CN106896169A - Sb in a kind of soil or deposit（V）Detection method - Google Patents
Sb in a kind of soil or deposit（V）Detection method Download PDFInfo
- Publication number
- CN106896169A CN106896169A CN201710079072.3A CN201710079072A CN106896169A CN 106896169 A CN106896169 A CN 106896169A CN 201710079072 A CN201710079072 A CN 201710079072A CN 106896169 A CN106896169 A CN 106896169A
- Authority
- CN
- China
- Prior art keywords
- soil
- deposit
- standard
- detection
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/065—Preparation using different phases to separate parts of sample
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
- G01N2030/146—Preparation by elimination of some components using membranes
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a kind of detection method of Sb (V) in soil or deposit, comprise the following steps：(1) sample collection and pre-treatment：Collection soil or sediment sample, air-dried successively, ground and sieved, sample is extracted using hydroxylamine hydrochloride, then sequentially pass through it is ultrasonically treated, centrifugation and supernatant liquid filtering after obtain extract solution；(2) standard curve of various concentrations Sb (V) is set up using high performance liquid chromatography hydride-generation atomic fluorescence method；(3) measure of recovery of standard addition；(4) extract solution for obtaining is detected, calculates the concentration of Sb (V) in soil.The detection method rate of recovery of Sb (V) is high in soil of the present invention or deposit, it is easy to operate, and 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 method of antimony, the detection side of Sb (V) in more particularly to a kind of soil or deposit
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, its
It is also the metallic element with its own strategic significance, irreplaceable effect is served in modern industry, main application is use
In manufacture lead accumulator, brominated or chlorine-containing flame retardant, semiconductor is ceramic, bullet, and its organic compound is used also as agricultural chemicals or medicine
In thing.The industry of industrial revolution post-modernism is sharply increased for the demand of antimony element, therefore in exploitation of mineral resources, industrial production and is used
During antimony pollution increasingly severe trend is also presented.Due to the extensive existence of antimony and potential carcinogenicity, it is most
Recent decades cause extensive concern.Used as the natural component in the earth's crust, average content is about 1mg/Kg to antimony in global soil,
And in China, this content is 1.34mg/Kg.In the more serious Polluted area of some Sb artificial disturbances, in surrounding medium
The more unpolluted soil of antimony content is higher by multiple orders of magnitude, the concentration of the Sb for such as being 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, and body can be caused to damage, and is considered as a kind of doubtful carcinogenic
Material, excessive antimony may liver, skin and respiratory system disease, antimony can be present in biology by bioconcentration
In body, the main presence in the form of Sb (V) and Sb (III) of antimony in environment, its 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, in the German soakage for specifying the daily Sb of human body not
Must be more than 23 μ g/d.EPA specifies that human body is 0.4 μ g/Kg, Dutch section to the acceptable daily intake of Sb and Sb (III)
The maximum acceptable concentration of scholar's suggestion Antimony In The Soils is respectively 3.5mg/Kg.
In view of antimony element is widely present, and the carcinogenicity for showing 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, extract
Antimony in soil or deposit simultaneously carries out detection and has larger difficulty, it is therefore necessary to the dense of the antimony in soil or deposit
Degree launches research, in view of physiological-toxicity and environmentology behavior between two kinds of Sb of common form (V) and Sb (III) in surrounding medium
The greatest differences of presence, it is necessary to carry out the antimony in the research to Sb in environment (V) detection method, but 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
The extraction efficiency of agent oxalic acid, citric acid, EDTA or phosphoric acid for Sb (V) is generally relatively low (generally only 60~80%), and extracts
During in view of different valence state antimony conversion be denatured.
The content of the invention
Sb (V) valence state is unstable and extraction difficulty during the technical problem to be solved in the present invention is directed to soil or deposit
Feature, develops a kind of rate of recovery high, it is easy to the analytical technology of operation, realizes to Sb micro in soil or deposition medium
(V) accurate analysis method.
During the present invention can preferably extract soil or deposit by selecting suitable extractant and chromatography column
Quinquevalence antimony, and can effectively keep the stabilization of antimony valence state in soil or deposit, the method to have the rate of recovery high, specificity is good and letter
The characteristic of easy row.The hydroxylamine hydrochloride extractant phase that other the method is used can reach higher for traditional extractant to Sb (V)
Recovery rate, the chromatographic separation technology for using can make up at present for different valence state antimony detection method in soil or deposit
Missing.
