CN116793999B - Method for testing Sb (III) under NaF masking condition and application - Google Patents
Method for testing Sb (III) under NaF masking condition and application Download PDFInfo
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- MABBGPMUOLWBII-RXSVEWSESA-N (2R)-2-[(1S)-1,2-dihydroxyethyl]-3,4-dihydroxy-2H-furan-5-one thiourea Chemical compound NC(N)=S.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O MABBGPMUOLWBII-RXSVEWSESA-N 0.000 claims abstract description 5
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- -1 sodium carboxylate Chemical class 0.000 claims description 14
- 238000005086 pumping Methods 0.000 claims description 12
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000003729 cation exchange resin Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
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- 238000001676 hydride generation atomic fluorescence spectroscopy Methods 0.000 abstract description 4
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Optics & Photonics (AREA)
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for testing Sb (III) under NaF masking conditions, which comprises the following steps: s1, preparing an on-machine sample; s2, debugging an instrument and testing Sb (III); the invention also discloses application of the method to exploration of the influence of the reduction time of a reducing agent comprising 5% of HCl by volume fraction and 1% of thiourea-ascorbic acid mixed solution by mass fraction on the test concentration of Sb (V); the method is applied to exploring the influence of common coexisting ions on the testing of the masking agent; the method is applied to the exploration of the dissolution and release process of jamesonite under weak acid condition under illumination; according to the method, the purpose of directly testing the Sb (III) by utilizing the hydride generation-atomic fluorescence spectrometry is achieved by adding the NaF solution as the masking agent, and the method has the advantages of being simpler in masking agent, wider in applicability and more comprehensive in consideration.
Description
Technical Field
The invention relates to the technical field of environmental remediation, in particular to a method for testing Sb (III) under NaF masking conditions and application thereof.
Background
With the development of industry and mining industry, a large amount of antimony enters the environment, and in recent years, research discovers that antimony is widely distributed in fresh water and land ecosystems near mining areas, printing and dyeing industries and shooting ranges, is a metalloid element with potential toxicity and carcinogenicity and can be transmitted for a long distance, and has caused a global pollution problem. After entering the environment, antimony can accumulate in animals and plants through a series of bio-geochemical actions, so that the whole ecological system is influenced, and the antimony can finally enter the human body through a food chain to further harm the health of the human body.
In the water environment, the biological geochemical processes such as dissolution and release, oxidation reduction, adsorption and desorption, complexation precipitation and the like can occur under the influence of the actions of pH, oxygen, illumination, metal oxide/hydroxide, organic matters, microorganisms and the like, so that the occurrence form and migration and conversion processes of the antimony in the water environment are changed. Furthermore, numerous studies have shown that the bio-geochemical process of antimony is mainly determined by the chemical form of the dissolved state, while Sb (iii) and Sb (v) are two ubiquitous forms of dissolved antimony in aqueous environments, where Sb (iii) is much more toxic than Sb (v) and Sb (v) has a greater mobility than Sb (iii).
For determining the mass concentration of Sb (III) in the coexistence of Sb (V) and Sb (III) in water environment, the existing method comprises the following steps: hydride generation-atomic fluorescence spectrometry, graphite furnace atomic absorption method and high performance liquid chromatography combined method, etc.; although the hydride generation-atomic fluorescence spectrometry has higher testing precision and relatively lower cost, if Sb (III) is to be tested, valence separation is required to be carried out first, then a reducing agent is added for testing, the process is complex, and the cost is raised.
Therefore, there is an urgent need to establish a method for directly determining the mass concentration of Sb (iii) in water environment, thereby promoting the research of the influence of valence state on the bio-geochemical process of antimony. The invention researches a method for masking Sb (V) by using a masking agent to determine the mass concentration of Sb (III) in a water environment sample, namely, masking Sb (V) by using NaF.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for testing Sb (III) under NaF masking conditions.
