CN110411817A - The method of the direct mercury vapourmeter measurement mercury in hair content of DMA-80 - Google Patents
The method of the direct mercury vapourmeter measurement mercury in hair content of DMA-80 Download PDFInfo
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Abstract
The invention discloses a kind of methods of the direct mercury vapourmeter measurement mercury in hair content of DMA-80, comprising the following steps: (1) hair preparation of samples: is shredded direct injected；Alternatively, impregnating 5-10min by after the cleaning of Hair grooming deionized water, then with organic solvent, then shredded after natural air drying, direct injection analysis；(2) it is measured using the direct mercury vapourmeter of DMA-80, location parameter are as follows: the range of drying temperature is 50 DEG C -100 DEG C, and decomposition temperature scope is 400 DEG C -700 DEG C.Using the method for the invention, the pre-treatment for carrying out micro-wave digestion or wet resolution method etc. is not needed, reduces loss of the pre-treating method to mercury, and easy to operate, pollution is few, detects accuracy quick and with higher, precision.
Description
Technical field
The present invention relates to analytical chemistry field, especially a kind of method for measuring mercury in hair content.
Background technique
Mercury, also known as mercury are unique metallic elements existing in liquid form under room temperature, are widely distributed in the table of the earth's crust
Face.Mercury is very widely used, is related to social various aspects, such as the industry of point solution, electric appliance and measurement instrument industry, agricultural, medical row
Industry, drawing pigment, organic synthesis industry etc..Mercury, which is primarily present form, can be divided into element mercury, inorganic mercury and organic mercury, can lead to
Cross food chain, thousands of times of biological concentration.Mercury can be volatilized into mercury vapour at room temperature, and mercury vapour is by respiratory tract, skin or disappears
Change the different approaches such as road and invades human body.The positions such as liver, kidney, brain, heart, marrow are collected in, lesion tissue is caused, are occurred corresponding
Clinical symptoms.Organic mercury has high toxicity, especially methyl mercury.Methyl mercury can damage nervous system after entering human body, and can
Fetus is encroached on by placenta, is enriched in Cord blood, leads to fetal congenital mercury poisoning or deformity or dementia.
The mensuration mode of traditional mercury has cold atomic absorption spectrometry, atomic fluorescence spectrometry, inductively coupled plasma body
Mass spectrograph etc..There are some drawbacks for these traditional detection methods.Firstly, these detection methods are required to locate sample in advance
Reason, based on micro-wave digestion or wet resolution method.Since the volatility of mercury is larger, pretreatment process easily loses the mercury in sample,
Cause biggish systematic error.Secondly, biological sample matrix is more complicated, traditional detection method exists during sample detection
Serious interference, such as Polyatomic ion etc..Moreover, mercury has stronger adsorptivity, it is adsorbed on sample in the detection process
On the materials such as product import pipe, it is easy to produce memory effect.Traditional detection method long flow path, generate a large amount of abandoned reagents and
Mercury vapour, pollutes environment, and harmful to human is cumbersome and time-consuming.The direct mercury vapourmeter of DMA-80 is by high-temperature oxydation decomposition-catalysis
Adsorption-edulcoration-amalgamation trapping-atomic absorption detecting integration.The principle of this method is mounted under the action of oxygen stream
Sample in example boat is catalytically decomposed and is inhaled in catalyst furnace through dry and high temperature thermal decomposition, the gas of generation in dore furnace
After attached dose of purification and impurity removal, the mercury in sample is completely reformed into oxidation mercury vapour, enters golden amalgamation device, mercury oxide with oxygen stream
It is reduced to element mercury and is trapped in the form of gold amalgam by selection, heat amalgamation device, desorb mercury, optics is brought by oxygen stream
Pond carries out Atomic absorption measurement, wavelength 253.7nm.Different from traditional detection method, the direct mercury vapourmeter detection of DMA-80 is solid
One of mercury content biggest advantage in body or liquid is not needing to handle, can direct injected detection, reduce pre-treatment
The advantages that systematic error generated in journey has accuracy high, favorable reproducibility, simple and quick.
