JP2002243698A - Biosensor type abnormal water quality detector - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biosensor type abnormal water quality detector, capable of rapidly detecting organic substances in water to be inspected, with high sensitivity. SOLUTION: The biosensor type abnormal water quality detector is equipped with a pair of flow cells 33 and 34, a cleaning liquid tank 1, an iron-made liquid tank 2, a water tank 3 and an intake tank 4. The cleaning liquid tank 1 and the flow cells 33 and 34 are connected by a cleaning liquid line so as to be freely changed over, and the iron-made liquid tank 2 and the flow cells 33 and 34 are connected by an iron liquid line so as to be freely changed over, and the water tank 3 and the flow cells 33 and 34 are connected by a water supply line, to be changed over freely, and the intake tank 4 and the flow cells 33 and 34 are connected by a line of water to be inspected to be changed over freely. Operation control is conducted by a control part 44 so that the flow cell 34 becomes a washing state, when one flow cell 33 is in measuring state the other flow cell 34 goes not a cleaning state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biosensor type abnormal water quality detection device which detects contamination of a harmful substance in an intake of a water purification plant and a sewage treatment plant and issues an alarm.

[0002]

2. Description of the Related Art In a water purification plant, river water is taken and the drinking water is produced through a sedimentation filtration layer. When harmful substances such as heavy metals, pesticides, environmental hormones and the like which cannot be removed by such normal treatment are mixed in river water, an emergency situation occurs in which water intake is stopped. On the other hand, due to a catastrophic accident, various heavy metal ions, organic solvents, arsenic cyanide, and the like may be mixed into sewage in a factory or a chemical plant, and such sewage may flow into a sewage treatment plant. In this case, the activated sludge microorganisms in the sewage treatment process are greatly inhibited, and the activity of the activated sludge is reduced, so that a long time is required until the treatment capacity is restored. Therefore, there is a demand for a device for quickly and sensitively detecting inflow water mixed with various harmful substances in a water purification plant or a sewage treatment plant.

[0003] For this reason, in water purification plants, a fish behavior monitoring type toxicant detection device is installed at the exit, or a device that detects toxic substances by measuring various respiratory activities by attaching various microbial membranes to a dissolved oxygen electrode is installed. . On the other hand, in sewage treatment plants,
Various sensors are installed to detect wastewater mixed with specific chemical substances.

[0004]

The fish behavior monitoring type toxic substance detection device installed in the water purification plant requires a long time for fishes to react with the toxic substance, and therefore requires a long time for the detection. In addition, the sensitivity of fish also varies considerably depending on the type of fish being bred, individual differences, and environmental conditions. Furthermore, these devices are large-scale devices and require large expenses in breeding and managing fish.

[0005] In a biosensor type water quality monitoring device in which a microbial membrane is attached to an oxygen electrode, the applied microorganisms are generally active when they are in a pH state near neutrality. For this reason, if the surface of the oxygen electrode is contaminated by organic matter or the like in the test water flowing into the sensor, the contamination is not easily removed even when the cleaning operation is performed, and the activity of the sensor itself is reduced. In addition, there is a problem that the activity of bacteria applied to the oxygen electrode changes because these organic substances serve as a nutrient source.

On the other hand, as a device for detecting an abnormality in water quality of inflow water of a sewage treatment plant, a device for specific chemical substances such as cyanide, arsenic, heavy metals, and pesticides has been devised. The fact is that no device capable of detecting substances has been developed.

[0007] The present invention has been made in view of the above points, and it is an object of the present invention to provide a biosensor type abnormal water quality detection device that can reliably detect the incorporation of harmful substances.

[0008]

The present invention comprises an oxygen electrode,
A membrane filter attached to the tip of the oxygen electrode and holding an iron-oxidizing bacterium, detecting contamination of an organic substance, and at least one pair of flow cells arranged in parallel with each other, and a cleaning liquid tank storing a cleaning liquid,
An iron liquid tank for storing iron liquid, an intake tank for storing test water, a cleaning liquid line for supplying cleaning liquid from the cleaning liquid tank to each flow cell, and an iron liquid line for supplying iron liquid from the iron liquid tank to each flow cell. A test water line for supplying test water from the intake tank to each flow cell, and each flow cell,
A control unit that drives and controls the cleaning liquid line, the iron liquid line, and the test water line, and when one of the flow cells is in the measurement state, the other of the flow cells is in the cleaning state, and simultaneously the one to the one of the flow cells. The iron liquid is supplied via the iron liquid line, the test water is supplied via the test water line, the cleaning liquid is supplied to the other flow cell via the cleaning liquid line, and the test liquid is supplied via the test water line. It is a biosensor type abnormal water quality detection device that supplies water.