The technical scheme of the invention is as follows: a method for testing Sb (iii) under NaF masking conditions, comprising the steps of:
s1, preparing an on-machine sample:
Diluting the total Sb concentration in a sample to be tested containing Sb to be less than 60 mug/L by using ultrapure water to obtain a diluted sample, then transferring 4mL of the diluted sample, sequentially adding 0.5mL of NaF solution with the mass fraction of 0.3% and 0.5mL of HCl solution with the volume fraction of 50% into the diluted sample to prepare 5mL of on-machine sample, and completing the test of the on-machine sample within 10-240 min after the preparation of the on-machine sample; wherein the mass fraction of NaF solution in the sample of the machine is 0.03%, and the volume fraction of HCl solution is 5%;
s2, debugging an instrument and testing Sb (III):
Introducing argon with the purity of 99.99% into an atomic fluorescence spectrometer, preheating for 29-31 min, pumping KBH 4 solution with the mass concentration of 20g/L at the pumping speed of 100r/min by using a peristaltic pump for 10s, pumping HNO 3 solution with the volume fraction of 5% at the pumping speed of 120r/min for 18s, regulating the negative high pressure, delay time and reading time of the atomic fluorescence spectrometer, establishing a standard curve, obtaining the highest concentration fluorescence intensity of the standard curve by using the atomic fluorescence spectrometer, and putting the sample into the atomic fluorescence spectrometer for testing when the fitting effect of the standard curve reaches 0.999.
Further, in the step S1, the negative high pressure of the atomic fluorescence spectrometer is 200-230V, the delay time is 1-5S, and the reading time is 14-17S.
Description: the highest concentration fluorescence intensity of the standard curve in the method can be obtained from 2800 to 3200 through the parameters.
Further, in step S1, the standard curve is a standard curve obtained by reducing and preparing the thiourea-ascorbic acid-hydrochloric acid system.
Description: the method of the invention is to add a masking agent when testing unknown samples, so that when Sb (III) and Sb (V) coexist, the purpose of directly measuring Sb (III) can be achieved without ion exchange, and the system is a masking agent-hydrochloric acid system at the moment.
Further, the standard curve is drawn in the following manner: firstly diluting 100mg/L total Sb standard solution with 100 times of ultrapure water to 1mg/L total Sb standard stock solution, then adding 0, 50, 100, 200, 300, 400 and 500 mu L total Sb standard stock solution into 710 mL volumetric flasks respectively, then adding 1mL of 10% thiourea and ascorbic acid mixed solution with 1mL of 50% HCl solution with volume fraction into the volume total Sb standard stock solution respectively, refrigerating for 6 hours at 4 ℃ after the ultrapure water is subjected to volume fixing, measuring by an atomic fluorescence meter, and drawing a standard curve with the solution concentration as an abscissa and the fluorescence intensity as an ordinate, wherein the range of Sb (III) in the standard curve is 0-50 mu g/L.
Description: the drawing of the standard curve can ensure that the sample on the machine has thiourea with the mass fraction of 1 percent, ascorbic acid with the mass fraction of 1 percent and hydrochloric acid with the volume fraction of 5 percent to ensure the accuracy of the standard sample, so that a certain masking agent is added when an unknown sample is tested, and the purpose of directly measuring the Sb (III) can be achieved without ion exchange when the Sb (III) and the Sb (V) coexist.
Further, the mass concentration of total Sb in the machine sample is less than 60 mug/L, and the mass concentration of 5 mug/L less than Sb (III) is less than 60 mug/L.
Description: the mass concentration of Sb (III) in the standard curve is 0-50 mug/L, and the total Sb of the machine is lower than 60 mug/L in order to ensure accurate data; the larger the influence caused by the instrument error preventing the mass concentration of Sb (III) from being too low, the mass concentration of Sb (III) should be higher than 5. Mu.g/L.