Mercury poisoning is mostly slow poisoning.Mercury content in hair can react the load level of mercury in human body, it is particularly possible to
The more accurate accumulation situation for obtaining ground reflection methyl mercury.Hair is widely used in assessment or long-term mercury exposure, to occupational disease
Diagnosis has important reference significance.Detect mercury content using the direct mercury vapourmeter of DMA-80, main research concentrate on water, soil,
Blood, urine in food and biological sample, the measurement of rare research mercury in hair content.
Summary of the invention
To solve the above problems, the object of the present invention is to provide a kind of direct mercury vapourmeters of DMA-80 to measure mercury in hair content
Method quick and precisely can provide strong evidence for medical diagnosis, clinical test and the detection of mercury poisoning case.
The object of the present invention is achieved like this: a kind of method of the direct mercury vapourmeter measurement mercury in hair content of DMA-80,
Characterized by the following steps:
(1) hair preparation of samples: is shredded into direct injected；Alternatively, by after the cleaning of Hair grooming deionized water, then with organic molten
5-10min is impregnated in agent, then shreds after natural air drying, direct injection analysis；
(2) it is measured using the direct mercury vapourmeter of DMA-80, location parameter are as follows: the range of drying temperature is 50 DEG C -100
DEG C, decomposition temperature scope is 400 DEG C -700 DEG C.
In the step (1), organic solvent is acetone.
In the step (2), the sampling amount of hair is 0.0500-1.0000g.
The parameter of the step (2) are as follows: drying time: 50-70s.
The parameter of the step (2) are as follows: resolving time: 80-100s.
The parameter of the step (2) are as follows: drying temperature: 100 DEG C, drying time: 60s.
The parameter of the step (2) are as follows: decomposition temperature: 650 DEG C；Resolving time: 90s；250 DEG C of start temperature.
Method of the invention does not need to carry out the pre-treatment of micro-wave digestion or wet resolution method etc., reduces pre-treating method
Loss to mercury, and easy to operate, pollution is few, detects accuracy quick and with higher, precision.
Detailed description of the invention
Fig. 1 is the optimization figure of drying temperature；
Fig. 2 is the optimization figure of decomposition temperature；
Fig. 3 is the optimization figure of hair sampling amount；
Fig. 4 A is the result that two kinds of instruments detect 2 μ g/L Hg standard solution；Fig. 4 B is that two kinds of instruments detect 100 μ g/L Hg
The result of standard solution；Wherein, DMA-80Direct Mercury Analyzer (continuously measure) is DMA-
80 direct mercury vapourmeters (METHOD FOR CONTINUOUS DETERMINATION), ICP-MS are icp ms, DMA-80Direct Mercury
Analyzer (individualy measure) is the direct mercury vapourmeter of DMA-80 (sample-adding detection one by one)；Abscissa Test
Times is testing time.
Specific embodiment
The present invention is a kind of method of direct mercury vapourmeter measurement mercury in hair content of DMA-80, it is characterised in that including following
Step:
(1) hair preparation of samples: is shredded into direct injected；Alternatively, by after the cleaning of Hair grooming deionized water, then with organic molten
5-10min is impregnated in agent, then shreds after natural air drying, direct injection analysis.Preferably, organic solvent is acetone.
(2) it is measured using the direct mercury vapourmeter of DMA-80, location parameter are as follows: the range of drying temperature is 50 DEG C -100
DEG C, decomposition temperature scope is 400 DEG C -700 DEG C.Preferably, the sampling amount of hair is 0.0500-1.0000g.Preferably, dry
Time: 50-70s.Preferably, the resolving time: 80-100s.Most preferably, parameter are as follows: drying temperature: 100 DEG C, drying time:
60s；Decomposition temperature: 650 DEG C；Resolving time: 90s；250 DEG C of start temperature.
Under operating condition identical with step (2), the drafting of mercury standard curve is first carried out.Preferably, the mercury standard
The plot step of curve are as follows: accurately pipette the 25 μ L of mercury standard solution of 1000 μ g/mL in 25mL Glass capacity bottle, be added 2%
Nitric acid and 10 μ g/mL gold element, with 18.2M Ω cm-1Deionized water constant volume, be configured to the mercury deposit of 1 μ g/mL
Liquid, then dilute the mercury series standard solution for being configured to 2,5,10,20,30,50,100 μ g/L step by step with deionized water, and be added
1% nitric acid solution and the gold element of 200ng/mL, are settled to 25mL with deionized water；Under the instrument operating condition of setting from
Low concentration is to high concentration successively sample introduction, and using mercury content as abscissa, unit ng draws mark using absorbance value Abs as ordinate
Quasi- working curve.
