CN101241103B - Abnormal water detecting device and poison response sensitivity prediction method thereof - Google Patents
Abnormal water detecting device and poison response sensitivity prediction method thereof Download PDFInfo
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- CN101241103B CN101241103B CN2008100054006A CN200810005400A CN101241103B CN 101241103 B CN101241103 B CN 101241103B CN 2008100054006 A CN2008100054006 A CN 2008100054006A CN 200810005400 A CN200810005400 A CN 200810005400A CN 101241103 B CN101241103 B CN 101241103B
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Abstract
The present invention provides a biosensor type abnormal water quality detector, the front end keeping the oxygen electrode of the microbial film of the iron-oxidizing bacteria is dipped in the detected water, the oxygen electrode detects the oxygen quantity passing through the microbial film, when the oxygen quantity exceeds the threshold, the existing mixture of the hazardous substance is detected. Wherein, a substance having no hazard to human but provisionally generating damage to iron-oxidizing bacterium is used as a simulating poison in a low concentration, added into the detected water from a simulating poison supplying part in a certain concentration. In the state of adding the simulating poison in the detected water, the oxygen quantity passing through the microbial film is input according to the detection value of the oxygen electrode, and a responsiveness prediction mechanism predicts the responsiveness to the specific poisonous substance according to the result.
Description
Technical field
The present invention relates in water purification field or sewage-farm etc., use biology sensor to survey the biosensor type detector set for anomalous water and the poisonous substance response Forecasting Methodology thereof of the objectionable impurities of sneaking into from its intake.
Background technology
In the former water purification field,, be water intaking from river water etc., and make this take water to supply with potable water through the sedimentation and filtration groove as the processing of routine.When inexpungible objectionable impurities in such conventional processing, when for example each heavy metal species and such material such as agricultural chemicals and Environmental Hormone are sneaked in the river water, will occur fetches water stops such emergency circumstance.
On the other hand, in the sewage-farm, if because of accident or careless; In the draining in factory or chemical plant, sneak into various heavy metal ion or organic solvent and arsenic cyanogen etc., and they are flowed in the draining, then the active sludge microorganism in the sewage treatment process receives bigger infringement; Consequently; The activity of active sludge reduces, thereby before processing power is recovered, needs great amount of time.
Therefore, in water purification field and sewage-farm etc., under the situation that above-mentioned various objectionable impuritiess are sneaked into, requirement can be rapidly and is detected the device that flows into water in high sensitivity.
According to such requirement, the general device that uses has in the water purification field: fish action monitor-type poisonous substance pick-up unit; Perhaps on dissolved oxygen electrode, install various microbial films, detect the device of poisonous substance from the measurement of its respiratory activity.In addition, in the sewage-farm, the various sensors of surveying the draining sneak into particular chemicals are arranged on the intake separately etc.
Among them, the set fish action monitor-type poisonous substance pick-up unit in water purification field needed spended time before fish poisonous substance being reacted, so its detection needs long time.In addition, the reaction sensitivity of fish also has a great difference because of the kinds of the fish raised and individual difference and the ambient condition of raising.Moreover as far as fish action monitor-type poisonous substance pick-up unit, existing problem is that its device itself is huge, at a large amount of necessary expense of the raisings of fish and management aspect needs etc.
Therefore, among biosensor type detector set for anomalous water is being developed.As an example, the iron-oxidizing bacterium that often will make objectionable impurities and assorted bacterium etc. be difficult to breed and can under lower pH value, move uses as probe.It is that the spy opens 2004-271441 communique (below be called patent documentation 1) that a day disclosure special permission communique is for example arranged.
In this biosensor type water monitoring device, at first, utilize air or oxygen concentration are adjusted into certain gas, to the water that will the check gas that in the pneumatic water tank that looses, looses, thereby make dissolved oxygen concentration be in saturated state.Water to be detected to such is supplied with acid solution, and supply simultaneously contains the solution of ferrous sulphate and mixes with water to be detected.This mixed liquor is under the saturated state at dissolved oxygen concentration, and it is flowed in the measuring flume.
