KR101016666B1 - A device for detecting toxicity of water using sulphur oxidizing bacteria - Google Patents

Abstract

PURPOSE: An ecotoxicity detector using sulfur oxidizing microorganisms is provided to prevent affect by air bubble and to ensure stable and reliable test result. CONSTITUTION: An ecotoxicity detector using sulfur oxidizing microorganisms comprises: a bioreactor(100) which has an inlet and outlet, contains sulfur oxidizing microorganisms, and changes sulfur granules and oxygen into sulfated salt ionization by the microorganisms; a first meter(200) having a first pH measuring unit(220) and first EC measuring unit; a second meter(300) having a second pH measuring unit and second EC measuring unit; a controller for determining toxicity of a water sample by comparing results of the first meter and second meter; and a second measuring tank(310) formed at the side of the bioreactor.

Description

Ecotoxicity detection device using sulfated microorganisms {A DEVICE FOR DETECTING TOXICITY OF WATER USING SULPHUR OXIDIZING BACTERIA}

The present invention relates to an ecotoxicity detection device using sulfated microorganisms, and more particularly, to an ecotoxicity detection device using sulfated microorganisms that can obtain accurate toxicity detection results even when aeration of water and air.

Various methods have been used to detect whether water is contaminated with toxic substances.

Among them, Patent Application No. 2007-0093476 previously filed by the present applicant discloses an underwater toxicity detection device using sulfur particles.

Figure 1 is a schematic diagram showing the configuration of the underwater toxicity detection apparatus disclosed in the above publication. As illustrated, the underwater toxicity detection device 1 includes a reaction tank 2 in which sulfate ions are present by the sulfated microorganism and water flows in and out, and a first measurement unit 4 provided at an inlet side of the reaction tank 2. ) And a second measurement unit 5 provided on the outlet side of the water. The underwater toxicity detection device 1 compares the electric conductivity (EC) and pH values measured by the first measurement unit 4 and the second measurement unit 5 to determine whether the water sample is toxic.

However, the conventional underwater toxicity detection device 1 disclosed in the above publication is provided from the lower region of the reaction tank 2 because the electrical conductivity measurement part and the pH measurement part of the second measurement part 5 are disposed in the reaction tank. In some cases, shaking of the pH and EC measurement values occurred while contacting the water sample and the bubbles generated by the aeration of the air. In particular, in the case of an electrical conductivity measurement unit, when an air bubble enters the inside of the electrode, data values are instantaneously flowed, which makes it difficult to obtain accurate experimental values.

In addition, the sulfated microorganism in the reaction tank uses carbon dioxide as a carbon source as an autotrophic microorganism, and requires micronutrients such as nitrogen, phosphorus, potassium, and the like. Therefore, there was a drawback that there was no practical use when trying to detect the toxicity of very clean water with little carbon dioxide and nutrients.

In addition, when the pH of the water sample is very high and the alkalinity is high, it is difficult to obtain accurate experimental data because of the activity of sulfated microorganisms that like low pH. Separately, a means for controlling the pH of the water sample was required.

In addition, the toxicity detection of additional water samples was continuously impossible when the activity of the sulfated microorganism disappeared by the toxic material inside the reactor. In other words, the sulfur particles need to be replaced, and the activity takes about 2-14 days to come back. While the activity of sulfated microorganisms was revived, there was a time constraint that it was impossible to detect the toxicity of water samples.

Patent application number 2007-0093476

An object of the present invention to solve the above problems is to provide an ecotoxicity detection device using sulfated microorganisms that can obtain accurate experimental results even in the aeration of air.

Another object of the present invention is to provide an ecotoxicity detection device using sulfated microorganisms, which can obtain accurate experimental results even in very clean water, very contaminated water, or a very high pH water sample.

In addition, another object of the present invention is to provide an ecotoxicity detection device using the sulfated microorganisms that can further detect the toxicity by further comprising another reactor that can be used continuously even if the sulfated microorganisms in one reactor is inactive To provide.

One aspect of the present invention for achieving the above technical problem relates to an apparatus for detecting ecotoxicity using sulfated microorganisms. The ecotoxicity detection device using the sulfated microorganism of the present invention has an inlet and an outlet through which water samples are introduced and discharged, and the microorganisms in which sulfated microorganisms are supported and sulfur particles and oxygen are oxidized to sulfate ions by the sulfated microorganism. A reactor; A first measuring unit provided at the inlet side and having a first pH measuring unit and a first EC measuring unit for measuring pH and electrical conductivity of the water sample; It is provided to have an independent space in the upper region of the microbial reaction tank is not affected by the air bubbles due to the aeration of air, the opening is formed so that the water sample generated the sulfate ion inside the microbial reaction tank can communicate with the sulfate ion A second measuring unit having a first pH measuring unit and a first EC measuring unit for measuring pH and electrical conductivity of the generated water sample; And a control unit for comparing the measured values of the first and second measurement units to determine whether the water sample is toxic.

