5% ascorbic acid mixed solution after cooling respectively
1.0mL, 1.0mL hydrochloric acid (18%), is then settled to the graduation position of 10.0mL with ultra-pure water,
It is configured to arsenic concentration and is respectively 0.00,10.0,30.0,50.0,70.0,100.0 μ g/L systems
Row arsenic standard solution, mixing, stand 20-30 minute, take 1.0ml sample size, upper configuration arsenic
Hollow cathode lamp and the dual channel atomic fluorescence photometers of supporting analysis software, respectively bioassay standard system
Row, draw standard curve；
4) sample determination: with 5% hydrochloric acid for current-carrying liquid, 2% potassium borohydride is reducing agent, argon
For carrier gas；In step 2) urine sample that digested adds 1.0mL hydrochloric acid (18%), 5% thiourea
-5% ascorbic acid mixed solution 1.0mL, adds ultra-pure water to 10.0mL, fully mixes, and stands
20-30 minute, take 1.0mL sample size, upper configuration as hollow cathode lamp and supporting analysis software
Dual channel atomic fluorescence photometers be measured.
The novel method of arsenic in described mensuration urine, the unit of solvent for use is quality volume basis
Ratio；
Further, described step 2), 3) in digestion instrument be ADE-DI porous self-controlling electrothermal
Clear up instrument；Digestive system is that sulphuric acid (96%), nitric acid (66%), hydrogen peroxide (30%) are by 2:3:5
Volume carries out the mixed liquor mixed；
Digestion vessel are the hard glass digestive tube that 10.0mL tool plug ground is with a scale.
Further, described step 2) if after middle digestion, liquid color is relatively deep or has brown color cigarette,
Illustrate that organic substance is more, after now taking out sample cooling, add 30% hydrogen peroxidase 10 .5mL,
Reheating and decompose, until no reflow phenomenon or white cigarette in tube wall, liquid level is tranquil, simultaneously views and disappears
Changing yellow or significantly white gas in pipe to disappear, liquid is water white transparency state, and digestion terminates.
Further, described step 4) 2% solution of potassium borohydride in, containing 0.5% hydrogen-oxygen
Change sodium or 0.2% potassium hydroxide；
Described step 4) in before carrying out sample determination, first instrument is preheated 20-30min,
Measure reagent blank again, after obtaining stable reagent blank fluorescence intensity, then sequentially determining mark
Quasi-series, instrument bales catch, except blank, is drawn standard curve, is calculated regression equation and phase relation
Number, finally measures sample.
Described step 3), 4) used by ultra-pure water >=18.2 Μ Ω .CM@25 DEG C.
After using preceding method to sample test, as hollow cathode lamp and supporting analysis software
Result can be automatically calculated according to linear equation and correlation coefficient.
Compared with the prior art, the invention have the advantages that
1, sample treatment aspect: new invention improves the speed of sample pre-treatments, optimizes and disappears
Change the composition of liquid, decrease Digestive system consumption and the concentration of reducing agent and consumption, reduce cost,
Improve economic benefit.Specifically it is shown in Table 1,2.
Table 1 sample sampling amount and Digestive system consumption information slip (unit: mL)
Operating procedure, reductant concentration and consumption information slip before the supreme machine of table 2 treatments of the sample
From table 1,2,1. in sample pre-treatments, the inventive method compares working standard
WT/T474-2015 method and document 1 greatly reduce on the consumption of Digestive system.Digestion 1
Part sample can save 2mL or 14mL, thus reduces Digestive system consumption 66.7% or 93.3%.
2. the inventive method optimizes Digestive system composition, in the Digestive system of working standard and document 1
All using perchloric acid, the inventive method uses hydrogen peroxide, can not only obtain than perchloric acid more
Preferably digestion effect, and be also greatly lowered from price: it is specifically shown in table 3 below.
Table 3 reagent catalog
Therefore, select hydrogen peroxide more reasonable, economical.
