CN102798657A - Site fast detection method for copper, zinc, lead and cadmium as heavy metals in seawater - Google Patents
Site fast detection method for copper, zinc, lead and cadmium as heavy metals in seawater Download PDFInfo
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Abstract
The invention discloses a site fast detection method for copper, zinc, lead and cadmium as heavy metals in seawater, and belongs to the technical field of environment monitoring. A conducting carbon black-ionic liquid paste electrode as a work electrode, Ag/AgCl as a reference electrode and platinum filament or glass carbon as a counter electrode are assembled to form an electrochemical sensor. The concentrations of ionic copper, zinc, lead and cadmium in seawater are respectively determined by adopting square wave anodic stripping voltammetry; and the site fast detection method has the advantages of high sensitivity, favorable repeatability, simple and convenient operation, low expense, quick response, accurate quantification, low requirement on the environment condition and the like, and can be used for site monitoring of offshore pollution and conventional ocean site investigation along with ships.
Description
Technical field
The invention belongs to the environmental monitoring technology field, relate to the field fast detection method of heavy metal copper, zinc, lead, cadmium in a kind of seawater particularly.
Background technology
The function that ocean resources can be brought into play seriously is subject to its environmental quality.Since the nearest century, pollution from land-based sources becomes the serious threat of effective ocean development day by day.Wherein the heavy metal class is polluted one of arch-criminal of marine environment infringement beyond doubt, is repeatedly attracted grave attention by its ecology that causes, aquatic product quality security problems.In monitored object list is all clearly listed it by numerous international organizations such as UNDP, FAO, WHO.Can promptly and accurately monitor contents of heavy metal elements in the seawater, pollute most important for effective assessment and early warning.
Because seawater component is complicated, matrix effect is big, and content of beary metal is very low, therefore measures the analytical approach that heavy metal adopted in the seawater and must guarantee to have high sensitivity that good selectivity is arranged again.At present; But the heavy metal analytical approach of approval has ultraviolet AAS (UV), atomic absorption method (AAS), atomic fluorescence method (AFS), X fluorescence spectrum (XRF), inductively coupled plasma mass spectroscopy (ICP-MS), immunological method (IA), test paper method (TP) and electrochemical process (ES) usually; Wherein ICP-MS, AAS detection limit are more excellent, and the part element is the PPT level, but instrument itself costs an arm and a leg; Environmental baseline is required high; Complicated operation, cost is high, and therefore now the use done canonical measure more; AFS is more to be used for analysis and the mensuration to environment and food mercury, arsenic element, can be quantitatively but complex operation, and expense is higher; UV sensitivity is lower and high to the requirement of analytic liquid transparency, is difficult for robotization.Also there is a common problem in said method: can only in the laboratory, carry out, can not use in test site.Deliver to the laboratory behind the seawater sample spot sampling and analyze, high, the poor in timeliness of cost not only, and owing in time do not detect water sample, change midway and the water sample transmission course in pollution all can have influence on the objectivity of testing result.In addition, when the burst Pollution incident, need report fast and accurately, and the speed of existing lab analysis method often can not satisfy the requirement of emergency monitoring.IA, TP are the method for quick that latest developments are got up, and the on-the site analysis possibility is provided, but sensitivity, precision and robotization wait to pay a lot of effort.
