CN106932511A - The detection method of different valence state antimony in a kind of environment water - Google Patents
The detection method of different valence state antimony in a kind of environment water Download PDFInfo
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- CN106932511A CN106932511A CN201710078825.9A CN201710078825A CN106932511A CN 106932511 A CN106932511 A CN 106932511A CN 201710078825 A CN201710078825 A CN 201710078825A CN 106932511 A CN106932511 A CN 106932511A
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- 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
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- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Abstract
The invention discloses a kind of detection method of different valence state antimony in environment water, comprise the following steps：(1) sample collection and pre-treatment：Collection environment water body example, with ammonium tartrate solution constant volume, filtering, filtrate is to be measured；(2) standard curve of different gradient concentrations 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 detect the Sb (V) and Sb (III) in the environment water body example of collection.The detection method of different valence state antimony can maintain the valence stability of antimony in water sample in environment water of the present invention, have the advantages that detection limit is low, the rate of recovery is high and favorable reproducibility.
Description
Technical field
The present invention relates to a kind of detection method of antimony, the detection side of different valence state antimony in more particularly to a kind of environment water
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, antimony are belonged in the periodic table of elements
It is a kind of metallic element with its own strategic significance, irreplaceable effect is served in modern industry, main application is
Making lead accumulator is used in, brominated or chlorine-containing flame retardant, semiconductor is ceramic, bullet, and its organic compound is used also as agricultural chemicals
Or in medicine.The industrial revolution post-modernism industry is sharply increased for the demand of antimony element, therefore exploitation of mineral resources, industrial production and
Antimony pollution during use is also presented increasingly severe trend.Due to the extensive existence of antimony and potential carcinogenicity, its
Extensive concern is caused in nearest decades.Used as the natural component in the earth's crust, average content is about antimony in global soil
1mg/Kg, and in China, this content is 1.34mg/Kg, in natural environment water, show that its is dense according to related data analysis
Spend the rank in μ g/L.In the more serious Polluted area of some Sb artificial disturbances, the antimony content in surrounding medium is compared with Natural Water
Body and soil are higher by multiple orders of magnitude, and the concentration of Sb can reach 29423 μ g/L such as in hunan stannary region detection to water body,
The same Sb detected in the regional soil at concentrations up to 5045mg/kg.Although the concern that Sb was received in recent years is more,
It is that for congeners As, the research to Sb also relatively lags 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, is embodied in：Sb(Ⅲ)>Sb (V), wherein Sb (III) are easy to show height parent by the cell membrane of red blood cell
And property, and Sb (III) can be with the reparation of DNA in block cell, and its bio-toxicity is about ten times of Sb (V).Therefore Sb quilts
USEPA and European Union are classified as priority pollutants, while being also classified as hazardous waste by Basel Convention.Therefore government concerned and machine
Structure has many regulations for the content of Sb in water body, and WHO specifies that the content of Sb must not exceed 20 μ g/L in drinking water, and in
In the standard that state formulates, Sb must not exceed 5 μ g/L in surface water and drinking water, and California, USA specifies the public of public's drinking water
Target is 20 μ g/L.23 μ g/d are must not exceed in the soakage of the German daily Sb of regulation human body.
Antimony widely uses the extensive concern that scholar and the public have been caused with poisonous effect due to it, and water body is that crowd absorbs
The important channel of accumulation antimony, it is contemplated that the greatest differences that physiological-toxicity and environmentology behavior are present between Sb (V) and Sb (III), because
This is necessary to launch the Determination of Different Valence States of the antimony in environment water research, but the detection method of the antimony of environment water is main at present
Its total quantifier elimination is concentrated on, the detection method on different valence state Sb in water body is then rarely found, and existing method operation step
It is rapid complex, it is unfavorable for the detection of Sb concentration in laboratory, and cannot ensure that the form for detecting preceding antimony keeps stabilization.
The content of the invention
The technical problem to be solved in the present invention is directed to the unstability and environmental content of different valence state antimony in environment water
Low the characteristics of, develop that a kind of detection limit that can keep valence stability in water is low, the rate of recovery is high, reappear the good measure side of effect
Method, realizes to Sb in environment water (V) and Sb (III) Accurate Determining.