3. present invention optimizes operating procedure, it is to avoid working standard WT/T474-2015 and literary composition
Offer the operating process also needing in 1 that the sample digested is sampled again transfer, without such as
Document 1 carries out water dissolution heating after digestion again, thus this law to shorten operating procedure timely
Between, reach purpose easy, quick；
4. present invention reduces concentration and the usage amount of reducing agent, make cost again reduce.Furthermore
Do not use sulphuric acid in document 1 Digestive system, because of sulphuric acid boiling point (DEG C): 315～338, digesting
In journey more stable, and nitric acid boiling point: 78 DEG C, perchloric acid boiling point (DEG C): 130 (note: big
Explode in 130 time), in digestion process, easily evaporation is dry, affects the accuracy of result, this
Invention solves this problem well.
2, instrumentation condition aspect: as seen from Table 4, new invention method have adjusted photoelectricity times
Increase the parameters such as pipe negative high voltage, carrier gas flux, atomizer height and shield gas flow amount, make instrument
Operating parameter condition be more suitable for the mensuration of different situations urine sample.
43 kinds of method instrument working condition of table
3, process aspect is measured: 1. use ADE-DI porous self-controlling electrothermal to clear up instrument and 10.0mL
The sample that tool plug ground hard glass digestive tube with a scale has digested need not to shift (note: its
The digestion vessel of its method are the conical flasks of 25mL-150mL), directly add reducing agent, salt
Acid carries out 5+To 3+After the reduction of arsenic, on constant volume, machine measures.Decrease the device such as volumetric flask, pipet
The use of ware, improves detection efficiency, reduces testing cost；2. widen urine sample and measure model
Enclose so that it is adjusted to 0-100 μ g/L by the 0-40 μ g/L of prior art, when running in urine sample
During arsenic content higher (as beyond 40 μ g/L), it is not required to dilution metering；3. minimum by sample
Detectable concentration is reduced to 0.07 μ g/L by 0.5 μ g/L of working standard, is more suitable for urine
The mensuration of low arsenic in sample.
The inventive method and the contrast of existing method, reagent dosage greatly reduces, surveys timed samples
Need not transfer and reheating process, decrease loaded down with trivial details operation, shorten minute；Again
Person uses the reagent that price low performance is good instead, had the most both reduced cost, and had improve again economic benefit.
It is simultaneously suitable for low arsenic, suitable arsenic and the survey of high arsenic in the mensuration of arsenic and urine sample in high-volume urine sample
Fixed, have that precision is high, sensitivity is good, accurately and reliably, simple and efficient, interference less, linearly
Wide ranges, practical, low cost and other advantages.
Detailed description of the invention
For making those skilled in the art more be apparent from the inventive method, applicant is specifically
Embodiment is further described in the way of proving experiment.
1. experimental section
1.1 principle
Urine sample is after wet digesting, in acid medium, adds ascorbic acid-thiourea mixed liquor
Make pentavalent arsenic be reduced into trivalent arsenic, then make reducing agent with potassium borohydride, generate arsenic hydride, by argon
Airborne enter quartz atomizer is decomposed into atomic state arsenic, in the transmitting of special as hollow cathode lamp
Light excites lower generation atomic fluorescence, and its fluorescence intensity is dense with the arsenic in test solution under rigid condition
Degree is directly proportional, and compares quantitative with standard series.
