CN106896169B - The detection method of Sb (V) in a kind of soil or deposit - Google Patents
The detection method of Sb (V) in a kind of soil or deposit Download PDFInfo
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Abstract
The invention discloses the detection methods of Sb (V) in soil or deposit a kind of, include the following steps：(1) sample collection and pre-treatment：Soil or sediment sample are acquired, air-dried, ground and is sieved successively, sample is extracted using hydroxylamine hydrochloride, then after supersound process, centrifugation and supernatant liquid filtering obtains extracting solution successively；(2) high performance liquid chromatography hydride-generation atomic fluorescence method is used to establish the standard curve of various concentration Sb (V)；(3) measurement of recovery of standard addition；(4) the obtained extracting solution is detected, calculates the concentration of Sb in soil (V).The detection method rate of recovery of Sb (V) is high in soil or deposit of the present invention, easily operated, realizes the accurate analysis method to Sb (V) micro in soil or deposition medium.
Description
Technical field
The present invention relates to a kind of detection methods of antimony, more particularly to the detection side of Sb (V) in soil or deposit a kind of
Method.
Background technology
Antimony is a kind of metallic element of distribution on global, and the 15th race element of the same clan with arsenic is belonged in the periodic table of elements,
It is also the metallic element with own strategic significance, irreplaceable role is played in modern industry, main application is to use
In manufacture lead accumulator, brominated or chlorine-containing flame retardant, semiconductor, ceramics, bullet, organic compound is used also as pesticide or medicine
In object.The industry of industrial revolution post-modernism sharply increases the demand of antimony element, therefore in exploitation of mineral resources, industrial production and use
Increasingly severe trend is also presented in antimony pollution in the process.Due to the extensive existence of antimony and potential carcinogenicity, most
Recent decades cause extensive concern.Antimony is as the natural component in the earth's crust, and average content is about 1mg/Kg in global soil,
And in China, this content is 1.34mg/Kg.In the more serious Polluted area of some Sb human interferences, surrounding medium
The more unpolluted soil of antimony content is higher by multiple orders of magnitude, the concentration of the Sb such as detected in hunan stannary regional soil
Up to 5045mg/kg.Although the concern that Sb was subject in recent years is more, for congeners As, the research to Sb
Also relatively lag behind.
Antimony is a kind of non-essential element for human body, can be caused to damage to body, and is considered a kind of doubtful carcinogenic
Substance, excessive antimony may liver, skin and respiratory system disease, antimony can be present in biology by bioconcentration
In body, antimony in environment mainly exists in the form of Sb (V) and Sb (III), for living organism physiological-toxicity also
Difference.Sb is classified as priority pollutants by USEPA and European Union, while being also classified as hazardous waste by Basel Convention.Therefore have
Close government and mechanism has many regulations for the content of Sb in water body and soil, and the soakage of the daily Sb of human body is provided not in Germany
It obtains more than 23 μ g/d.U.S.EPA provides that human body is 0.4 μ g/Kg, Dutch section to the acceptable daily intake of Sb and Sb (III)
Scholar suggests that the maximum acceptable concentration of Antimony In The Soils is respectively 3.5mg/Kg.
In view of being widely present for antimony element, and the carcinogenicity shown causes concern of the researcher for the pollutant.
Soil or deposit are the surrounding mediums that human consumption accumulates antimony element, but soil or deposit mesostroma are complicated, extraction
Antimony in soil or deposit is simultaneously detected with larger difficulty, it is therefore necessary to the dense of the antimony in soil or deposit
Degree expansion research, in view of physiological-toxicity and environmentology behavior between the Sb (V) and Sb (III) of two kinds of common forms in surrounding medium
Existing greatest differences, it is necessary to carry out the research to Sb in environment (V) detection method, but the antimony in current soil or deposit
Detection method focus primarily upon its total quantifier elimination, and extraction more rare to the extracting method of different valence state antimony, common
Agent oxalic acid, citric acid, EDTA or phosphoric acid are usual relatively low (usually only 60~80%) for the extraction efficiency of Sb (V), and extract
Do not consider that the conversion of different valence state antimony is denaturalized in the process.
Invention content
The technical problem to be solved by the present invention is to be directed to that Sb (V) valence state in soil or deposit is unstable and extraction is difficult
Feature is developed a kind of analytical technology that the rate of recovery is high, easily operated, is realized to Sb micro in soil or deposition medium
(V) accurate analysis method.