The present invention utilizes ammonium tartrate pre-treatment, high-efficiency anion chromatogram post separation-Hydride Generation-Atomic Fluorescence Spectrometric
(HPLC-HG-AFS) set up that detection limit is low, the rate of recovery is high, reappear Sb (V) in effect stability, simple and easy to do detection environment water
With the detection method of Sb (III), the valence stability of antimony in water sample can be maintained, can effectively evade environment water body example in detection
Preceding conversion denaturation, it is possible to make up the missing of different valence state antimony detection method in environment water.
The detection method of different valence state antimony, comprises the following steps in a kind of environment water：
(1) sample collection and pre-treatment：Collection environment water body example, with ammonium tartrate solution constant volume, filtering, filtrate is treated
Survey；
(2) standard curve of different gradient concentrations 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 collection
The environment water body example in Sb (V) and Sb (III) detected.
The detection method of different valence state antimony in environment water of the present invention, wherein, the ammonium tartrate solution it is dense
It is 0.2mol/L to spend.
The detection method of different valence state antimony in environment water of the present invention, wherein, the environment water body example is
100mL, 200mL is settled to the ammonium tartrate solution of 0.2mol/L, and using 0.22 μm of membrane filtration, filtrate is to be measured.
The detection method of different valence state antimony in environment water of the present invention, wherein, standard is also included in step (2)
The preparation of solution：A certain amount of hexahydroxy potassium antimonate (KSb (OH) is weighed respectively6) and potassium antimony tartrate (C8H4K2O12Sb2), match somebody with somebody
The 1000mg/L mother liquors of Sb (V) and Sb (III) are made, the mother liquor for diluting Sb (V) with ultra-pure water is made 10mg/L standard liquids, used
The mother liquor of ammonium tartrate dilution Sb (III) of 0.2mol/L is made the standard liquid of 10mg/L, then is respectively prepared Sb (V) and Sb
(III) mixed standard solution, concentration includes respectively：0 μ g/L, 1 μ g/L, 2.5 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 different valence state antimony in environment water of the present invention, wherein, step (2) high performance liquid chromatography-
Be used to separating in Hydride Generation-Atomic Fluorescence Spectrometric 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 1.0mL/min, the sample size of each water sample is 200 μ L, and the pressure of high-purity argon gas is set to 2068.4Pa.
The detection method of different valence state antimony in environment water of the present invention, wherein, step (2) high performance liquid chromatography-
In Hydride Generation-Atomic Fluorescence Spectrometric, the detection of different valence state antimony is determined using atomic fluorescence spectrophotometer PSA-10.055,
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 concentrated hydrochloric acid, KI
The HCl solution of the 1.8mol/L containing 3%KI+1% thiocarbamides is prepared as reagent blank with thiocarbamide, wherein, the stream of reagent blank
Speed is set to 7.5mL/min, and the flow velocity of reducing agent is 3.75mL/min, uses high-performance Sb hollow cathode lamps.
The detection method of different valence state antimony in environment water of the present invention, wherein, step (2) high performance liquid chromatography-
In Hydride Generation-Atomic Fluorescence Spectrometric, the detection of Sb is carried out using SAMS softwares, and the detection time of method is set to 12min, obtains
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, in 3~4min, Sb (III's) goes out the appearance time of Sb (V)
Peak time draws 0 μ g/L, 1 μ g/L, 2.5 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/L in 8~10min, 100 μ g/L's
Standard curve, 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 big
In 0.999, instrument preheating 30min before detection, chromatographic column 1min is balanced each other with extensive after the completion of each sample detection with flowing every time
Biprism is imitated.