In this manner, one or more pairs of flow cells are arranged in parallel, and when one of the flow cells is in the measurement state, the other flow cell is operated complementarily so as to be in the cleaning state. . When the flow cell is in the measurement state, the iron liquid is constantly supplied to the flow cell, so that the iron liquid line is gradually contaminated with iron oxide. This contamination is caused by the oxidation of Fe ²⁺ by iron bacteria in the flow cell
Since e ³⁺ occurs, it becomes more prominent at the flow cell outlet side.

Further, when iron oxide accumulates on the oxygen electrode surface, the oxygen concentration reaching the membrane filter decreases, and the span current of the oxygen electrode decreases. Therefore, it is necessary to periodically clean the flow cell with an acid to remove dirt. For this reason, one of the flow cells is kept in a measurement state, and the other flow cell is cleaned in the cleaning state during this time.

The above is alternately measured between a pair of flow cells.
It is configured to repeat washing, but if the number of flow cells operated in parallel is increased to three or four, the cycle of washing and measurement can be freely changed, and the measurement state can be changed with multiple cells. Measurement accuracy can be improved.

In the flow cell arranged in such a configuration, when a water-soluble harmful substance is mixed in the test water with respect to the cell in the measurement state in which the iron solution is flowing, the output current of the oxygen electrode increases. By doing so, contamination of harmful substances is detected, and when this value exceeds a certain value, an alarm is issued.

In the present invention, when a microbial membrane is attached to the oxygen electrode, for example, a cellulose mixed ester type membrane filter (pore size: 0.5 μm or less) is used as a microorganism holder, and the membrane filter is provided with a glass filter base. Place it on a filter holder, place a glass funnel on it, hold it with a clamp, put a liquid containing a predetermined amount of iron-oxidizing bacteria into the funnel, and suction-filter this with a vacuum pump to remove the iron to the membrane filter. Give bacteria.

Further, according to the present invention, the iron solution comprises a ferrous sulfate solution which is acidic to sulfuric acid. The ferrous sulfate solution contains K, Mg and Ca salts as inorganic metal ions and simultaneously contains a certain amount of ammonium sulfate. It is a biosensor type abnormal water quality detection device characterized by including:

[0015] Iron oxidizing bacteria are Fe ^{2+ as an} energy source.
Is generally grown in an acidic environment of pH 3 or less because it can exist relatively stably under acidic conditions. Thiobacillus ferrooxidans, a typical iron-oxidizing bacterium, is a Gram-negative bacterium isolated and identified from the acidic mine water of a coal mine in the eastern United States. It uses CO ₂ as a carbon source and independently obtains energy by oxidizing Fe ^2+. It is known to be a vegetative bacterium. T.ferrooxidans is K, Mg, Ca
And cultured at 30 ° C. in a medium (pH 3) containing a certain amount of ammonium sulfate. Therefore, in order for iron bacteria to grow, an iron solution containing these several kinds of inorganic metals must be supplied.

In the present apparatus, a liquid in which the test water and the iron liquid, which are sucked up at a constant flow rate, are sent to the flow cell in the measurement state. Each flow rate is about 100 to 200 ml / min. , Iron liquid 3 ~
6 ml / min. Therefore, when the mixed solution reaches the oxygen electrode portion of the flow cell and the pH of the mixed solution becomes a value near 3 which is the optimum pH (optimum pH) of the iron bacteria, the pH of the iron solution is usually 2 or less ( 1.6 to 1.9).

The present invention is a biosensor type abnormal water quality detection device, wherein a filtration device is provided in an intake tank.

At the intake of the water purification plant, dead leaves, wood chips,
Sand (mud), pebbles, lint, glass chips, microorganisms, etc. may be mixed into the influent water. When these are directly sent to the test water line, the test water line is a thin one having an inner diameter of about 1 mm, so that the inlet portion is clogged and liquid cannot be sent. Therefore, it is necessary to completely remove these foreign substances before the test water enters the apparatus. Therefore, the test water is passed through a filtration device before entering the device.