It is finally qualitative according to retention time to step (2) detection gained working curve, according to absorbance value external standard method meter
Calculate the content of measured target object.Preferably, the content method of the calculating measured target object are as follows: standard curve is utilized, according to
The absorbance value of sample to be tested seeks the content for calculating mercury in sample.
Calculation formula X=C × 1000/m (1)
In formula:
X --- the content of mercury in sample, unit be milligrams per kilogram, mg/kg；
C --- the quality of mercury, ng in sample；
M --- sample mass, g.
It is indicated with the arithmetic mean of instantaneous value of the measurement result independent twice obtained under the conditions of repeatability, when result is more than or equal to
When 1.0mg/kg, retain three effective digitals；When result is less than 1.0mg/kg, retain two effective digitals.
Below by way of specific example, the present invention is further elaborated, but the present invention is not limited thereto specific examples.
When being detected below using DMA-80 mercury vapourmeter, unless otherwise instructed, location parameter are as follows: drying temperature: 100
℃；Drying time: 60s；Decomposition temperature: 650 DEG C；Resolving time: 90s；250 DEG C of start temperature.
1.1 instrument
DMA-80 mercury vapourmeter (Italian MILESTONE)；Icp ms (ICP-MS)
(PerkinElmer NexION 350X)；Oxygen (purity is 99% or more)；(Pudong, Shanghai Rong Feng scientific instrument have Muffle furnace
Limit company)；Quartz boat；Nickel boat；Glass capacity bottle (25mL, 10mL, 50mL)；Scissors；Tweezers；1/1000 electronic balance BS423S
(sensibility reciprocal 0.01mg and 0.01g) (Shanghai Sai Duolisi company)；1/10000 electronic balance (Shanghai Sai Duolisi company)；Centrifugation
It manages (2mL and 10mL)；Microwave dissolver (U.S. MARS Xpress)；Counteracting tank；DHG-9145A electric heating constant-temperature blowing drying box
(the permanent Science and Technology Ltd. in Shanghai one)；Adjustable liquid-transfering gun (100-1000uL, 10-100uL, 2-20uL) (GILSON)；Numerical control is super
Sound wave washer (Kunshan ultrasonic instrument Co., Ltd).
1.2 chemical reagent
Mercury, goldstandard solution (1000ug/mL, Iron and Steel Research Geueral Institute, national steel material test center)；65% nitric acid (point
Analyse pure, Buddhist nun's chemical reagent factory is sent in Zhengzhou)；30% hydrogen peroxide (analyzes pure, Guangzhou Chemical Reagent Factory)；Ether (analyzes pure, Guangzhou
Chemical reagent factory)；Methanol (Fisher company)；Ultrapure water is prepared (in Mi Libo by the ultrapure hydrotreater of Milli-Q Element
Co., Ltd).
The preparation of 1.3 solution
The preparation of Hg standard solution: accurately pipetting mercury standard solution (1000 μ g/mL) 25 μ L in 25mL Glass capacity bottle,
2% nitric acid and the gold element of 10 μ g/mL is added, with deionized water (18.2M Ω cm-1) constant volume, it is configured to 1 μ g/mL's
Mercury stock solution, then dilute the mercury series standard solution for being configured to 2,5,10,20,30,50,100 μ g/L step by step with deionized water, and
1% nitric acid solution and the gold element of 200ng/mL is added, is settled to 25mL with deionized water.
Under the instrument operating condition of setting from low concentration to high concentration successively sample introduction, with mercury content (ng) for abscissa,
Absorbance value Abs is ordinate, draws standard working curve.
The pre-treatment of 1.4 samples
Sample: collecting hair swatch, picks up from Healthy People, and hair swatch is had hair dyed without hair-waving.It is enough with stainless steel scissors clip
Hair, fill it and be fitted into polyethylene bags, at room temperature save in case detection.
Sample treatment: after the cleaning of Hair grooming deionized water, then with acetone soak 5-10min, it is therefore an objective to remove table
Face grease after immersion, is outwelled acetone, is shredded after waiting hair sample natural air drying, weighs 0.0500g hair on nickel boat, puts down
Row measurement is three times.