The detection method of different valence state antimony in environment water of the present invention, wherein, in step (3), by what is gathered
Environment water body example is divided into uniform two parts after mixing, the mixed standard solution of Sb (V) and Sb (III) by adding 20 μ g/L
Recovery testu calculate Sb (V) and Sb (III) recovery of standard addition：
The following two groups of experiments of contrast：
(A) it is not added with the environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L；
(B) environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L of addition；
Using both the above solution as testing sample, detected respectively according to step (4), the concentration that detection draws is
C0And C；
And calculate recovery of standard addition according to below equation：
Wherein：
R- recovery of standard addition, %；
Sb (V) and Sb in the environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L of C- additions
(III) content, μ g/L；
C0- it is not added with Sb (V) and Sb in the environment water body example of the mixed standard solution of the Sb (V) of 20 μ g/L and Sb (III)
(III) content, μ g/L；
The recovery of standard addition of Sb (V) and Sb (III) in water body environment sample is calculated, 3 are calculated using same method
Secondary, average and draw final recovery of standard addition, Sb (V) and Sb (III) is calculated further according to 3 times of signal to noise ratios (S/N)) inspection
Rising limit.
The detection method of different valence state antimony in environment water of the present invention, wherein, in step (4), if ambient water
The response peak of body sample is too high and has exceeded the detection range of instrument, then need to be diluted environment water body example, and sample is dense
The measure of degree is carried out using SAMSCalc softwares.
The detection method difference from prior art of different valence state antimony is in environment water of the present invention：
The present invention is to add ammonium tartrate solution after environmental water sample collection, and the oxidation for suppressing Sb (III) is appraised at the current rate (Fig. 2 and Tu
3, the inhibition of the oxidative deformation of the trivalent antimony that to be ammonium tartrate prevent for long-time of expression)；Using high-efficiency anion
Splitter PRP-X100 and flow visualizing ammonium tartrate solution are separated to the antimony of the different valence state of water sample, with preferable
Specificity and novelty；Program sensitivity is high to be detected to separate antimony with reference to Hydride Generation-Atomic Fluorescence Spectrometric, weight
Existing property is good, can avoid the interference of other impurities ion, and with the rate of recovery higher.The present invention is reasonable in design, by adjusting apparatus
Device parameter and reagent concentration and flow velocity, establish the detection method of different valence state antimony in environment water, low with test limit, easy
Easy the characteristics of.
The detection method to different valence state antimony in environment water of the invention is described further below in conjunction with the accompanying drawings.
Brief description of the drawings
Fig. 1 is the Sb (V) and Sb (III) chromatogram (Sb (V) appearance is preceding) of 100 μ g/L mixed standard solutions in the present invention；
Fig. 2 is the chromatogram after the placement 48h of 40 μ g/L Sb (III) water samples in the present invention；
Fig. 3 in the present invention 40 μ g/L Sb (III) water samples with the addition of the chromatogram placed after ammonium tartrate solution after 48h；
Fig. 4 is the Concentration Testing result of Sb (V) and Sb (III) in water body example 1 in the embodiment of the present invention 2；
Fig. 5 is the Concentration Testing result of Sb (V) and Sb (III) in water body example 2 in the embodiment of the present invention 3.
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 different valence state antimony, comprises the following steps in a kind of environment water：
(1) sample collection and pre-treatment：Collection environment water body example 100mL, is determined with the ammonium tartrate solution of 0.2mol/L
Hold to 200mL, and using 0.22 μm of membrane filtration, filtrate is to be measured.
(2) standard curve of different gradient concentrations 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 (KSb (OH) is weighed respectively6) and potassium antimony tartrate
(C8H4K2O12Sb2), the 1000mg/L mother liquors of Sb (V) and Sb (III) are configured to, the mother liquor for diluting Sb (V) with ultra-pure water is made
10mg/L standard liquids, the mother liquor for diluting Sb (III) with the ammonium tartrate of 0.2mol/L is made the standard liquid of 10mg/L, then divides
The mixed standard solution of Sb (V) and Sb (III) is not made, and concentration includes respectively：0 μ g/L, 1 μ g/L, 2.5 μ g/L, 5 μ g/L, 10 μ
G/L, 20 μ g/L, 40 μ g/L, 100 μ g/L.Wherein, the Sb (V) of 100 μ g/L mixed standard solutions and Sb (III) chromatogram such as Fig. 1
Shown (Sb (V) appearance is preceding).
