CN102507713B - Electrochemical stripping voltammetry for continuously measuring arsenic, stibonium and lead in mine groundwater - Google Patents
Electrochemical stripping voltammetry for continuously measuring arsenic, stibonium and lead in mine groundwater Download PDFInfo
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- CN102507713B CN102507713B CN 201110349485 CN201110349485A CN102507713B CN 102507713 B CN102507713 B CN 102507713B CN 201110349485 CN201110349485 CN 201110349485 CN 201110349485 A CN201110349485 A CN 201110349485A CN 102507713 B CN102507713 B CN 102507713B
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Abstract
The invention discloses an electrochemical stripping voltammetry for continuously measuring arsenic, stibonium and lead in mine groundwater, which utilizes a gold electrode as a working electrode and measures the concentrations of arsenic, stibonium and lead in a test sample solution by an electrochemical method; the method comprises the following steps of: pre-treating the gold electrode, firstly polarizing the electrode, and activating the electrode in a circular voltammetry; varying the potential of the gold electrode toward a negative potential direction, simultaneously depositing arsenic and stibonium on the surface of the gold electrode under the same potential, and measuring the total concentration of arsenic and stibonium by potential dissolution; and then, changing the deposition potential, singly depositing the stibonium, measuring the stibonium concentration by the potential stripping, and obtaining the arsenic concentration according to a difference value; firstly depositing the arsenic and lead on the gold electrode under the same potential, scanning the gold electrode toward the positive potential direction, separating out the arsenic and lead electrically deposited on the surface of the gold electrode under different potentials, and respectively measuring the concentrations of the arsenic and lead. The method provided by the invention has the advantages of continuously measuring the concentrations of arsenic, stibonium and lead in the same solution in a convenient and sensitive manner.
Description
Technical field
The present invention relates to a kind of method of surveying arsenic in water, antimony, lead content, especially to the tie-in method of arsenic, antimony, lead content in Mine Underground Water.
Background technology
Heavy metal pollution is one of environmentally hazardous greatest problem.Arsenic, lead, antimony are the important analysis projects of environmental monitoring.Arsenic is a kind ofly easily by potable water and food, to enter into human body, in human body, after savings, causes arsenic poisoning, and a kind of extremely harmful element that can be lethal.Arsenic is in occurring in nature generally is present in water body and soil with sodium arsenite, arsenic trioxide, natrium arsenicum form, and trivalent arsenic is stronger than pentavalent arsenic toxicity, and inorganic arsenic chemicals is stronger than organoarsenium compound toxicity.Lead is a kind of of quantity maximum in heavy metal pollution, is also one of metal the most serious to mankind's harm, can poison nervous system and hemopoietic system, causes spasm, hyponea, anaemia etc.Antimony can be combined with sulfydryl in human body, and the activity of inhibition succinic oxidase etc., destroy ionic equilibrium in cell, makes potassium deficiency in cell, causes the internal metabolism disorder, causes multisystem, many organ injuries.Poisonous element as arsenic, lead, antimony, water pollution prevents that in the law regulation discharge water, its content benchmark is 0.1ppm(100ppb) below.For this reason, need a kind of easy and detection method that precision is good, can detect the concentration of arsenic, lead, antimony in discharge water and mine water.The electrochemical method that detects separately arsenic, lead, antimony more report, but, in the same electrolyte solution, uses gold electrode METHOD FOR CONTINUOUS DETERMINATION arsenic, lead, antimony concentration have not been reported.
Summary of the invention
The purpose of this invention is to provide a kind of volt-ampere of the Electrochemical Stripping for Mine Underground Water arsenic, antimony and plumbous tie-in method, the method can the easy arsenic of continuous detecting delicately, antimony and plumbous concentration.