The optimization of 2.1 drying temperatures and decomposition temperature
The direct mercury vapourmeter of DMA-80 is surveyed based on high-temperature oxydation decomposition-catalytic adsorption removal of impurities-amalgamation trapping-Atomic absorption
Due to the direct analysis instrument of mercury of one.Pyrolysis process is under the action of oxygen stream, in quartz ampoule or nickel boat
Sample, into dry and high temperature thermal decomposition, generates gas in dore furnace.The control of the temperature of the process directly affects in hair
The accuracy of mercury content detection, therefore the drying temperature of pyrolysis process is optimized with decomposition temperature by the application.
2.1.1 the optimization of drying temperature
The sample prepared using the 1.4th point is detected after adjusting drying temperature.Measurement result such as Fig. 1.
Sample reduces the interference to sclera remodeling removing moisture after drying.Different from high-moisture sample such as soil
The water content of earth, food etc., hair is low, so drying temperature is unobvious on the detection influence of mercury content in hair.However consider
To the unstability due to mercury, the excessively high loss that will cause mercury of temperature, secondly, the main component of hair is protein, belonging to has
Machine object, it is inflammable, therefore, it is not recommended that drying temperature is arranged excessive.It will be seen from figure 1 that in this conditions, 50
Mercury in hair measured value highest at DEG C -100 DEG C, it is therefore preferred that the range of setting drying temperature is 50 DEG C -100 DEG C.
2.1.2 the optimization of decomposition temperature
The sample prepared using the 1.4th point is detected after adjusting decomposition temperature.Measurement result such as Fig. 2.
Sample decomposition is the committed step of mercury content in direct mercury vapourmeter test sample, therefore selects suitable decomposition temperature
It is directly related with the accuracy of measurement result.Figure it is seen that the mercury in hair has failed when decomposition temperature is lower than 400 DEG C
Complete decompose releases, and leads to that measurement result is relatively low and inspection result is unstable.When decomposition temperature is greater than 400 DEG C, in hair
Mercury almost decompose and release, measurement result is higher.The settable temperature of the highest of instrument is 750 DEG C, it is contemplated that instrument
The protection of device and the excessively high loss for being likely to cause mercury of temperature, it is not recommended that temperature setting is excessively high.Preferably, the decomposition of setting
Temperature range is 400 DEG C -700 DEG C.
The optimization of 2.2 sample pre-treatments
2.2.1 direct-injection technique
Direct-injection technique: hair is shredded, and claims the hair of 0.0500g on nickel boat, direct injection analysis is measured in parallel three
It is secondary.Measurement result is shown in Table 1.
2.2.2 ablution
After the cleaning of Hair grooming deionized water, then with acetone soak 5-10min, it is therefore an objective to surface grease is removed, after immersion,
Acetone is outwelled, is shredded after waiting hair sample natural air drying, 0.0500g hair is weighed on nickel boat, is measured in parallel three times.Detection
It the results are shown in Table 1.
2.2.3 Microwave Digestion one
0.100g hair is weighed in counteracting tank, 65% nitric acid (analysis is pure) of 3mL is added, adds the peroxide of 0.5mL
Change hydrogen (analysis is pure), carries out micro-wave digestion, sample prepares three parts in parallel.Micro-wave digestion condition setting are as follows: 800W, 150 DEG C, heating
5min keeps 10min.Counteracting tank, static 30min, cooling are taken out after resolution.Sample after resolution is fallen in the volumetric flask of 10mL
In, it spends and dilutes constant volume from water, mix.Take 100uL in quartz boat, sample-adding measures three to METHOD FOR CONTINUOUS DETERMINATION three times and one by one respectively
It is secondary.Testing result is shown in Table 1.
2.2.4 Microwave Digestion two
0.100g hair is weighed in counteracting tank, 65% nitric acid (analysis is pure) of 3mL is added, adds the peroxide of 0.5mL
Change hydrogen (analysis is pure), carries out micro-wave digestion, sample prepares three parts in parallel.Micro-wave digestion condition setting are as follows: 800W, 150 DEG C, heating
5min keeps 10min.Counteracting tank is taken out after resolution, is placed in and catches up on sour instrument, 100 DEG C, catches up with sour 10h.To catch up with the sample after acid fall in
It is spent in the volumetric flask of 10mL and dilutes constant volume from water, mixed.Take 100uL in quartz boat, METHOD FOR CONTINUOUS DETERMINATION is three times and one by one respectively
Sample-adding measurement is three times.Testing result is shown in Table 1.