The present invention is by selecting suitable extractant and chromatography column that can preferably extract in soil or deposit
Quinquevalence antimony, and the stabilization of antimony valence state in soil or deposit can be effectively kept, this method has the rate of recovery high, and specificity is well and simple
The characteristic of easy row.In addition the hydroxylamine hydrochloride extractant phase that this method uses can reach higher for traditional extractant to Sb (V)
Recovery rate, the chromatographic separation technology used can make up at present for different valence state antimony detection method in soil or deposit
Missing.
The detection method of Sb (V), includes the following steps in a kind of soil or deposit：
(1) sample collection and pre-treatment：Soil or sediment sample are acquired, air-dried, ground and is sieved successively, is used
Hydroxylamine hydrochloride extracts sample, then after supersound process, centrifugation and supernatant liquid filtering obtains extracting solution successively；
(2) high performance liquid chromatography-hydride generation-atomic fluorescence method is used to establish the standard curve of various concentration Sb (V)；
(3) measurement of recovery of standard addition；
(4) method of step (1) is used to be acquired to sample and pre-treatment, and using the method for step (2) to obtaining
The extracting solution be detected, calculate the concentration of Sb in soil (V).
The detection method of Sb (V) in soil or deposit of the present invention, wherein the hydroxylamine hydrochloride uses anaerobic water
It prepares, a concentration of 0.1mol/L.
The detection method of Sb (V) in soil or deposit of the present invention, wherein step (1) specifically includes following step
Suddenly：
Acquisition soil or sediment sample air-dry at room temperature, are sieved with 100 mesh sieve after grinding to be measured；0.2g samples are weighed in poly-
In ethylene centrifuge tube, 0.1mol/L hydroxylamine hydrochloride 10ml are added, and 3min is handled under 50W power using sonicator,
Obtained solution supercentrifuge high speed centrifugation 5min under the rotating speed of 10000rpm, after taking supernatant to cross 0.22 μm of filter membrane
To extracting solution.
The detection method of Sb (V) in soil or deposit of the present invention, wherein in step (2) further include standard
The preparation of solution：A certain amount of hexahydroxy potassium antimonate is weighed respectively, is configured to the 1000mg/L mother liquors of Sb (V), it is dilute with ultra-pure water
The standard solution of various concentration is made in the mother liquor for releasing Sb (V)：0 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/L, 100 μ g/L.
The detection method of Sb (V) in soil or deposit of the present invention, wherein step (2) high performance liquid chromatography-hydrogen
In compound generation-atomic fluorescence method for detach chromatographic column in water body be anion separation column PRP-X100,250mm ×
4.1mm, 10 μm, mobile phase is the ammonium tartrate solution of 0.2mol/L, and adjustment pH value is 5 after crossing 0.22 μm of nylon leaching film, flow velocity
It is set as 1.5mL/min, the sample size of each solution is 200 μ L, and the pressure of high-purity argon gas is set as 2068.4Pa.
The detection method of Sb (V) in soil or deposit of the present invention, wherein step (2) high performance liquid chromatography-hydrogen
In compound generation-atomic fluorescence method, the detection of antimony is measured using atomic fluorescence spectrophotometer PSA-10.055, weighs 4g's
NaOH solution dissolves, and adds the NaBH of 8g4, ultra-pure water is settled to 1L as reducing agent, in addition matched with concentrated hydrochloric acid, KI and thiocarbamide
System contains the HCl solution of the 1.8mol/L of 3%KI+1% thiocarbamides as reagent blank, wherein the flow velocity of reagent blank is set as
The flow velocity of 7.5mL/min, reducing agent are 3.75mL/min, use high-performance Sb hollow cathode lamps.
The detection method of Sb (V) in soil or deposit of the present invention, wherein step (2) high performance liquid chromatography-hydrogen
In compound generation-atomic fluorescence method, the detection of Sb is carried out using SAMS softwares, and the detection time of method is set as 9min, is obtained
Value (Gain) value is set as 10, and the rotating speed of flow pumps is both configured to 75%, and lamp current is set as principal current (Primary)：
17.5mA, supercharging electric current (Boost)：15mA, in detection process, the appearance time of Sb (V) in 2~3min, standard curve
Drafting is carried out using SAMSCalc softwares, and the linearly dependent coefficient R of the standard curve of drafting must be more than 0.999, every time before detection
Instrument preheats 30min, and balance each other chromatographic column 1min with flowing after the completion of each sample detection is imitated with restoring column.