1.2 instruments and reagent
1.2.1 instrument: AFS-230E dual channel atomic fluorescence photometers, as hollow cathode lamp and
Supporting analysis software (Beijing Rayleigh Analytical Instrument Co., Ltd), ADE-DI porous self-controlling electrothermal is cleared up
Instrument (Beijing thin Rui Saike Co., Ltd), 10.0mL tool scale and the hard of frosted mouth plug
Glass digestive tube, one of percentage electronic balance (Sai Duolisi scientific instrument (Beijing) limited public affairs
Department)
1.2.2 reagent:
5% hydrochloric acid, 30% hydrogen peroxide, 96% sulphuric acid, 66% nitric acid, 18% hydrochloric acid etc., above examination
Agent is top grade pure (GR)；
2% potassium borohydride (includes 0.5% sodium hydroxide or 0.2% potassium hydroxide), 5% thiourea-5%
Ascorbic acid mixed solution, reagent is analytical pure (AR)；
Arsenic Standard Applying Solution (concentration 1.0 μ g/mL): take arsenic titer (concentration is 100.0 μ g/L,
It is purchased from State center for standard matter, standard No. GSB 04-1714-2004), it is formulated into step by step
Concentration is the application liquid of 1.0 μ g/mL；
Experimental water is the ultra-pure water of >=18.2 Μ Ω .CM@25 DEG C；
Carrier gas is ＞ 99.99 high-purity argon gas；
Test uses urine: be mixed into by normal person's urine.
1.3 instrument working condition: be shown in Table 5.
Table 5 instrument working condition table
1.4 data and interpretation of result
Excel and SPSS10.0 is used to carry out Correlation method for data processing and statistical analysis.
2. result
2.1 the selection of current-carrying-salt acidity concentration
In the case of other condition is certain, change the concentration of current-carrying hydrochloric acid (at 2%～20% model
In enclosing) measure corresponding fluorescence intensity, when the volume fraction of hydrochloric acid is 5%, fluorescence intensity
The highest, i.e. sensitivity is the highest, and the volume fraction therefore selecting hydrochloric acid is 5%.
The concentration of 2.2 potassium borohydrides
Finding in test, the concentration of potassium borohydride has considerable influence to measurement result.We use
Internal control sample concentration is 25.0 μ g/L (GSBZ 5004-88 environmental standard lot numbers: 200432)
As comparison, when solution of potassium borohydride concentration is 30 μ g/L, fluorescence intensity is best, secondly
Be concentration be 20 μ g/L.In view of the economy of reagent dosage, therefore selecting concentration is 20 μ g/L,
I.e. 2%.Paying special attention to, potassium borohydride less stable, need to add concentration during dissolving is 2g/L
(0.2%) potassium hydroxide or 5g/L (0.5%) sodium hydroxide, to ensure the stability of solution.
2.3 interference test
From test in laboratory is analyzed, research worker finds alkali and alkaline earth metal ions class concurrent
Not interference measurement, during as measured the arsenic of 20 μ g/L, the Fe3+ of 600 times, Ni2+, Al3+, Mn2+,
V5+, Cr6+, Sn4, the Se of 200 times4+, Te4+, Cu2+, Pb2+, Bi3+, Ge4+The most do not disturb arsenic
Mensuration.After i.e. adding these ions, the fluorescent value of mensuration is compared with being not added with, and fluorescence is strong
The change of angle value is respectively less than 10%, and thiourea and ascorbic acid mixed solution can not only be by (V) simultaneously
Valency arsenic is reduced into (III) valency, and has anti-interference hidden agent effect.Additionally use urine sample to add
The standard curve of mark preparation also be enough to eliminate interference that may be present, the chaff element in general urine sample
The content of element is all not up to interference level.
2.4 standard curves and the range of linearity
Take 6 10.0mL tool plug ground hard glass digestive tubes with a scale, be separately added into
0.00,0.10,0.30,0.50,0.70,1.00mL arsenic standard working solution (0.10 μ g/L),
Rear each addition 1.0mL normal person mixes urine solution, adds 30% hydrogen peroxidase 10 .5mL, 96% sulphuric acid
0.2mL and 66% nitric acid 0.3mL, is placed on the ADE-DL self-controlling electrothermal digestion instrument of 200 DEG C and disappears
Changing 40～60 minutes, be about 0.2mL to volume, solution is colourless or faint yellow.After cooling
Add 5% thiourea-5% ascorbic acid mixed solution 1.0mL, hydrochloric acid (18%) 1.0mL respectively, so
Be settled to the position of 10.0mL afterwards with ultra-pure water, be configured to arsenic concentration be respectively 0.0,10.0,
30.0,50.0,70.0,100.0 μ g/L series arsenic standard solution, mixing, stand 20～30
Minute, the machine on 1.0ml that takes measures.With arsenic concentration C as abscissa, with fluorescence intensity If it is
Vertical coordinate carries out linear regression, and obtaining linear equation is If=79.192*C+100.843, phase relation
Number γ=0.9999.