For achieving the above object, the present invention takes following design proposal:
A kind of volt-ampere of the Electrochemical Stripping for Mine Underground Water arsenic, antimony and plumbous tie-in method, directly used gold electrode for working electrode, with electrochemical means, measures arsenic, antimony, lead concentration in sample solution, and it comprises the following steps:
A) gold electrode is carried out to pre-service, first polarized electrode, then use the cyclic voltammetry activated electrode;
B) adopt two steps to realize the arsenic in sample solution, antimony and plumbous tie-in:
One of them step is to the arsenic in sample solution, antimony tie-in, first make the current potential of the gold electrode of above-mentioned steps in a) change to the negative potential direction, under identical current potential, allow arsenic, antimony first be deposited on above-mentioned gold electrode surfaces, the total concentration of arsenic and antimony is measured in the current potential stripping simultaneously; And then the change sedimentation potential, depositing separately antimony, the concentration of antimony is surveyed in the current potential stripping, obtains the concentration of arsenic according to difference;
Another step is to the arsenic in sample solution, plumbous tie-in, under same current potential, first make arsenic, plumbous deposit on the gold electrode in a) in above-mentioned steps, to the above-mentioned gold electrode of positive potential scanning direction, arsenic, the lead of electro-deposition on above-mentioned gold electrode surfaces is separated out under different current potentials, measure respectively arsenic and plumbous concentration;
In above-mentioned two steps, a selection pacing wherein goes out arsenic concentration and gets final product.
In the Electrochemical Stripping volt-ampere method of described arsenic, antimony and plumbous tie-in, the pre-service of gold electrode comprise respectively+2V ,-0.35V polarized electrode 10s, then from-10～15 activated electrodes of 0.3V to 1.6V cyclic voltammetry scan.
In the Electrochemical Stripping volt-ampere method of described arsenic, antimony and plumbous tie-in, in the arsenic in sample solution, antimony tie-in, the sedimentation potential of surveying its total concentration is-0.3V; The sedimentation potential of surveying separately antimony is 0.1V.
In the Electrochemical Stripping volt-ampere method of described arsenic, antimony and plumbous tie-in, in the arsenic in sample solution, plumbous tie-in, sedimentation potential is-0.3V.
In the Electrochemical Stripping volt-ampere method of described arsenic, antimony and plumbous tie-in, in sample solution, the concentration of supporting electrolyte is 1M H
2sO
4+ 0.1M HCl.
In the Electrochemical Stripping volt-ampere method of described arsenic, antimony and plumbous tie-in, add reductive agent hydrazine hydrochloride, vitamin C or Na2SO3 in sample solution; Be preferably Na2SO3.
The present invention is that a kind of direct use gold electrode is working electrode, measures the method for arsenic, antimony and lead concentration in sample solution with electrochemical means, can be for the monitoring to Mine Underground Water.
Advantage of the present invention is: it is with easy operation, can high precision and detect continuously in high sensitivity arsenic, antimony, plumbous concentration in same solution.
The accompanying drawing explanation
Fig. 1 is arsenic in the continuous coverage water sample in one embodiment of the invention, plumbous Electrochemical Stripping voltammogram.
Fig. 2 is the Electrochemical Stripping voltammogram of arsenic, antimony in the continuous coverage water sample in one embodiment of the invention.
Fig. 3 is that the inventive method and ICP method are measured arsenic (As) in water sample, plumbous (Pb), antimony (Sb) content results table.
Embodiment
The electrochemical method of arsenic of the present invention, antimony and plumbous tie-in is the concentration of using arsenic, lead, antimony in the three-electrode system METHOD FOR CONTINUOUS DETERMINATION sample solution that gold electrode is working electrode, it is characterized in that possessing following operation: the pretreatment process of gold electrode; The reduction operation of arsenic and antimony; The electro-deposition operation of gold electrode surfaces is arrived in arsenic, lead, antimony electro-deposition; To positive potential scanning direction gold electrode, and arsenic, lead, the antimony of above-mentioned gold electrode surfaces electro-deposition are parsed in said sample solution separate out operation.
At first the present invention measures in the method for arsenic in sample solution, antimony, lead concentration is that gold electrode is carried out to the mechanical buffing pre-service, then polarized electrode, then uses the cyclic voltammetry activated electrode.By two steps of mechanical buffing and activation polarization activation, with the only mechanical treatment of routine, to compare, gold electrode surfaces is cleaner, and activity is higher, more is conducive to the electro-deposition of arsenic, lead, antimony, and uses more conveniently, is convenient to robotization and controls.The polarized electrode pre-service of gold electrode comprise respectively+2V ,-0.35V polarized electrode 10s, then from-10～15 activated electrodes of 0.3V to 1.6V cyclic voltammetry scan.