The detection method of Sb (V) in soil or deposit of the present invention, wherein in step (3), choose soil or
Deposit Standard Reference Materials for Determination (GBW07406 or GBW07312), it is real by the mark-on reclaims for adding Sb (V) standard substance
Test the recovery of standard addition for calculating Sb (V)：
The following two groups of experiments of comparison：
(A) soil or deposit Standard Reference Materials for Determination of the standard solution of 20 μ g/L Sb (V) are not added with；
(B) soil or deposit Standard Reference Materials for Determination of the standard solution of 20 μ g/L Sb (V) of addition；
Using both the above solution as soil or sediment sample, it is detected respectively according to step (4), detection obtains
A concentration of C0And C；
And calculate recovery of standard addition according to following formula：
Wherein：
R- recovery of standard addition, %；
The content of Sb (V), μ g/ in the soil or deposit Standard Reference Materials for Determination of the standard solution of C- addition Sb (V)
L；
C0It is not added with the soil of the standard solution of Sb (V) or the content of Sb (V) in deposit Standard Reference Materials for Determination, μ
g/L；
Recovery of standard addition of the Sb (V) in soil or deposit Standard Reference Materials for Determination finally is calculated, in addition presses
The detection limit of Sb (V) is calculated according to 3 times of signal-to-noise ratio (S/N).
The detection method of Sb (V) in soil or deposit of the present invention, wherein further include Accuracy Verification experiment：
Following contrast test is carried out in soil or deposit Standard Reference Materials for Determination：
(a) soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances are added；
(b) soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances are not added；
Using both the above solution as soil or sediment sample, the experiment of step (4) is carried out respectively, has been verified whether
Sb (III) transforms into Sb (V), and such as finally obtained result is：The generation of Sb (III) → Sb (V) is not detected, that is, demonstrates this examination
The accuracy tested.
The detection method of Sb (V) in soil or deposit of the present invention, wherein in step (4), if extracting solution
Response peak is excessively high and has been more than the detection range of instrument, then is diluted to extracting solution with ultra-pure water, the calculating profit of sample concentration
It is calculated with SAMSCalc softwares.
The detection method difference from prior art of Sb (V) is in soil or deposit of the present invention：
The present invention utilizes the separating effect and Hydride Generation-Atomic Fluorescence Spectrometric of efficient anion separation column
(HPLC-HG-AFS) establish the good high sensitivity rate of recovery and in easy-to-use soil or deposit Sb (V) detection method.
In the present invention, soil or sediment sample are extracted using 0.1mol/L hydroxylamine hydrochlorides, it can be effective
Extract the main valence state Sb (V) in soil or deposit；The Sb (III) of extraction is detached using high-efficiency anion chromatographic column
And be detected, there is preferable specificity and novelty；The antimony of separation is examined in conjunction with Hydride Generation-Atomic Fluorescence Spectrometric
It surveys, reasonable design of the present invention establishes the detection side of Sb in soil (V) by conditioning instrumentation parameter and reagent concentration and flow velocity
Method has preferable specificity, the metastable rate of recovery and higher stability.
The detection method of Sb (V) in the soil or deposit of the present invention is described further below in conjunction with the accompanying drawings.
Description of the drawings
Fig. 1 is the soil or deposit Standard Reference Materials for Determination of Sb (V) standard solution that 20 μ g/L are added in the present invention
Chromatogram；
Fig. 2 is the result figure in Accuracy Verification experiment in the present invention；
The chromatogram that Fig. 3 is Sb (V) in soil or deposit in the embodiment of the present invention；
The bilingual of the English occurred in all attached drawings of the present invention is as follows：
Time:Time；
Signal:Signal value；
chromatography:Chromatogram.
Specific implementation mode
Embodiment 1
The detection method of Sb (V), includes the following steps in a kind of soil or deposit：
(1) sample collection and pre-treatment：Soil or sediment sample are acquired, air-dried, ground and is sieved successively, is used
Hydroxylamine hydrochloride extracts sample, then after supersound process, centrifugation and supernatant liquid filtering obtains extracting solution successively；
In more detail, specifically comprise the following steps：
Acquisition soil or sediment sample air-dry at room temperature, are sieved with 100 mesh sieve after grinding to be measured；0.2g samples are weighed in poly-
In ethylene centrifuge tube, 0.1mol/L hydroxylamine hydrochloride 10ml are added, hydroxylamine hydrochloride is prepared using anaerobic water, and uses ultrasonic disruption
Instrument handles 3min under 50W power, and obtained solution supercentrifuge high speed centrifugation 5min under the rotating speed of 10000rpm takes
Supernatant obtains extracting solution after crossing 0.22 μm of filter membrane.