In recent years, the anodic stripping voltammetry (ASV) based on the ES technology obtains paying attention to again.Its principle is: the first step is " electricity is analysed ", promptly under a constant potential, with tested ion electrolytic deposition, is enriched on the working electrode; Second step was " stripping ", i.e. enrichment finishes the back and on working electrode, applies a reverse voltage, was just being scanned by negative sense metal is oxidized in the ion recurrence solution again, produced oxidation current, recording voltage-current curve, i.e. volt-ampere curve.Curve is peak shape, and spike potential can be used as the foundation of qualitative analysis, is directly proportional by the concentration of measured ion in peak point current and the solution, can be used as the foundation of quantitative test.As everyone knows, different with methods such as spectrum, mass spectrum, immunity, what electrochemical method obtained directly is electric signal; Thereby need not change and to export easily; Not only energy consumption low, be convenient to robotization, and instrument is simply portable, therefore has superiority in essence.Lot of domestic and international report confirms that ASV is easy to operate, cost is low, but the multiple metallic ion of METHOD FOR CONTINUOUS DETERMINATION once, normally several min of Measuring Time, and sensitivity very high (10
-7-10
-9Mol/L).Thereby, become one of important development direction of heavy metal field quick detection technology for " high timeliness, scene, low expense, accurate detection by quantitative " provides possibility.Yet the above ASV method and instrument want to reach ideal performance does not have the mercuri of not relying on working electrode (quiet mercury, outstanding mercury, mercury film etc.), and this has brought great obstacle for applying: one, use mercury itself to have the environmental hazard risk; Two, the mercury in can not working sample; Three, testing result receives vibration, wobble effects is serious, is inappropriate for aboard ship using.Therefore, the scientific worker is making great efforts the development of exempting from the mercury working electrode in eco-friendly.Bismuth is a kind of eco-friendly metallic element, has the electrochemical properties close with mercury, and the existing at present bismuth film electrode that adopts carries out pertinent literature report and patented claim that heavy metal detects.The main preplating bismuth embrane method that adopts or plate the detection that the bismuth embrane method is carried out heavy metal altogether.It is unstable, oxidized easily that yet the bismuth film that preplating is good is exposed in the air, causes detection signal unstable, poor reproducibility.Plate the bismuth embrane method altogether again because the easy hydrolysis of bismuth ion, make this method in acid medium, to use, limited its application in detecting at the scene.
Summary of the invention
The technical matters that the present invention will solve provides the field fast detection method of heavy metal copper, zinc, lead, cadmium in a kind of seawater; This method can go out the content of heavy metal copper in the seawater, zinc, lead, cadmium in the on-the-spot accurate detection of sampling, has overcome the defective in existing heavy metal in sea water detection method and the technological detection at the scene.
The present invention specifically realizes through following steps:
The field fast detection method of heavy metal copper, zinc, lead, cadmium in a kind of seawater may further comprise the steps:
(1) preparation high performance operation electrode: the conductive carbon black or the superconduct carbon black of certain mass ratio are inserted in the mortar with ionic liquid, grind more than 50 minutes fully mixing, the interior compaction moulding of the pipe of packing into then, the rear end is a lead with the copper post; Ionic liquid is N-octyl group pyridine hexafluorophosphate, N-octyl group pyridinium tetrafluoroborate salt, N-octyl group pyridine nitrate, N-hexyl pyridine hexafluorophosphate, N-hexyl pyridinium tetrafluoroborate salt or N-hexyl pyridine nitrate; Conductive carbon black and ion liquid mass ratio are 1:1~1:0.6, according to the mass ratio of the different adjustment of ion liquid kind itself and conductive carbon black;
(2) assembling three-electrode system sensor and connect the portable electrochemical analyser: sensor comprises electrode, contrast electrode, shaft collar and working electrode; Working electrode is conductive carbon black-ionic liquid paste electrode; To electrode is platinum or glass-carbon electrode; Contrast electrode is the Ag/AgCl electrode, and electrode, contrast electrode and working electrode are installed on the shaft collar, and sensor is connected with commercially available portable electrochemical analyser;
(3) formulate heavy metal testing curve: at first adopt electrolytic process to remove the heavy metal in the seawater of ocean; Be blank solution with it then; Adding heavy metal standard solution makes the series standard detection liquid of gradient concentration in blank solution, and series standard detects liquid and mixes formation measurement liquid with supporting electrolyte with volume ratio 1:1, setting electrochemical analyser anodic stripping voltammetry detected parameters; Sequentially determining is respectively measured liquid current-responsive value, obtains working curve and is prestored into electrochemical analyser;
(4) seawater sample pre-service: the investigation scene takes water sample to pass through disposable syringe and 0.45 μ m water system filter makes up manually filtration, filters the back water sample and in electrolytic cell, mixes the formation analyte sample fluid with supporting electrolyte with volume ratio 1:1;
(5) seawater sample detects: sensor is put into the electrolytic cell that fills analyte sample fluid; Open electrochemical analyser; Adopt the parameter anodic stripping voltammetry identical to detect the target heavy metal, bring measurement result into working curve and obtain concentration of heavy metal ion in the measurement liquid to be measured with formulating working curve.