The present invention is a biosensor type abnormal water quality detecting device, wherein the filtering device has a built-in hollow fiber membrane.

The flow cell can be operated satisfactorily by passing the sampled water that has been taken through the filtration device, and if a soluble harmful substance is present, it can be detected.

The present invention is a biosensor type abnormal water quality detection apparatus characterized in that the filtration apparatus is used after being automatically cleaned periodically.

In this case, foreign matter in the hollow fiber membrane can be removed, and the filter can operate normally for a long period of time. As a method of automatic washing, there is a method of supplying a constant-pressure air from a filtered water outlet portion by a compressor after taking a sample water for a predetermined time, or a method of supplying a constant-pressure water flow.

According to the present invention, the pH of the iron solution and the cleaning solution is set to a constant value so that the pH in each flow cell becomes an optimum pH value for the inhabitation of iron-oxidizing bacteria, and the control unit controls the cleaning solution and the iron solution in the cleaning solution line. A biosensor type abnormal water quality detection device, wherein the amounts of an iron solution in a line and a test solution in a test solution are adjusted.

According to the present invention, the pH after mixing the iron solution and the test water, and the washing solution and the test water, is maintained at 2.5 to 3.5, which is the optimum pH of the iron bacteria. , The flow rates of both liquids are adjusted. In order to keep the consumption of the iron liquid and the cleaning liquid as small as possible and to operate the iron liquid line and the cleaning liquid line smoothly, the flow rate of the iron liquid and the cleaning liquid is about 3 to 6 m.
1 / min. Must be secured. The pH of the iron solution is 2
Since the pH of the test water is around neutral,
In order to reach a value near pH 3 in a mixed state, the test water is supplied at about 100 to 200 ml / min. Distribute in. These flow rate values are affected by conditions such as the performance of the iron liquid line and the cleaning liquid line, and the pH of the test water, and therefore need to be adjusted as appropriate.

The present invention is a biosensor type abnormal water quality detecting device, wherein the temperature in each flow cell is maintained at 30 ± 5 ° C., which is the optimum temperature for the inhabitation of iron-oxidizing bacteria.

According to the present invention, a water supply line for supplying water is connected to each flow cell, and the control unit supplies water to the flow cell at an initial stage when the iron solution is flowing and the cleaning solution is flowing. A biosensor-type abnormal water quality detection device characterized in that zero current and span current are calibrated.

Here, the zero current refers to the current value in the measurement state in which the iron liquid flows, and the span current refers to the current value in the cleaning state in which the cleaning liquid flows, in a normal state in which no harmful substances are mixed. The output current of the dissolved oxygen electrode is measured before the measurement of the test water, and the state of the test water is measured using this value as a reference value.

In the present invention, the iron liquid tank is formed of a sealed polyethylene or Teflon bag, and the iron liquid is supplied to the flow cell at a constant flow rate from the bag by a tube pump provided in the iron liquid line without being exposed to the outside air. It is a biosensor type abnormal water quality detection device characterized by being fed.

Preferably, the iron solution is a sulfuric acid-acidic iron sulfate solution having a pH of 2 or less. The dissolved iron is a divalent ion (Fe ²⁺ ), which is easily oxidized to a trivalent ion (Fe ³⁺ ) when exposed to air. Such an oxidized state not only does not become a nutrient source for iron bacteria, but also causes precipitation and clogging of the iron liquid line.
For this reason, it is placed in a closed container as described above, from which it is sucked by a tube pump without touching the outside air and sent to the flow cell. Thus, long-term operation can be stably continued.

According to the present invention, a discharge line is connected to each flow cell, and a dilution line is attached to the discharge line. The discharge from each flow cell is diluted with the diluent from the dilution line to have a pH of 6. A biosensor-type abnormal water quality detection device characterized by being discharged as described above.

The effluent discharged from the flow cell is p
Since H is an acidic water having a pH of about 3, it is diluted with a diluting liquid, for example, a branched water of water at the time of water intake, to obtain a neutral pH.
Return to and discharge. As a result, the effluent does not contaminate the intake of the water purification plant or the river.

[0032]

Embodiments of the present invention will be described below with reference to the drawings. FIGS. 1 to 3 are views showing an embodiment of a biosensor type abnormal water quality detecting device according to the present invention.

