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 PDF

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CN102798657A
CN102798657A CN2012103217285A CN201210321728A CN102798657A CN 102798657 A CN102798657 A CN 102798657A CN 2012103217285 A CN2012103217285 A CN 2012103217285A CN 201210321728 A CN201210321728 A CN 201210321728A CN 102798657 A CN102798657 A CN 102798657A
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electrode
seawater
heavy metal
liquid
detection method
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CN102798657B (en
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张旭志
曲克明
陈碧鹃
马绍赛
崔毅
赵俊
陈聚法
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Yellow Sea Fisheries Research Institute Chinese Academy of Fishery Sciences
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Yellow Sea Fisheries Research Institute Chinese Academy of Fishery Sciences
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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

The field fast detection method of heavy metal copper, zinc, lead, cadmium in a kind of seawater
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
Step 1, preparation high performance operation electrode: with 1.5g conductive carbon black (the photochemical factory of Shandong Zibo China) and 1.2g ionic liquid N-octyl group pyridine hexafluorophosphate (OPFP; The prompt chemical company limited of last marine origin) insert in the agate mortar, 50 minutes mixings of underhand polish under the nitrogen protection are packed potpourri in the internal thread polyfluortetraethylene pipe 2 of 5 internal diameter 6mm into then; Compaction moulding; The rear end is a lead with external thread copper post 1, and structure is as shown in Figure 1, on pan paper, polishes before using.Twisting external thread copper post 1 is extruded about 0.5mm with pastel and is polished and can upgrade.This electrode air at room temperature held did not influence use in 2 months.
Step 2, assembling three-electrode system sensor also connect the portable electrochemical analyser: like Fig. 2, shown in 3; Sensor comprises electrode, contrast electrode, shaft collar 3 and working electrode 5; In order to shorten detection time; Teflon matter stirrer 6 also is housed on the shaft collar of sensor, and platinum is combined formation combination electrode 4 to electrode and Ag/AgCl contrast electrode, and combination electrode, teflon matter stirrer and working electrode be " one " word symmetric offset spread on circular shaft collar; Sensor is connected with commercially available PDV 6000 type portable electrochemical analysers 7, and the work synoptic diagram is seen Fig. 4.
Step 3, formulation heavy metal lead testing curve: get the ocean seawater 100mL that picks up from Huanghai Sea middle part; Manually filter through disposable syringe and the combination of 0.45 μ m water system filter, put into 150mL glass electrolytic cell to the seawater after filtering, insert sensor; Electrolysis 10min under the-1.5V current potential; Take off working electrode then, twisting copper post is extruded about 0.5mm with pastel and is polished and upgrade electrode.Then adopt identical parameter and method electrolysis 10min once more, multiple 4 times of gross weight makes the blank solution that copper, zinc, lead, cadmium are lower than 0.04 μ g/L, 0.05 μ gL, 0.01 μ gL, 0.01 μ g/L respectively.Get the 10mL blank solution respectively, add plumbous standard solution and make 0.1 μ g/L, 0.2 μ g/L, 0.4 μ gL, 0.8 μ g/L, 1.6 μ g/L, 3.2 μ g/L, 6.4 μ gL and 12.8 μ g/L series standards detection liquid.Standard detection liquid is mixed formation with 0.8mol/L phosphate buffer (pH 2.0) with volume ratio 1:1 measure liquid.Set electrochemical analyser square wave anodic stripping voltammetry detected parameters: amplitude, 25mV; The current potential increment, 4mV; Frequency, 15Hz; Accumulating potential-0.9V; Enrichment time 480s; Stir speed (S.S.) 150r/min; Rest time 20s; Stripping take-off potential-0.8V stops current potential-0.4V.Sequentially determining is respectively measured liquid current-responsive value, obtains working curve and preserves (as shown in Figure 5).The splicer who is formulated makes curve and can use for a long time, all formulates before need not detecting actual sample at every turn.
Step 4, seawater sample pre-service: obtain Jiaozhou Bay's coastal seawater with bucket; Manually filter through disposable syringe and the combination of 0.45 μ m water system filter; 10mL filtrating is mixed in 25mL plastics electrolytic cell 8 with volume ratio 1:1 with 0.8mol/L phosphate buffer (pH 2.0), obtain analyte sample fluid.
Step 5, seawater sample detect: sensor is put into the electrolytic cell that fills analyte sample fluid; Open electrochemical analyser 7; Adopt the parameter square wave anodic stripping voltammetry identical to the analyte sample fluid analysis, with the plumbum ion concentration of substitution working curve acquisition as a result 0.88 μ g/L with formulating working curve.Replicate determination 11 times, reading relative standard deviation are 6.5%.