Further, before step S1, a pretreatment is performed on the sample to be tested, the pretreatment includes the following steps:
adding an active agent accounting for 0.5-1.5% of the volume of the sample to be detected into the sample to be detected, adding the active agent with the same initial adding amount every 2-5 min, and applying an electric field to the sample to be detected under the infrared heating condition, wherein the heating time and the application time are all continuous until the addition of the active agent is finished;
when the volume of the added active agent accounts for 3 percent of the volume of the sample to be measured, the wavelength of infrared is adjusted to 4-6 um from the initial wavelength of 7-9 um, and when the wavelength of infrared is weakened by 0.4-0.6 um, the intensity of an electric field is weakened by 2-5 MHz from the initial intensity of 180-190 MHz;
wherein the total addition amount of the active agent is 5-7% of the volume of the sample to be detected, and the active agent comprises the following components in parts by weight: 5 to 6 parts of sodium carboxylate, 2 to 4 parts of dodecyl trimethyl ammonium chloride and 1 to 2 parts of polyacrylic weak acid cation exchange resin.
Description: through adding a certain amount of active agent at intervals, the activity of ions in a sample to be detected is improved, and Ca 2+ plasma is decontaminated through polyacrylic acid-based weak acid cation exchange resin; the ion activity is further improved by the wavelength of infrared heating which changes along with the dosage of the active agent, and the impurity removing effect is enhanced under the auxiliary effect that the electric field changes along with the infrared.
The method for testing Sb (III) is applied to exploring the influence of the reduction time of a reducing agent on the test concentration of Sb (V), wherein the reducing agent is 5% by volume of HCl and 1% by mass of thiourea-ascorbic acid mixed solution.
The method for testing Sb (III) by using any one of the above is applied to the influence of common coexisting ions on the masking agent test; the common coexisting ions include Ca 2+,K+、Na+、SO4 2-、Cl-、Fe3+ and Mn 2+.
The method for testing Sb (III) is applied to exploring the dissolution and release process of jamesonite under weak acid condition under illumination; the weak acid condition is weak acid solution obtained by adjusting the pH of ultrapure water to 6 by nitric acid or hydrochloric acid.
The beneficial effects of the invention are as follows:
(1) According to the testing method, the purpose of directly testing the Sb (III) by utilizing a hydride generation-atomic fluorescence spectrometry is achieved by adding the NaF masking agent, a certain amount of NaF and HCl solution is added into a Sb-containing sample to be tested, and the characteristic that F - and Sb (V) form stable SbF 6 - ions is achieved by utilizing the acidic condition of the HCl solution, so that the effect of masking the Sb (III) is achieved, and the mass concentration of the Sb (III) in the sample is directly measured.
(2) The masking agent used in the test method only needs NaF solution, does not need to be prepared and mixed with other solutions, and is more concise and saves time; the mass concentration ratio of Sb (III) and Sb (V) can be adjusted, so that the applicability is wide; and the influence of other anions and cations in the natural water body is considered, so that the test is more comprehensive and has a general meaning.
(3) According to the test method, the Sb-containing sample to be tested is pretreated, a certain amount of active agent is added at intervals, so that the activity of ions in the sample to be tested is improved, and Ca 2+ plasma is purified by the polyacrylic acid-based weak acid cation exchange resin; the ion activity is further improved by the wavelength of infrared heating which changes along with the dosage of the active agent, and the impurity removing effect is enhanced under the auxiliary effect of the electric field which changes along with the infrared, so that the influence of other ions on the test Sb (III) is reduced.
Drawings
FIG. 1 is a graph showing the effect of five different mass fractions of NaF solutions on different concentration ratios of Sb (III) to Sb (V) in Experimental example 1;
FIG. 2 is a graph showing the effect of four different mass fractions of NaF solutions, except 0.01%, on the different concentration ratios of Sb (III) to Sb (V) in experimental example 1;
FIG. 3 is a graph showing the effect trend of K +、Na+、Ca2+ ion on Sb (III) test in application example 2;
FIG. 4 is a graph showing the trend of SO 4 2-、Cl-、Fe3+ and Mn 2+ ions in application example 2 on the effect of Sb (III) test;
FIG. 5 is a graph showing the trend of the total Sb change in the dissolution and release process in the weak acid environment of jamesonite in application example 3;
FIG. 6 is a graph showing the change trend of Sb (III) in the dissolution and release process in the weak acid environment of jamesonite in application example 3;
FIG. 7 is a graph showing the change in the dissolution and release of Sb (V) in the weak acid environment of jamesonite in application example 3.