As shown in FIG. 1, the biosensor type abnormal water quality detecting device includes a pair of flow cells 33 and 34 for detecting contamination of harmful substances, and a circulation tank 37. 38, 39 and a circulation line 4
0 and 41 are connected.

Each of the flow cells 33, 34 includes tanks 33a, 34a, oxygen electrodes 35, 36 housed in the tanks 33a, 34a, and membrane filters 35a, 36a attached to the oxygen electrodes 35, 36. have. Of these, the membrane filters 35a and 36a
Holds iron oxidizing bacteria.

The oxygen electrode 3 of each flow cell 33, 34
The ion meters 42 and 43 are respectively connected to 5 and 36, and these ion meters 42 and 43 are connected to the control unit 44.

On the other hand, a cleaning liquid tank 1 for storing a cleaning liquid (H ₂ SO ₄ ) solution, an iron liquid tank 2 for storing an iron liquid (FeSO ₄ solution), and a water tank 3 for storing water (H ₂ O)
And a water intake tank 4 for storing the sampled liquid. In the water intake tank 4, a filtration device 4a made of a hollow fiber membrane is installed.

Further, the cleaning liquid tank 1 is connected via pipes 7 and 9, pinch valves 15 and 17, pipe tubes 23 and 24, tube pumps 27 and 28, and pipes 31 and 32.
It is connected to flow cells 33 and 34. In this case, a line from the cleaning liquid tank 1 to the flow cells 33 and 34 forms a cleaning liquid line.

The iron liquid tank 2 is connected to flow cells 33 and 34 via pipes 8 and 10, pinch valves 16 and 18, pipe tubes 23 and 24, tube pumps 27 and 28, and pipes 31 and 32. In this case, a line from the iron liquid tank 2 to the flow cells 33 and 34 forms an iron liquid line.

The water tank 3 is connected to flow cells 33 and 34 via pipes 11 and 13, pinch valves 19 and 21, pipe tubes 25 and 26, tube pumps 29 and 30 and pipes 31 and 32. In this case, a line from the water tank 3 to the flow cells 33 and 34 constitutes a water supply line.

Further, the water intake tank 4 is connected to the pipes 12, 1
4, pinch valves 20, 22, piping tubes 25, 2
6. They are connected to flow cells 33, 34 via tube pumps 29, 30 and pipes 31, 32. In this case, a line from the water intake tank 4 to the flow cells 33 and 34 constitutes a test water line.

The test water flows into the water intake tank 4 via a water intake pipe 6 and a water intake pump 5. Further, drain lines 45 and 46 are connected to the flow cells 33 and 34, and branch pipes 47 and 48 branched from the water intake pipe 6 are connected to the drain lines 45 and 46.

Next, the operation of the present embodiment having the above configuration will be described.

The two flow cells 33 and 34 are operated according to the operation pattern shown in FIG. That is, when one flow cell 33 is in the measurement state, the other flow cell 34 is in the cleaning state. That is, when one of the flow cells 33 is in the measurement state, the iron liquid is supplied from the iron liquid tank 2 to the one flow cell 33 via the pipe 8, the pinch valve 16, the pipe tube 23, the tube pump 27, and the pipe 31. In this case, the pinch valve 16 is in a closed state.

On the other hand, the test water is sent to the water intake tank 4 by the water intake pipe 6 and the water intake pump 5 via the filtration device 4a. The test water in the water intake tank 4 is supplied to the flow cell 33 through the pipe 12, the pinch valve 20, the pipe tube 25, the tube pump 29 and the pipe 31, and is mixed with the iron liquid.

In this case, the cleaning liquid is supplied from the cleaning liquid tank 1 to the other flow cell 34 via the pipe 9, the pinch valve 17, the pipe tube 24, the tube pump 28 and the pipe 32. At the same time, from the intake tank 4,
4. The test water is supplied to the flow cell 34 via the pinch valve 22, the tube pump 30, and the pipe 32, and mixed with the cleaning liquid in the flow cell 34.

The effluent of each flow cell 33, 34 is discharged through effluent lines 45, 46. At this time, the effluent in the effluent lines 45 and 46 is
The water is diluted by the water in the branch pipes 47 and 48 branched from and returned to near neutral water, and finally discharged.