Using the extractant of 0.1mol/L hydroxylamine hydrochlorides, the subsequent separation of extractant cooperation of the concentration gradient and extraction hand
Section can effectively realize the detection to soil or sediment sample.
(2) high performance liquid chromatography-hydride generation-atomic fluorescence method is used to establish the standard curve of various concentration Sb (V)；
The preparation of standard solution：A certain amount of hexahydroxy potassium antimonate is weighed respectively, and the 1000mg/L for being configured to Sb (V) is female
The standard solution of various concentration is made of the mother liquor of ultra-pure water dilution Sb (V) for liquid：0 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 40
μ g/L, 100 μ g/L.
It is anion separation column PRP-X100,250mm × 4.1mm, 10 μm, mobile phase for detaching the chromatographic column in water body
For the ammonium tartrate solution of 0.2mol/L, pH value is adjusted for 5, flow rate set 1.5mL/min, often after crossing 0.22 μm of nylon leaching film
The sample size of secondary solution is 200 μ L, and the pressure of high-purity argon gas is set as 2068.4Pa.Using anion-exchange column PRP-X100 and
Flow visualizing ammonium tartrate solution detaches the Sb (V) of extraction, and separating effect is notable.
The detection of antimony is measured using atomic fluorescence spectrophotometer PSA-10.055, weighs the NaOH solution dissolving of 4g, then
The NaBH of 8g is added4, ultra-pure water is settled to 1L as reducing agent, in addition contains 3%KI+1% with the preparation of concentrated hydrochloric acid, KI and thiocarbamide
The HCl solution of the 1.8mol/L of thiocarbamide is as reagent blank, wherein the flow velocity of reagent blank is set as 7.5mL/min, reducing agent
Flow velocity be 3.75mL/min, use high-performance Sb hollow cathode lamps.
The detection of Sb is carried out using SAMS softwares, and the detection time of method is set as 9min, the setting of acquired value (Gain) value
It is 10, the rotating speed of flow pumps is both configured to 75%, and lamp current is set as principal current (Primary)：17.5mA is pressurized electric current
(Boost)：15mA, in detection process, for the appearance time of Sb (V) in 2~3min, the drafting of standard curve uses SAMSCalc
Software carries out, and the linearly dependent coefficient R of the standard curve of drafting must be more than 0.999, and instrument preheats 30min before detection every time, often
Chromatographic column 1min is balanced each other to restore column effect with flowing after the completion of a sample detection.
(3) measurement of recovery of standard addition；
Soil or deposit Standard Reference Materials for Determination (GBW07406 or GBW07312) are chosen, is marked by adding Sb (V)
The recovery testu of quasi- substance calculates the recovery of standard addition of Sb (V)：
The following two groups of experiments of comparison：
(A) soil or deposit Standard Reference Materials for Determination of the standard solution of 20 μ g/L Sb (V) are not added with；
(B) soil or deposit Standard Reference Materials for Determination of the standard solution of 20 μ g/L Sb (V) of addition；
Using both the above solution as soil or sediment sample, it is detected respectively according to step (4), detection obtains
A concentration of C0And C；
And calculate recovery of standard addition according to following formula：
Wherein：
R- recovery of standard addition, %；
The content of Sb (V), μ g/ in the soil or deposit Standard Reference Materials for Determination of the standard solution of C- addition Sb (V)
L；
C0It is not added with the soil of the standard solution of Sb (V) or the content of Sb (V) in deposit Standard Reference Materials for Determination, μ
g/L；
Recovery of standard addition of the Sb (V) in soil or deposit Standard Reference Materials for Determination finally is calculated, in addition presses
The detection limit of Sb (V) is calculated according to 3 times of signal-to-noise ratio (S/N).
(4) method of step (1) is used to be acquired to sample and pre-treatment, and using the method for step (2) to obtaining
Extracting solution be detected, calculate the concentration of Sb in soil (V).
