CN102798657B - 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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CN102798657B
CN102798657B CN201210321728.5A CN201210321728A CN102798657B CN 102798657 B CN102798657 B CN 102798657B CN 201210321728 A CN201210321728 A CN 201210321728A CN 102798657 B CN102798657 B CN 102798657B
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seawater
heavy metal
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copper
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CN102798657A (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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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 a kind of heavy metal in seawater copper, zinc, lead, cadmium
Technical field
The invention belongs to environmental monitoring technology field, relate to particularly the field fast detection method of a kind of heavy metal in seawater copper, zinc, lead, cadmium.
Background technology
The function that ocean resources can be brought into play is seriously limited 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 heavy metal class is polluted one of arch-criminal of marine environment infringement beyond doubt, and the problem such as ecology, fish quality being caused by it repeatedly attracts grave attention.Monitored object list is all clearly listed in by numerous international organizations such as UNDP, FAO, WHO.Can promptly and accurately monitor heavy metal in seawater constituent content, pollute most important for Efficient Evaluation and early warning.
Because seawater component complexity, matrix effect are large, and content of beary metal is very low, therefore measures the analytical approach that heavy metal in seawater adopts and must guarantee to have high sensitivity to have again good selectivity.At present, conventionally the Analysis of Heavy Metal method of approval have ultraviolet can spectrophotometric method (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), wherein ICP-MS, AAS detection limit are more excellent, Partial Elements is PPT level, but instrument itself is expensive, high to requirement for environmental conditions, complicated operation, cost is high, and therefore use done canonical measure more now; AFS is used for analysis and the mensuration to environment and Mercury In Food, 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 laboratory, carry out, can not use in test site.After seawater sample spot sampling, deliver to laboratory and analyze, not only high, the poor in timeliness of cost, and owing to not detecting in time water sample, change midway and water sample transmitting procedure in pollution all can have influence on the objectivity of testing result.In addition in the time of burst Pollution event, need to report fast and accurately, and the speed of existing lab analysis method often can not meet the requirement of emergency monitoring.IA, TP are the method for quick that latest developments are got up, and 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 based on ES technology (ASV) is paid attention to again.Its principle is: the first step is " electrolysis ",, under a constant potential, by tested ion electrolytic deposition, is enriched on working electrode; Second step is " stripping ", i.e. after enrichment finishes, on working electrode, apply a reverse voltage, is just being scanned metal is oxidized in ion recurrence solution again by negative sense, produces 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, peak point current in solution, be directly proportional by the concentration of measured ion, can be used as the foundation of quantitative test.As everyone knows, different from methods such as spectrum, mass spectrum, immunity, what electrochemical method obtained is directly electric signal, thereby do not need conversion 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, once can METHOD FOR CONTINUOUS DETERMINATION many kinds of metal ions, and normally several min of Measuring Time, and also sensitivity is very high by (10 -7-10 -9mol/L).Thereby for " high timeliness, scene, low expense, accurate quantitative analysis detect " provides possibility, become one of important development direction of heavy metal field quick detection technology.But the above ASV method and instrument want to reach ideal performance without not relying on mercuri working electrode (quiet mercury, outstanding mercury, mercury film etc.), this has brought great obstacle for applying: one, use mercury itself to have environmental hazard risk; Two, the mercury in can not working sample; Three, testing result is vibrated, wobble effects is serious, is unsuitable for aboard ship using.Therefore, scientific worker is making great efforts the development of exempting from mercury working electrode in eco-friendly.Bismuth is a kind of eco-friendly metallic element, has the electrochemical properties close with mercury, at present existing pertinent literature report and the patented claim that adopts bismuth film electrode to carry out heavy metal detection.The main preplating bismuth embrane method adopting or plate altogether bismuth embrane method and carry out the detection of heavy metal.But that the good bismuth film of preplating is exposed in air is unstable, easily oxidized, cause detection signal unstable, poor reproducibility.Plate altogether bismuth embrane method again because bismuth ion is easily hydrolyzed, this method can only be used in acid medium, limited its application in detecting at the scene.