2.2.5 the optimization brief summary of pre-treating method
As it can be seen from table 1 the measurement result of sampling system is essentially identical after direct-injection technique, cleaning, Microwave Digestion is surveyed
Definite value is relatively low, main reasons is that Hg volatility is big, in the pretreatment process of micro-wave digestion, high temperature can accelerate the evaporation of mercury, leads
Cause Hg loss in sample.The RSD that sampling system continuous sample introduction detects after direct-injection technique, cleaning is lower, illustrates both pre-treatments
It is preferable that method detects precision.Microwave Digestion, if continuous sample introduction, RSD is higher, and the precision of measured value is bad；If adding one by one
Sample, i.e., equal instrument temperatures are reduced to initial temperature hereinafter, quartz boat analyzes next sample, Parallel testing three after cooling down completely again
Secondary, measurement result RSD is lower.Therefore, the pretreatment mode for carrying out micro-wave digestion to hair is not suitable for direct mercury vapourmeter.Consider
To the cleaning in order to guarantee sample, it is advantageous to direct-injection techniques after cleaning.
The optimization of 1 pre-treatment of table
| Pre-treating method | Hg measures mean value (mg/kg) | RSD (%) |
| Direct-injection technique | 0.26±0.001 | 0.36 |
| Sampling system after cleaning | 0.22±0.009 | 3.83 |
| Microwave Digestion one (continuous detection) | 0.17±0.197 | 11.3 |
| Microwave Digestion one (is loaded) one by one | 0.17±0.001 | 0.53 |
| Microwave Digestion two (continuous detection) | 0.16±0.026 | 16.1 |
| Microwave Digestion two (is loaded) one by one | 0.18±0.002 | 1.29 |
The optimization of 2.3 sampling amounts
Hair is shredded, different weight is weighed, is placed in nickel boat, is detected.
It is shown according to experimental result, when sampling amount is less than 0.0500g, the testing result of mercury in hair content is unstable；
When sampling amount is greater than 0.1000g, measurement result numerical value is more stable, but when sampling amount is more than 0.2000g, nickel boat has been expired.Sampling
The too low detection limit for being unable to satisfy instrument is measured, it is unstable to will lead to measurement result；Sampling amount is too big and is more than the meeting of example boat volume
Causing the loss of sample during sample introduction leads to measurement result because excessive hair can spread out example boat during sample introduction
Error is generated, secondly because hair is inflammable, excessive hair may make example boat fall to pipe in the process that high-temperature oxydation decomposes
In road, lead to the damage of instrument.Comprehensively consider lower preferred sampling amount is set as 0.0500-1.0000g.Testing result is shown in Fig. 3.
2.4DMA-80 the comparison of direct mercury vapourmeter and icp ms
2.4.1 the preparation of sample
Microwave Digestion three: weighing 0.1000g hair in counteracting tank, is added 65% nitric acid (analysis pure) of 3mL, then plus
The hydrogen peroxide (analysis is pure) for entering 0.5mL, carries out micro-wave digestion, sample prepares three parts in parallel.Micro-wave digestion condition setting are as follows:
800W, 150 DEG C, heat up 5min, keeps 10min.Counteracting tank, static 30min, cooling are taken out after resolution.By the sample after resolution
It pours into the volumetric flask of 50mL, spends and dilute constant volume from water, mix.
2.4.2ICP-MS the setting of parameter
The parameter setting of ICP-MS is shown in Table 2:
The setting of 2 ICP-MS parameter of table
2.4.3 the stability of the direct mercury vapourmeter continuous sample introduction of DMA-80 and ICP-MS detection is investigated
Take the 100 μ L of Hg standard solution of 2 μ g/L and 100 μ g/L in quartz boat respectively, with direct mercury vapourmeter METHOD FOR CONTINUOUS DETERMINATION
10 times.In addition, taking 2 μ g/L and 100 μ g/L standard solution, 100 μ L in quartz boat respectively again, it is loaded one by one, i.e., equal instrument temperatures
Analyze next sample after initial temperature is reduced to hereinafter, quartz boat is completely cooling again, Parallel testing 10 times.Meanwhile it using
ICP-MS is compared research, with the Hg standard solution of 2 μ g/L and 100 μ g/L, Parallel testing 10 times.Obtain result such as Fig. 4 A,
Fig. 4 B and table 3, table 4.