According to one embodiment, the opening is formed on the side of the microbial reaction tank, the second measuring unit further comprises a second measuring tank coupled to the outer surface of the microbial reaction tank in which the opening is formed, the second pH measuring unit and The second EC measuring unit is provided in the second measuring tank.

According to one embodiment, the opening is coupled to the inner surface of the microbial reaction tank is formed on one side of the shielding plate for partitioning the inner space up and down, the second pH measuring unit and the second EC measuring unit is the upper portion of the shielding plate It may be provided in the area.

According to one embodiment, it is provided on one side of the inlet further comprises a pH adjusting tank for supplying an acidic material to the water sample supplied to the microbial reaction tank to adjust the pH of the water sample to the reference range.

According to one embodiment, the microbial reactor further comprises at least one auxiliary microbial reaction tank is provided on one side of the active microbial reaction tank, there is no activity of the sulfated microorganism of the microbial reaction tank due to the river toxic substances In this case, the water sample is supplied to the auxiliary microbial reactor to determine the toxicity of the water sample.

According to one embodiment, the auxiliary microbial reactor is operated by supplying only a minimum of water and a minimum of air while determining the toxicity of the water sample using the microbial reactor, and monitors the electrical conductivity by measuring the electrical conductivity.

According to an embodiment, the microbial reaction tank may further include an auxiliary microbial reaction tank provided on one side of the microbial reaction tank and alternately supplied with the microbial reaction tank to determine whether the water sample is toxic.

According to an embodiment, the controller may determine whether the water sample is toxic by a batch method of diluting the water sample with artificial river water in several stages and reacting for a predetermined time to calculate the EC50 value and the degree of inhibition (%).

Ecotoxicity detection device using the sulfated microorganism according to the present invention is provided with a second measuring unit on the outside of the microbial reaction tank or the inside of the microbial reaction tank so that the air in the aeration tank does not collide with the pH, the conductivity electrode when supplying air and water samples To prevent the effects of air bubbles generated in advance. As a result, more stable and reliable experimental results can be obtained.

In addition, when the pH of the water sample is high or the alkalinity is high, the acid controller supplies an acidic material in advance to adjust the water sample to an appropriate pH range in which sulfate microorganisms can survive, and then supply it to the microbial reactor. This reduces the inhibition of the activity of sulfated microorganisms by the pH of the water sample can determine the correct toxicity.

 In addition, the auxiliary microbial reaction tank is provided to assist the microbial reaction tank to be used when the activity of the sulfated microorganisms in the microbial reaction tank is inhibited, or can be used to supplement the sulfated microorganisms immediately can run the experiment continuously.

1 is a schematic diagram schematically showing the configuration of a conventional toxicity detection device using sulfur particles,
Figure 2 is a schematic diagram showing the configuration of the ecological toxicity detection device using the sulfated microorganism according to the present invention,
3 and 4 are perspective views showing the configuration of the second measurement unit of the ecotoxicity detection apparatus using sulfated microorganism according to the present invention,
5 is a perspective view showing the configuration of a second measurement unit according to another embodiment of the ecotoxicity detection apparatus using the sulfated microorganism of the present invention,
6 to 14 are graphs showing the experimental results of detecting the toxicity of the actual river water using the ecotoxicity detection device using the sulfated microorganism of the present invention,
15 is a mineral composition table used for the artificial river water production.

In order to fully understand the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. Embodiment of the present invention may be modified in various forms, the scope of the invention should not be construed as limited to the embodiments described in detail below. This embodiment is provided to more completely explain the present invention to those skilled in the art. Therefore, the shape of the elements in the drawings and the like may be exaggerated to emphasize a more clear description. It should be noted that the same members in each drawing are sometimes shown with the same reference numerals. Detailed descriptions of well-known functions and constructions which may be unnecessarily obscured by the gist of the present invention are omitted.

Figure 2 is a schematic diagram showing the configuration of the ecological toxicity detection apparatus using the sulfated microorganism according to the present invention.

