CN103512934B - Method and device for monitoring algal toxin-LR in water body on line - Google Patents

Method and device for monitoring algal toxin-LR in water body on line Download PDF

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CN103512934B
CN103512934B CN201310478107.2A CN201310478107A CN103512934B CN 103512934 B CN103512934 B CN 103512934B CN 201310478107 A CN201310478107 A CN 201310478107A CN 103512934 B CN103512934 B CN 103512934B
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microcystins
water body
anode
chamber
cathode
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CN103512934A (en
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赵春城
赵烟桥
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100 Olson Jiangsu Food Safety Technology Co Ltd
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Wuxi Xresearch Product Design and Research Co Ltd
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Abstract

The invention discloses a method and a device for monitoring algal toxin-LR in a water body on line, and belongs to the technical field of environment detection. The device comprises an anode chamber and a cathode chamber, wherein the anode chamber and the cathode chamber are separated through a proton exchange membrane; an outer resistor is arranged between an anode and a cathode; the outer resistor and the anode and the cathode are communicated through a lead; a paperless recorder is connected with the outer resistor in parallel and is used for monitoring the current/voltage of the outer resistor; the paperless recorder is connected with a computer; the cathode is made of gold, copper or titanium and the like plated with gold on the surface; algal toxin-LR aptamers are fixed on the gold surface. The method comprises the following steps: a to-be-tested water sample which is mixed with a [Fe(CN)6]3-/4-solution is continuously fed into the cathode chamber, an electric output signal is acquired, when the electric signal exceeds a preset range, the computer makes an alarm automatically so as to show that the algal toxin-LR content in the water sample to be tested exceeds the standard. The method and the device have the advantages that the structure is simple, the operation is convenient, the detection limit is low, the selectivity is good, the stability is high, the energy consumption is small, and are applicable to real-time on-line monitoring of algal toxin-LR in the drinkable water body.