The detection method of Sb (V), comprises the following steps in a kind of soil or deposit：
(1) sample collection and pre-treatment：Collection soil or sediment sample, are air-dried, ground and are sieved successively, are used
Hydroxylamine hydrochloride is extracted to sample, then sequentially pass through it is ultrasonically treated, centrifugation and supernatant liquid filtering after obtain extract solution；
(2) standard curve of various concentrations Sb (V) is set up using high performance liquid chromatography-hydride generation-atomic fluorescence method；
(3) measure of recovery of standard addition；
(4) sample is acquired and pre-treatment using the method for step (1), and uses the method for step (2) to obtaining
The extract solution detected, calculate the concentration of Sb (V) in soil.
The detection method of Sb (V) in soil of the present invention or deposit, wherein, the hydroxylamine hydrochloride uses anaerobic water
Prepare, concentration is 0.1mol/L.
The detection method of Sb (V) in soil of the present invention or deposit, wherein, step (1) specifically includes following step
Suddenly：
Collection soil or sediment sample are air-dried at room temperature, 100 mesh sieves are crossed after grinding to be measured；0.2g samples are weighed in poly-
In ethene centrifuge tube, 0.1mol/L hydroxylamine hydrochloride 10ml are added, and 3min are processed under 50W power using sonicator,
The solution supercentrifuge for obtaining high speed centrifugation 5min under the rotating speed of 10000rpm, takes after supernatant crosses 0.22 μm of filter membrane and obtains
To extract solution.
The detection method of Sb (V) in soil of the present invention or deposit, wherein, standard is also included in step (2)
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 mother liquor for releasing Sb (V) is made the standard liquid of various concentrations：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 of the present invention or deposit, wherein, step (2) high performance liquid chromatography-hydrogen
Be used to separating in compound generation-atomic fluorescence method chromatographic column in water body for 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, flow velocity after crossing 0.22 μm of nylon leaching film
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 to 2068.4Pa.
The detection method of Sb (V) in soil of the present invention or deposit, wherein, step (2) high performance liquid chromatography-hydrogen
In compound generation-atomic fluorescence method, the detection of antimony is determined 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, matched somebody with somebody with concentrated hydrochloric acid, KI and thiocarbamide in addition
The HCl solution of the 1.8mol/L containing 3%KI+1% thiocarbamides is made as reagent blank, wherein, the flow velocity of reagent blank is set to
7.5mL/min, the flow velocity of reducing agent is 3.75mL/min, uses high-performance Sb hollow cathode lamps.
The detection method of Sb (V) in soil of the present invention or deposit, 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 to 9min, is obtained
Value (Gain) value is set to 10, and the rotating speed of flow pumps is both configured to 75%, and lamp current is set to 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, balances each other chromatographic column 1min to recover post effect with flowing after the completion of each sample detection.
The detection method of Sb (V) in soil of the present invention or deposit, wherein, in step (3), choose soil or
Deposit Standard Reference Materials for Determination (GBW07406 or GBW07312), by the mark-on reclaims reality for adding Sb (V) standard substance
Test the recovery of standard addition for calculating Sb (V)：
The following two groups of experiments of contrast：
(A) soil or deposit Standard Reference Materials for Determination of the standard liquid of 20 μ g/L Sb (V) are not added with；
(B) soil or deposit Standard Reference Materials for Determination of the standard liquid of 20 μ g/L Sb (V) of addition；
Using both the above solution as soil or sediment sample, detected that detection draws respectively according to step (4)
Concentration be C0And C；
And calculate recovery of standard addition according to below equation：
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 liquid of C- additions Sb (V)
L；
C0- it is not added with the content of Sb (V) in the soil of the standard liquid of Sb (V) or 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, is pressed in addition
The detection limit of Sb (V) is calculated according to 3 times of signal to noise ratios (S/N).
The detection method of Sb (V) in soil of the present invention or deposit, wherein, also tested including Accuracy Verification：
Following contrast test is carried out in soil or deposit Standard Reference Materials for Determination：
A () adds the soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances；
The soil or deposit Standard Reference Materials for Determination of (b) without 20 μ g/L Sb (III) standard substances；
Using both the above solution as soil or sediment sample, the experiment of step (4) is carried out respectively, verified whether
Sb (III) transforms into Sb (V), and the result for such as finally giving 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 of the present invention or deposit, wherein, in step (4), if extract solution
Response peak is too high and has exceeded the detection range of instrument, then extract solution is diluted with ultra-pure water, the calculating profit of sample concentration
Calculated with SAMSCalc softwares.