As described above, the two flow cells 33 and 34 are arranged in parallel, and the measurement and washing operations are alternately repeated for them. As a result, the flow cells 33 and 34 periodically change.
In addition, since the measurement can be performed while cleaning the piping lines, the oxygen electrodes 35 and 36 of the flow cells 33 and 34 and the piping lines do not become clogged with iron oxides, and are continuously stable for a long time. Thus, the flow cells 33 and 34 can be operated.

During this time, the entire flow cells 33 and 34 are maintained at a temperature of 30 ± 0.5 ° C., which is the optimum temperature for iron bacteria, by constant temperature water circulated from the circulation tank 37.

Although an example in which a pair of flow cells 33 and 34 are operated in parallel has been described, the piping system becomes somewhat complicated by increasing the number of flow cells to be used, but as shown in FIG. Since the cycle of the measurement operation of each flow cell 33, 34 can be shortened, more reliable measurement can be performed. The principle of detecting harmful substances in the abnormal water quality monitoring device of the biosensor type having such a configuration is disclosed in
-198768.

That is, the flow cell 33 in the measurement state
When a healthy test water flows, the iron bacterium applied to the membrane filter 35a consumes Fe ²⁺ ions and dissolved oxygen in the water to perform a respiratory action. Therefore, the oxygen concentration that reaches the oxygen electrode 35 after passing through the membrane filter 35a is low, and the current value measured by the ion meter 42 becomes almost zero. At this time,
A voltage of 0.7 V is applied by the ion meter 42.

On the other hand, if harmful substances are mixed in the test water, the respiration of iron bacteria is inhibited or killed, so that the consumption of oxygen and Fe ²⁺ ions is suppressed. The reached oxygen concentration increases (the same level as the dissolved oxygen concentration), and the current value measured by the ion meter 42 increases. Control unit 4
Numeral 4 detects that abnormal water quality has flowed in with an increase in the current value in this measurement state, and issues an alarm.

[0052] Membrane filters 35a, 36a as holders for the microbial membrane attached to the oxygen electrodes 35, 36
There are various materials such as PTFE (tetrafluoroethylene), hydrophobic and hydrophilic polyvinylidene, polycarbonate, etc. As a result of the examination, the cellulose mixed ester type is most preferable in terms of compatibility with the oxygen electrodes 35 and 36. Are suitable. The pore size of the membrane filters 35a and 36a is 0.2 μm because the size of iron bacteria is ~ 0.2 μm.
It is as follows.

The method of attaching microorganisms to the membrane filters 35a and 36a is as follows. A filter is placed on a filter holder with a glass filter base (not shown), a glass funnel is placed on the filter and held by a clamp, and a predetermined amount of iron-oxidizing bacteria is removed. The contained liquid is put into a funnel, and this is suction-filtered by a vacuum pump. As a result, the iron oxidizing bacteria are retained in the membrane filters 35a and 36a.

The amount of the iron-oxidizing bacteria to be applied can be made constant by measuring the number of cells per unit volume by microscopic measurement, and usually sufficient activity is provided if about 10 ⁸ cells / cm ^2. Can be maintained. As described above, the growth conditions of the iron-oxidizing bacteria are such that the growth is possible at a pH of 1.3 to 4.5 and a growth temperature of 10 to 37 ° C. As a medium component, iron, ammonium salt, phosphate, sulfate, potassium, and magnesium are used. Including.

As an iron solution, a sulfuric acid solution having a pH of about 3 containing a predetermined amount of dipotassium hydrogen phosphate, ammonium sulfate, potassium chloride, magnesium sulfate, ferrous sulfate, and calcium nitrate in pure water is typically used. Used. The operation is started by putting such an iron solution into the iron solution tank 2 and sending it to the flow cells 33 and 34 by the tube pumps 27 and 28.

By the way, the water intake tank 4 is provided with a filtering device 4a, which removes various foreign substances and solid components in the waste water, and can prevent clogging of a pipe through which the test water flows. . This filtration device 4a uses a device having a built-in hollow fiber membrane.
The filter is cleaned and used by an operation such as pressurization by a compressor (not shown) so that the filtration ability can always be normally maintained. The conditions for this cleaning vary depending on the installation state of the apparatus.