Further, described mortar material is agate, pottery, glass, stainless steel or teflon.
Further, described tubing matter is pottery, glass, resin, plastics or teflon.
Further, on the sensor shaft collar in the described step (2) stirrer is housed, when described seawater sample detects,, stirs in order further to shorten detection time.
The beneficial effect of the present invention and prior art contrast:
1, three of sensor electrodes are all to solid-state, can under static state use, and also can use having necessarily to rock or shake under (on ship) situation.
2, replace mercuri working electrode in the prior art with conductive carbon black-ionic liquid paste electrode, avoided the use of mercury, security is good, exempts potential health and environmental pollution risk; Need not preplating bismuth or plate bismuth altogether, raise the efficiency, the reduction expense; Corrosion-resistant, antipollution, the seawater that is suitable for high salt, component complicacy detects; Good stability, the air at room temperature held did not influence use in 2 months; Be easy to upgrade.
3, highly sensitive, good stability, favorable reproducibility promptly satisfy heavy metal pollution and detect needs, also can be applicable to the accurate quantitative test of copper trace in the conventional marine monitoring, zinc, lead, cadmium, mercury, arsenic.
4, equipment is simply portable, and is simple to operate, and energy consumption is low, and on-the-spot low expense detection by quantitative requirement is satisfied in the automatic digitizing output of result.
5, sample pretreatment is simple, and response is fast, obtains the result in a few minutes, and data have high-timeliness.
Description of drawings
Fig. 1: working electrode: 1 external thread copper post, 2 internal thread bodys;
Fig. 2: sensor is inverted vertical view: 3 shaft collars, 4 combination electrodes, 5 working electrodes, 6 stirrers;
Fig. 3: sensor side view: 3 shaft collars, 4 combination electrodes, 5 working electrodes, 6 stirrers;
Fig. 4: electrochemical heavy metals testing synoptic diagram: 7 portable electrochemical analysers, 8 electrolytic cells;
Fig. 5: the working curve diagram of heavy metal lead sample detection;
Fig. 6: the working curve diagram of heavy metal cadmium sample detection;
Fig. 7: the working curve diagram of heavy metal copper sample detection;
Fig. 8: the working curve diagram of heavy metal zinc sample detection.
Embodiment
Below in conjunction with accompanying drawing and embodiment, describe the present invention.
The on-site measurement of heavy metal lead in embodiment 1 Jiaozhou Bay's coastal seawater
Disregard working curve and formulate step, read plumbum ion concentration value required time and be about 15min from sampling.
The on-site measurement of heavy metal cadmium in embodiment 2 Jiaozhou Bay's coastal seawaters
Disregard working curve and formulate step, read concentration of cadmium ions value required time and be about 15min from sampling.
The on-site measurement of heavy metal copper in the embodiment 3 Laoshan sand mouth harbour seawater
Disregard working curve and formulate step, read copper ion concentration value required time and be about 15min from sampling.
The on-site measurement of heavy metal zinc in the embodiment 4 Laoshan sand mouth harbour seawater
Disregard working curve and formulate step, read copper ion concentration value required time and be about 20min from sampling.