The detection method difference from prior art of Sb (V) is in soil of the present invention or deposit：
The present invention utilizes the separating effect of efficient anion separation column, and Hydride Generation-Atomic Fluorescence Spectrometric
(HPLC-HG-AFS) detection method of Sb (V) in the good and simple and easy to do soil of sensitivity high-recovery or deposit is set up.
In the present invention, soil or sediment sample are extracted using 0.1mol/L hydroxylamine hydrochlorides, can be effective
Extract the main valence state Sb (V) in soil or deposit；The Sb (III) for extracting is separated using high-efficiency anion chromatographic column
And detected, with preferable specificity and novelty；Separate antimony is examined with reference to Hydride Generation-Atomic Fluorescence Spectrometric
Survey, the present invention is reasonable in design, by conditioning instrumentation parameter and reagent concentration and flow velocity, establishes the detection side of Sb (V) in soil
Method, with preferable specificity, the metastable rate of recovery and stability higher.
The detection method to Sb (V) in soil of the invention or deposit is described further below in conjunction with the accompanying drawings.
Brief description of the drawings
Fig. 1 is the soil or deposit Standard Reference Materials for Determination of Sb (V) standard liquid 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；
Fig. 3 is the chromatogram of Sb (V) in soil in the embodiment of the present invention or deposit；
The English bilingual occurred in all accompanying drawings of the present invention is as follows：
Time:Time；
Signal:Signal value；
chromatography:Chromatogram.
Specific embodiment
Embodiment 1
The detection method of Sb (V), comprises the following steps in a kind of soil or deposit：
(1) sample collection and pre-treatment：Collection soil or sediment sample, are air-dried, ground and are sieved successively, are used
Hydroxylamine hydrochloride is extracted to sample, then sequentially pass through it is ultrasonically treated, centrifugation and supernatant liquid filtering after obtain extract solution；
In more detail, following steps are specifically included：
Collection soil or sediment sample are air-dried at room temperature, 100 mesh sieves are crossed after grinding to be measured；0.2g samples are weighed in poly-
In ethene centrifuge tube, 0.1mol/L hydroxylamine hydrochloride 10ml are added, hydroxylamine hydrochloride is prepared using anaerobic water, and uses ultrasonic disruption
Instrument processes 3min under 50W power, the solution supercentrifuge for obtaining high speed centrifugation 5min under the rotating speed of 10000rpm, takes
Supernatant obtains extract solution after crossing 0.22 μm of filter membrane.
Using the extractant of 0.1mol/L hydroxylamine hydrochlorides, the extractant of the concentration gradient coordinates follow-up separation and extraction hand
Section can effectively realize the detection to soil or sediment sample.
(2) standard curve of various concentrations Sb (V) is set up using high performance liquid chromatography-hydride generation-atomic fluorescence method；
The preparation of standard liquid：A certain amount of hexahydroxy potassium antimonate is weighed respectively, and the 1000mg/L for being configured to Sb (V) is female
Liquid, the mother liquor for diluting Sb (V) with ultra-pure water is made the standard liquid of various concentrations：The μ of 0 μ g/L, 5 μ g/L, 10 g/L, 20 μ g/L, 40
μ g/L, 100 μ g/L.
For separating the chromatographic column in water body for anion separation column PRP-X100,250mm × 4.1mm, 10 μm, mobile phase
It is the ammonium tartrate solution of 0.2mol/L, adjustment pH value is 5 after crossing 0.22 μm of nylon leaching film, and flow rate set is 1.5mL/min, often
The sample size of secondary solution is 200 μ L, and the pressure of high-purity argon gas is set to 2068.4Pa.Using anion-exchange column PRP-X100 and
Flow visualizing ammonium tartrate solution is separated to the Sb (V) for extracting, and separating effect is notable.