In measuring flume, be provided with oxygen electrode, still,, often make the water to be detected dissolved oxygen concentration that reaches capacity, thereby make the output maximal value of oxygen electrode become stable through air or oxygen concentration being adjusted into the supply of certain gas.Above-mentioned oxygen electrode is provided with the state of installing microbial film and this front end at its front end and being immersed in the water to be detected in the measuring flume.Microbial film maintains the iron-oxidizing bacterium (being also referred to as iron bacteria) that can utilize oxygen and ferrous sulphate become iron sulfate.The electric power output that comes from this oxygen electrode is able to amplify and conversion through transform operation mechanism, can distinguish the exception water quality of water to be detected after the computing of stipulating.
In measuring flume, the microbial film that contacts with water to be detected is under the effect of iron bacteria, and the chemical equation of caused chemical behavior is following:
4FeSO
4+O
2+2H
2SO
4→2Fe
2(SO
4)
3+2H
2O (1)
In above-mentioned (1), 2Fe
2(SO
4)
3Ionization in water generates Fe
3+Ion.This Fe
3+Ion further and water (H
2O) reaction generates ferric hydroxide Fe (OH)
3And precipitate.
In this abnormal water quality detecting device, to being the mixed liquor of sending into water to be detected and iron liquid on the dissolved oxygen electrode installed of probe with the iron-oxidizing bacterium, and monitoring comes from the electric power output of oxygen electrode when sending into this mixed liquor.That is to say, in water to be detected, do not sneak under the situation of objectionable impurities, owing to the oxidation of the dissolved oxygen DO in the water to be detected because of iron consumes, so the numerical value that is detected by oxygen electrode is very low.In contrast, in water to be detected, sneaked under the situation of water-soluble objectionable impurities, this objectionable impurities reduces the respiratory activity of the iron-oxidizing bacterium on the microbial film.Consequently, owing to do not seen through microbial film, increase so arrive the oxygen amount of oxygen electrode, thereby the current value that oxygen electrode is exported just increases by the oxygen that iron-oxidizing bacterium consumed.Therefore, through comparing the output current value and the threshold value of oxygen electrode, just can judge whether sneaking into of objectionable impurities.
In addition, if such biosensor type detector set for anomalous water turns round continuously, the dirty material in the water then to be detected will adhere to and be deposited on the inwall of each delivery tube.In addition, the part of the ferrous sulphate in the iron liquid is oxidized to iron sulfate, and this also can progressively deposit.These will cause the providing and delivering obstruction of piping or reductions of the sensitivity that exception water quality detects, thus accuracy of detection might be reduced.For this reason; Carried out following " acid elution "; Promptly in the water ingress pipe to be detected of sending into the water to be detected and the mixed liquor of the solution that contains ferrous sulphate, supply with acid solution, make the dirty material and the iron oxide that adhere on the current to be detected roads such as water ingress pipe to be detected and measuring flume and deposit be able to remove and discharge.
In such biosensor type detector set for anomalous water, there are deviation in the thalline quantity and the activity of the iron-oxidizing bacterium that microbial film kept, are difficult to thalline quantity is often kept certain with active.Therefore,, see on the whole that its degree of damage is different for a certain certain density poisonous substance from microbial film.In a fairly large number of situation of thalline, whole as microbial film, the influence of poisonous substance reduces.In addition, each thalline for the stronger situation of the tolerance of poisonous substance under, for the poisonous substance of same concentration, the respiratory activity of iron-oxidizing bacterium can not reduce too much.Consequently, not by iron-oxidizing bacterium consumption but to see through microbial film whole and to reach the oxygen amount of oxygen electrode different, the current value of oxygen electrode output simultaneously also is different for the poisonous substance of same concentration.
In addition, in water quality monitoring, continue sometime at current value and under the situation about exporting, will send the water quality anomalous signals of water to be detected more than or equal to a certain threshold value.This is the mistake alarm of accompanying for the rising with the immediate current value that the influence that prevents when the water quality monitoring because of the bubble that flows into oxygen electrode etc. produces, and generally speaking, the thalline quantity on the microbial film is many more, just feels bad the Effects of Noise of bubble etc. more.And then as stated; Because there are deviation in the thalline quantity and the activity of the iron-oxidizing bacterium that microbial film kept; For a certain certain density poisonous substance, different from the current value that oxygen electrode is exported, so must change the unusual threshold value of water quality according to the state of microbial film.Therefore, for the threshold value that determines that water quality is unusual, the state of grasping microbial film is indispensable.