Very approaching due to arsenic, antimony chemical property, their stripping current potential is basically identical, is difficult to distinguish, and adopts and controls the sedimentation potential method in the present invention, realizes METHOD FOR CONTINUOUS DETERMINATION arsenic antimony concentration.In addition, because the arsenic antimony of pentavalent does not have electrochemical activity, need to add a certain amount of reductive agent in electrolyte solution, prevent oxidation and the reduction highly charged ions of arsenic antimony, in the present invention relatively reductive agent hydrazine hydrochloride, vitamin C and Na
2s0
3, draw sodium sulphite Na
2s0
3be comparatively desirable reductive agent, its concentration is controlled in 10～20 times of scopes of institute's test specimens ion concentration.
According to the present invention, while utilizing electrochemical reaction to detect the concentration of arsenic, lead, antimony, by the pre-service gold electrode, control sedimentation potential, with easy operation and device, can high precision and high sensitivity, and there is good reproduction ground continuous detecting arsenic, lead and antimony and measure its concentration.Wherein, while specifically measuring, can realize the arsenic in sample solution, antimony and plumbous tie-in by two steps:
One of them step is to the arsenic in sample solution, antimony tie-in, first make the current potential of pretreated gold electrode change to the negative potential direction, under identical current potential, (sedimentation potential is-the 0.3V left and right) allows arsenic, antimony first be deposited on above-mentioned gold electrode surfaces simultaneously, and the total concentration of arsenic and antimony is measured in the current potential stripping; And then the change sedimentation potential, sedimentation potential is 0.1V, deposits separately antimony, the concentration of antimony is surveyed in the current potential stripping, obtains the concentration of arsenic according to difference;
Another step is to the arsenic in sample solution, plumbous tie-in, under same current potential, first make arsenic, lead deposit on pretreated gold electrode, to the above-mentioned gold electrode of positive potential scanning direction, arsenic, the lead of electro-deposition on above-mentioned gold electrode surfaces is separated out under different current potentials, sedimentation potential is-0.3V to measure respectively arsenic and plumbous concentration;
In above-mentioned two steps, all can in each step, can measure the concentration of arsenic, therefore only select a pacing wherein to go out arsenic concentration, get final product.
Can add supporting electrolyte in sample solution, the concentration of this supporting electrolyte is 1M H
2sO
4+ 0.1M HCl.
Below, with reference to specific embodiment, to of the present invention, further illustrate.
embodiment 1
1) pre-service of gold electrode
Al with 0.05mm
2o
3burnishing powder mechanical grinding gold electrode on polishing paper, about two minutes, thoroughly cleans gold electrode with intermediate water after polishing; Electrochemical oxidation and reduction gold thereupon, with chronoamperometry respectively 2V ,-0.35V polarized electrode 10s, then at 0.5 M H
2sO
4middle scan round activated electrode 10 circle (sweep limit :-300～1600mV, sweep speeds: 4V/s); Finally at 0.5 M H
2sO
4the middle gold electrode of crossing by the cyclic voltammetry characterization process (sweep limit :-300～1600mV, sweep speed: 0.1V/s), used in experiment is platinum electrode to electrode, and contrast electrode is saturated calomel electrode;
2) concentration of METHOD FOR CONTINUOUS DETERMINATION arsenic, lead and antimony:
A) concentration of METHOD FOR CONTINUOUS DETERMINATION As (III), Pb (II) solution
Use NaAsO2, Pb (NO
3)
2for standard substance, As (III), Pb (II) solution of preparation variable concentrations, and it is measured.At first, preparation end liquid.In end liquid, select redistilled water as solvent, add H
2sO
4making its concentration is 1M, and it is 0.1M that interpolation HCl makes its concentration, adds Na
2s0
3making its concentration is 1mg/l.Then, by NaAsO
2, Pb (NO
3)
2join in end liquid, be mixed with As (III), Pb (II) aqueous solution as measuring;
In the mensuration system, selecting the gold electrode of processing is working electrode, and saturated calomel electrode is contrast electrode, and platinum electrode is to electrode.Then, employing can effectively detect the Linear Sweep Stripping Voltammetric of micro constitutent, additional negative potential originally, As, Pb electro-deposition on electrode after, to positive potential scanning direction current potential, measure current value now;
Condition determination is as follows:
Electro-deposition current potential-0.3V, electrodeposition time 180s (stirring 180s);
Rest potential-0.3V, rest time 30s;
Sweep speed 100mV/s, sweep limit-0.3V～0.4V;
Result as shown in Figure 1.