Summary of the invention
The technical problem to be solved in the present invention is to provide the field fast detection method of a kind of heavy metal in seawater copper, zinc, lead, cadmium, the method can be at the on-the-spot content that detect fast and accurately heavy metal in seawater copper, zinc, lead, cadmium of sampling, has overcome existing heavy metal in sea water detection method and the technology defect in detecting at the scene.
The present invention specifically realizes by following steps:
A field fast detection method for heavy metal in seawater copper, zinc, lead, cadmium, comprises the following steps:
(1) prepare high performance operation electrode: the conductive carbon black of certain mass ratio or Super-conductive carbon and ionic liquid are inserted in mortar, grind and fully mix above for 50 minutes, then pack compaction moulding in pipe into, rear end is take copper post as wire; 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, the mass ratio of conductive carbon black and ionic liquid is 1:1～1:0.6, according to the different mass ratioes of adjusting itself and conductive carbon black of the kind of ionic liquid;
(2) assemble three-electrode system sensor and connect portable electrochemical analyser: sensor comprises electrode, contrast electrode, shaft collar and working electrode, working electrode is conductive carbon black-ionic liquid paste electrode, be platinum or glass-carbon electrode to electrode, contrast electrode is Ag/AgCl electrode, electrode, contrast electrode and working electrode are arranged on shaft collar, sensor is connected with commercially available portable electrochemical analyser;
(3) formulate heavy metal testing curve: first adopt electrolytic process to remove the heavy metal in the seawater of ocean, then take it as blank solution, the series standard that adds heavy metal standard solution to make gradient concentration in blank solution detects liquid, series standard detects liquid and supporting electrolyte is mixed to form measurement liquid 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;
(4) seawater sample pre-service: investigation scene takes water sample manually to filter by disposable syringe and 0.45 μ m water system filter combination, after filtering, water sample is mixed to form analyte sample fluid with supporting electrolyte with volume ratio 1:1 in electrolytic cell;
(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 with formulating working curve to detect target heavy metal, bring measurement result into working curve and obtain concentration of heavy metal ion in measurement liquid to be measured.
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 described step (2), stirrer is housed, in the time that described seawater sample detects, in order further to shorten detection time, stirs.
The beneficial effect that the present invention is compared with the prior art:
1, three of sensor electrodes are all as solid-state, can under static state use, and also can use having necessarily to rock or shake in (on ship) situation.
2, replace mercuri working electrode in prior art with conductive carbon black-ionic liquid paste electrode, avoided the use of mercury, security is good, exempts potential health and risk of environmental pollution; Without preplating bismuth or plate altogether bismuth, raise the efficiency, reduction expense; Corrosion-resistant, antipollution, the seawater that is suitable for high salt, complicated components detects; Good stability, places under air at room temperature and within 2 months, does not affect use; Be easy to upgrade.
3, highly sensitive, good stability, favorable reproducibility, meets heavy metal pollution and detects needs, also can be applicable to the accurate quantitative analysis analysis of copper trace, zinc, lead, cadmium, mercury, arsenic in conventional marine monitoring.
4, equipment is simply portable, simple to operate, and energy consumption is low, and the output of result automatic digital, meets the quantitative testing requirement of on-the-spot low expense.
5, sample pretreatment is simple, and response is fast, obtains result in a few minutes, and data have high-timeliness.
Accompanying drawing explanation
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 schematic 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 drawings and Examples, 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: by 1.5g conductive carbon black (photochemical factory of Shandong Zibo China) and 1.2g ionic liquid N-octyl group pyridine hexafluorophosphate (OPFP; the prompt Chemical Co., Ltd. of upper marine origin) insert in agate mortar; under nitrogen protection, underhand polish mixes for 50 minutes; then potpourri is packed in the internal thread polyfluortetraethylene pipe 2 of 5 internal diameter 6mm; compaction moulding; rear end is take external thread copper post 1 as wire, and structure as shown in Figure 1, polishes before using on pan paper.Twisting external thread copper post 1, extrudes about 0.5mm by pastel and polishes and can upgrade.Under this electrode air at room temperature, place and within 2 months, do not affect use.