As illustrated, the toxicity detecting device 10 using sulfur particles according to the present invention is a microbial reaction tank in which sulfated microorganisms are supported and sulfur particles ionize sulfate by oxygen and sulfated microorganisms, thereby serving as a biosensor (100). And a first measurement unit 200 provided at the sample inlet 120 side of the microbial reaction tank 100 to measure pH and electric conductivity (EC) of the water sample, and independent of the upper region of the microbial reaction tank 100. It is provided with a second measurement unit 300 for measuring the pH and electrical conductivity of the water sample in which the sulfate ion is generated, the raw water supply unit 400 for supplying the water sample, the raw water supply unit 400 and the sample inlet 120 A control unit for determining whether the water sample is toxic based on a measurement result of the pH adjusting tank 500 and the first measuring unit 200 and the second measuring unit 300 disposed between And 600.

The microbial reaction tank 100 carries sulfur particles and an active sulfated microorganism therein to generate sulfate ion. The microbial reaction tank 100 is coupled to the reaction tank main body 110 in which the water sample and the sulfated microorganisms are supported, and the inlet port 120 for introducing the water sample into the reaction tank main body 110 and the reaction tank main body 110. The outlet 140 is coupled to the upper region of the reaction tank body 110 and discharges the samples in the reaction tank body 110, and the air supply port 130 supplies air to the reaction tank body 110.

Here, the water sample may be used for various kinds of water, such as river water, wastewater, purified water.

The sulfated microorganism present in the reaction tank body 110 grows by being attached to the surface of the sulfur particles, and sulfur is oxidized at a constant rate to generate sulfate ions. If the water sample is not toxic, since sulfate ions are generated, the concentration of sulfate ions increases on the outlet 140 side than on the inlet 120 side. On the other hand, if the toxicity is strong in the water sample, since the activity of the sulfated microorganisms do not oxidize the sulfur particles, the concentration of sulfate ions on the inlet 120 and outlet 140 side after a certain time is similar. The microbial reactor 100 serves as a biosensor to determine whether the water sample is toxic using this principle.

The first measurement unit 200 is disposed on the pipeline of the first supply pipe 410 connecting the raw water supply unit 400 and the reaction tank body 110 to measure the pH and electrical conductivity of the water sample supplied to the inlet 120 do. The first measuring unit 200 includes a first measuring tank 210 in which a water sample is accommodated, a first pH measuring unit 220 measuring pH, and a first EC measuring unit 230 measuring electric conductivity. Include.

The second measuring unit 300 is provided in the upper region of the reaction tank body 110 to measure the pH and electrical conductivity of the water sample in which the sulfate ion is formed. The second measuring unit 300 includes a second measuring tank 310 for receiving a water sample, a second pH measuring unit 320 and a second EC measuring unit 330 disposed in the second measuring tank 310. do. The second pH measuring unit 320 and the second EC measuring unit 330 are provided in the form of an electrode having a length.

The second measuring unit 300 is designed such that the second pH measuring unit 320 and the second EC measuring unit 330 are not affected by the air bubbles caused by the aeration of the water sample and the air.

To this end, as shown in FIGS. 3 and 4, the second measurement unit 300 according to the preferred embodiment of the present invention is coupled to the outside of the reaction tank body 110 to measure the second pH. The part 320 and the second EC measuring unit 330 are not affected by the air bubbles due to the water sample and the aeration of the air. The second measuring tank 310 is coupled to the side of the upper region of the reaction tank body 110, a communication hole 311 through which the water sample can communicate is formed in the coupling region. The second pH measuring unit 320 and the second EC measuring unit 330 are accommodated in the second measuring tank 310 filled with the water sample through the communication hole 311 to measure the physical properties of the water sample.

In this case, since the second pH measuring unit 320 and the second EC measuring unit 330 are provided in a direction away from the air droplets due to the aeration of the water sample and the air through the inlet 120 and the air supply port 130. In addition, the water sample and the air bubbles generated while the air flows in contact with the second pH measuring unit 320 and the second EC measuring unit 330 may prevent the risk of applying an impact. Accordingly, the second pH measuring unit 320 and the second EC measuring unit 330 can obtain more accurate measurement data.

5 is a perspective view illustrating a configuration of a second measuring unit 300a according to another exemplary embodiment of the present invention. The second measuring unit 300 according to the preferred embodiment of the present invention described above has a second measuring unit 310 according to another embodiment of the present invention, whereas the second measuring tank 310 is provided outside the reaction tank body 110. 300a is provided with a second pH measuring unit 320a and a second EC measuring unit 330a inside the reactor body 110. However, the shielding plate 150 shields the supply paths of the water sample and the air so that the water sample and the air flow, and there is no danger of impacting the second pH measuring unit 320a and the second EC measuring unit 330a. You can prevent it.