The detection of antimony is determined using atomic fluorescence spectrophotometer PSA-10.055, weighs the NaOH solution dissolving of 4g, then
Add the NaBH of 8g4, ultra-pure water is settled to 1L as reducing agent, prepared with concentrated hydrochloric acid, KI and thiocarbamide contain 3%KI+1% in addition
The HCl solution of the 1.8mol/L of thiocarbamide as reagent blank, wherein, the flow velocity of reagent blank is set to 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 to 9min, and acquired value (Gain) value is set
It is 10, the rotating speed of flow pumps is both configured to 75%, and lamp current is set to principal current (Primary)：17.5mA, is pressurized electric current
(Boost)：15mA, in detection process, in 2~3min, the drafting of standard curve uses SAMSCalc to the appearance time of Sb (V)
Software is carried out, and the linearly dependent coefficient R of the standard curve of drafting must be more than 0.999, every time instrument preheating 30min before detection, often
Balance each other chromatographic column 1min to recover post effect with flowing after the completion of individual sample detection.
(3) measure 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- material calculates the recovery of standard addition of Sb (V)：
The following two groups of experiments of contrast：
(A) soil or deposit Standard Reference Materials for Determination of the standard liquid of 20 μ g/L Sb (V) are not added with；
(B) soil or deposit Standard Reference Materials for Determination of the standard liquid of 20 μ g/L Sb (V) of addition；
Using both the above solution as soil or sediment sample, detected that detection draws respectively according to step (4)
Concentration be C0And C；
And calculate recovery of standard addition according to below equation：
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 liquid of C- additions Sb (V)
L；
C0- it is not added with the content of Sb (V) in the soil of the standard liquid of Sb (V) or 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, is pressed in addition
The detection limit of Sb (V) is calculated according to 3 times of signal to noise ratios (S/N).
(4) sample is acquired and pre-treatment using the method for step (1), and uses the method for step (2) to obtaining
Extract solution detected, calculate the concentration of Sb (V) in soil.
Add the soil or chromatogram such as Fig. 1 of deposit Standard Reference Materials for Determination of Sb (V) standard liquid of 20 μ g/L
It is shown.
In step (4) of the present invention, if the response peak of extract solution is too high and has exceeded the detection range of instrument, with ultrapure
Water is diluted to extract solution, and the calculating of sample concentration is calculated using SAMSCalc softwares.
Embodiment 2
On the basis of embodiment 1, the present embodiment is also tested including Accuracy Verification：
Following contrast test is carried out in soil or deposit Standard Reference Materials for Determination：
A () adds the soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances；
The soil or deposit Standard Reference Materials for Determination of (b) without 20 μ g/L Sb (III) standard substances；
Using both the above solution as soil or sediment sample, the experiment of step (4) is carried out respectively, verified whether
Sb (III) transforms into Sb (V), and the result for such as finally giving 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 of certain Near Antimony Mine Area is gathered, after transporting laboratory back, 100 mesh sieve sealing preserves, detection are crossed in the grinding of natural wind dry doubling
When weigh the soil or deposit of 0.2g, add 0.1mol/L hydroxylamine hydrochlorides (NH2OHHCl) solution 10mL is broken with ultrasonic wave
Broken instrument processes 3min under 50W power, and 5min is centrifuged with the rotating speed of 10000rpm in supercentrifuge, 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 liquid：It is configured to Sb's (V)
1000mg/L mother liquors, the mother liquor for diluting Sb (V) with ultra-pure water is made the standard liquid of various concentrations：0 μ g/L, 5 μ g/L, 10 μ g/
L, 20 μ g/L, 40 μ g/L, 100 μ g/L.