In order to hold the thalline quantity on the microbial film, must temporarily take microbial film from electrode, adopt microscope to calculate its quantity practically.But this work itself needs considerable time, and in the front and back of work, because thalline quantity and activation of microorganism are changed, thereby be unpractical.
In addition, flow out incident about the particular chemicals that on the river, takes place, the material with representative has cyano compound; But; In order to hold the poisonous substance response of microbial film, make in the cyanic acid inflow device as routine test, this will be accompanied by difficulty aspect its operation and the discharge opeing processing.
Summary of the invention
The object of the present invention is to provide a kind of abnormal water quality detecting device and poisonous substance response sensitivity prediction method thereof; Its use simulation poisonous substance harmless and its processing ease under low concentration is held the poisonous substance response of microbial film, and can predict the poisonous substance response for specific noxious material according to its result.
The present invention relates to a kind of abnormal water quality detecting device; It is a kind of biosensor type detector set for anomalous water; It will be immersed in the water to be detected at the said fore-end that fore-end has an oxygen electrode of the microbial film that is keeping iron-oxidizing bacterium; Detect the oxygen amount that sees through said microbial film with said oxygen electrode, when this oxygen amount surpasses threshold value, just detect and have sneaking into of harmful substances; Said abnormal water quality detecting device is characterised in that it comprises: simulation poisonous substance supply unit, and it, and joins in the water to be detected with a certain concentration as the simulation poisonous substance with material harmless under low concentration but that will temporarily produce infringement for iron-oxidizing bacterium; And response sensitivity projecting body; It is added under the state in the said water to be detected at said simulation poisonous substance; Detected value according to said oxygen electrode is imported the oxygen amount through said microbial film, and according to the response sensitivity of this prediction of result for specific noxious material.
In abnormal water quality detecting device of the present invention, also can further set up more new mechanism of threshold value, it is based on the response sensitivity of being predicted according to the response sensitivity projecting body, upgrades the threshold value for said oxygen amount to be detected.
In addition, in abnormal water quality detecting device of the present invention, also can further be built up under the situation of response sensitivity smaller or equal to predefined reference value of being predicted according to the response sensitivity projecting body, the mechanism of the replacing of microbial film is carried out in report.
Moreover in abnormal water quality detecting device of the present invention, the simulation poisonous substance is a nitrous acid, and the prediction of response sensitivity projecting body is to the response sensitivity of cyanic acid.
The present invention relates to a kind of poisonous substance response sensitivity prediction method of abnormal water quality detecting device; It is a kind of poisonous substance response sensitivity prediction method of biosensor type detector set for anomalous water; Said biosensor type detector set for anomalous water will be immersed in the water to be detected at the said fore-end that fore-end has an oxygen electrode of the microbial film that is keeping iron-oxidizing bacterium; Detect the oxygen amount that sees through said microbial film with said oxygen electrode; When this oxygen amount surpasses threshold value, just detect and have sneaking into of harmful substances; The poisonous substance response sensitivity prediction method of said abnormal water quality detecting device is characterised in that: its with harmless under low concentration but the material that will temporarily produce infringement for iron-oxidizing bacterium as the simulation poisonous substance; And join in the water to be detected with a certain concentration; Measure the oxygen amount that sees through said microbial film according to the detected value of said oxygen electrode then, and according to the response sensitivity of this prediction of result for specific noxious material.
In addition; In the poisonous substance response sensitivity prediction method of abnormal water quality detecting device of the present invention; The activation recovering operation can be set, and it adds the simulation poisonous substance in water to be detected, and behind the response sensitivity of prediction for specific noxious material; On said microbial film, supply with the solution that contains ferrous sulphate, up to the activation recovering original state of microbial film.
Moreover, in the poisonous substance response sensitivity prediction method of abnormal water quality detecting device of the present invention, in water to be detected, add nitrous acid as the simulation poisonous substance, with the response of prediction for cyanic acid.
According to the present invention; Because through using the simulation poisonous substance of harmless and its processing ease; Poisonous substance response sensitivity with accurate assurance microbial film; And can predict poisonous substance response sensitivity for specific noxious material according to its result, thereby can access correct detection response, thus can improve detection performance as abnormal water quality detecting device.
Description of drawings
Fig. 1 is the whole body pie graph of an embodiment of expression abnormal water quality detecting device of the present invention.
Fig. 2 is the whole pie graph of other embodiment of expression abnormal water quality detecting device of the present invention.