Add the soil of Sb (V) standard solution of 20 μ g/L or chromatogram such as Fig. 1 of deposit Standard Reference Materials for Determination
It is shown.
In step (4) of the present invention, if the response peak of extracting solution is excessively high and has been more than the detection range of instrument, with ultrapure
Water is diluted extracting solution, and the calculating of sample concentration is calculated using SAMSCalc softwares.
Embodiment 2
On the basis of embodiment 1, the present embodiment further includes Accuracy Verification experiment：
Following contrast test is carried out in soil or deposit Standard Reference Materials for Determination：
(a) soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances are added；
(b) soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances are not added；
Using both the above solution as soil or sediment sample, the experiment of step (4) is carried out respectively, has been verified whether
Sb (III) transforms into Sb (V), and such as finally obtained result is：The generation of Sb (III) → Sb (V) is not detected, that is, demonstrates this examination
The accuracy tested.
Accuracy Verification experiment is optimal technical scheme, more ensure that the accuracy of result.
Embodiment 3
The soil sample for acquiring certain Near Antimony Mine Area, after transporting laboratory back, the grinding of natural wind dry doubling is sieved with 100 mesh sieve and is sealed, detects
When weigh the soil or deposit of 0.2g, 0.1mol/L hydroxylamine hydrochlorides (NH is added2OHHCl) solution 10mL is broken with ultrasonic wave
Broken instrument handles 3min under 50W power, and centrifuges 5min in supercentrifuge with the rotating speed of 10000rpm, takes supernatant mistake
0.22 μm of filter membrane is detected.
Weigh a certain amount of hexahydroxy potassium antimonate (KSb (OH)6), the preparation of standard solution：It is configured to Sb's (V)
The standard solution of various concentration is made of the mother liquor of ultra-pure water dilution Sb (V) for 1000mg/L mother liquors：0 μ g/L, 5 μ g/L, 10 μ g/
L, 20 μ g/L, 40 μ g/L, 100 μ g/L.
It is detached in soil or deposit extracting solution using anion separation column PRP-X100 (250mm × 4.1mm, 10 μm)
Sb (V), the ammonium tartrate solution (adjustment pH value is 5 after crossing 0.22 μm of nylon leaching film) that mobile phase is 0.2mol/L, flow rate set
Sample size for 1.5mL/min, each solution is 200 μ L, and the pressure of high-purity argon gas is set as 2068.4Pa.The detection of antimony uses
Atomic fluorescence spectrophotometer measures (PSA-10.055, Millennium Excalibur System, United
Kingdom), reducing agent uses the NaBH of the NaOH and 8g of 4g41L preparations are settled to, are contained using the preparation of concentrated hydrochloric acid, KI and thiocarbamide
There is the HCl solution (1.8mol/L) of 3%KI+1% thiocarbamides to be used as reagent blank.Flow velocity is set as 7.5mL/min (reagent blank)
With 3.75mL/min (reducing agent), high-performance Sb hollow cathode lamps (Photron, Victoria, Australia) are used.Sb's
Detection is carried out using SAMS softwares, and the detection time of method is set as 9min, and Gain values are set as 10, the rotating speed setting of flow pumps
It is 75%, lamp current is set as Primary：17.5mA Boost：15mA.In detection process, the appearance time of Sb (V) is 2
~3min.The drafting of standard curve is carried out using SAMSCalc softwares, and the linearly dependent coefficient R of the standard curve of drafting must be more than
0.999。
Obtained soil or deposit extracting solution are detected using method identical with standard curve, wherein if carrying
It takes the response peak of liquid excessively high and has been more than the detection range of instrument, then extracting solution is diluted.The calculating of sample concentration utilizes
SAMSCalc softwares are calculated.