2.5 detection limit
(ρ (As))=10.0 μ g/L under instrumentation table 5 working condition, to content constant
Titer carries out 11 evaluating and measurings, calculates the standard deviation RSD=1.96% of measurement result,
With the standard deviations of 3 times divided by slope, try to achieve detection and be limited to 0.07 μ g/L.
2.6 precision and accuracy test
2.6.1 precision: prepare 3 kinds of variable concentrations of 10.0,50.0,100.0 μ g/L respectively
Arsenic standard solution, each concentration measures 11 times, and result relative standard deviation (RSD) is respectively
It is 1.96%, 3.97%, 2.73%, meets the requirement of " biological material analysis method grinds criterion "；
And the precision of document 1 is 2.21% (obtaining in data), essence in standard WT/T474-2015
Density is 2.5%-4.9% (obtaining in data), illustrates that this law is than document and standard
WT/T474-2015 precision is high.
Present aspect carries out 6 times with working standard WS/T 474-2015 and document 1 to same urine sample
The com-parison and analysis of parallel assay, is shown in Table 6.
The relative analysis that same urine sample is measured by 6 three kinds of methods of table
The inventive method measures average and working standard WS/T 474-2015 method as shown in Table 6
And document 1 is all in standard deviation deviation range, and relative standard deviation is less than 10%, illustrates point
Analysis process has higher preci-sion and accuracy.On the other hand, working standard WS/T 474-2015
The relative standard deviation of " the mensuration hydride-generation atomic fluorescence method of arsenic in urine " is 4.9%,
The relative standard deviation 4.0% of document 1, and the relative standard deviation of the inventive method is 2.8%,
Demonstrate again that the inventive method precision than standard WT/T474-2015 and document 1 is high.
Data of the present invention and standard WT/T474-2015 data are carried out Grubbs inspection respectively
(GB/T 4883-2008 " sentencing of the statistical processing and analysis normal sample outlier of data
Break and process " and GB/T 4882-2001 " statistical disposition of data and explanation normality inspection
Test "), data the most without exception.Two groups of data are carried out the bilateral inspection of F, given α simultaneously
=0.05, look into F table and obtain marginal value and be: F0.025 (5.5)=7.15, according to 5 liang of groups of table
Data calculate F=S2max/S2Min=0.122/0.072=2.939, F < F0.025 (5.5),
Therefore the precision of two kinds of methods there was no significant difference.Two groups of data are carried out t inspection.Calculate
Statistic t=0.353, when α=0.05, during degree of freedom f=10, table look-up to obtain t0.05 (10)
=2.228, t < 0.05 (10), working standard WS/T 474-2015 " arsenic in urine is described
Measure hydride-generation atomic fluorescence method " poor without significance with the measurement result of the inventive method
Different, illustrate that this method is accurately and reliably.
2.6.2 accuracy: new method takes normal person and mixes the urine high, normal, basic variable concentrations of addition
Arsenic standard solution is measured.Result measured value is in Standard deviation-Range, and the response rate exists
Between 95.1%～105%, i.e. accuracy is high.Specifically it is shown in Table 7.
Table 7 accuracy test
2.7 stability tests: take urine sample 42 parts, each addition arsenic standard solution application, it is allowed to
Spiked levels is 10.0 μ g/L.Measuring 6 parts, other preserve at 4 DEG C, the most respectively
2, within 4,6,8,10,12,14 days, respectively 6 parts are measured.Result shows, sample 4 DEG C down to
Can preserve less 2 weeks.