Fig. 3 is the curve map of the relation between expression nitrite nitrogen concentration of the present invention and the water coning.
Fig. 4 is the curve map of the relation between expression cyanic acid concentration of the present invention and the water coning.
Symbol description:
2 water ingress pipes to be detected
4 measuring flumes
7 diffusing pneumatic water tanks
9 microbial films
10 oxygen electrodes
11 transform operation mechanisms (response projecting body)
20 nitrous acid solution bags (pack) (simulation poisonous substance supply unit)
Embodiment
Use accompanying drawing below, carry out detailed explanation with regard to an embodiment of abnormal water quality detecting device of the present invention.
Fig. 1 representes that the integral body of this embodiment constitutes.In Fig. 1, the 7 expressions pneumatic water tank that looses, the former water at the water source that check (for example, the inflow in river or to the inflow water of water purification field, to the inflow water in sewage-farm etc.) be by means of former water charge pump 18, and supply with via ingress pipe 17.In this diffusing pneumatic water tank 7, the former water for supplying with is adjusted into certain gas by gas feeder 8 air supplies or oxygen concentration, makes it become the water to be detected that dissolved oxygen concentration is in state of saturation.Dissolved oxygen concentration is in the water to be detected of state of saturation in this wise via solenoid valve 22, is transported to water ingress pipe 2 to be detected by means of water charge pump 6 to be detected.
4 expression measuring flumes are connected on the water ingress pipe 2 to be detected, to import water to be detected.This mensuration groove 4 is adjusted into set point of temperature through temperature regulator 5.In addition, in measuring flume 4, be provided with the oxygen electrode 10 that microbial film 9 is installed in front end.On microbial film 9, maintain and to utilize oxygen ferrous sulphate to be become the iron-oxidizing bacterium (also claiming iron bacteria) of iron sulfate.Oxygen electrode 10 is provided with the state that the leading section that is installed on this microbial film 9 is immersed in the water to be detected in the measuring flume 4.In addition, on oxygen electrode 10, be connected with transform operation mechanism 11, the electric power output that also conversion is taken out from oxygen electrode 10 is amplified by this transform operation mechanism 11, after the computing of stipulating, as after to state the water quality of such differentiation water to be detected unusual.
12 expression acid solution bags; 13 expression iron liquid bags; 20 expression microbial activities reduce the liquid bags, and they are connected with common soup ingress pipe 19 via corresponding solenoid valve 14,15,21 with it, are connected with above-mentioned water ingress pipe 2 to be detected via soup charge pump 16 then.
At this, by microbial activity reduce microbial activity that liquid bag 20 supplies with reduce liquid contain under low concentration harmless but will temporarily produce the material of infringement to iron-oxidizing bacterium, in this embodiment, as after be used as the simulation poisonous substance stating.That is to say; Microbial activity reduces liquid bag 20 and plays a role as following simulation poisonous substance supply unit:, and join in the water to be detected with a certain concentration as the simulation poisonous substance with material harmless under low concentration but that will temporarily produce infringement to iron-oxidizing bacterium.
As stated, water to be detected is adjusted into certain gas by means of air or the oxygen concentration supplied with by gas feeder 8 in diffusing pneumatic water tank 7, often be in the state of saturated dissolved oxygen concentration.For water to be detected, its details holds the back narration, still; When common testing, supply with the solution that contains ferrous sulphate from iron liquid bag 13, and after state washing the time; Supply with acid solution from acid solution bag 12; And then when differentiating the activity of iron-oxidizing bacterium, reduce liquid bag 20 from microbial activity and supply with microbial activity reduction liquid, mix with water to be detected in each comfortable water ingress pipe 2 to be detected.These mixed liquors are set to as above-mentioned at dissolved oxygen concentration under the state of state of saturation, flow in the measuring flume 4 from water ingress pipe 2 to be detected.
The water to be detected that is directed in the above-mentioned measuring flume 4 must often be in the state of saturated dissolved oxygen concentration, thereby makes the maximal value of the output of oxygen electrode 10 be able to stablize.Saturated dissolved oxygen concentration is owing to changing with fluid temperature, so as above-mentioned, importantly through temperature regulator 5 measuring flume 4 is maintained certain temperature.