The shielding plate 150 is horizontally coupled to the inside of the reaction tank body 110 to divide the reaction tank body 110 into two spaces. The shielding plate 150 shields the supply paths of the water sample and the air supplied from the lower region to the upper region, thereby preventing the air bubbles from directly contacting the second pH measuring unit 320 and the second EC measuring unit 330. .

Here, the shield plate 150 is formed smaller than the area of the reaction tank body 110 by a predetermined area. Accordingly, an opening 151 is formed in which the shielding plate 150 and the reaction tank body 110 do not contact each other, and the water sample communicates with the upper and lower spaces through the opening 151.

 As described above, since the structure of the second measuring unit 300 according to the present invention is improved so that the second pH measuring unit 320 and the second EC measuring unit 330 are in contact with air and water samples, the conventional air is improved. And due to the shaking of the measuring unit caused by the contact with the water sample it is possible to significantly improve the inaccuracy of the data to obtain a stable and reliable data.

The raw water supply unit 400 accommodates the water sample therein and supplies the water sample to the microbial reaction tank 100 through the first supply pipe 410. The first supply pump 411 is provided on the pipeline of the first supply pipe 410 to supply the water sample to the inlet 120.

pH control tank 500 is disposed between the raw water supply unit 400 and the microbial reaction tank 100 to adjust the pH of the water sample. The pH adjusting tank 500 detects the pH of the water sample supplied from the raw water supply unit 400 and adjusts the pH to be within a reference range. Here, the reference range of pH may be 3 to 5 suitable for the survival of sulfated microorganisms.

The pH control tank 500 supplies an acidic substance such as sulfuric acid, hydrochloric acid, phosphoric acid to the first supply pipe 410 or an alkaline substance so that the water sample is supplied to the reaction tank body 110 in a pH-adjusted state. This makes it possible to detect the toxicity of microbial reactors in wastewater with very high pH or very high alkalinity.

On the other hand, although not shown in the drawing may further include a nutrient element supply tank (not shown) for supplying nutrients to the water sample supplied to the raw water supply unit 400. The nutrient element supply tank (not shown) is disposed on the pipeline of the first supply pipe 410 to supply a carbon source and essential nutrients necessary for the growth of microorganisms. The nutrient supply tank (not shown) supplies a small amount of bicarbonate (NaHCO ₃ ), nitrogen, phosphorus, and minerals necessary for the growth of microorganisms when the water sample is a very clean purified water to detect the toxicity of the purified water.

Here, in the case of general river water, even though the nutrient supply tank (not shown) does not artificially supply the carbon source and the essential nutrient, it contains a small amount of the carbon source and the essential nutrient, so that accurate experimental results can be measured.

The controller 600 determines whether the ratio of the difference between the electric conductivity measured by the first measuring unit 200 and the electric conductivity value measured by the second measuring unit 300 is less than or equal to the reference range, and an alarm is generated when the ratio is less than or equal to the reference range. To help. Then, the control unit 600 receives the pH value measured from the first pH measuring unit for the water sample flowing into the first measuring tank to control the amount of acidic material supplied from the pH adjusting tank to the first supply pipe.

When the toxicity of river water is high, the EC value drops sharply, so it is easy to determine the toxicity of river water with only one reactor without control. However, when the toxicity of river water is very low, a constant effluent EC is produced, so it is not easy to determine whether it is toxic or non-toxic. Therefore, it is necessary to determine the toxicity compared to non-toxic water. To this end, two or more microbial reactors 100 are installed, and the microbial reactor 1 is injected with river water for 0.5-2 hours, and the microbial reactor 2 is injected with 10-100-fold diluted river water as a control. 0.5-2 hours later, dilute raw water is injected into the microbial reactor 1, which has been injected with river water, and river water is injected into the microbial reactor 2. In this way, the river water is injected at regular intervals. In addition, by monitoring the difference between the inflow EC and the outflow EC between the first measurement unit 200 and the second measurement unit 300 can determine whether or not toxicity.

When sulfur particles in the auxiliary microbial reactor 100a are supplied to the microbial reactor 100 due to the inhibition of sulfated microorganisms in the microbial reactor 100, the amount of new sulfur particles is reduced as the amount of sulfur particles in the auxiliary microbial reactor 100a decreases. Operate in a way to replenish.