In FIG. 1, the pH and the flow rate of the iron solution, the washing solution and the test water are adjusted so that the flow cells 33 and 34 maintain the optimum state of the iron-oxidizing bacteria. Therefore, the pH of the iron solution and the cleaning solution are 1.6 to 1.9 and 0.1 to 0.3, respectively.
The flow rate of the iron liquid is 3 to 6 ml / mi, which is a value that secures the minimum flow rate for operating the pump.
n. It has become. The flow rate of the test water is 100 to 150 ml / min correspondingly.
The flow rate of each liquid can be changed at any time depending on the performance of the tube pump 27-30.

In the initial stage when the iron solution is flowing and the cleaning solution is flowing, zero current and span current are calibrated by using pure water from the water tank 3 as diluting water. Here, the zero current refers to the current value from the oxygen electrodes 35 and 36 in the measurement state in which the iron liquid flows, and the span current refers to the oxygen electrodes 35 and 36 in the cleaning state in which the cleaning liquid flows.
From the current value. The output current of the oxygen electrodes 35 and 36 in a normal state in which no harmful substance is mixed is measured prior to the measurement of the test water, and the state of the test water is measured using this value as a reference value.

Even in the cleaning state, iron oxide gradually accumulates on the surfaces of the electrodes 35 and 36 during long-term operation, and the permeation of dissolved oxygen to the oxygen electrodes 35 and 36 decreases. The current value gradually decreases. Therefore, by performing these measurements at all times before starting the measurement, it is possible to perform the measurement in a form in which the temporal change of the microbial membrane is corrected. FIG. 2 shows an operation pattern of the present apparatus including such an automatic calibration function. When the detection device operates according to the operation pattern shown in FIG. 2 and harmful substances are mixed in the test water,
The controller 44 uses the values of the zero current and the span current to determine the degree of contamination of the test water (the degree of contamination of harmful substances) with a water quality index defined as follows.

Water quality index = current current value / (span current−zero current) In this case, when the water quality index becomes a value of 10% or more, the control unit 44 issues an alarm.

Using the values of the zero current and the span current, it is possible to estimate the degree of deterioration of the oxidation electrodes 35 and 36 themselves, and the control unit 44 divides the value of the span current-zero current into several stages to degrade the deterioration. Oxygen electrodes 35 and 36
Is a guide for replacement.

That is, as described above, the oxygen electrodes 35, 3
When iron oxides adhere to 6, the span current decreases.
In addition, when the activity of the iron bacterium decreases, the zero current increases. As a result, the difference between the span current and the zero current decreases with time. The measure of the degree of deterioration of the oxygen electrode is based on this principle.

In FIG. 1, a closed type bag made of polyethylene or Teflon may be used as the iron liquid tank 2. At this time, the iron liquid in the bag is supplied to the pipe 3 via the pipes 8 and 10 and the pipe tubes 23 and 24.
The constant flow rate can be supplied to the flow cells 33 and 34 without touching the outside air from the outside and outside air 32, thereby preventing the iron liquid from being oxidized and deteriorated. By using two 5-liter Tedla bags in parallel, maintenance-free operation for about three months is possible. The cleaning liquid having a pH of 0.4 is not deteriorated by oxidation even in the cleaning liquid tank 1, so that it is not necessary to put the cleaning liquid in a sealed bag, and a maintenance capacity of about 6 months can be achieved with a capacity of 10 liters.

During the operation, the effluents from the flow cells 33 and 34 are acidic water having a pH of around 3, and this effluent is diluted with the branch water from the raw water at the time of water supply to dilute the pH around neutral. Return to and discharge. As a result, the effluent does not pollute the intake of the water treatment plant or the river.

In the configuration shown in FIG. 1, switching of the operation of the flow cells 33 and 34, switching of the operation of the pinch valves 15-22, and switching of the operation of the tube pumps 27-30 are all performed by the control unit 44. .

[0066]

As described above, according to the present invention, a water purification plant,
Alternatively, when various harmful substances are mixed in the test water from the intake port of the sewage treatment plant, the mixing of these harmful substances can be detected quickly and with high sensitivity. In addition, compared to conventional fish behavior monitoring type harmful substance detection systems, the price of the equipment itself and its maintenance and management costs can be significantly reduced, and a highly reliable harmful substance detection system should be provided. Can be.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing one embodiment of a biosensor type abnormal water quality detection device according to the present invention.

FIG. 2 is a view showing an operation pattern of the biosensor type abnormal water quality detection device according to the present invention.