B) concentration of METHOD FOR CONTINUOUS DETERMINATION As (III), Sb (III) solution
Use NaAsO
2, the Sb powder is standard substance, As (III), Sb (III) solution of preparation variable concentrations, and it is measured.At first, preparation end liquid.In end liquid, select redistilled water as solvent, add H
2sO
4making its concentration is 1M, and it is 0.1M that interpolation HCl makes its concentration, adds Na
2s0
3making its concentration is 1mg/l.Then, the As (III), the Sb (III) that prepare are joined in end liquid, be modulated into As (III), Pb (II) aqueous solution as measuring;
In the mensuration system, selecting the gold electrode of processing is working electrode, and saturated calomel electrode is contrast electrode, and platinum electrode is to electrode.Then, employing can effectively detect the Linear Sweep Stripping Voltammetric of micro constitutent, additional negative potential-0.3V originally, As, Sb electro-deposition on electrode after, to positive potential scanning direction current potential, measure current value now, be now the total concentration signal of arsenic antimony; Then changing additional negative potential is sedimentation potential 0.1V, now only has the Sb electro-deposition on electrode, to positive potential scanning direction current potential, measures current value now, is now the concentration signal of antimony; Ask its difference, can realize the METHOD FOR CONTINUOUS DETERMINATION of arsenic antimony;
Condition determination is as follows:
Electro-deposition current potential-0.3V or 0.1V, electrodeposition time 180s (stirring 180s);
Rest potential-0.3V, rest time 30s;
Sweep speed 100mV/s, sweep limit-0.3V～0.4V;
Result as shown in Figure 2 (wherein: a: sedimentation potential 0.1v; B: sedimentation potential-0.3v).
embodiment 2
Arsenic in the mine underground water sample, lead and antimony are measured
Get mine underground water sample 50ml and add H
2sO
4, HCl and Na
2s0
3, H in solution
2sO
4concentration is that 1M, HCl concentration are 0.1M, Na
2s0
3concentration is 1mg/l.Be heated to micro-boiling 10 minutes, be cooled to room temperature.
The concentration of METHOD FOR CONTINUOUS DETERMINATION As (III), Pb (II) solution
In the mensuration process, selecting the gold electrode of processing is working electrode, and saturated calomel electrode is contrast electrode, and platinum electrode is to electrode.Condition determination is as follows:
Electro-deposition current potential-0.3V, electrodeposition time 180s (stirring 180s);
Rest potential-0.3V, rest time 30s;
Sweep speed 100mV/s, sweep limit-0.3V-0.4V;
The concentration determination condition of METHOD FOR CONTINUOUS DETERMINATION As (III), Sb (III) solution is as follows:
Electro-deposition current potential-0.3V or 0.1V,, electrodeposition time 180s (stirring 180s);
Rest potential-0.3V, rest time 30s;
Sweep speed 100mV/s, sweep limit-0.3V～0.4V;
Add negative potential-0.3V, As, Sb electro-deposition on electrode after, to positive potential scanning direction current potential, measure current value now, be now the total concentration signal of arsenic antimony; Then changing additional negative potential is sedimentation potential 0.1V, now only has the Sb electro-deposition on electrode, to positive potential scanning direction current potential, measures current value now, is now the concentration signal of antimony; Ask its difference, can realize the METHOD FOR CONTINUOUS DETERMINATION of arsenic antimony.
With said method, the arsenic in the water sample of mine (As), plumbous (Pb), antimony (Sb) assay be the results are shown in Table to 1, adopt inductively coupled plasma emission (ICP) atomic absorption spectrum to be measured simultaneously.Result in table 1 show this method and Results of Atomic Absorption Spectrometry basically identical.