Description

The method of microcystins-LR and device in a kind of on-line monitoring water body
Technical field
In a kind of on-line monitoring water body, the method for microcystins-LR and device belong to the technical field of environment measuring.
Background technology
Microcystin is stable ring-type seven peptide that a class produces primarily of cyanobacteria, is all found in global water source.Due to the eutrophication of lake and reservoir, the water body sustainable growth of Pollution of Microcystin.The toxicology mechanism of Microcystin is to protein phosphatase 1 and 2A(PP1, PP2A by them) strong inhibition effect cause serious hepatic lesion.The water body being chronically exposed to low concentration Microcystin can promote the generation of tumour.In the deformable body of Microcystin, microcystins-LR is the virose kind of modal tool.In order to protect water quality and health, in world health organisation recommendations potable water, the provisional upper limit standard of microcystins-LR is 1.0mg l -1.Therefore, the content that the reliable and stable analytical approach of development one detects microcystins-LR in water body is badly in need of.Up to now, a lot of analytical technology is had for detecting the content of microcystins-LR in water body, such as immunoassays (ELISA), high performance liquid chromatography (HLPC) etc.The detection method of these routines has good detection limit, but complicated operation is time-consuming, sample pretreatment is expensive and apparatus expensive, and this constrains the instant detection of microcystins-LR to a great extent.
Summary of the invention
In order to solve the problem, the invention provides method and the device of microcystins-LR in a kind of on-line monitoring water body, this apparatus structure is simple, easy to operate, highly sensitive; The method can realize microcystins-LR in water body Real-Time Monitoring, operation cost is low and result reliability is high.
The object of the present invention is achieved like this:
The device of microcystins-LR in a kind of on-line monitoring water body, it is characterized in that comprising anode chamber and cathode chamber, separated by PEM between described anode chamber and cathode chamber, anode is arranged in anode chamber, negative electrode is arranged in cathode chamber, and arrange an external resistance between anode with negative electrode and be communicated with by wire, recording instrument without paper is in parallel with external resistance, for the current/voltage size of Real-Time Monitoring external resistance, recording instrument without paper is connected with computer; Described negative electrode material is gold or the metal such as copper, titanium of surface gold-plating, and gold surface to be fixed with microcystins-LR fit.
In above-mentioned a kind of on-line monitoring water body, the device of microcystins-LR, is provided with alert program in described computer, when recording instrument without paper output current/magnitude of voltage exceeds preset range, and computer automatic alarm.
A method for microcystins-LR in on-line monitoring water body, comprises the following steps:
Step a, employing nutrient solution pass into anode chamber, [Fe (CN) 6] 3-/4-solution passes into cathode chamber, is cultured to collects constant electrical output signal to system;
The nutrient solution of constant density is passed into continuously, with the stable operation of keeping system in step b, anode chamber;
Step c, by [the Fe (CN) of 50 ~ 200mmol/L 6] 3-/4-solution mixes in 1:5 ~ 1:10 ratio with water sample to be measured;
Steps d, mixed sample to be passed into continuously in cathode chamber and Real-time Collection electrical output signal;
Step e, when electrical output signal exceeds preset range, computer automatic alarm, shows microcystins-LR content overproof in water sample to be measured.
The method of microcystins-LR in above-mentioned a kind of on-line monitoring water body, described polluted-water comprises the source water such as river, lake polluted by blue-green algae breeding.
Because the method for microcystins-LR in a kind of on-line monitoring water body of the present invention and apparatus main body only comprise the anode chamber and the cathode chamber, anodic-cathodic and PEM, therefore there is the advantages such as structure is simple, easy to operate; Because the method for microcystins-LR in a kind of on-line monitoring water body of the present invention and device make use of the principle of electrochemical impedance biology sensor, therefore have that detection limit is low, selectivity good and the beneficial effect such as stability is high; Present invention utilizes the principle of microorganism electricity generation, electrochemical impedance biology sensor can be made to reflect the electric signal that the response of microcystins-LR is directly produced by Institute of Micro-biology, can realize the Real-Time Monitoring of microcystins-LR, energy consumption is lower simultaneously.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram of microcystins-LR in a kind of on-line monitoring water body of the present invention.
In figure: 1 anode chamber, 2 cathode chambers, 3 PEMs, 4 anodes, 5 negative electrodes, 6 external resistances, 7 recording instrument without paper, 8 computers.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the invention is described in further detail.
Specific embodiment one
Water body handled by the present embodiment is the water body containing microcystins-LR of laboratory preparation.
The device of microcystins-LR in a kind of on-line monitoring water body of the present embodiment, structural representation as shown in Figure 1.This device comprises anode chamber 1 and cathode chamber 2, separated by PEM 3 between described anode chamber 1 and cathode chamber 2, anode 4 is arranged in anode chamber 1, negative electrode 5 is arranged in cathode chamber 2, one external resistance 6 is set between anode 4 with negative electrode 5 and is communicated with by wire, recording instrument without paper 7 is in parallel with external resistance 6, and for the current/voltage size of Real-Time Monitoring external resistance 6, recording instrument without paper 7 is connected with computer 8; Described negative electrode 5 material is gold or the metal such as copper, titanium of surface gold-plating, and gold surface to be fixed with microcystins-LR fit.
Alert program is provided with in described computer 8, when recording instrument without paper 7 output currents/magnitude of voltage exceeds preset range, computer 8 automatic alarm.
The method of microcystins-LR in a kind of on-line monitoring water body of the present embodiment, comprises the following steps:
Step a, employing nutrient solution pass into anode chamber 1, [Fe (CN) 6] 3-/4-solution passes into cathode chamber 2, is cultured to collects constant electrical output signal to system;
The nutrient solution of constant density is passed into continuously, with the stable operation of keeping system in step b, anode chamber 1;
Step c, by [the Fe (CN) of 50mmol/L 6] 3-/4-solution mixes in 1:5 ratio with water sample to be measured;
Steps d, mixed sample to be passed into continuously in negative electrode 2 and Real-time Collection electrical output signal;
Step e, when electrical output signal exceeds preset range, computer 8 automatic alarm, shows microcystins-LR content overproof in water sample to be measured.
Specific embodiment two
Water body handled by the present embodiment is the water body containing microcystins-LR of laboratory preparation.
The method of microcystins-LR in a kind of on-line monitoring water body of the present embodiment, comprises the following steps:
Step a, employing nutrient solution pass into anode chamber 1, [Fe (CN) 6] 3-/4-solution passes into cathode chamber 2, is cultured to collects constant electrical output signal to system;
The nutrient solution of constant density is passed into continuously, with the stable operation of keeping system in step b, anode chamber 1;
Step c, by [the Fe (CN) of 200mmol/L 6] 3-/4-solution mixes in 1:10 ratio with water sample to be measured;
Steps d, mixed sample to be passed into continuously in negative electrode 2 and Real-time Collection electrical output signal;
Step e, when electrical output signal exceeds preset range, computer 8 automatic alarm, shows microcystins-LR content overproof in water sample to be measured.
Specific embodiment three
Water body handled by the present embodiment is the water body containing microcystins-LR of laboratory preparation.
The method of microcystins-LR in a kind of on-line monitoring water body of the present embodiment, comprises the following steps:
Step a, employing nutrient solution pass into anode chamber 1, [Fe (CN) 6] 3-/4-solution passes into cathode chamber 2, is cultured to collects constant electrical output signal to system;
The nutrient solution of constant density is passed into continuously, with the stable operation of keeping system in step b, anode chamber 1;
Step c, by [the Fe (CN) of 100mmol/L 6] 3-/4-solution mixes in 1:10 ratio with water sample to be measured;
Steps d, mixed sample to be passed into continuously in negative electrode 2 and Real-time Collection electrical output signal;
Step e, when electrical output signal exceeds preset range, computer 8 automatic alarm, shows microcystins-LR content overproof in water sample to be measured.
Specific embodiment four
The present embodiment is the monitoring device embodiment of microcystins-LR in the water sample adopting tap water to prepare.
The device of microcystins-LR in a kind of on-line monitoring water body of the present embodiment, structural representation as shown in Figure 1.This device comprises anode chamber 1 and cathode chamber 2, separated by PEM 3 between described anode chamber 1 and cathode chamber 2, anode 4 is arranged in anode chamber 1, negative electrode 5 is arranged in cathode chamber 2, one external resistance 6 is set between anode 4 with negative electrode 5 and is communicated with by wire, recording instrument without paper 7 is in parallel with external resistance 6, and for the current/voltage size of Real-Time Monitoring external resistance 6, recording instrument without paper 7 is connected with computer 8; Described negative electrode 5 material is gold or the metal such as copper, titanium of surface gold-plating, and gold surface to be fixed with microcystins-LR fit.
Alert program is provided with in described computer 8, when recording instrument without paper 7 output currents/magnitude of voltage exceeds preset range, computer 8 automatic alarm.
The device of microcystins-LR in described a kind of on-line monitoring water body, its principle is that microcystins-LR is fit and is fixed on gold electrode surfaces when there is target thing (microcystins-LR) by the mating reaction of Au-S; The change that the binding effect of microcystins-LR and fit probe causes electrode surface complex to be formed, and cause the minimizing of impedance.In microcystins-LR concentration 1.0 × 10 -7– 5.0 × 10 -11within the scope of mol/L, the minimizing speed of impedance and microcystins-LR concentration linear correlation, detect and be limited to 1.8 × 10 -11mol/L.
Specific embodiment five
The present embodiment is the monitoring method embodiment of microcystins-LR in the water sample adopting tap water to prepare.
Use for laboratory tap water preparation water sample, the content of its microcystins-LR is 1.0 × 10 -6mmol/L.Adopt Fig. 1 device.Comprise the following steps:
Step a, the nutrient solution adopting the glucose of 500mg/L and trace element to prepare pass into anode chamber 1, [Fe (CN) 6] 3-/4-solution passes into cathode chamber 2, is cultured to collects constant electrical output signal to system;
The nutrient solution that the glucose passing into 300mg/L in step b, anode chamber 1 is continuously prepared with trace element, to keep the stable operation of microorganism electrochemical system;
Step c, by [the Fe (CN) of 50 mmol/L 6] 3-/4-solution mixes in 1:5 ratio with water sample to be measured;
Steps d, mixed sample to be passed into continuously in negative electrode 2 and Real-time Collection electrical output signal;
Step e, when electrical output signal exceeds preset range, computer 8 automatic alarm, shows microcystins-LR content overproof in water sample to be measured.
Specific embodiment six
The present embodiment is the monitoring method embodiment of microcystins-LR in the water sample taking from certain water body in lake.
Adopt Fig. 1 device.Comprise the following steps:
Step a, employing sanitary sewage pass into anode chamber 1,10 mmol/L [Fe (CN) as nutrient solution 6] 3-/4-solution passes into cathode chamber 2, is cultured to collects constant electrical output signal to system;
Sanitary sewage nutrient solution is passed into continuously, to keep the stable operation of microorganism electrochemical system in step b, anode chamber 1;
Step c, by [the Fe (CN) of 100 mmol/L 6] 3-/4-solution mixes in 1:10 ratio with water sample to be measured;
Steps d, mixed sample to be passed into continuously in negative electrode 2 and Real-time Collection electrical output signal;
Step e, when electrical output signal exceeds preset range, computer 8 automatic alarm, shows microcystins-LR content overproof in water sample to be measured.