Detailed Description
The invention will be described in further detail with reference to the following embodiments to better embody the advantages of the invention.
Example 1
A method for testing Sb (iii) under NaF masking conditions, comprising the steps of:
s1, preparing an on-machine sample:
Diluting the total Sb concentration in a sample to be tested containing Sb to be less than 60g/L by using ultrapure water to obtain a diluted sample, then transferring 4mL of the diluted sample, sequentially adding 0.5mL of NaF solution with the mass fraction of 0.3% and 0.5mL of HCl solution with the volume fraction of 50% into the diluted sample to prepare 5mL of upper sample, and completing the test of the upper sample after 170min of the preparation of the upper sample; wherein the mass fraction of NaF solution in the sample of the machine is 0.03%, and the volume fraction of HCl solution is 5%; the mass concentration of the total Sb in the on-machine sample is 30 mug/L, and the mass concentration of the Sb (III) is 10 mug/L;
s2, debugging an instrument and testing Sb (III):
Introducing argon with the purity of 99.99% into an atomic fluorescence spectrometer, preheating for 30min, pumping KBH 4 solution with the mass concentration of 20g/L at the pumping speed of 100r/min by using a peristaltic pump for 10s, pumping HNO 3 solution with the volume fraction of 5% at the pumping speed of 120r/min for 18s, regulating the negative high pressure, delay time and reading time of the atomic fluorescence spectrometer, establishing a standard curve prepared by reducing a thiourea-ascorbic acid-hydrochloric acid system, obtaining the highest concentration fluorescence intensity of the standard curve by using the atomic fluorescence spectrometer, and putting the sample into the atomic fluorescence spectrometer for testing when the fitting effect of the standard curve reaches 0.999;
the negative high pressure of the atomic fluorescence spectrometer is 215V, the delay time is 3s, and the reading time is 16s;
The standard curve is drawn in the following manner: firstly diluting 100mg/L total Sb standard solution with 100 times of ultrapure water to 1mg/L total Sb standard stock solution, then adding 0, 50, 100, 200, 300, 400 and 500 mu L total Sb standard stock solution into 710 mL volumetric flasks respectively, then adding 1mL of 10% thiourea and ascorbic acid mixed solution with 1mL of 50% HCl solution with volume fraction into the volume total Sb standard stock solution respectively, refrigerating for 6 hours at 4 ℃ after the ultrapure water is subjected to volume fixing, measuring by an atomic fluorescence meter, and drawing a standard curve with the solution concentration as an abscissa and the fluorescence intensity as an ordinate, wherein the range of Sb (III) in the standard curve is 0-50 mu g/L.
Example 2
This example differs from example 1 in that in step S1, the mass fraction of the NaF solution added to the sample to be measured is 0.01%.
Example 3
This example differs from example 1 in that in step S1, the mass fraction of the NaF solution added to the sample to be measured is 0.05%.
Example 4
This example differs from example 1 in that in step S1, the mass concentration of total Sb in the on-press sample is 40. Mu.g/L, and the mass concentration of Sb (III) is 20. Mu.g/L.
Example 5
This embodiment differs from embodiment 1 in that, before step S1 is performed, a pretreatment is performed on the sample to be tested, the pretreatment including the steps of:
after adding an active agent accounting for 1% of the volume of the sample to be detected into the sample to be detected, adding the active agent with the same initial addition amount every 3min, and applying an electric field to the sample to be detected under the infrared heating condition, wherein the heating time and the application time are all continuous until the addition of the active agent is finished;
When the volume of the added active agent accounts for 3 percent of the volume of the sample to be measured, the wavelength of infrared is adjusted from the initial wavelength of 8um to 5um, and when the wavelength of infrared is weakened by 0.5um, the intensity of an electric field is weakened by 3MHz from the initial intensity of 185 MHz;
Wherein, the total addition amount of the active agent is 6% of the volume of the sample to be detected, and the active agent comprises the following components in parts by weight: 5.5 parts of sodium carboxylate, 3 parts of dodecyl trimethyl ammonium chloride and 1.5 parts of polyacrylic acid based weakly acidic cation exchange resin.