Here, although the microbial toxicity detection apparatus 10 according to the preferred embodiment of the present invention is illustrated as having only one auxiliary microbial reaction tank 100a, two or more auxiliary microbial reaction tanks 100a may be provided. It can also be operated in a semi-continuous manner to monitor toxicity from gradients of change in conductivity over time. When the toxic river water enters the batch operation for a certain time, there is no increase in electrical conductivity with time, and when the non-toxic river water comes in, it shows a constant rate of increase in electrical conductivity over time. If there is little toxicity, the rate of electrical conductivity increase will be lower than if it is toxic. This slope can be used to monitor toxicity.

On the other hand, microbial toxicity detection device 10 according to the present invention Microbial reaction tank (100) and  With assistant Microbial reaction tank (100a)  Equipped. assistant Microbial reaction tank (100a) Microbial reactor 100 inside Sulfated microorganisms  It may be replaced or used when the activity is lost by toxic substances. Water reactor (100) active inside Sulfated Microorganisms  Covered Sulfur particles  Supplementary feeds allow the experiment to proceed continuously.

The auxiliary microbial reaction tank 100a is provided at one side of the microbial reaction tank 100 and is connected to the second supply pipe 420 of the auxiliary raw water supply unit 400a to receive a water sample. At this time, the pH control tank 500 and the nutrient element supply tank (not shown) is connected on the pipeline of the second supply pipe 420 to adjust the pH of the water sample or supply a carbon source and essential nutrients.

In addition, the dilution tank 700 is coupled to the second supply pipe 420 of the auxiliary microorganism reaction tank (not shown). The dilution tank 700 stores the artificial river water therein and supplies the artificial river water to the water sample supplied through the second supply pipe 420 so that the diluted water sample is supplied to the auxiliary microbial reactor 100a.

Auxiliary microbial reactor (100a) is to maintain the environment in which the sulfated microorganisms can survive when the microbial reaction tank (100) is used to detect toxicity, so that it is possible to supply the sulfated microorganisms used or replaced at any time. The auxiliary microbial reactor can supply sulfur particles with sulfated microorganisms in a predetermined state to the microbial reactor 100 when the microbial reactor 100 is inactive due to the influx of toxic substances, thereby reducing the microbial attachment time and operating within a short time. To help.

To this end, the auxiliary microbial reactor (100a) minimizes the inflow of air and is supplied with a diluted sample diluted with artificial river water and water samples (river water) at a ratio of 10 to 100: 1. In addition, the HRT (hydraulic residence time) is extended to allow sulfur and sulfated microorganisms to survive for a long time without the consumption of sulfur.

The above described technique is a description of a device for continuously monitoring the toxicity of river water and the like continuously.

On the other hand, in order to detect the toxicity of a sample in a laboratory in a laboratory, a microbial reactor (not shown) capable of supplying sulfur supported with sulfated microorganisms is operated. In a practical example, when the total volume of the auxiliary microbial reactor is 1 L, 0.5 L of liquid volume and 300 mL of sulfur particles (1 mm or less) may be filled, and the liquid medium may be discarded and re-injected every 7 days. At the first operation, the plant was planted using aerobic sludge of sewage treatment plant and air is continuously added to create aerobic conditions. Monitor pH and EC to determine the activity of sulfated microorganisms.

Dilute the water sample using artificial river water (containing test water stock (%): 0, 0.5, 5, 10, 25, 50, 85, 100). Dilute the water sample in a batch reactor, and use sulfur particles less than 1 mm in diameter and prepare a fixed volume in each reactor. It is preferable to wrap the inlet with aluminum foil so that moisture does not evaporate.

   Incubate at 150 rpm using a shaking incubator maintained at 30 ° C. PH and EC were measured at 6 and 12 hours after the start of the experiment. Based on the change in EC, the inhibition of sulfated microorganisms is calculated and the toxicity is determined by calculating the EC50 and TU values using TOXCALC software.

Hereinafter will be described the use process and effect of the microbial toxicity detecting apparatus 10 through the actual experimental example of the microbial toxicity detecting apparatus 10 according to the present invention having such a configuration.

To this end, the actual river water was introduced into the microbial reactor (100) to evaluate the ecotoxicity through the change of the EC. The microbial reactor 100 was filled with 50 mL of sulfur particles having a diameter of 2-4 mm, injected air from the bottom through the air supply hole 130, and the water sample to be measured was flowed upstream for 30 minutes. Continuous injection and low dwell time operation is possible.