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
Step 1, preparation high performance operation electrode: 5g superconduct carbon black (the photochemical factory of Shandong Zibo China) and 3g ionic liquid N-hexyl pyridinium tetrafluoroborate salt (going up the prompt chemical company limited of marine origin) are inserted in the stainless steel mortar; 120 minutes mixings of mechanical lapping under the nitrogen protection; Then potpourri is packed in the internal thread polyfluortetraethylene pipe of 5 internal diameter 10mm; Compaction moulding, the rear end is a lead with external thread copper post, structure is as shown in Figure 1.On pan paper, polish before using.Twisting copper post is extruded about 0.5mm with pastel and is polished and can upgrade.
Step 2, assembling three-electrode system sensor also connect the portable electrochemical analyser: like Fig. 2, shown in 3; Sensor comprises electrode, contrast electrode, shaft collar 3 and working electrode 5; In order to shorten detection time; Teflon matter stirrer 6 also is housed on the shaft collar of sensor; Platinum is combined formation combination electrode 4 to electrode and Ag/AgCl contrast electrode, and combination electrode, teflon matter stirrer and working electrode " " word symmetric offset spread are connected (synoptic diagram is seen accompanying drawing 4) with sensor with commercially available HM-3000P type portable electrochemical analyser.
Step 3, formulation heavy metal cadmium testing curve: get the ocean seawater 100mL that picks up from Huanghai Sea middle part; Manually filter through disposable syringe and the combination of 0.45 μ m water system filter, put into 150mL glass electrolytic cell, insert sensor; Electrolysis 10min under the-1.5V current potential; Take off working electrode then, twisting copper post is extruded about 0.5mm with pastel and is polished and upgrade electrode.Then adopt identical parameter and method electrolysis 10min once more, multiple 4 times of gross weight makes the blank solution that copper, zinc, lead, cadmium are lower than 0.04 μ g/L, 0.05 μ g/L, 0.01 μ g/L, 0.01 μ g/L respectively.Get the 10mL blank solution respectively, add the cadmium standard solution and make 0.1 μ g/L, 0.2 μ g/L, 0.4 μ g/L, 0.6 μ g/L, 0.8 μ g/L, 1.0 μ g/L, 1.2 μ g/L and 1.4 μ g/L series standards detection liquid.Standard detection liquid is mixed with volume ratio 1:1 with 0.2mol/L acetic acid-sodium acetate buffer solution (pH 4.0).Set electrochemical analyser square wave anodic stripping voltammetry detected parameters: amplitude, 25mV; The current potential increment, 4mV; Frequency, 15Hz; Accumulating potential-1.0V; Enrichment time 600s; Stir speed (S.S.) 150r/min; Rest time 20s; Stripping take-off potential-1.0V stops current potential-0.8V.Sequentially determining is respectively measured liquid current-responsive value, obtains working curve and preserves (as shown in Figure 6).The cadmium working curve of being formulated can use for a long time, all formulates before need not detecting actual sample at every turn.
Step 4, seawater sample pre-service: obtain Jiaozhou Bay's coastal seawater with bucket, manually filter through disposable syringe and the combination of 0.45 μ m water system filter.10mL filtrating is mixed in 25mL plastics electrolytic cell with volume ratio 1:1 with 0.2mol/L acetic acid-sodium acetate buffer solution (pH 4.0), obtain analyte sample fluid.
Step 5, seawater sample detect: sensor is put into the electrolytic cell 8 that fills analyte sample fluid; Open electrochemical analyser 7; Adopt the parameter anodic stripping voltammetry identical to the analyte sample fluid analysis, with the concentration of cadmium ions of substitution working curve acquisition as a result 0.35 μ g/L with formulating working curve.Replicate determination 11 times, reading relative standard deviation are 7.1%.
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
Step 1, preparation high performance operation electrode: 5g conductive carbon black (the photochemical factory of Shandong Zibo China) and 3.2g ionic liquid N-hexyl pyridine nitrate (going up the prompt chemical company limited of marine origin) are inserted in the ceramic mortar; 120 minutes mixings of mechanical lapping under the nitrogen protection; Then potpourri is packed in the internal thread polyfluortetraethylene pipe of 5 internal diameter 6mm; Compaction moulding, the rear end is a lead with external thread copper post, structure is as shown in Figure 1.On pan paper, polish before using.Twisting copper post is extruded about 0.5mm with pastel and is polished and can upgrade.
Step 2, assembling three-electrode system sensor also connect the portable electrochemical analyser: like Fig. 2, shown in 3; Sensor comprises electrode, contrast electrode, shaft collar 3 and working electrode 5; In order to shorten detection time, teflon matter stirrer 6 also is housed on the shaft collar of sensor, platinum is combined formation combination electrode 4 to electrode and Ag/AgCl contrast electrode; Combination electrode, teflon matter stirrer and working electrode " " word symmetric offset spread are formed sensor.Sensor is connected (synoptic diagram is seen accompanying drawing 4) with commercially available HM-3000P type portable electrochemical analyser 7.