Claims (3)

1. the device of microcystins-LR in an on-line monitoring water body, it is characterized in that comprising anode chamber (1) and cathode chamber (2), separated by PEM (3) between described anode chamber (1) and cathode chamber (2), anode (4) is arranged in anode chamber (1), negative electrode (5) is arranged in cathode chamber (2), one external resistance (6) is set between anode (4) with negative electrode (5) and is communicated with by wire, recording instrument without paper (7) is in parallel with external resistance (6), for the current/voltage size of Real-Time Monitoring external resistance (6), recording instrument without paper (7) is connected with computer (8), described negative electrode (5) material is gold or the copper of surface gold-plating or titanium, and gold surface to be fixed with microcystins-LR fit.
2. the device of microcystins-LR in a kind of on-line monitoring water body according to claim 1, it is characterized in that being provided with alert program in described computer (8), when recording instrument without paper (7) output current/magnitude of voltage exceeds preset range, computer (8) automatic alarm.
3. application rights requires a method for microcystins-LR in the on-line monitoring water body of the device of microcystins-LR in on-line monitoring water body described in 1, it is characterized in that comprising the following steps:
Step a, employing nutrient solution pass into anode chamber (1), [Fe (CN) 6] 3-/4-solution passes into cathode chamber (2), is cultured to collects constant electrical output signal to system;
The nutrient solution of constant density is passed into continuously, with the stable operation of keeping system in step b, anode chamber (1);
Step c, by [the Fe (CN) of 50 ~ 200mmol/L 6] 3-/4-solution mixes in 1:5 ~ 1:10 ratio with water sample to be measured;
Steps d, mixed sample to be passed into continuously in cathode chamber (2) and Real-time Collection electrical output signal;
Step e, when electrical output signal exceeds preset range, computer (8) automatic alarm, shows microcystins-LR content overproof in water sample to be measured.
CN201310478107.2A 2013-10-14 2013-10-14 Method and device for monitoring algal toxin-LR in water body on line Active CN103512934B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1228628C (en) * 2003-11-04 2005-11-23 武汉大学 Determination method of microcapsule algal toxin
CN101458223B (en) * 2008-12-26 2012-01-25 江南大学 Preparation of quantitative rapid detecting sensor of microcapsule algae toxin and applications
BRMU9102088U2 (en) * 2011-08-25 2016-04-26 Univ Fed Pernambuco use of a protein nanopore for detection, identification, quantification and real time monitoring of microcystins in aqueous systems
CN103308675B (en) * 2013-05-08 2015-08-12 北京工业大学 The preparation of the screen printing electrode immunosensor of quick detection Microcystin and detection method
CN203643390U (en) * 2013-10-14 2014-06-11 无锡艾科瑞思产品设计与研究有限公司 Device for monitoring algal toxin-LR in water body online

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Address after: No. 499 Olin garden B District Li Xi Road 214072 Jiangsu city of Wuxi province No. 86 402

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Address before: No. 499 Olin garden B District Li Xi Road 214072 Jiangsu city of Wuxi province No. 86 402

Patentee before: Wuxi Baiaosen Technology Co., Ltd.