Step 2, assembling three-electrode system sensor also connects portable electrochemical analyser: as 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 is also 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 be " one " word symmetric offset spread on circular shaft collar, sensor is connected with commercially available PDV 6000 type portable electrochemical analysers 7, Fig. 4 is shown in by work schematic diagram.
Step 3, formulation heavy metal lead testing curve: get the ocean seawater 100mL that picks up from Middle of The Huanghai Sea, manually filter by disposable syringe and 0.45 μ m water system filter combination, seawater after filtering is put into 150mL glass electrolytic cell, insert sensor, electrolysis 10min under-1.5V current potential, then take off working electrode, twisting copper post, extrudes about 0.5mm by pastel and polishes to upgrade electrode again.Then adopt identical parameter and method electrolysis 10min again, repeat altogether 4 times, make copper, zinc, lead, cadmium respectively lower than the blank solution of 0.04 μ g/L, 0.05 μ gL, 0.01 μ gL, 0.01 μ g/L.Get respectively 10mL blank solution, add plumbous standard solution to 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 and detect liquid.Standard detection liquid and 0.8mol/L phosphate buffer (pH 2.0) are mixed to form to measurement liquid with volume ratio 1:1.Set electrochemical analyser square wave anodic stripping voltammetry detected parameters: amplitude, 25mV; 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 plumbous working curve of formulating 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 by disposable syringe and 0.45 μ m water system filter combination, 10mL filtrate is mixed with volume ratio 1:1 with 0.8mol/L phosphate buffer (pH 2.0) in 25mL plastics electrolytic cell 8, 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 with formulating working curve to analyte sample fluid analysis, result substitution working curve is obtained to plumbum ion concentration 0.88 μ g/L.Replicate determination 11 times, reading relative standard deviation is 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 Super-conductive carbon (photochemical factory of Shandong Zibo China) and 3g ionic liquid N-hexyl pyridinium tetrafluoroborate salt (the prompt Chemical Co., Ltd. of upper marine origin) are inserted in stainless steel mortar; under nitrogen protection, mechanical lapping mixes for 120 minutes; then potpourri is packed in the internal thread polyfluortetraethylene pipe of 5 internal diameter 10mm; compaction moulding; rear end is take external thread copper post as wire, and structure as shown in Figure 1.Before using, on pan paper, polish.Twisting copper post, extrudes about 0.5mm by pastel and polishes and can upgrade.
Step 2, assembling three-electrode system sensor also connect portable electrochemical analyser: as shown in Figure 2,3, sensor comprises electrode, contrast electrode, shaft collar 3 and working electrode 5, in order to shorten detection time, teflon matter stirrer 6 is also 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, be connected (accompanying drawing 4 is shown in by schematic diagram) by 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 Middle of The Huanghai Sea, manually filter by disposable syringe and 0.45 μ m water system filter combination, put into 150mL glass electrolytic cell, insert sensor, electrolysis 10min under-1.5V current potential, then take off working electrode, twisting copper post, extrudes about 0.5mm by pastel and polishes to upgrade electrode again.Then adopt identical parameter and method electrolysis 10min again, repeat altogether 4 times, make copper, zinc, lead, cadmium respectively lower than the blank solution of 0.04 μ g/L, 0.05 μ g/L, 0.01 μ g/L, 0.01 μ g/L.Get respectively 10mL blank solution, add cadmium standard solution to 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 and detect liquid.Standard detection liquid is mixed with volume ratio 1:1 with 0.2mol/L NaAc_HAc buffer solution (pH 4.0).Set electrochemical analyser square wave anodic stripping voltammetry detected parameters: amplitude, 25mV; 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 formulating 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 by disposable syringe and 0.45 μ m water system filter combination.10mL filtrate is mixed with volume ratio 1:1 with 0.2mol/L NaAc_HAc buffer solution (pH 4.0) in 25mL plastics electrolytic cell, 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 with formulating working curve to analyte sample fluid analysis, result substitution working curve is obtained to concentration of cadmium ions 0.35 μ g/L.Replicate determination 11 times, reading relative standard deviation is 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 embodiment 3 Laoshan sand mouth harbour heavy metal in seawater copper
Step 1, preparation high performance operation electrode: 5g conductive carbon black (photochemical factory of Shandong Zibo China) and 3.2g ionic liquid N-hexyl pyridine nitrate (the prompt Chemical Co., Ltd. of upper marine origin) are inserted in ceramic mortar; under nitrogen protection, mechanical lapping mixes for 120 minutes; then potpourri is packed in the internal thread polyfluortetraethylene pipe of 5 internal diameter 6mm; compaction moulding; rear end is take external thread copper post as wire, and structure as shown in Figure 1.Before using, on pan paper, polish.Twisting copper post, extrudes about 0.5mm by pastel and polishes and can upgrade.