Example 6
The difference between this example and example 5 is that after the active agent accounting for 0.5% of the volume of the sample to be measured is added to the sample to be measured, the same amount of active agent as the initial addition is added every 2 minutes, and the total volume of the active agent accounts for 5%.
Example 7
The difference between this example and example 5 is that, after the active agent accounting for 1.5% of the volume of the sample to be measured is added to the sample to be measured, the same amount of active agent as the initial addition is added every 5min, and the total volume of the active agent accounts for 7%.
Example 8
This example differs from example 5 in that the active agent comprises, in parts by weight: 5 parts of sodium carboxylate, 2 parts of dodecyl trimethyl ammonium chloride and 1 part of polyacrylic acid based weak acid cation exchange resin.
Example 9
This example differs from example 5 in that the active agent comprises, in parts by weight: 6 parts of sodium carboxylate, 4 parts of dodecyl trimethyl ammonium chloride and 2 parts of polyacrylic acid based weak acid cation exchange resin.
Example 10
This example differs from example 5 in that the wavelength of the infrared light is adjusted from an initial wavelength of 7um to 6um when the total addition amount of the active agent is 3% of the volume of the sample to be measured.
Example 11
This example differs from example 5 in that the wavelength of the infrared light is adjusted from an initial wavelength of 9um to 4um when the total addition amount of the active agent is 3% of the volume of the sample to be measured.
Example 12
This embodiment differs from embodiment 5 in that the intensity of the electric field is reduced by 2MHz from the initial intensity of 180MHz for every 0.4um reduction in infrared wavelength.
Example 13
This embodiment differs from embodiment 5 in that the intensity of the electric field is reduced by 5MHz from the initial intensity of 190MHz for every 0.6um reduction in infrared wavelength.
Experimental example
For the test method of each example, 5 on-machine samples of each example were taken to test the mass concentration and recovery rate of Sb (iii), and the test results of the 5 samples of each example were averaged to be the test results of this example, and specifically studied as follows:
1. Masking effects of Sb (v) in different mass fractions of NaF solution on different mass concentration ratios of Sb (iii) to Sb (v) were investigated.
NaF solutions of 0.04%, 0.02% and 0% by mass were prepared again in 4 groups except for examples 1 to 4, and the mass concentration ratio (in ug/L) of Sb (III) to Sb (V) of 5 groups was 1:4 (5/20), 1:10 (2/20), 1:20 (1/20), 1:40 (0.5/20), 0 (0/20);
and then 5 groups of NaF solutions with different mass fractions are respectively added into 7 groups of mixed solutions for testing, the time interval from the addition of the NaF solutions to the completion of the sample testing is 10-30 min, and the results are shown in Table 1:
TABLE 1 test concentration and recovery of Sb (III) in NaF solutions of different mass fractions versus different mass concentration ratios of Sb (III) to Sb (V)
Recovery = test concentration/actual concentration of Sb (iii);
Taking the mass concentration ratio of Sb (III) to Sb (V) as the ordinate and taking the mass concentration ratio of Sb (III) as the abscissa, and combining the results of Table 1 with those of FIG. 1 and FIG. 2, it can be seen that when the mass concentration of Sb (III) is lower than 5 mug/L (i.e., when the mass concentration ratio of Sb (III) is smaller than 1:4), the recovery rate of Sb (III) is significantly reduced, thus indicating that the mass concentration of Sb (III) should be > 5 mug/L;
It is evident from a combination of Table 1 and FIG. 1 that the recovery rate of Sb (III) exceeds 100% when the mass fraction of NaF is 0.01% and 0, indicating that the test of Sb (V) on Sb (III) is significantly disturbed, and that the lower the mass concentration of Sb (III), the more disturbed, so that the mass fraction of NaF is required to be higher than 0.01%; and the recovery rate of Sb (III) is not greatly different when the mass fraction of NaF solution is 0.02% and 0.03%, but when the mass fraction of NaF solution is more than 0.03%, the recovery rate of Sb (III) is lower when the mass concentration is larger, so that the mass fraction of NaF solution is preferably 0.02% or 0.03%;
And then comparing the NaF solution with the mass fraction of 0.02% and 0.03%, and calculating and removing errors through multiple comparison results to obtain the NaF solution with the mass fraction of 0.03%, the recovery rate of Sb (iii) was higher and more stable than that of the NaF solution at a mass fraction of 0.02%, so that the recovery rate of Sb (iii) was relatively best when the mass fraction of the NaF solution was 0.03% (i.e. example 1).