Using in anion separation column PRP-X100 (250mm × 4.1mm, 10 μm) separation soil or deposit extract solution
Sb (V), mobile phase is the ammonium tartrate solution (it is 5 to cross and pH value is adjusted after 0.22 μm of nylon leaching film) of 0.2mol/L, flow rate set
It is 1.5mL/min, the sample size of each solution is 200 μ L, and the pressure of high-purity argon gas is set to 2068.4Pa.The detection of antimony is used
Atomic fluorescence spectrophotometer determines (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 prepared using concentrated hydrochloric acid, KI and thiocarbamide and contained
There is the HCl solution (1.8mol/L) of 3%KI+1% thiocarbamides as reagent blank.Flow velocity is set to 7.5mL/min (reagent blank)
With 3.75mL/min (reducing agent), high-performance Sb hollow cathode lamps (Photron, Victoria, Australia) is used.Sb's
Detection is carried out using SAMS softwares, and the detection time of method is set to 9min, and Gain values are set to 10, and the rotating speed of flow pumps is set
It is 75%, lamp current is set to 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。
The soil or deposit extract solution that obtain are detected using with standard curve identical method, if wherein carried
The response peak for taking liquid is too high and exceeded the detection range of instrument, then extract solution is diluted.The calculating of sample concentration is utilized
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
Material (GBW07406 or GBW07312), the mark-on for calculating Sb (V) by the recovery testu for adding Sb (V) standard substance is returned
Yield：
The following two groups of experiments of contrast：
(A) soil or deposit Standard Reference Materials for Determination of the standard liquid of 20 μ g/L Sb (V) are not added with；
(B) soil or deposit Standard Reference Materials for Determination of the standard liquid of 20 μ g/L Sb (V) of addition；
Using both the above solution as soil or sediment sample, detected that detection draws respectively according to step (4)
Concentration be C0And C；
And calculate recovery of standard addition according to below equation：
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 liquid of C- additions Sb (V)
L；
C0- it is not added with the content of Sb (V) in the soil of the standard liquid of Sb (V) or deposit Standard Reference Materials for Determination, μ
g/L；
Finally calculating recovery of standard addition of the Sb (V) in soil or deposit Standard Reference Materials for Determination is
102.5%.The detection for calculating Sb (V) further according to 3 times of signal to noise ratios (S/N) is limited to 3.16 μ g/L.
Sb (III) is may result in view of the extraction in the present invention and experiment condition transform into Sb (V), may be right
The rate of recovery of experiment produces influence, therefore using the experimental procedure in the present invention, in soil or deposit constituent analysis reference material
Following contrast test is carried out in matter：
A () adds the soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances；
The soil or deposit Standard Reference Materials for Determination of (b) without 20 μ g/L Sb (III) standard substances；
Using both the above solution as soil or sediment sample, the experiment of step (4) is carried out respectively, verified whether
Sb (III) transforms into Sb (V), and the result for finally giving is：The generation of Sb (III) → Sb (V), this result verification are not detected
The accuracy (Fig. 2) of this experiment.
(4) sample is acquired and pre-treatment using the method for step (1), and uses the method for step (2) to obtaining
The extract solution detected, finally calculate 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 days, checking such scheme 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 model of the invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical side of the invention
Various modifications and improvement that case is made, all should fall into the protection domain of claims of the present invention determination.
Claims (10)
1. in a kind of soil or deposit Sb (V) detection method, it is characterised in that：Comprise the following steps：
(1) sample collection and pre-treatment：Collection soil or sediment sample, are air-dried, ground and are sieved, using hydrochloric acid successively
Azanol is extracted to sample, then sequentially pass through it is ultrasonically treated, centrifugation and supernatant liquid filtering after obtain extract solution；
(2) standard curve of various concentrations Sb (V) is set up using high performance liquid chromatography-hydride generation-atomic fluorescence method；
(3) measure of recovery of standard addition；
(4) sample is acquired and pre-treatment using the method for step (1), and using step (2) method to the institute that obtains
State extract solution to be detected, calculate the concentration of Sb (V) in soil.
2. in soil according to claim 1 or deposit Sb (V) detection method, it is characterised in that：The hydrochloric acid hydroxyl
Amine is prepared using anaerobic water, and concentration is 0.1mol/L.
3. in soil according to claim 2 or deposit Sb (V) detection method, it is characterised in that：Step (1) is specific
Comprise the following steps：
Collection soil or sediment sample are air-dried at room temperature, 100 mesh sieves are crossed after grinding to be measured；0.2g samples are weighed in polyethylene
In centrifuge tube, 0.1mol/L hydroxylamine hydrochloride 10ml are added, and 3min is processed under 50W power using sonicator, obtained
Solution supercentrifuge under the rotating speed of 10000rpm high speed centrifugation 5min, take after supernatant crosses 0.22 μm of filter membrane and carried
Take liquid.
4. in soil according to claim 1 or deposit Sb (V) detection method, it is characterised in that：In step (2)
The also preparation including standard liquid：A certain amount of hexahydroxy potassium antimonate is weighed respectively, is configured to the 1000mg/L mother liquors of Sb (V),
The mother liquor for diluting Sb (V) with ultra-pure water is made the standard liquid of various concentrations：0 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/
L, 100 μ g/L.