The various embodiments described above can some variations in addition under not departing from the scope of the present invention, thus above explanation comprises and accompanying drawing shown in structure should be considered as exemplary, but not in order to limit the protection domain of the present patent application patent.
Claims (4)
1. the volt-ampere of the Electrochemical Stripping for Mine Underground Water arsenic, an antimony and plumbous tie-in method, directly used gold electrode for working electrode, with electrochemical means, measures arsenic, antimony, lead concentration in sample solution, it is characterized in that, comprises the following steps:
A) gold electrode is carried out to pre-service, then polarized electrode, then uses the cyclic voltammetry activated electrode, comprise respectively+2V ,-0.35V polarized electrode 10s, then from-10～15 activated electrodes of 0.3V to 1.6V cyclic voltammetry scan; Add supporting electrolyte in sample solution, the concentration of this supporting electrolyte is 1M H
2sO
4+ 0.1M HCl; Add the reductive agent sodium sulphite, Na
2sO
3concentration is 1mg/l;
B) adopt two steps to realize the arsenic in sample solution, antimony and plumbous tie-in:
One of them step is to the arsenic in sample solution, antimony tie-in, first make the current potential of the gold electrode of above-mentioned steps in a) change to the negative potential direction, under identical current potential, allow arsenic, antimony first be deposited on above-mentioned gold electrode surfaces, the total concentration of arsenic and antimony is measured in the current potential stripping simultaneously; And then the change sedimentation potential, depositing separately antimony, the concentration of antimony is surveyed in the current potential stripping, obtains the concentration of arsenic according to difference;
Another step is to the arsenic in sample solution, plumbous tie-in, under same current potential, first make arsenic, plumbous deposit on the gold electrode in a) in above-mentioned steps, to the above-mentioned gold electrode of positive potential scanning direction, arsenic, the lead of electro-deposition on above-mentioned gold electrode surfaces is separated out under different current potentials, measure plumbous concentration;
In above-mentioned two steps, condition determination is: electro-deposition current potential-0.3V or 0.1V, electrodeposition time 180s and be under stirring; Rest potential-0.3V, rest time 30s; Sweep speed 100mV/s, sweep limit-0.3V～0.4V.
2. the Electrochemical Stripping volt-ampere method of arsenic according to claim 1, antimony and plumbous tie-in, it is characterized in that: in the arsenic in sample solution, antimony tie-in, the sedimentation potential of surveying its total concentration is-0.3V; The sedimentation potential of surveying separately antimony is 0.1V.
3. the Electrochemical Stripping volt-ampere method of arsenic according to claim 1, antimony and plumbous tie-in, it is characterized in that: in the arsenic in sample solution, plumbous tie-in, sedimentation potential is-0.3V.
4. the Electrochemical Stripping volt-ampere method of arsenic according to claim 1, antimony and plumbous tie-in, it is characterized in that: concentration of sodium sulfite is controlled in 10～20 times of scopes of institute's test specimens ion concentration.
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| CN103408108B (en) * | 2013-07-26 | 2014-09-10 | 中国科学院生态环境研究中心 | Method for quickly removing pentavalent antimony pollutant in water by combining sodium sulfite and electrochemistry |
| US10274451B2 (en) | 2015-02-18 | 2019-04-30 | Santa Clara University | Affordable electrochemical detection of environmental contaminants |
| CN108793515B (en) * | 2018-06-15 | 2021-12-10 | 甘肃省合作早子沟金矿有限责任公司 | Method for treating underground gushing water of gold-antimony mine and discharging water up to standard |
| CN111624243A (en) * | 2020-06-09 | 2020-09-04 | 中国科学院生态环境研究中心 | Core-shell structure electrode material for arsenic-antimony electrochemical detection |
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| GB0609926D0 (en) * | 2006-05-19 | 2006-06-28 | Univ Liverpool | Electrochemical cell |
| KR100955710B1 (en) * | 2007-11-15 | 2010-05-03 | 한국바이오시스템(주) | On-line analysis system for heavy metal using a electrochemical method |
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