2. The effect of pretreatment on the test concentration and recovery of Sb (iii) was investigated.
TABLE 2 test concentration and recovery of Sb (III) for examples 1, 5-13, comparative examples 1-4
Comparative example 1 differs from example 5 in that the active agent comprises, in parts by weight: 6-8 parts of sodium carboxylate and 2-4 parts of dodecyl trimethyl ammonium chloride;
Comparative example 2 differs from example 5 in that the infrared wavelength remains unchanged by the original wavelength of 8 um;
comparative example 3 is different from example 5 in that the electric field strength is kept constant at 185MHz at the initial strength when the infrared wavelength is changed;
Comparative example 4 is different from example 5 in that the active agent, which is 6% of the volume of the sample to be measured in total, is added all at once;
As can be seen from table 2, after pretreatment, the test concentration of Sb (iii) is closer to the actual concentration, and thus the recovery rate is also higher; it is also clear from comparative example 1 that the effect of the activator lacking the polyacrylic acid group weakly acidic cation exchange resin was weaker than that of examples 5 to 13, that the change law of the infrared wavelength and the electric field intensity had a certain effect on the test concentration and recovery rate of Sb (iii) from comparative example 2 and comparative example 3, and that the addition mode of the activator had a certain effect on the test concentration and recovery rate of Sb (iii) from comparative example 4.
From examples 5 to 13, it is known that too long or too short and too large or too small of the change in infrared wavelength, too high or too low of the electric field strength and too large or too small of the change in electric field strength reduce the effect of the recovery rate of Sb (III), and too fast or too slow of the addition of the active agent, too large or too small of the addition amount reduce the effect of the recovery rate of Sb (III);
thus, considering the process parameters of example 5 in combination, the masking effect of the masking agent is relatively better.
Application example
1) The effect of reducing agent (5% HCl by volume and 1% thiourea-ascorbic acid mixed solution by mass) reduction time on Sb (V) test concentration was investigated.
TABLE 3 test concentration of Sb (V) at different reduction times for reducing agent (5% HCl by volume, 1% thiourea-ascorbic acid mixed solution by mass)
| Time of | 0.5h | 1h | 1.5h | 2h | 2.5h | 3h |
| Parallel sample 1 | 22.83952 | 24.91413 | 25.53175 | 29.9204 | 30.0292 | 34.95487 |
| Parallel sample 2 | 22.48673 | 24.06816 | 25.02966 | 28.98479 | 30.9351 | 31.44655 |
| Parallel sample 3 | 22.99686 | 25.34019 | 27.26989 | 29.58664 | 31.16572 | 32.37144 |
| Mean value of | 22.77437 | 24.77416 | 25.94377 | 29.49728 | 30.71001 | 32.92429 |
| Time of | 3.5h | 4h | 4.5h | 5h | 5.5h | 6h |
| Parallel sample 1 | 33.83137 | 33.92276 | 34.85227 | 34.48122 | 35.90657 | 35.18146 |
| Parallel sample 2 | 32.61312 | 34.73944 | 34.86063 | 34.96143 | 35.07126 | 36.27084 |
| Parallel sample 3 | 32.61457 | 34.16762 | 33.88692 | 35.38821 | 35.66149 | 36.37223 |
| Mean value of | 33.01969 | 34.27661 | 34.53327 | 34.94362 | 35.54644 | 35.94151 |
Note that: the test concentration of Sb (V) in the Table is given in μg/L, and the actual concentration of Sb (V) is given in 50 μg/L.