2.8 sample determination
2.8.1 sample pre-treatments: take 1.0mL urine sample in 10.0mL tool plug scale ground hard
In glass digestive tube, add 0.5mL and cross 30% hydrogen oxide, 96% sulphuric acid 0.2mL and 66% nitric acid
0.3mL, is placed on the ADE-DL self-controlling electrothermal digestion instrument of 200 DEG C and digests about 40-60 minute,
Being about 0.2mL to volume, now solution is colourless or faint yellow.If color is relatively deep or has pale brown
Color cigarette, illustrates that organic substance is more, now takes out cooling, then adds 0.5mL hydrogen peroxide,
Reheating and decompose, until no reflow phenomenon in tube wall, liquid level is tranquil, simultaneously views in digestive tube
Yellow or significantly white gas disappear, and liquid is water white transparency state, and digestion terminates (i.e. sample
Product pre-treatment completes), then take off to put and be cooled to room temperature.Make 3 blank experiments simultaneously.
2.8.2 measure: with hydrochloric acid (5%) as current-carrying, potassium borohydride (2%) is reducing agent, argon
Gas is carrier gas.The urine sample digested is added 1.0mL hydrochloric acid (18%), and 5% thiourea-5% is anti-bad
Hematic acid solution 1.0mL, adds ultra-pure water to 10.0mL, fully mixes, stand 20-30 minute,
Start shooting to be measured；Before mensuration, instrument first preheats 20min, is measuring reagent blank.Steady obtaining
After fixed reagent blank fluorescence intensity, then surveying standard series successively, instrument bales catch removes blank,
Draw standard curve, calculate regression equation and correlation coefficient, finally measure sample.But mensuration sample
Before product, instrument need to measure a reagent blank and sample blank again, just measures sample, sample
Sample size is 1.0ml.Instrument calculates result automatically according to the parameter given.Measure complete,
Clean instrument immediately.
2.9 calculate
2.9.1 by formula (1), urine sample is converted into the concentration correction under standard specific gravity (1.020)
COEFFICIENT K.
2.9.2 the concentration of arsenic, X=C*K ... (2) in urine is calculated
In formula: X, it it is arsenic concentration (mg/L) in urine；The arsenic concentration (mg/L) that K is checked in by standard curve.
3. conclusion
Result above shows, the inventive method and the contrast of existing method, and reagent dosage subtracts significantly
Few, survey timed samples and need not transfer and reheating process, decrease loaded down with trivial details operation, shorten
Minute；Furthermore use the reagent that price low performance is good instead, the most both reduce cost, again
Improve economic benefit.The minimal detectable concentration of its method is 0.07 μ g/L, measures precision
(n=6) urine sample recovery of standard addition is between 95.1%～105.0%, and relative standard deviation is 2.8%
Below.It is simultaneously suitable in high-volume urine sample low arsenic, suitable arsenic and height in the mensuration of arsenic and urine sample
The mensuration of arsenic.Have that precision is high, sensitivity is good relative to other method, accurately and reliably, letter
Just quick, interference less, range of linearity width, practical, low cost and other advantages, at urine arsenic
Measure in analyzing, simple, it is worthy of promotion and application.