Due to lacking the soil or Sediment Reference Materials of different valence state antimony, soil or deposit constituent analysis standard are chosen
Substance (GBW07406 or GBW07312), the mark-on that the recovery testu by adding Sb (V) standard substance calculates Sb (V) return
Yield：
The following two groups of experiments of comparison：
(A) soil or deposit Standard Reference Materials for Determination of the standard solution of 20 μ g/L Sb (V) are not added with；
(B) soil or deposit Standard Reference Materials for Determination of the standard solution of 20 μ g/L Sb (V) of addition；
Using both the above solution as soil or sediment sample, it is detected respectively according to step (4), detection obtains
A concentration of C0And C；
And calculate recovery of standard addition according to following formula：
Wherein：
R- recovery of standard addition, %；
The content of Sb (V), μ g/ in the soil or deposit Standard Reference Materials for Determination of the standard solution of C- addition Sb (V)
L；
C0It is not added with the soil of the standard solution of Sb (V) or the content of Sb (V) in deposit Standard Reference Materials for Determination, μ
g/L；
Recovery of standard addition of the Sb (V) in soil or deposit Standard Reference Materials for Determination finally, which is calculated, is
102.5%.The detection that Sb (V) is calculated further according to 3 times of signal-to-noise ratio (S/N) is limited to 3.16 μ g/L.
In view of in the present invention extraction and experiment condition may result in Sb (III) and transform into Sb (V), may be right
The rate of recovery of experiment has an impact, therefore using the experimental procedure in the present invention, in soil or deposit constituent analysis reference substance
Following contrast test is carried out in matter：
(a) soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances are added；
(b) soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances are not added；
Using both the above solution as soil or sediment sample, the experiment of step (4) is carried out respectively, has been verified whether
Sb (III) transforms into Sb (V), and finally obtained result is：The generation of Sb (III) → Sb (V), this result verification is not detected
The accuracy (Fig. 2) of this experiment.
(4) method of step (1) is used to be acquired to sample and pre-treatment, and using the method for step (2) to obtaining
The extracting solution be detected, be finally calculated Sb (V) in soil or deposit content be 13.1mg/Kg (Fig. 3).Point
The extraction effect of Sb (V), as a result shows sample during at the 2nd, 5,10 day, verification said program was not for soil or deposit again
The relative standard deviation (RSD) of concentration is less than 5%.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
It encloses and is defined, under the premise of not departing from design spirit of the present invention, technical side of the those of ordinary skill in the art to the present invention
The various modifications and improvement that case is made should all be fallen into the protection domain of claims of the present invention determination.
Claims (9)
1. the detection method of Sb (V) in a kind of soil or deposit, it is characterised in that：Include the following steps：
(1) sample collection and pre-treatment：Soil or sediment sample are acquired, air-dried, ground and is sieved successively, using hydrochloric acid
Azanol extracts sample, then after supersound process, centrifugation and supernatant liquid filtering obtains extracting solution successively；The hydrochloric acid hydroxyl
Amine is prepared using anaerobic water, a concentration of 0.1mol/L；
(2) high performance liquid chromatography-hydride generation-atomic fluorescence method is used to establish the standard curve of various concentration Sb (V)；
(3) measurement of recovery of standard addition；
(4) method of step (1) is used to be acquired to sample and pre-treatment, and using the method for step (2) to obtained institute
It states extracting solution to be detected, calculates the concentration of Sb in soil (V)；
2. the detection method of Sb (V) in soil according to claim 1 or deposit, it is characterised in that：Step (1) is specific
Include the following steps：
Acquisition soil or sediment sample air-dry at room temperature, are sieved with 100 mesh sieve after grinding to be measured；0.2g samples are weighed in polyethylene
In centrifuge tube, 0.1mol/L hydroxylamine hydrochloride 10ml is added, and 3min is handled under 50W power using sonicator, obtains
Solution supercentrifuge under the rotating speed of 10000rpm high speed centrifugation 5min, carried after taking supernatant to cross 0.22 μm of filter membrane
Take liquid.
3. the detection method of Sb (V) in soil according to claim 1 or deposit, it is characterised in that：In step (2)
It further include the preparation of standard solution：A certain amount of hexahydroxy potassium antimonate is weighed respectively, is configured to the 1000mg/L mother liquors of Sb (V),
The standard solution of various concentration is made of the mother liquor of ultra-pure water dilution Sb (V)：0 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/
L, 100 μ g/L.
4. the detection method of Sb (V) in soil according to claim 3 or deposit, it is characterised in that：Step (2) is efficient
The chromatographic column for being used to detach in liquid chromatogram-Hydride Generation-Atomic Fluorescence Spectrometric in water body is anion separation column PRP-X100,
250mm × 4.1mm, 10 μm, mobile phase is the ammonium tartrate solution of 0.2mol/L, and adjustment pH value is after crossing 0.22 μm of nylon leaching film
The sample size of 5, flow rate set 1.5mL/min, each solution are 200 μ L, and the pressure of high-purity argon gas is set as 2068.4Pa.