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 1.0mL/min, often
The sample size of secondary water sample is 200 μ L, and the pressure of high-purity argon gas is set to 2068.4Pa.
The detection of different valence state antimony is determined using atomic fluorescence spectrophotometer PSA-10.055, weighs the NaOH solution of 4g
Dissolving, adds the NaBH of 8g4, ultra-pure water is settled to 1L as reducing agent, prepared with concentrated hydrochloric acid, KI and thiocarbamide contain in addition
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 to 7.5mL/
Min, the flow velocity of reducing agent is 3.75mL/min, uses 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 12min, and acquired value (Gain) is set to
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, the appearance time of Sb (V) in 3~4min, the appearance time of Sb (III) 8~
10min, draws 0 μ g/L, 1 μ g/L, 2.5 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/L, the standard curve of 100 μ g/L, mark
The drafting of directrix 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, often
Instrument preheating 30min before secondary detection, balances each other chromatographic column 1min to recover post effect after the completion of each sample detection with flowing.
(3) measure of recovery of standard addition；
It is divided into uniform two parts after the environment water body example of collection is mixed, by the Sb (V) and Sb that add 20 μ g/L
(III) recovery testu of mixed standard solution calculates the recovery of standard addition of Sb (V) and Sb (III)：
The following two groups of experiments of contrast：
(A) it is not added with the environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L；
(B) environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L of addition；
Using both the above solution as testing sample, detected respectively according to step (4), the concentration that detection draws is
C0And C；
And calculate recovery of standard addition according to below equation：
Wherein：
R- recovery of standard addition, %；
Sb (V) and Sb in the environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L of C- additions
(III) content, μ g/L；
C0- it is not added with Sb (V) and Sb in the environment water body example of the mixed standard solution of the Sb (V) of 20 μ g/L and Sb (III)
(III) content, μ g/L；
The recovery of standard addition of Sb (V) and Sb (III) in water body environment sample is calculated, 3 are calculated using same method
Secondary, average and draw final recovery of standard addition, Sb (V) and Sb (III) is calculated further according to 3 times of signal to noise ratios (S/N)) inspection
Rising limit.
(4) sample is acquired and pre-treatment using the method for step (1), and uses the method for step (2) to collection
Environment water body example in Sb (V) and Sb (III) detected.
In the present invention, if the response peak of environment water body example is too high and has exceeded the detection range of instrument, it is right to need
Environment water body example is diluted, and the measure of sample concentration is carried out using SAMSCalc softwares.
Embodiment 2
Water body example 1 in collection environment, adds the ammonium tartrate solution of 0.2mol/L, and cross 0.22 μm of filter membrane
(Whatman, UK) is to be measured.
A certain amount of hexahydroxy potassium antimonate (KSb (OH) is weighed respectively6) and potassium antimony tartrate (C8H4K2O12Sb2), it is configured to
The 1000mg/L mother liquors of Sb (V) and Sb (III), then diluted with the ammonium tartrate solution of ultra-pure water and 0.2mol be made 10mg/ respectively
The mother liquor of L, then it is respectively prepared the mixed standard solution of Sb (V) and Sb (III)：0 μ g/L, 1 μ g/L, 2.5 μ g/L, 5 μ g/L, 10 μ g/
L, 20 μ g/L, 40 μ g/L, 100 μ g/L.Wherein, Sb (V) and Sb (III) chromatogram such as Fig. 1 institute of 100 μ g/L mixed standard solutions
Show (Sb (V) appearance is preceding).
For separating the chromatographic column in water body for anion separation column PRP-X100 (250mm × 4.1mm, 10 μm), flowing
It is mutually 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 is 1.0mL/
Min, the sample size of each water sample is 200 μ L, and the pressure of high-purity argon gas is set to 2068.4Pa.