As can be seen from the data in Table 3, the test concentration of Sb (V) was increasing over time, but the rate of increase of the test concentration of Sb (V) was retarded from 4 hours, indicating that the degree of reduction of Sb (V) gradually tended to stabilize.
2) The method is used for exploring the influence of common coexisting ions on the testing of the masking agent;
7 groups of solutions containing different coexisting ions and having mass concentrations of Sb (III) and Sb (V) of 10 mug/L and 50 mug/L respectively were prepared, wherein the mass concentrations of the coexisting ions in each group of solutions were 0, 50, 100, 200, 400, 600, 800, 1000, 1500, 2000, 3000, 4000 and 5000 mug/L in order, and after NaF (mass fraction of 0.03%) was added, the test was completed within 10 to 30 minutes, and the results are shown in Table 4:
TABLE 4 test concentrations of different interfering ions and their mass concentrations against Sb (III)
The recovery rate of Sb (III) is taken as an ordinate, the mass concentration of coexisting ions is taken as an abscissa, the results of the table 4 are summarized into the tables 3 and 4, and as can be seen from the tables 4, 3 and 4, the test influence of different coexisting ions such as K +、Na+、SO4 2-、Cl-、Fe3+, mn 2+ and the like and the mass concentration thereof on the Sb (III) under NaF masking is not great except for Ca 2+, and the test recovery rate of Sb (III) fluctuates within the range of 90% -110%; after Ca 2+ is higher than 1000 mug/L, the mass concentration tested by Sb (III) is obviously lower and possibly influenced by CaF 2 precipitation.
3) The dissolution and release process of jamesonite under weak acid condition under illumination is explored.
0.25G of jamesonite powder (passing through a 400-target quasi-nylon sieve) is added into two groups of 500mL solutions obtained by respectively adjusting the pH value of ultrapure water to 6 by nitric acid and hydrochloric acid, the illumination groups are subjected to uninterrupted illumination by using a xenon lamp (Shanghai Ji Guang, CEL-300, 300W), the dark groups are wrapped by aluminum foils, and the two groups are placed in a water bath constant temperature magnetic stirrer for stirring in the experimental process, and the temperature is controlled to be 25 ℃. Sampling in the reaction of 0.5, 1, 1.5, 2, 3, 4, 6 and 8 hours, filtering, testing total Sb in the sample by using a thiourea-ascorbic acid-hydrochloric acid method, testing Sb (III) in the sample by using a masking agent method, and obtaining the results shown in figures 5-7;
As shown in fig. 5 and 6, the total Sb and Sb (iii) release amounts in the water environment increase with time, and the release rate and release amount under the illumination condition are higher than those under the dark condition, and generally, electron holes are easily generated on the surface of the mineral under the illumination condition to form free radicals, and in the reaction, the free radicals may be generated on the surface of the jamesonite, so that the dissolution and release of the jamesonite are promoted by oxidizing Sb (iii);
As shown in FIG. 7, the formation rate of Sb (V) under the illumination condition is obviously higher than that under the dark condition, which indicates that the dissolution and release process of the jamesonite in water can be an oxidation dissolution process controlled by oxidation.