Claims (4)
1. the field fast detection method of heavy metal copper, zinc, lead, cadmium in the seawater is characterized in that it may further comprise the steps:
(1) preparation high performance operation electrode: the conductive carbon black or the superconduct carbon black of certain mass ratio are inserted in the mortar with ionic liquid, grind more than 50 minutes fully mixing, the interior compaction moulding of the pipe of packing into then, the rear end is a lead with the copper post; Ionic liquid is N-octyl group pyridine hexafluorophosphate, N-octyl group pyridinium tetrafluoroborate salt, N-octyl group pyridine nitrate, N-hexyl pyridine hexafluorophosphate, N-hexyl pyridinium tetrafluoroborate salt or N-hexyl pyridine nitrate; Conductive carbon black and ion liquid mass ratio are 1:1~1:0.6, according to the mass ratio of the different adjustment of ion liquid kind itself and conductive carbon black;
(2) assembling three-electrode system sensor and connect the portable electrochemical analyser: sensor comprises electrode, contrast electrode, shaft collar (3) and working electrode (5); Working electrode is conductive carbon black-ionic liquid paste electrode; To electrode is platinum or glass-carbon electrode; Contrast electrode is the Ag/AgCl electrode, and electrode, contrast electrode and working electrode (5) are installed on the shaft collar (3), and sensor is connected with commercially available portable electrochemical analyser (7);
(3) formulate heavy metal testing curve: at first adopt electrolytic process to remove the heavy metal in the seawater of ocean; Be blank solution with it then; Adding heavy metal standard solution makes the series standard detection liquid of gradient concentration in blank solution; Series standard detects liquid and mixes formation measurement liquid with supporting electrolyte with volume ratio 1:1; Set electrochemical analyser anodic stripping voltammetry detected parameters, sequentially determining is respectively measured liquid current-responsive value, obtains working curve and is prestored into electrochemical analyser (7);
(4) seawater sample pre-service: the investigation scene takes water sample to pass through disposable syringe and 0.45 μ m water system filter makes up manually filtration, filters the back water sample and in electrolytic cell, mixes the formation analyte sample fluid with supporting electrolyte with volume ratio 1:1;
(5) seawater sample detects: sensor is put into the electrolytic cell (8) that fills analyte sample fluid; Open electrochemical analyser; Adopt the parameter anodic stripping voltammetry identical to detect the target heavy metal, bring measurement result into working curve and obtain concentration of heavy metal ion in the measurement liquid to be measured with formulating working curve.
2. detection method according to claim 1 is characterized in that described mortar material is agate, pottery, glass, stainless steel or teflon.
3. detection method according to claim 1 is characterized in that the tubing matter in the described step 1 is pottery, glass, resin, plastics or teflon.
4. detection method according to claim 1 is characterized in that on the sensor shaft collar in the described step 2 stirrer being housed, and when described seawater sample detects, in order further to shorten detection time, stirs.
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CN103913490A (en) * | 2012-12-28 | 2014-07-09 | 株式会社堀场制作所 | Electrochemistry Analysis Method, Electrochemistry Analysis Device And Test Kit |
CN104316499A (en) * | 2014-08-11 | 2015-01-28 | 广西大学 | A method of indirectly measuring gold in seawater by adoption of an atomic fluorescence spectrophotometer |
CN104655473A (en) * | 2015-02-26 | 2015-05-27 | 中国科学院电子学研究所 | Method for detecting trace mercury in water |
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CN106979968A (en) * | 2016-01-15 | 2017-07-25 | 刘文涛 | The washing methods and measuring method of a kind of Anodic stripping voltammetry method |
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CN108508076A (en) * | 2018-04-01 | 2018-09-07 | 桂林理工大学 | The method that ion liquid abstraction differential pulse voltammetry measures copper ion concentration |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101762627A (en) * | 2010-02-02 | 2010-06-30 | 中国科学院长春应用化学研究所 | Carbon paste electrode and preparation method thereof |
CN102642955A (en) * | 2012-04-24 | 2012-08-22 | 中国水产科学研究院黄海水产研究所 | Electrochemical removal method for heavy metals in breeding circulating seawater |
-
2012
- 2012-09-04 CN CN201210321728.5A patent/CN102798657B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101762627A (en) * | 2010-02-02 | 2010-06-30 | 中国科学院长春应用化学研究所 | Carbon paste electrode and preparation method thereof |
CN102642955A (en) * | 2012-04-24 | 2012-08-22 | 中国水产科学研究院黄海水产研究所 | Electrochemical removal method for heavy metals in breeding circulating seawater |
Non-Patent Citations (4)
Title |
---|
《ELECTROCHEMICAL SCIENCE》 20120301 Keming Qu et al "Simultaneous Detection of Diethylstilbestrol and Malachite Green Using Conductive Carbon Black Paste Electrode" 第1827-1839页 1-4 , * |
《西北大学学报(自然科学网络版)》 20070731 杨平平等 "离子液体在电分析化学领域中的应用" 1-4 第5卷, 第4期 * |
KEMING QU ET AL: ""Simultaneous Detection of Diethylstilbestrol and Malachite Green Using Conductive Carbon Black Paste Electrode"", 《ELECTROCHEMICAL SCIENCE》 * |
杨平平等: ""离子液体在电分析化学领域中的应用"", 《西北大学学报(自然科学网络版)》 * |
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