Claims (9)
1. measure a novel method for arsenic in urine, comprise the following steps:
1) instrumentation condition: AFS-230E dual channel atomic fluorescence photometers, photomultiplier tube
Negative high voltage is 280V, lamp current 50mA, auxiliary cathode current 25mA, atom height of instrument 8mm,
Carrier gas flux 400mL/min, shield gas flow amount 900mL/min, calm the anger flow 0.2MPa；2%
Solution of potassium borohydride, 5% hydrochloric acid solution；
2) sample pre-treatments: taking 1.0mL urine sample and put in 10.0mL digestion vessel, addition disappears
Change liquid 1.0mL, mixing, then digestion vessel are placed on the digestion instrument that temperature is 200 DEG C and disappear
Changing 40～60 minutes, be about 0.2ml to volume, liquid level is tranquil, in digestion vessel yellow or
Significantly white gas disappears, and liquid is colourless or pale yellow transparent state, standby；
3) preparation of standard curve: take 6 10.0mL and digest vessel, be separately added into 0.00,
0.10,0.30,0.50,0.70,1.00mL concentration be the arsenic standard working solution of 0.1 μ g/L,
Respectively add 1.0mL normal person and mix urine, add Digestive system 1.0mL, mixing, put
Digest 40～60 minutes on the digestion instrument that temperature is 200 DEG C, be about 0.2mL to volume, molten
Liquid is colourless or faint yellow, adds 5% thiourea-5% ascorbic acid mixed solution after cooling respectively
1.0mL, 1.0mL hydrochloric acid (18%), is then settled to 10.0mL with ultra-pure water in digestion vessel
Graduation position, be configured to arsenic concentration be respectively 0.00,10.0,30.0,50.0,70.0,
100.0 μ g/L series arsenic standard solutions, mixing, stand 20-30 minute, take 1.0ml sample introduction
Amount, upper configuration as hollow cathode lamp and the AFS-230E dnal-channel atomic fluorescence of supporting analysis software
Photometer, bioassay standard series, draw standard curve；
4) sample determination: with 5% hydrochloric acid as current-carrying, 2% potassium borohydride is reducing agent, and argon is
Carrier gas；In step 2) urine sample that digested adds 1.0mL hydrochloric acid (18%), 5% thiourea-5%
Ascorbic acid mixed solution 1.0mL, adds ultra-pure water to 10.0mL, fully mixes, and stands 20-30
Minute, take 1.0mL sample size, upper configuration as hollow cathode lamp and supporting analysis software
AFS-230E dual channel atomic fluorescence photometers is measured.
The novel method of arsenic in mensuration urine the most according to claim 1, it is characterised in that:
The unit of solvent for use is quality percent by volume.
The novel method of arsenic in mensuration urine the most according to claim 1, it is characterised in that:
Described step 2), 3) in digestion instrument be that ADE-DI porous self-controlling electrothermal clears up instrument.
The novel method of arsenic in mensuration urine the most according to claim 1, it is characterised in that:
Described step 2), 3) in Digestive system be sulphuric acid (96%), nitric acid (66%), hydrogen peroxide (30%)
The mixed liquor mixed is carried out by 2:3:5 volume.
The novel method of arsenic in mensuration urine the most according to claim 1, it is characterised in that:
Described step 2), 3) in digestion vessel be 10.0mL tool plug ground hard glass with a scale
Digestive tube.
The novel method of arsenic in mensuration urine the most according to claim 1, it is characterised in that:
Described step 2) if liquid color is relatively deep after middle digestion or has brown color cigarette, organic substance is described
More, add 0.5mL hydrogen peroxide (30%) after now taking out digestion sample cooling, reheat and divide
Solving, until no reflow phenomenon or white cigarette in tube wall, liquid level is tranquil, simultaneously views in digestive tube yellow
Color or significantly white gas disappear, and liquid is water white transparency state, and digestion terminates.
The novel method of arsenic in mensuration urine the most according to claim 1, it is characterised in that:
Described step 4) 2% solution of potassium borohydride in, containing 0.5% sodium hydroxide or 0.2% hydrogen-oxygen
Change potassium.
The novel method of arsenic in mensuration urine the most according to claim 1, it is characterised in that:
Described step 4) in before carrying out sample determination, first instrument is preheated 20-30min, then surveys
Determine reagent blank, after obtaining stable reagent blank fluorescence intensity, then sequentially determining standard system
Row, instrument bales catch removes blank, draws standard curve, calculate regression equation and correlation coefficient,
Finally measure sample.
The novel method of arsenic in mensuration urine the most according to claim 1, it is characterised in that:
Described step 3), 4) used by ultra-pure water >=18.2 Μ Ω .CM@25 DEG C.
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