Step 2, assembling three-electrode system sensor also connect portable electrochemical analyser: as shown in Figure 2,3, sensor comprises electrode, contrast electrode, shaft collar 3 and working electrode 5, in order to shorten detection time, teflon matter stirrer 6 is also 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, composition sensor.Sensor is connected to (accompanying drawing 4 is shown in by schematic diagram) 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 Middle of The Huanghai Sea, manually filter by disposable syringe and 0.45 μ m water system filter combination, put into 150mL glass electrolytic cell, insert sensor, electrolysis 10min under-1.5V current potential, then take off working electrode, twisting copper post, extrudes about 0.5mm by pastel and polishes to upgrade electrode again.Then adopt identical parameter and method electrolysis 10min again, repeat altogether 4 times, make copper, zinc, lead, cadmium respectively lower than the blank solution of 0.04 μ g/L, 0.05 μ g/L, 0.01 μ g/L, 0.01 μ g/L.Get respectively 10mL blank solution, add copper standard solution to 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 and detect 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; 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 copper working curve of formulating 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 by disposable syringe and 0.45 μ m water system filter combination.10mL filtrate is mixed with volume ratio 1:1 with 0.1mol/L ammonium acetate-hac buffer (pH 5.0) in 25mL plastics electrolytic cell, 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 with formulating working curve to analyte sample fluid analysis, result substitution working curve is obtained to copper ion concentration 2.08 μ g/L.Replicate determination 11 times, reading relative standard deviation is 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 embodiment 4 Laoshan sand mouth harbour heavy metal in seawater zinc
Step 1, preparation high performance operation electrode: 5g conductive carbon black (photochemical factory of Shandong Zibo China) and 4g ionic liquid N-octyl group pyridinium tetrafluoroborate salt (the prompt Chemical Co., Ltd. of upper marine origin) are inserted in teflon mortar; under nitrogen protection, mechanical lapping mixes for 120 minutes; then potpourri is packed in the internal thread pitch tube of 5 internal diameter 6mm; compaction moulding; rear end is take external thread copper post as wire, and structure as shown in Figure 1.Before using, on pan paper, polish.Twisting copper post, extrudes about 0.5mm by pastel and polishes and can upgrade.
Step 2, assembling three-electrode system sensor also connect portable electrochemical analyser: sensor comprises electrode, contrast electrode, shaft collar and working electrode, platinum post is " product " font to electrode, Ag/AgCl contrast electrode and working electrode on shaft collar to be arranged, 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 Middle of The Huanghai Sea, manually filter by disposable syringe and 0.45 μ m water system filter combination, put into 150mL glass electrolytic cell, insert sensor, electrolysis 10min under-1.5V current potential, then take off working electrode, twisting copper post, extrudes about 0.5mm by pastel and polishes to upgrade electrode again.Then adopt identical parameter and method electrolysis 10min again, repeat altogether 4 times, make copper, zinc, lead, cadmium respectively lower than the blank solution of 0.04 μ g/L, 0.05 μ g/L, 0.01 μ g/L, 0.01 μ g/L.Get respectively 10mL blank solution, add Zinc standard solution to 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 and detect liquid.Standard detection liquid and 0.1mol/L ammonium acetate-hac buffer (pH5.0) are mixed to form to measurement liquid with volume ratio 1:1.Set electrochemical analyser square wave anodic stripping voltammetry detected parameters: amplitude, 25mV; 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 formulating 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 by disposable syringe and 0.45 μ m water system filter combination.10mL filtrate is mixed with volume ratio 1:1 with 0.1mol/L ammonium acetate-hac buffer (pH 5.0) in 25mL plastics electrolytic cell, 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 with formulating working curve to analyte sample fluid analysis, result substitution working curve is obtained to zinc ion concentration 9.2 μ g/L.Replicate determination 11 times, reading relative standard deviation is 5.4%.