In addition, in measuring flume 4, the front end that is arranged at oxygen electrode 10, maintain and can utilize oxygen ferrous sulphate to be become between the microbial film 9 and water to be detected of iron bacteria of iron sulfate, with the reaction below producing.The iron bacteria that is kept by microbial film 9 for example is Thiobacillus ferrooxidans (Thiobacillus ferrooxidans).The reaction equation of this chemical behavior as above-mentioned (1) formula, 2Fe
2(SO
4)
3Ionization in water generates Fe
3+Ion.This Fe
3+Ion and then and water (H
2O) reaction generates ferric hydroxide Fe (OH)
3And precipitate.
In addition, the iron bacteria as microbial film 9 is kept except that Thiobacillus ferrooxidans (Thiobacillus ferrooxidans), also can be suitable for all microorganisms of the function with above-mentioned chemical equation.For example, confirmed gallionella ferruginea (Gallionellaferruginea), soak ore deposit bacterium (Leptospirillum ferrooxidans), Leptothrix (Leptothrix), Sphaerotilus (Sphaerotilus) etc. and be fit to.
The activity of iron bacteria is that the amount of oxidation of iron might also change through Influence of Temperature, so measuring flume 4 preferably by means of temperature regulator 5, is able to stable temperature to keep the activity that makes iron bacteria.Being arranged on of temperature regulator 5 says it also is very important on this meaning.
So; Abnormal water quality detecting device is by means of water charge pump 6 to be detected and soup charge pump 16 and to being installed on the dissolved oxygen electrode 10 of iron-oxidizing bacterium as probe; Carry the mixed liquor of water to be detected and iron liquid, and when sending into this mixed liquor, monitor the electric power output that comes from oxygen electrode 10.In addition, in water to be detected, sneaked under the situation of water miscible objectionable impurities, this objectionable impurities will make the respiratory activity of the iron-oxidizing bacterium on the microbial film 9 reduce.Consequently, owing to do not seen through microbial film 9, increase so arrive the oxygen amount of oxygen electrode 10 by the oxygen that iron-oxidizing bacterium consumed.Consequently, because the current value increase of oxygen electrode 10 outputs, thereby can judge sneaking into of objectionable impurities thus.
In above-mentioned formation; When the toxic reaction of predicted anomaly water quality detecting device; At first; Supply with acid solutions via solenoid valve 14, soup ingress pipe 19 and soup charge pump 16 to water ingress pipe to be detected 2 from acid solution bag 12, implementing acid elution, thereby remove and discharge the dirty material and the iron oxide of adventitious deposit on current to be detected roads such as water ingress pipe 2 to be detected and measuring flume 4.During acid elution, the ferrous sulphate that absorbs owing to iron-oxidizing bacterium does not exist, so the dissolved oxygen DO in the water to be detected can not be consumed.For this reason, the dissolved oxygen content in the output valve of oxygen electrode 10 and the water to be detected becomes greatly pro rata, and this just becomes span (span) corrected value.
Secondly, supply with the solution that contains ferrous sulphate via solenoid valve 15, soup ingress pipe 19 and soup charge pump 16 to water ingress pipe 2 to be detected from iron liquid bag 13.If iron-oxidizing bacterium is active normal, then since oxygen be consumed and ferrous sulphate be oxidized to iron sulfate, so near very near oxygen electrode, the dissolved oxygen DO in the water to be detected is roughly zero.At this moment, it is minimum that the output valve of oxygen electrode 10 reaches, and this just becomes the zero correction value.The output area of oxygen electrode 10 when the difference of span corrected value and zero correction value becomes the device operation.
Secondly, under the situation of the activity that detects the iron-oxidizing bacterium that microbial film 9 kept, supply with the active liquid that reduce of microbial films via solenoid valve 21, soup ingress pipe 19 and soup charge pump 16 to water ingress pipe 2 to be detected from the active liquid bag 20 that reduces of microbial film.Through the supply of this liquid, the part of the iron-oxidizing bacterium that microbial film 9 is kept is with suffer damage instantaneously.For this reason, can not oxygen consumed and ferrous sulphate is oxidized to iron sulfate, the oxygen that does not have to consume is detected on oxygen electrode 10.
For the output area of above-mentioned oxygen electrode 10, represent that the output valve of current oxygen electrode 10 is big more, then more oxygen can not be consumed and see through microbial film 9.In the case, from seeing on the whole of microbial film 9, the thalline negligible amounts of expression iron-oxidizing bacterium, perhaps less for the tolerance of poisonous substance.In other words, expression is very strong for the detection sensitivity of poisonous substance.