When continuously detecting the Hg standard solution of 2 μ g/L and 100 μ g/L using the direct mercury vapourmeter of DMA-80, RSD is higher, says
The bright measurement result continuously detected using direct mercury vapourmeter is highly unstable, and possible cause is that Hg can evaporate at room temperature, into
The temperature of specimen chamber is higher, accelerates the volatilization of Hg, and when continuous detection, the mercury in Sample Room in sample to be detected can be different degrees of
Volatilization.Particularly with the lower weak solution sample of mercury content, continuous detection will appear that RSD is higher, and measured value is unstable.When by
When the Hg standard solution of a sample-adding detection 2 μ g/L and 100 μ g/L, RSD is lower, and testing result stability is preferable, therefore uses
When direct mercury vapourmeter detects mercurous concentration relatively low weak solution sample, for example, urine, preferably sample-adding detection one by one.ICP-MS connects
When the Hg standard solution of continuous measurement 2 μ g/L and 100 μ g/L, RSD is lower, illustrate to use ICP-MS continuously detect stability compared with
Height, but mean value is measured than using the result of the direct mercury vapourmeter of DMA-80 sample detection one by one low.
The result of 3 two kinds of instrument detection 2ug/L Hg standard solution of table
The result of 4 two kinds of instrument 100ug/L Hg standard solution of table
2.4.4 comparative example: the direct mercury vapourmeter of DMA-80 same sample after sample introduction and ICP-MS detection micro-wave digestion one by one
Sample after taking 100 μ L to clear up respectively is placed on quartz boat, using the direct mercury vapourmeter of DMA-80, is loaded one by one, is put down
Row measurement is three times.Simultaneously using the same sample after ICP-MS detection resolution, it is measured in parallel three times.With direct-injection technique, directly
The hair that the mercury vapourmeter detection same person does not clear up, is measured in parallel three times.By it is preceding it is described utilize standard curve, according to sample to be tested
Absorbance value, seek the content for calculating mercury in sample, testing result is shown in Table 5.
Two kinds of instrument detected value no significant differences, precision is preferable, illustrates that the direct mercury vapourmeter of DMA-80 and ICP-MS exist
The result of same sample is without significant difference after detection resolution.But the result of the hair that do not clear up, direct mercury vapourmeter detection is compared
Compared with the sample measurements after resolution are relatively low, and main cause is in the pretreatment process of micro-wave digestion, and high temperature can accelerate waving for Hg
Method causes the different degrees of loss of Hg in sample.And micro-wave digestion pre-treatment is cumbersome, takes time and effort.Therefore for inspection
Hg content in gauge head hair, with greater advantage compared with ICP-MS using the detection of direct mercury vapourmeter.
The comparison of the different Instrument measuring mercury in hair contents of table 5
2.5 methodology validation
2.5.1 standard curve
It takes placebo solution 100uL in quartz boat, then takes 2,5,10,20,30,50,100 μ g/L mercury series marks respectively
Quasi- 100 μ L of solution is measured under optimal testing conditions in quartz boat.Least square is done with amount (Hg) of the peak height (A) to mercury
Regression analysis obtains respective standard curve are as follows: A=0.008+0.047Hg+0.02Hg2, r2=0.9999, standard curve it is linear
Well.Testing result is shown in Table 6.
2.5.2 detection limit
Using empty boat as blank, replication (10 times), standard deviation S=0.0002,3S=0.0060, by 3S/K, (K is school
Directrix curve slope) minimum detectability is obtained as 0.013ng.Method detection is limited to 0.13 μ g/kg.Testing result is shown in Table 6.