The Sb of different valence state determines (PSA-10.055, Millennium using atomic fluorescence spectrophotometer
Excalibur System, United Kingdom), the NaOH solution dissolving of 4g is weighed, add the NaBH of 8g4, ultra-pure water
1L is settled to as reducing agent, the HCl solution containing 3%KI+1% thiocarbamides is prepared with concentrated hydrochloric acid, KI and thiocarbamide in addition
(1.8mol/L) is used as reagent blank.Wherein the flow velocity of reagent blank is 7.5mL/min, and the flow velocity of reducing agent is 3.75mL/
min.Use high-performance Sb hollow cathode lamps (Photron, Victoria, Australia).
The detection of Sb is carried out using SAMS softwares, and the detection time of method is set to 12min, and Gain values are set to 10, stream
The rotating speed of dynamic pump is both configured to 75%, and lamp current is set to Primary：17.5mA, Boost：15mA.In detection process, Sb
(V) between 3~4min, the appearance time of Sb (III) is between 8~10min for appearance time.Draw 0 μ g/L, 1 μ g/L, 2.5
μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/L, the standard curve of 100 μ g/L, the linearly dependent coefficient R of its standard curve
0.999 must be more than, the drafting of standard curve is carried out using SAMSCalc softwares.
The water body example of environment is gathered, uniform two parts are divided into after mixing, the Sb's (V) and Sb (III) of 20 μ g/L of addition is mixed
Standardization sample, the rate of recovery of Sb (V) or Sb (III) is calculated according to below equation：
Wherein：The R- rate of recovery, %；
The content of Sb (V) or Sb (III), μ g/L in the water sample of C- addition standard liquids；
C0- it is not added with the content of Sb (V) or Sb (III) in the water sample of standard liquid, μ g/L；
The method is calculated for Sb in environmental sample (V) and the recovery of standard addition of Sb (III), using same method
Calculate 3 times, average and draw final recovery of standard addition, be as shown in table 1, and with preferable reappearance.Further according to 3
Times signal to noise ratio (S/N) calculates the detection limit of Sb (V) and Sb (III).The rate of recovery and minimum detectability of this method are as shown in table 1.
The detection limit of the different valence state antimony of table 1
The environmental water sample sample 1 for gathering is detected using the method for step (4), if the response peak that environmental sample is produced
Detection range higher than instrument is then diluted and redeterminated with ultra-pure water to water sample, and the measure of environmental water sample is equally used
SAMSCalc softwares carry out quantitative calculating.The concentration for eventually detecting Sb (V) and Sb (III) is 12.70 μ g/L and 22.63 μ g/L
(Fig. 4).Measured in the 2nd, 3,5,10 pairs of identical samples respectively, the relative standard of the concentration of wherein Sb (V) and Sb (III)
Deviation is respectively lower than 6 and 8%.
Embodiment 3
Water body example 2 in collection environment, collecting location is different from the water body example 1 in embodiment 2, using of the invention
The detection method of different valence state antimony is detected to Sb therein (V) and Sb (III) concentration in environment water, specific detection method
With embodiment 2, final detection result is：The concentration of Sb (V) and Sb (III) is 258.38 μ g/L and does not detect in water body example 2
(Fig. 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 (9)
1. in a kind of environment water different valence state antimony detection method, it is characterised in that：Comprise the following steps：
(1) sample collection and pre-treatment：Collection environment water body example, with ammonium tartrate solution constant volume, filtering, filtrate is to be measured；
(2) standard curve of different gradient concentrations 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 the institute of collection
The Sb (V) and Sb (III) stated in environment water body example are detected.
2. in environment water according to claim 1 different valence state antimony detection method, it is characterised in that：The tartaric acid
The concentration of ammonium salt solution is 0.2mol/L.
3. in environment water according to claim 2 different valence state antimony detection method, it is characterised in that：The ambient water
Body sample is 100mL, is settled to 200mL with the ammonium tartrate solution of 0.2mol/L, and use 0.22 μm of membrane filtration, filtrate
It is to be measured.