5. the detection method of Sb (V) in soil according to claim 4 or deposit, it is characterised in that：Step (2) is efficient
In liquid chromatogram-Hydride Generation-Atomic Fluorescence Spectrometric, the detection of antimony is surveyed using atomic fluorescence spectrophotometer PSA-10.055
It is fixed, the NaOH solution dissolving of 4g is weighed, the NaBH of 8g is added4, ultra-pure water is settled to 1L as reducing agent, in addition with dense salt
Acid, KI and thiocarbamide prepare the HCl solution for the 1.8mol/L for containing 3%KI+1% thiocarbamides as reagent blank, wherein reagent blank
Flow velocity be set as 7.5mL/min, the flow velocity of reducing agent is 3.75mL/min, uses high-performance Sb hollow cathode lamps.
6. the detection method of Sb (V) in soil according to claim 5 or deposit, it is characterised in that：Step (2) is efficient
In liquid chromatogram-Hydride Generation-Atomic Fluorescence Spectrometric, the detection of Sb is carried out using SAMS softwares, the detection time setting of method
For 9min, acquired value (Gain) value is set as 10, and the rotating speed of flow pumps is both configured to 75%, and lamp current is set as principal current
(Primary)：17.5mA, supercharging electric current (Boost)：15mA, in detection process, the appearance time of Sb (V) in 2~3min,
The drafting of standard curve is carried out using SAMSCalc softwares, and the linearly dependent coefficient R of the standard curve of drafting must be more than 0.999,
Instrument preheats 30min before detection every time, and each sample detection balances each other chromatographic column 1min to restore column effect with flowing after the completion.
7. the detection method of Sb (V) in soil according to claim 1 or deposit, it is characterised in that：In step (3)
In, soil or deposit Standard Reference Materials for Determination GBW07406 or GBW07312 are chosen, by adding Sb (V) standard substance
Recovery testu calculates the recovery of standard addition of Sb (V)：
The following two groups of experiments of comparison：
(A) soil or deposit Standard Reference Materials for Determination of the standard solution of 20 μ g/L Sb (V) are not added with；
(B) soil or deposit Standard Reference Materials for Determination of the standard solution of 20 μ g/L Sb (V) of addition；
Using both the above solution as soil or sediment sample, be detected respectively according to step (4), detect obtain it is dense
Degree is C0And C；
And calculate recovery of standard addition according to following formula：
Wherein：
R- recovery of standard addition, %；
The content of Sb (V), μ g/L in the soil or deposit Standard Reference Materials for Determination of the standard solution of C- addition Sb (V)；
C0It is not added with the soil of the standard solution of Sb (V) or the content of Sb (V) in deposit Standard Reference Materials for Determination, μ g/L；
Recovery of standard addition of the Sb (V) in soil or deposit Standard Reference Materials for Determination finally is calculated, further according to 3 times
Signal-to-noise ratio (S/N) calculates the detection limit of Sb (V).
8. the detection method of Sb (V) in soil according to claim 7 or deposit, it is characterised in that：Further include accurate
Property confirmatory experiment：
Following contrast experiment is carried out in soil or deposit Standard Reference Materials for Determination：
(a) soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances are added；
(b) soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances are not added；
Using both the above solution as soil or sediment sample, the experiment of step (4) is carried out respectively, has verified whether Sb
(III) Sb (V) is transformed into, such as finally obtained result is：The generation of Sb (III) → Sb (V) is not detected, that is, demonstrates this experiment
Accuracy.
9. the detection method of Sb (V) in soil according to claim 1 or deposit, it is characterised in that：In step (4),
If the response peak of extracting solution is excessively high and has been more than the detection range of instrument, extracting solution is diluted with ultra-pure water, sample
The calculating of concentration is calculated using SAMSCalc softwares.
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| JP2010014500A (en) * | 2008-07-02 | 2010-01-21 | Saitama Prefecture | Simple component analyzing method of metal material |
| JP2012037252A (en) * | 2010-08-03 | 2012-02-23 | Miura Co Ltd | Quantitative method of phosphate ion |
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| JP2012037252A (en) * | 2010-08-03 | 2012-02-23 | Miura Co Ltd | Quantitative method of phosphate ion |
| CN102706866A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Detection reagent for rapidly detecting multiple single metal ions, preparation and application thereof |
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