In contrast, if the output area of oxygen electrode 10 and output numerical value is smaller, then expression is not consumed and to see through the oxygen of microbial film 9 less.This expression sees on the whole that from microbial film 9 iron-oxidizing bacterium can suffer damage hardly.That is to say that the increase of the thalline quantity of expression iron-oxidizing bacterium is too much, or bigger for the tolerance of poisonous substance.In other words, expression is blunt for the detection sensitivity of poisonous substance.
So; Supply with that microbial film is active to be reduced liquid and detect the activity of the iron-oxidizing bacterium that microbial film 9 kept; Mean the response sensitivity for poisonous substance of detection based on oxygen electrode 10; Transform operation mechanism 11 has the function as the response sensitivity projecting body, i.e. input comes from the detected value of oxygen electrode 10, thereby prediction is for the response sensitivity of specific noxious material.
In addition, utilizing the output area of the oxygen electrode of obtaining in this wise 10 and the ratio of output valve is response sensitivity, holds the microbial film state of 9 every days, just can suitably upgrade the unusual threshold value of water quality that is used to report water to be detected according to this state.That is to say that transform operation mechanism 11 also can be based on the response sensitivity of being predicted according to above-mentioned response sensitivity projecting body, as upgrade for the threshold value of the above-mentioned threshold value that is detected the oxygen amount more new mechanism play a role.In addition, if the ratio of the output area of oxygen electrode 10 and output valve be response sensitivity smaller or equal to a certain reference value, then preferably change microbial film 9.Therefore, when the response sensitivity of being predicted according to the response sensitivity projecting body during smaller or equal to predefined reference value, transform operation mechanism 11 also plays a role as the mechanism that the replacing of microbial film is carried out in report.
Moreover; After the state of grasping mentioned microorganism film 9; Setting via solenoid valve 15, soup ingress pipe 19 and soup charge pump 16, to the water ingress pipe to be detected 2 temporary transient operations of supplying with the solution that contains ferrous sulphate, is an original state up to the activation recovering of microbial film 9 from iron liquid bag 13.Thus, just can eliminate iron-oxidizing bacterium and reduce the instantaneous influence that suffers damage and brought of liquid because of microbial film is active.That is to say, will simulate poisonous substance and add in the water to be detected that after the response sensitivity of prediction for specific noxious material, implementing to supply with the solution that contains ferrous sulphate to above-mentioned microbial film is the activation recovering operation of original state up to the activation recovering of microbial film.
At this, the active reduction of the microbial film liquid of being supplied with by bag 13 is the liquid of iron-oxidizing bacterium being given to damage instantaneously, and it is dead that iron-oxidizing bacterium itself is taken place.For example, if the nitrous acid solution of low concentration then can confirm to suppose to stop the supply of its liquid, the activity of iron-oxidizing bacterium will return to original state.
In addition, in this embodiment, reduce in the liquid bag 20 in that microbial film is active, reduce the liquid, also comprise the same solution that contains ferrous sulphate of concentration and iron liquid bag 13 except microbial film is active.
Through above enforcement; Can when operation device make termly to microbial film 9 on iron-oxidizing bacterium with the infringement of moment but flow for the active liquid (simulation poisonous substance) that reduces of the harmless microbial film of the mankind; Estimating its response sensitivity, thus the threshold value of timely replacement water quality exception reporting.Moreover, also can circulate a notice of the microbial film 9 of the sensitivity that can not guarantee to use as the water quality abnormality detection is changed, to realize the detection of long-term high-precision exception water quality.
Below the embodiment represented with regard to Fig. 2 describe.In the embodiment that Fig. 2 representes, when the embodiment with Fig. 1 compared, the active reduction of microbial film liquid bag 20 was not with soup charge pump 16 but is connected with water charge pump 6 to be detected via solenoid valve 21.In the case, in the active reduction of microbial film liquid 20, do not comprise the solution that contains ferrous sulphate.
In this embodiment, also be when operation device make termly to microbial film 9 on iron-oxidizing bacterium with the infringement of moment but flow for the active liquid (simulation poisonous substance) that reduces of the harmless microbial film of the mankind.Then, through estimating the response sensitivity of microbial film, threshold value that can timely replacement water quality exception reporting, and then can circulate a notice of the microbial film 9 of the sensitivity that can not guarantee to use as the water quality abnormality detection is changed.Therefore, can realize the detection of long-term high-precision exception water quality.