4. in environment water according to claim 1 different valence state antimony detection method, it is characterised in that：In step (2)
In also including standard liquid preparation：A certain amount of hexahydroxy potassium antimonate (KSb (OH) is weighed respectively6) and potassium antimony tartrate
(C8H4K2O12Sb2), the 1000mg/L mother liquors of Sb (V) and Sb (III) are configured to, the mother liquor for diluting Sb (V) with ultra-pure water is made
10mg/L standard liquids, the mother liquor for diluting Sb (III) with the ammonium tartrate of 0.2mol/L is made the standard liquid of 10mg/L, then divides
The mixed standard solution of Sb (V) and Sb (III) is not made, and concentration includes respectively：0 μ g/L, 1 μ g/L, 2.5 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 environment water according to claim 4 different valence state antimony detection method, it is characterised in that：Step (2) is high
The chromatographic column for being used to separate in water body in effect liquid phase 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, is adjusted after crossing 0.22 μm of nylon leaching film
PH value is 5, and flow rate set is 1.0mL/min, and the sample size of each water sample is 200 μ L, and the pressure of high-purity argon gas is set to
2068.4Pa。
6. in environment water according to claim 5 different valence state antimony detection method, it is characterised in that：Step (2) is high
In effect liquid phase chromatogram-Hydride Generation-Atomic Fluorescence Spectrometric, the detection of different valence state antimony uses atomic fluorescence spectrophotometer PSA-
10.055 determine, and weigh the NaOH solution dissolving of 4g, add the NaBH of 8g4, ultra-pure water is settled to 1L as reducing agent, in addition
The HCl solution of the 1.8mol/L containing 3%KI+1% thiocarbamides is prepared as reagent blank with concentrated hydrochloric acid, KI and thiocarbamide, wherein, examination
The flow velocity of agent blank is set to 7.5mL/min, and the flow velocity of reducing agent is 3.75mL/min, uses high-performance Sb hollow cathode lamps.
7. in environment water according to claim 6 different valence state antimony detection method, it is characterised in that：Step (2) is high
In effect liquid phase chromatogram-Hydride Generation-Atomic Fluorescence Spectrometric, the detection of Sb is carried out using SAMS softwares, and the detection time of method sets
12min is set to, 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 3~4min,
The appearance time of Sb (III) draws 0 μ g/L, 1 μ g/L, 2.5 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 40 μ g/ in 8~10min
L, the standard curve of 100 μ g/L, the drafting of standard curve is carried out using SAMSCalc softwares, the linear phase of the standard curve of drafting
Closing coefficients R must be more than 0.999, and instrument preheating 30min before detection, is balanced each other chromatogram after the completion of each sample detection with flowing every time
Post 1min is imitated with recovering post.
8. in environment water according to claim 1 different valence state antimony detection method, it is characterised in that：In step (3)
In, will collection environment water body example mix after be divided into uniform two parts, by add 20 μ g/L Sb (V) and Sb (III) mix
The recovery testu of standardization solution calculates the recovery of standard addition of Sb (V) and Sb (III)：
The following two groups of experiments of contrast：
(A) it is not added with the environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L；
(B) environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L of addition；
Using both the above solution as testing sample, detected respectively according to step (4), the concentration that detection draws is C0With
C；
And calculate recovery of standard addition according to below equation：
Wherein：
R- recovery of standard addition, %；
Sb (V) and Sb (III) in the environment water body example of the mixed standard solution of the Sb (V) and Sb (III) of 20 μ g/L of C- additions
Content, μ g/L；
C0- it is not added with Sb (V) and Sb (III) in the environment water body example of the mixed standard solution of the Sb (V) of 20 μ g/L and Sb (III)
Content, μ g/L；
The recovery of standard addition of Sb (V) and Sb (III) in water body environment sample is calculated, is calculated 3 times using same method,
Average and draw final recovery of standard addition, Sb (V) and Sb (III) is calculated further according to 3 times of signal to noise ratios (S/N)) detection
Limit.
9. in environment water according to claim 1 different valence state antimony detection method, it is characterised in that：In step (4),
If the response peak of environment water body example is too high and has exceeded the detection range of instrument, need to carry out environment water body example dilute
Release, the measure of sample concentration is carried out using SAMSCalc softwares.
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