Step 3, formulation heavy metal copper testing curve: get the ocean seawater 100mL that picks up from Huanghai Sea middle part; Manually filter through disposable syringe and the combination of 0.45 μ m water system filter, put into 150mL glass electrolytic cell, insert sensor; Electrolysis 10min under the-1.5V current potential; Take off working electrode then, twisting copper post is extruded about 0.5mm with pastel and is polished and upgrade electrode.Then adopt identical parameter and method electrolysis 10min once more, multiple 4 times of gross weight makes the blank solution that copper, zinc, lead, cadmium are lower than 0.04 μ g/L, 0.05 μ g/L, 0.01 μ g/L, 0.01 μ g/L respectively.Get the 10mL blank solution respectively, add the copper standard solution and make 0.1 μ g/L, 0.5 μ g/L, 1.0 μ g/L, 2.0 μ g/L, 3.0 μ g/L, 4.0 μ g/L, 5.0 μ g/L and 6.0 μ g/L series standards detection liquid.Standard detection liquid is mixed with volume ratio 1:1 with 0.1mol/L ammonium acetate-hac buffer (pH 5.0).Set electrochemical analyser square wave anodic stripping voltammetry detected parameters: amplitude, 25mV; The current potential increment, 4mV; Frequency, 15Hz; Accumulating potential-0.5V; Enrichment time 360s; Stir speed (S.S.) 150r/min; Rest time 20s; Stripping take-off potential-0.25V stops current potential 0.3V.Sequentially determining is respectively measured liquid current-responsive value, obtains working curve and preserves (as shown in Figure 7).The coppersmith of being formulated is made curve and can be used for a long time, all formulates before need not detecting actual sample at every turn.
Step 4, seawater sample pre-service: obtain Laoshan sand mouth harbour seawater with bucket, manually filter through disposable syringe and the combination of 0.45 μ m water system filter.10mL filtrating is mixed in 25mL plastics electrolytic cell with volume ratio 1:1 with 0.1mol/L ammonium acetate-hac buffer (pH 5.0), obtain analyte sample fluid.
Step 5, seawater sample detect: sensor is put into the electrolytic cell that fills analyte sample fluid; Open electrochemical analyser; Adopt the parameter square wave anodic stripping voltammetry identical to the analyte sample fluid analysis, with the copper ion concentration of substitution working curve acquisition as a result 2.08 μ g/L with formulating working curve.Replicate determination 11 times, reading relative standard deviation are 6.0%.
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
Step 1, preparation high performance operation electrode: 5g conductive carbon black (the photochemical factory of Shandong Zibo China) and 4g ionic liquid N-octyl group pyridinium tetrafluoroborate salt (going up the prompt chemical company limited of marine origin) are inserted in the teflon mortar; 120 minutes mixings of mechanical lapping under the nitrogen protection; Then potpourri is packed in the internal thread pitch tube of 5 internal diameter 6mm; Compaction moulding, the rear end is a lead with external thread copper post, structure is as shown in Figure 1.On pan paper, polish before using.Twisting copper post is extruded about 0.5mm with pastel and is polished and can upgrade.
Step 2, assembling three-electrode system sensor also connect the portable electrochemical analyser: sensor comprises electrode, contrast electrode, shaft collar and working electrode; The platinum post is " article " font to electrode, Ag/AgCl contrast electrode and working electrode on shaft collar arranges, and sensor is connected with commercially available HM-3000P type portable electrochemical analyser.
Step 3, formulation heavy metal zinc testing curve: get the ocean seawater 100mL that picks up from Huanghai Sea middle part; Manually filter through disposable syringe and the combination of 0.45 μ m water system filter, put into 150mL glass electrolytic cell, insert sensor; Electrolysis 10min under the-1.5V current potential; Take off working electrode then, twisting copper post is extruded about 0.5mm with pastel and is polished and upgrade electrode.Then adopt identical parameter and method electrolysis 10min once more, multiple 4 times of gross weight makes the blank solution that copper, zinc, lead, cadmium are lower than 0.04 μ g/L, 0.05 μ g/L, 0.01 μ g/L, 0.01 μ g/L respectively.Get the 10mL blank solution respectively, add the zinc standard solution and make 1.0 μ g/L, 2.0 μ g/L, 4.0 μ g/L, 8.0 μ g/L, 12.0 μ g/L, 16.0 μ g/L, 20.0 μ g/L, 24.0 μ g/L and 28.0 μ g/L series standards detection liquid.Standard detection liquid is mixed formation with 0.1mol/L ammonium acetate-hac buffer (pH5.0) with volume ratio 1:1 measure liquid.Set electrochemical analyser square wave anodic stripping voltammetry detected parameters: amplitude, 25mV; The current potential increment, 4mV; Frequency, 15Hz; Accumulating potential-1.35V; Enrichment time 600s; Rest time 20s; Stripping take-off potential-1.15V stops current potential-0.85V.Sequentially determining is respectively measured liquid current-responsive value, obtains working curve and preserves (as shown in Figure 8).The zinc working curve of being formulated can use for a long time, all formulates before need not detecting actual sample at every turn.