Situation about will explain below is: use nitrous acid solution as the active solution (simulation poisonous substance) that reduces of microbial film; With its as the simulation poisonous substance from wrapping 20, to detect for reaction sensitivity as the cyanic acid of specific poisonous substance through water ingress pipes 2 to be detected and be supplied to microbial film 9.
Supplying with the microbial film 9 of nitrous acid solutions from wrapping 20, iron-oxidizing bacterium suffers damage instantaneously, and wherein a part can not oxygen consumed and ferrous sulphate is oxidized to iron sulfate, not have the oxygen of consumption to be detected by oxygen electrode 10, and outputs to transform operation mechanism 11.The output valve of this oxygen electrode 10 is big more with respect to the output area of above-mentioned oxygen electrode 10, sees through microbial film 9 with regard to not consuming more oxygen more.In the case, the thalline negligible amounts of the iron-oxidizing bacterium on the expression microbial film 9, perhaps less for the tolerance of poisonous substance.The output area of this oxygen electrode 10 is water coning (%) with likening to of numerical value of output, is set the index of the possibility of sneaking into for the expression poisonous substance.These computings can be carried out through above-mentioned transform operation mechanism 11; Therefore; This transform operation mechanism 11 plays a role as following response sensitivity projecting body as above-mentioned; Promptly be added under the state in the water to be detected, import oxygen amount through microbial film 9 according to the detected value of oxygen electrode 10 at said simulation poisonous substance, thereby according to the response sensitivity of this prediction of result for specific noxious material.
Fig. 3 and Fig. 4 be expression for during with 2 different microbial film A, B that use down with environment, separately for the response instance of nitrous acid and cyanic acid.Can know from this figure, nitrite nitrogen is 0.19mg/l, cyanic acid is 0.025mg/l for making water coning rise to 20% needed concentration.Consequently, for the influence degree of iron-oxidizing bacterium when equal, the cyanic acid of 0.025mg/l is equivalent to the relation of the nitrite nitrogen of 0.19mg/l and just sets up.
Based on this relation,,, can infer the response sensitivity of this microbial film 9 under the cyanic acid concentration of 0.025mg/l thus to study its response sensitivity from the nitrite nitrogen of the microbial film 9 supply 0.19mg/l of nitrous acid solution bag 20 to using.Utilize this result, just can set the unusual threshold value of water quality again.
In addition; In above-mentioned embodiment; As simulation poisonous substance illustration nitrous acid; And as specific noxious material illustration cyanic acid, but the present invention is not limited thereto, goes for all simulation poisonous substances (under low concentration harmless but be the material that be harmful to iron-oxidizing bacterium) and iron-oxidizing bacterium and produce the particular chemicals of response.
Like this; The present invention, and joins in the water to be detected with a certain concentration as the simulation poisonous substance with harmless under low concentration but the material that will temporarily produce infringement to iron-oxidizing bacterium, according to the detected value of above-mentioned oxygen electrode; Measure the oxygen amount that sees through the mentioned microorganism film; According to the response sensitivity of its prediction of result, detect response accurately so can access, thereby the detection performance as abnormal water quality detecting device is improved again for specific noxious material.
Claims (7)
1. abnormal water quality detecting device; It is a kind of biosensor type detector set for anomalous water; It will be immersed in the water to be detected at the said fore-end that fore-end has an oxygen electrode of the microbial film that is keeping iron-oxidizing bacterium; Detect the oxygen amount that sees through said microbial film with said oxygen electrode, when this oxygen amount surpasses threshold value, just detect and have sneaking into of harmful substances; Said abnormal water quality detecting device is characterised in that it comprises:
Simulation poisonous substance supply unit, it, and joins in the water to be detected with a certain concentration as the simulation poisonous substance with material harmless under low concentration but that will temporarily produce infringement for iron-oxidizing bacterium; And
The response sensitivity projecting body; It is added under the state in the said water to be detected at said simulation poisonous substance; Detected value according to said oxygen electrode is imported the oxygen amount through said microbial film, and according to the response sensitivity of this prediction of result for specific noxious material.
2. abnormal water quality detecting device according to claim 1 is characterized in that: also have more new mechanism of threshold value, it is based on the response sensitivity of being predicted according to the response sensitivity projecting body, upgrades the threshold value for said oxygen amount to be detected.