5. in soil according to claim 4 or deposit Sb (V) detection method, it is characterised in that：Step (2) is efficiently
The chromatographic column for being used to separate in water body in liquid chromatogram-Hydride Generation-Atomic Fluorescence Spectrometric 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
5, flow rate set is 1.5mL/min, and the sample size of each solution is 200 μ L, and the pressure of high-purity argon gas is set to 2068.4Pa.
6. in soil according to claim 5 or deposit Sb (V) detection method, it is characterised in that：Step (2) is efficiently
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, add the NaBH of 8g4, ultra-pure water is settled to 1L as reducing agent, dense salt used in addition
Acid, KI and thiocarbamide prepare the HCl solution of the 1.8mol/L containing 3%KI+1% thiocarbamides as reagent blank, wherein, reagent blank
Flow velocity be set to 7.5mL/min, the flow velocity of reducing agent is 3.75mL/min, uses high-performance Sb hollow cathode lamps.
7. in soil according to claim 6 or deposit Sb (V) detection method, it is characterised in that：Step (2) is efficiently
In liquid chromatogram-Hydride Generation-Atomic Fluorescence Spectrometric, the detection of Sb is carried out using SAMS softwares, and the detection time of method is set
It is 9min, acquired value (Gain) value is set to 10, and the rotating speed of flow pumps is both configured to 75%, and lamp current is set to 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 preheating 30min before detection, balances each other chromatographic column 1min to recover post effect after the completion of each sample detection with flowing every time.
8. in soil according to claim 1 or deposit Sb (V) detection method, 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 calculate Sb (V) recovery of standard addition：
The following two groups of experiments of contrast：
(A) soil or deposit Standard Reference Materials for Determination of the standard liquid of 20 μ g/L Sb (V) are not added with；
(B) soil or deposit Standard Reference Materials for Determination of the standard liquid of 20 μ g/L Sb (V) of addition；
Using both the above solution as soil or sediment sample, detected respectively according to step (4), it is dense that detection draws
It is C to spend0And C；
And calculate recovery of standard addition according to below equation：
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 liquid of C- additions Sb (V)；
C0- it is not added with the content of Sb (V) in the soil of the standard liquid of Sb (V) or 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).
9. in soil according to claim 8 or deposit Sb (V) detection method, it is characterised in that：It is accurate also to include
Property confirmatory experiment：
Following contrast experiment is carried out in soil or deposit Standard Reference Materials for Determination：
A () adds the soil or deposit Standard Reference Materials for Determination of 20 μ g/L Sb (III) standard substances；
The soil or deposit Standard Reference Materials for Determination of (b) without 20 μ g/L Sb (III) standard substances；
Using both the above solution as soil or sediment sample, the experiment of step (4) is carried out respectively, verified whether Sb
(III) Sb (V) is transformed into, the result for such as finally giving is：The generation of Sb (III) → Sb (V) is not detected, that is, demonstrates this experiment
Accuracy.
10. in soil according to claim 1 or deposit Sb (V) detection method, it is characterised in that：In step (4),
If the response peak of extract solution is too high and has exceeded the detection range of instrument, extract solution is diluted with ultra-pure water, sample
The calculating of concentration is calculated using SAMSCalc softwares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710079072.3A CN106896169B (en) | 2017-02-14 | 2017-02-14 | The detection method of Sb (V) in a kind of soil or deposit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710079072.3A CN106896169B (en) | 2017-02-14 | 2017-02-14 | The detection method of Sb (V) in a kind of soil or deposit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106896169A true CN106896169A (en) | 2017-06-27 |
| CN106896169B CN106896169B (en) | 2018-08-17 |
Family
ID=59198688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710079072.3A Expired - Fee Related CN106896169B (en) | 2017-02-14 | 2017-02-14 | The detection method of Sb (V) in a kind of soil or deposit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106896169B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112710756A (en) * | 2020-12-23 | 2021-04-27 | 广东省科学院生态环境与土壤研究所 | Method for measuring content of trivalent antimony and pentavalent antimony by liquid chromatography-atomic fluorescence spectrometry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103528973A (en) * | 2012-07-04 | 2014-01-22 | 北京当升材料科技股份有限公司 | Method for precisely detecting phosphorus content and iron content of iron phosphate |