FIG. 3 is a diagram showing another operation pattern of the biosensor type abnormal water quality detection device according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Cleaning liquid tank 2 Iron liquid tank 3 Water tank 4 Water intake tank 4a Filtration device 15,16,17,18,19,20,21,22 Pinch valve 27,28,29,30 Tube pump 33,34 Flow cell 35,36 Oxygen Electrode 35a, 36a Membrane filter 42, 43 Ion meter 44 Controller

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G01N 33/18 G01N 27/30 355 (72) Inventor Masao Kaneko No. 1, Toshiba-cho, Fuchu-shi, Tokyo Stock (72) Minoru Fujisawa, Inventor Toshiba, Fuchu, Tokyo, Japan Inside Fuchu Office, Toshiba Corporation (72) Inventor, Hirotaka Uno 1, Toshiba, Fuchu, Tokyo, Japan Toshiba, Fuchu Office (72) Inventor Akira Hiramoto 1-1-1, Shibaura, Minato-ku, Tokyo Inside the Toshiba head office

Claims (11)

[Claims] An oxygen electrode and a membrane filter attached to a tip of the oxygen electrode and holding an iron-oxidizing bacterium, detecting at least a mixture of organic substances, and at least one pair of flow cells arranged in parallel with each other. , A cleaning liquid line that supplies a cleaning liquid to each flow cell, an iron liquid line that supplies an iron liquid to each flow cell, a test water line that supplies a test water to each flow cell, and a flow cell, a cleaning liquid line, an iron liquid line, and the like. And a control unit for driving and controlling the test water line, wherein the control unit includes:
Put the other flow cell in the cleaning state, supply the iron liquid to the one flow cell side via the iron liquid line and supply the test water via the test water line at the same time, and supply the test water to the other flow cell side via the cleaning liquid line. A biosensor type abnormal water quality detection device, which supplies a cleaning liquid and a test water via a test water line. 2. A biosensor type abnormal water quality detecting device, wherein iron oxidizing bacteria are applied to a membrane filter by a suction filtration method. 3. An iron solution comprising a sulfuric acid ferrous sulfate solution, wherein the ferrous sulfate solution comprises, as inorganic metal ions,
2. The biosensor type abnormal water quality detecting device according to claim 1, wherein the biosensor-type abnormal water quality detecting device contains a salt of K, Mg, and Ca, and also contains a certain amount of ammonium sulfate. 4. The biosensor type abnormal water quality detection device according to claim 1, further comprising a water intake tank having a filtration device and supplying test water to each flow cell. 5. The biosensor type abnormal water quality detecting device according to claim 4, wherein the filtering device has a built-in hollow fiber membrane. 6. The biosensor type abnormal water quality detecting device according to claim 4, wherein the filtering device is used after being automatically washed periodically. 7. The pH of the iron solution and the cleaning solution is set to a constant value so that the pH in each flow cell is an optimum pH value for the inhabitation of the iron-oxidizing bacteria, and the control unit controls the cleaning solution in the cleaning solution line and the iron solution line. The biosensor type abnormal water quality detection device according to claim 1, wherein the amounts of the test solution in the test solution and the iron solution are adjusted. 8. The biosensor type abnormal water quality detecting apparatus according to claim 1, wherein the temperature in each flow cell is maintained at 30 ± 5 ° C., which is the optimum temperature for inhabiting the iron-oxidizing bacteria. 9. A water supply line for supplying water to each flow cell is connected, and the control unit supplies water to the flow cell at an initial stage when the iron solution is flowing and when the cleaning solution is flowing, so that zero current and zero current are supplied. The biosensor type abnormal water quality detecting device according to claim 1, wherein the calibration of the span current is performed. 10. An iron liquid tank comprising a sealed polyethylene or Teflon (registered trademark) bag, wherein the iron liquid is kept constant from the bag by a tube pump provided in an iron liquid line without being exposed to outside air. 2. The biosensor type abnormal water quality detection device according to claim 1, wherein the liquid is sent to the flow cell at each flow rate. 11. A discharge line is connected to each flow cell, and a dilution line is attached to the discharge line. The discharge from each flow cell is diluted with the diluent from the dilution line to have a pH of 6 or more. 2. The biosensor type abnormal water quality detecting device according to claim 1, wherein the device is discharged in such a manner.