Disregard working curve and formulate step, read copper ion concentration value required time and be about 20min from sampling.

Claims (4)

1. a field fast detection method for heavy metal in seawater copper, zinc, lead, cadmium, is characterized in that it comprises the following steps:
(1) prepare high performance operation electrode: the conductive carbon black of certain mass ratio and ionic liquid are inserted in mortar, grind and fully mix above for 50 minutes, then pack compaction moulding in pipe into, rear end is take copper post as wire; 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, the mass ratio of conductive carbon black and ionic liquid is 1:1～1:0.6, according to the different mass ratioes of adjusting itself and conductive carbon black of the kind of ionic liquid;
(2) assemble three-electrode system sensor and connect 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, be platinum or glass-carbon electrode to electrode, contrast electrode is Ag/AgCl electrode, electrode, contrast electrode and working electrode (5) are arranged on to shaft collar (3) upper, sensor is connected with commercially available portable electrochemical analyser (7);
(3) formulate heavy metal testing curve: first adopt electrolytic process to remove the heavy metal in the seawater of ocean, then take it as blank solution, the series standard that adds heavy metal standard solution to make gradient concentration in blank solution detects liquid, series standard detects liquid and supporting electrolyte is mixed to form measurement liquid with volume ratio 1:1, set portable electrochemical analyser anodic stripping voltammetry detected parameters, sequentially determining is respectively measured liquid current-responsive value, obtains working curve and is prestored into portable electrochemical analyser (7);
(4) seawater sample pre-service: investigation scene takes water sample manually to filter by disposable syringe and 0.45 μ m water system filter combination, after filtering, water sample is mixed to form analyte sample fluid with supporting electrolyte with volume ratio 1:1 in electrolytic cell;
(5) seawater sample detects: sensor is put into the electrolytic cell (8) that fills analyte sample fluid, open portable electrochemical analyser, adopt the parameter anodic stripping voltammetry identical with formulating working curve to detect target heavy metal, bring measurement result into working curve and obtain concentration of heavy metal ion in analyte sample fluid.
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 described step 1 is pottery, glass, resin, plastics.
4. detection method according to claim 1, is characterized in that, on the sensor shaft collar in described step 2, stirrer is housed, and in the time that described seawater sample detects, in order further to shorten detection time, stirs.
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CN105866213A (en) * 2016-06-21 2016-08-17 河南理工大学 Mercury ion selective electrode based on sulfydryl functionalized ionic liquid-carboxylated multi-walled carbon nanotube and 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
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
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

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
"Simultaneous Detection of Diethylstilbestrol and Malachite Green Using Conductive Carbon Black Paste Electrode";Keming Qu et al;《ELECTROCHEMICAL SCIENCE》;20120301;第1827-1839页 *
"离子液体在电分析化学领域中的应用";杨平平等;《西北大学学报(自然科学网络版)》;20070731;第5卷(第4期);第3页倒数第1段 *
Keming Qu et al."Simultaneous Detection of Diethylstilbestrol and Malachite Green Using Conductive Carbon Black Paste Electrode".《ELECTROCHEMICAL SCIENCE》.2012,第1827-1839页.
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)》.2007,第5卷(第4期),

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