-
2017
- 2017-02-14 CN CN201710079072.3A patent/CN106896169B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103528973A (en) * | 2012-07-04 | 2014-01-22 | 北京当升材料科技股份有限公司 | Method for precisely detecting phosphorus content and iron content of iron phosphate |
Non-Patent Citations (3)
| Title |
|---|
| J.M. BRANNON ET AL: "Fixation and Mobilization of Antimony in Sediments", 《ENVIRONMENTAL POLLUTION (SERIES B) 》 * |
| JOSEPH LINTSCHINGER ET AL: "Studies on Speciation of Antimony in Soil Contaminated by Industrial Activity", 《INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY》 * |
| JOZICA MAJDA SERAFIMOVSKA ET AL: "Study of the antimony species distribution in industrially contaminated soils", 《J SOILS SEDIMENTS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112710756A (en) * | 2020-12-23 | 2021-04-27 | 广东省科学院生态环境与土壤研究所 | Method for measuring content of trivalent antimony and pentavalent antimony by liquid chromatography-atomic fluorescence spectrometry |
| WO2022134255A1 (en) * | 2020-12-23 | 2022-06-30 | 广东省科学院生态环境与土壤研究所 | Method for measuring contents of trivalent stibium and pentavalent stibium by means of liquid chromatography combined with atomic fluorescence spectrometry |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106896169B (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Adnan et al. | Research progress on heavy metals pollution in the soil of smelting sites in China | |
| Zänker et al. | Engineered nanoparticles and their identification among natural nanoparticles | |
| CN103884785B (en) | A kind of detection method of selenium | |
| CN102721779A (en) | Detection method of selenium forms in plants | |
| Larner et al. | Evaluation of Stable Isotope Tracing for ZnO Nanomaterials New Constraints from High Precision Isotope Analyses and Modeling. | |
| CN103822999B (en) | A kind of full-automatic QuEChERS pre-treatment all-in-one and pre-treating method | |
| Barefoot | Determination of the precious metals in geological materials by inductively coupled plasma mass spectrometry | |
| CN1254683C (en) | Speciated isotope dilution mass spectrometry of reactive species and related methods | |
| Falkner et al. | Determination of gold at femtomolar levels in natural waters by flow-injection inductively coupled plasma quadrupole mass spectrometry | |
| CN109387411B (en) | Method for detecting biological available lead in soil | |
| Tziaras et al. | Investigating the occurrence and environmental significance of methylated arsenic species in atmospheric particles by overcoming analytical method limitations | |
| CN104713939A (en) | Method for measuring cadmium isotope ratio in rice by using multi-receiving inductance coupling plasma mass spectrum | |
| Ospina-Alvarez et al. | TlI and TlIII presence in suspended particulate matter: speciation analysis of thallium in wastewater | |
| Leybourne et al. | Measuring arsenic speciation in environmental media: sampling, preservation, and analysis | |
| Liu et al. | Sample digestion and combined preconcentration methods for the determination of ultra-low gold levels in rocks | |
| de Souza Dias et al. | Development and optimization of analytical method for the determination of cadmium from mineral water samples by off-line solid phase extraction system using sisal fiber loaded TAR by FAAS | |
| CN114062476B (en) | Method and system for analyzing Cd/Pb composite pollution bimetallic isotope source of soil | |
| Grygoyć et al. | Development of a tellurium speciation study using IC-ICP-MS on soil samples taken from an area associated with the storage, processing, and recovery of electrowaste | |
| Elmayel et al. | Evolution of the speciation and mobility of Pb, Zn and Cd in relation to transport processes in a mining environment | |
| Guo et al. | Retention behavior of dissolved uranium during ultrafiltration: Implications for colloidal U in surface waters | |
| CN106896168A (en) | Sb in a kind of soil or deposit（Ⅲ）Detection method | |
| CN106896169B (en) | The detection method of Sb (V) in a kind of soil or deposit | |
| CN104849385B (en) | Gas chromatographic mass spectrometry determination method for chlorobenzene compounds | |
| CN106932511A (en) | The detection method of different valence state antimony in a kind of environment water | |
| Howe et al. | Determination of uranium concentration and isotopic composition by means of ICP-MS in sequential extracts of sediment from the vicinity of a uranium enrichment plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180817 Termination date: 20220214 |