3. abnormal water quality detecting device according to claim 1 and 2; It is characterized in that: also have under the situation of response sensitivity smaller or equal to predefined reference value of being predicted according to the response sensitivity projecting body, the mechanism of the replacing of microbial film is carried out in report.
4. abnormal water quality detecting device according to claim 1 and 2 is characterized in that: the simulation poisonous substance is a nitrous acid, and the prediction of response sensitivity projecting body is to the response sensitivity of cyanic acid.
5. the poisonous substance response sensitivity prediction method of an abnormal water quality detecting device; It is a kind of poisonous substance response sensitivity prediction method of biosensor type detector set for anomalous water; Said biosensor type detector set for anomalous water will be immersed in the water to be detected at the said fore-end that fore-end has an oxygen electrode of the microbial film that is keeping iron-oxidizing bacterium; Detect the oxygen amount that sees through said microbial film with said oxygen electrode; When this oxygen amount surpasses threshold value, just detect and have sneaking into of harmful substances; The poisonous substance response sensitivity prediction method of said abnormal water quality detecting device is characterised in that:
Its with harmless under low concentration but the material that will temporarily produce infringement for iron-oxidizing bacterium as the simulation poisonous substance; And join in the water to be detected with a certain concentration; Measure the oxygen amount that sees through said microbial film according to the detected value of said oxygen electrode then, and according to the response sensitivity of this prediction of result for specific noxious material.
6. the poisonous substance response sensitivity prediction method of abnormal water quality detecting device according to claim 5; It is characterized in that: be provided with the activation recovering operation; It adds the simulation poisonous substance in water to be detected; And behind the response sensitivity of prediction for specific noxious material, on said microbial film, supply with the solution that contains ferrous sulphate, up to the activation recovering original state of microbial film.
7. according to the poisonous substance response sensitivity prediction method of claim 5 or 6 described abnormal water quality detecting devices, it is characterized in that: in water to be detected, add nitrous acid as the simulation poisonous substance, with the response of prediction for cyanic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP029389/2007 | 2007-02-08 | ||
| JP2007029389A JP4410264B2 (en) | 2007-02-08 | 2007-02-08 | Abnormal water quality detection device and its toxic response sensitivity prediction method |
Publications (2)
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| CN101241103B true CN101241103B (en) | 2012-03-21 |
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| CN2008100054006A Expired - Fee Related CN101241103B (en) | 2007-02-08 | 2008-02-05 | Abnormal water detecting device and poison response sensitivity prediction method thereof |
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| CN (1) | CN101241103B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010204043A (en) * | 2009-03-05 | 2010-09-16 | Toshiba Corp | Water quality monitoring device |
| CN101871928B (en) * | 2010-06-17 | 2013-11-13 | 浙江工业大学 | Abnormal water detection method based on immune negative selection |
| CN102252881A (en) * | 2011-04-27 | 2011-11-23 | 杭州慕迪科技有限公司 | On-line monitoring device of cyanides in water |
| CN112461338B (en) * | 2020-11-18 | 2021-12-03 | 珠海格力电器股份有限公司 | Liquid level detection abnormity judgment device and method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0441327A2 (en) * | 1990-02-05 | 1991-08-14 | Fuji Electric Co., Ltd. | Toxic substance-detecting device and water quality-monitoring system employing the same |
| CN1290859A (en) * | 2000-10-25 | 2001-04-11 | 中国科学院武汉病毒研究所 | Method and device for on-line monitoring waste water |
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2007
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0441327A2 (en) * | 1990-02-05 | 1991-08-14 | Fuji Electric Co., Ltd. | Toxic substance-detecting device and water quality-monitoring system employing the same |
| US5160604A (en) * | 1990-02-05 | 1992-11-03 | Fuji Electric Co., Ltd. | Toxic substance-detecting system with fixed microorganism membrane for water quality-monitoring |
| CN1290859A (en) * | 2000-10-25 | 2001-04-11 | 中国科学院武汉病毒研究所 | Method and device for on-line monitoring waste water |
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| Publication number | Publication date |
|---|---|
| JP2008196861A (en) | 2008-08-28 |
| CN101241103A (en) | 2008-08-13 |
| JP4410264B2 (en) | 2010-02-03 |
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