6 range of linearity of table, r2, regression equation, LOD, MDL
2.5.3 instrument precision
Take 25mL volumetric flask, the mercury standard solution (1000 μ g/mL) of 250 μ L be added, be added 1% nitric acid (analysis is pure) and
The gold element of 200ng/mL is mixed with deionized water constant volume, is configured to the Hg stock solution of 10 μ g/mL.25mL volumetric flask is taken, is added
Enter 50 μ L stock solutions, the gold element that 1% nitric acid (analysis is pure) and 200ng/mL is added is mixed with deionized water constant volume, is prepared
At the mercury standard solution of 20 μ g/L.It takes 100 μ L mercury standard solutions (20 μ g/L) in quartz boat, is loaded one by one, be measured in parallel 7
Secondary, calculating RSD is 1.37%, illustrates that instrument precision is preferable.
2.5.4 recovery of standard addition and method precision
Weigh hair swatch 0.0500g, be added in hair sample respectively low (2 μ g/L), in (20 μ g/L), height (50 μ g/
L) the 100 μ L of mercury standard solution of 3 various concentrations is measured in parallel three times, calculates recovery of standard addition and RSD.Low concentration is horizontal
Under, recovery of standard addition 107%, RSD 0.42%；Under intermediate concentration level, recovery of standard addition 102%, RSD is
1.23%；Under high concentration is horizontal, recovery of standard addition 100%, RSD 0.32%.The rate of recovery in the normal range, and RSD
Respectively less than 5%, illustrate that the accuracy of this method is high, precision is good.Testing result is shown in Table 7.
The test of 7 recovery of standard addition of table
Claims (9)
1. a kind of method of the direct mercury vapourmeter measurement mercury in hair content of DMA-80, it is characterised in that the following steps are included:
(1) hair preparation of samples: is shredded into direct injected；Alternatively, being soaked by after the cleaning of Hair grooming deionized water, then with organic solvent
5-10min is steeped, is then shredded after natural air drying, direct injection analysis；
(2) it being measured using the direct mercury vapourmeter of DMA-80, location parameter are as follows: the range of drying temperature is 50 DEG C -100 DEG C, point
Solving temperature range is 400 DEG C -700 DEG C.
2. according to the method described in claim 1, it is characterized by: organic solvent is acetone in the step (1).
3. according to the method described in claim 1, it is characterized by: the sampling amount of hair is 0.0500- in the step (2)
1.0000g。
4. according to the method described in claim 1, it is characterized by: the parameter of the step (2) are as follows: drying time: 50-70s.
5. according to the method described in claim 1, it is characterized by: the parameter of the step (2) are as follows: the resolving time: 80-
100s。
6. according to the method described in claim 1, it is characterized by: the parameter of the step (2) are as follows: drying temperature: 100 DEG C,
Drying time: 60s.
7. according to the method described in claim 1, it is characterized by: the parameter of the step (2) are as follows: decomposition temperature: 650 DEG C；
Resolving time: 90s；250 DEG C of start temperature.
8. method described in -7 any claims according to claim 1, it is characterised in that further include: identical as step (2)
Operating condition under, carry out mercury standard curve drafting；It is fixed according to retention time that gained working curve finally is detected to step (2)
Property, the content of measured target object is calculated with external standard method according to chromatographic peak area.
9. according to the method described in claim 8, it is characterized by:
The plot step of the mercury standard curve are as follows:
2% nitric acid and 10 μ is added in 25mL Glass capacity bottle in the 25 μ L of mercury standard solution for accurately pipetting 1000 μ g/mL
The gold element of g/mL, with 18.2M Ω cm-1Deionized water constant volume, be configured to the mercury stock solution of 1 μ g/mL, then use deionized water
Dilution is configured to the mercury series standard solution of 2,5,10,20,30,50,100 μ g/L step by step, and be added 1% nitric acid solution and
The gold element of 200ng/mL is settled to 25mL with deionized water；Under the instrument operating condition of setting from low concentration to high concentration
Successively sample introduction, using mercury content as abscissa, unit ng draws standard working curve using absorbance value Abs as ordinate；
The content method of the calculating measured target object are as follows: calculation is asked according to the absorbance value of sample to be tested using standard curve
The content of mercury in sample:
Calculation formula X=C × 1000/m (1)
In formula:
X --- the content of mercury in sample, unit be milligrams per kilogram, mg/kg；
C --- the quality of mercury, ng in sample；
M --- sample mass, g.
It is indicated with the arithmetic mean of instantaneous value of the measurement result independent twice obtained under the conditions of repeatability, when result is more than or equal to 1.0mg/
When kg, retain three effective digitals；When result is less than 1.0mg/kg, retain two effective digitals.
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