Step 4, seawater sample pre-service: obtain Laoshan sand mouth harbour seawater with bucket, manually filter through disposable syringe and the combination of 0.45 μ m water system filter.10mL filtrating is mixed in 25mL plastics electrolytic cell with volume ratio 1:1 with 0.1mol/L ammonium acetate-hac buffer (pH 5.0), obtain analyte sample fluid.
Step 5, seawater sample detect: sensor is put into the electrolytic cell that fills analyte sample fluid; Open electrochemical analyser; Adopt the parameter square wave anodic stripping voltammetry identical to the analyte sample fluid analysis, with the zinc ion concentration of substitution working curve acquisition as a result 9.2 μ g/L with formulating working curve.Replicate determination 11 times, reading relative standard deviation are 5.4%.
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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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
CN105699467A (en) * 2016-01-15 2016-06-22 刘文涛 Improved electrochemical analysis method and application
CN105866213A (en) * 2016-06-21 2016-08-17 河南理工大学 Mercury ion selective electrode based on sulfydryl functional ion liquid-carboxylated multi-walled carbon nanotubes as well as preparation method and application thereof
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
CN107843636A (en) * 2017-10-09 2018-03-27 广州盈思传感科技有限公司 A kind of method with heavy metal fast-field evaluation in ship rivers and lakes and ocean
CN108318559A (en) * 2018-04-23 2018-07-24 厦门斯坦道科学仪器股份有限公司 A kind of heavy metal analysis plug module, heavy metal detection system and heavy metal analysis flow based on electrochemistry
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
CN109738419A (en) * 2018-12-18 2019-05-10 郑州磨料磨具磨削研究所有限公司 The measuring method of boron content in a kind of aluminum-based boron carbide material
CN113092564A (en) * 2019-12-23 2021-07-09 上海雄图生物科技有限公司 Method for rapidly detecting heavy metals in water
CN113466010A (en) * 2021-07-09 2021-10-01 利晟（杭州）科技有限公司 Water pollution detection system based on electrochemical sensor

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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
CN103913490B (en) * 2012-12-28 2018-10-16 株式会社堀场制作所 Electrochemical analysis method, electrochemical analysis device and reagent set
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
CN104655473B (en) * 2015-02-26 2017-08-11 中国科学院电子学研究所 Enrichment and the method for detection Determination of Trace Mercury In Water
CN106979968B (en) * 2016-01-15 2019-06-11 刘文涛 A kind of washing methods and measurement method of Anodic stripping voltammetry method
CN105699467A (en) * 2016-01-15 2016-06-22 刘文涛 Improved electrochemical analysis method and application
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
CN105699467B (en) * 2016-01-15 2018-11-13 刘文涛 A kind of improved electrochemical analysis method and application
CN105866213A (en) * 2016-06-21 2016-08-17 河南理工大学 Mercury ion selective electrode based on sulfydryl functional ion liquid-carboxylated multi-walled carbon nanotubes as well as preparation method and application thereof
CN107843636A (en) * 2017-10-09 2018-03-27 广州盈思传感科技有限公司 A kind of method with heavy metal fast-field evaluation in ship rivers and lakes and ocean
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
CN108318559A (en) * 2018-04-23 2018-07-24 厦门斯坦道科学仪器股份有限公司 A kind of heavy metal analysis plug module, heavy metal detection system and heavy metal analysis flow based on electrochemistry
CN108318559B (en) * 2018-04-23 2023-10-13 厦门斯坦道科学仪器股份有限公司 Electrochemical-based heavy metal detection plugging module, heavy metal detection system and heavy metal detection flow
CN109738419A (en) * 2018-12-18 2019-05-10 郑州磨料磨具磨削研究所有限公司 The measuring method of boron content in a kind of aluminum-based boron carbide material
CN109738419B (en) * 2018-12-18 2022-07-01 郑州磨料磨具磨削研究所有限公司 Method for measuring boron content in aluminum-based boron carbide material
CN113092564A (en) * 2019-12-23 2021-07-09 上海雄图生物科技有限公司 Method for rapidly detecting heavy metals in water
CN113466010A (en) * 2021-07-09 2021-10-01 利晟（杭州）科技有限公司 Water pollution detection system based on electrochemical sensor

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