Claims (8)
1. A method for testing Sb (iii) under NaF masking conditions, comprising the steps of:
Pretreating a sample to be tested, wherein the pretreatment comprises the following steps:
Adding an active agent accounting for 0.5-1.5% of the volume of the sample to be detected into the sample to be detected, adding the active agent with the same initial adding amount every 2-5 min, and applying an electric field to the sample to be detected under the infrared heating condition, wherein the heating time and the application time are all continuous until the addition of the active agent is finished;
when the volume of the added active agent accounts for 3% of the volume of the sample to be measured, the wavelength of infrared is adjusted to 4-6 um from the initial wavelength of 7-9 um, and when the wavelength of infrared is weakened by 0.4-0.6 um, the intensity of an electric field is weakened by 2-5 MHz from the initial intensity of 180-190 MHz;
The total addition amount of the active agent is 5-7% of the volume of a sample to be detected, and the active agent comprises the following components in parts by weight: 5-6 parts of sodium carboxylate, 2-4 parts of dodecyl trimethyl ammonium chloride and 1-2 parts of polyacrylic weak acid cation exchange resin;
s1, preparing an on-machine sample:
Diluting the total Sb concentration in a sample to be tested containing Sb to be less than 60 mug/L by using ultrapure water to obtain a diluted sample, then transferring 4mL of the diluted sample, sequentially adding 0.5mL of NaF solution with the mass fraction of 0.3% and 0.5mL of HCl solution with the volume fraction of 50% into the diluted sample to prepare 5mL of on-machine sample, and completing the test of the on-machine sample within 10-240 min after the preparation of the on-machine sample; wherein the mass fraction of NaF solution in the sample of the machine is 0.03%, and the volume fraction of HCl solution is 5%;
s2, debugging an instrument and testing Sb (III):
Introducing argon with the purity of 99.99% into an atomic fluorescence spectrometer, preheating for 29-31 min, pumping KBH 4 solution with the mass concentration of 20g/L at the pumping speed of 100r/min by using a peristaltic pump for 10s, pumping HNO 3 solution with the volume fraction of 5% at the pumping speed of 120r/min for 18s, regulating the negative high pressure, delay time and reading time of the atomic fluorescence spectrometer, establishing a standard curve, obtaining the highest concentration fluorescence intensity of the standard curve by using the atomic fluorescence spectrometer, and putting the sample into the atomic fluorescence spectrometer for testing when the fitting effect of the standard curve reaches 0.999.
2. The method for testing Sb (iii) under NaF masking conditions according to claim 1, wherein in step S1, the negative high pressure of the atomic fluorescence spectrometer is 200-230 v, and the reading time is 14-17S.
3. The method according to claim 1, wherein in step S1, the standard curve is a standard curve prepared by reducing thiourea-ascorbic acid-hydrochloric acid system.
4. A method for testing Sb (iii) under NaF masking conditions according to claim 3, wherein the standard curve prepared by reduction of thiourea-ascorbic acid-hydrochloric acid system is drawn by: firstly diluting 100mg/L total Sb standard solution with 100 times of ultrapure water to 1mg/L total Sb standard stock solution, then adding 0, 50, 100, 200, 300, 400 and 500 mu L total Sb standard stock solution into 7 10mL volumetric flasks respectively, then adding 1mL of 10% thiourea and ascorbic acid mixed solution with 1mL of 50% HCl solution with volume fraction into the volume total Sb standard stock solution respectively, refrigerating for 6 hours at 4 ℃ after the ultrapure water is subjected to volume fixing, measuring by an atomic fluorescence meter, and drawing a standard curve with the solution concentration as an abscissa and the fluorescence intensity as an ordinate, wherein the range of Sb (III) in the standard curve is 0-50 mu g/L.
5. The method of claim 1, wherein the total Sb mass concentration in the on-machine sample is less than 60 μg/L, and 5 μg/L is less than 60 μg/L.
6. Use of the method for testing Sb (iii) according to any one of claims 1 to 5, wherein the method is applied to investigate the effect of the reduction time of a reducing agent on the Sb (v) test concentration, the reducing agent being 5% HCl by volume and 1% thiourea-ascorbic acid mixed solution by mass.
7. The use of a method for testing Sb (iii) according to any one of claims 1 to 5, wherein the method is applied to explore the effect of common coexisting ions on masking agent testing; the common coexisting ions include Ca 2+,K+、Na+、SO4 2-、Cl-、Fe3+ and Mn 2+.
8. Use of the method for testing Sb (iii) according to any one of claims 1 to 5, characterized in that it is applied to the investigation of the dissolution release process of jamesonite under weak acid conditions under light irradiation; the weak acid condition is weak acid solution obtained by adjusting the pH of ultrapure water to 6 by nitric acid or hydrochloric acid.
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