In order to determine the toxicity of real river water, experiments were conducted in the form of supplying artificial river water without toxicity and then supplying real river water after a certain time. Since the EC value of real river water is rather high, a small amount of KCl and MgSO ₄ were added to the artificial river water to adjust it to match the EC of the river water.

At this time, when the pH of the river water exceeds the standard range 3 ~ 5, the pH control unit 500 controls the pH of the river water by supplying an acidic substance or an alkali substance.

Figure 6 shows the EC change of effluent according to the inflow of artificial river water and highly polluted river water 1 (HRT: 30 min, sulfur particles: 2-4 mm, temperature: 30 ° C., air flow rate: 150-250 mL / min) It is a graph shown. When 10L of contaminated stream water (stream water 1) is collected and applied to the microbial toxicity detector (10), artificial stream water is introduced for up to 7 hours, and the actual river water is put in after 7 hours. After 30 minutes of operation, the EC value decreased by 2/3 over 3 hours.

Figure 7 shows the EC change of the effluent according to the inflow of artificial river water and two-fold dilution (HRT: 30 min, sulfur particles: 2-4 mm, temperature: 30 ° C, air flow rate: 150-250 mL / min). The graph shown. As a result of introducing the river water 1 into the microbial reactor 100, a decrease in the EC value is shown.

FIG. 8 shows the change of EC (HRT: 30 min, sulfur particles: 2-4 mm, temperature: 30 ° C, air flow rate: 150-250 mL / min) according to the inflow of artificial water and 100 times diluted stream 1 Experimental results are shown. As shown, when the actual river water is diluted 100 times, it can be seen that it coincides with the effluent EC of artificial river water. This is because the toxicity of river water is reduced by the dilution. As a result of analyzing the water quality of real river water, 0.5 mg / L of nitrous nitrogen, 2.6 mg / L of normal nucleic acid and 65 ppb of dichloromethane were measured as toxic substances.

Fig. 9 shows the EC change of the effluent according to the inflow of artificial and uncontaminated stream 2 (HRT: 30 min, sulfur particles: 2-4 mm, temperature: 30 ° C, air flow rate: 150-250 mL / min). Figure 10 shows the changes in the EC of the effluent with the inflow of artificial and uncontaminated river water 3 (HRT: 30 min, sulfur particles: 2-4 mm, temperature: 30 ° C, air flow rate: 150-250 mL / min) is a graph. As shown, non-toxic streams 2 and 3 showed little change in EC. This can be judged because river water 2 and river water 3 contain little or no toxic substances that can affect sulfated microorganisms.

On the other hand, when the toxicity of the river water is high, the EC value drops rapidly, so it is easy to determine whether the river water is toxic. However, when the toxicity of river water is very low, it is not easy to determine the toxicity. Therefore, the toxicity is compared with non-toxic water.

To this end, two or more microbial reactors 100 are installed, and the microbial reactor 1 is injected with river water for 0.5-2 hours, and the microbial reactor 2 is injected with 10-100-fold diluted river water. 0.5-2 hours later, dilute raw water is injected into the microbial reactor 1, which has been injected with river water, and river water is injected into the microbial reactor 2. In this way, the river water is injected at regular intervals. In addition, by monitoring the difference between the inflow EC and the outflow EC between the first measurement unit 200 and the second measurement unit 300 can determine whether or not toxicity.

11 shows effluent pH and EC changes (HRT = 30 minute; influent pH = 7.0 and EC = 0.14 mS / cm) when hexavalent chromium 2,000 ppb is added to the influent. Graphs are shown by river water. The control unit 600 may determine whether the toxicity by monitoring the difference between the inlet EC and the outlet EC of the microbial reaction tank 1 (R1) and the microbial reaction tank 2 (R2).

On the other hand, in some cases, the microbial reactor (not shown) may be operated in a batch to dilute the water sample to be toxic in several stages and react for a certain time to determine the toxicity by calculating EC50 value and TU (toxicity unit). have.

In the case of batch operation, sulfur particles are incubated in the microbial reactor in order to over-cultivate the sulfur particles carrying the sulfated microorganisms and supply them to the batch beaker, and supply artificial river water with pH adjusted to 3-4. Livestock wastewater is planted in a microbial reactor and air is aerated using an air pump. The microbial reactor is placed in the incubator to maintain the operating temperature at 30 ℃, and the semi-continuous operation is performed to discard all the solutions other than the sulfur particles and put the artificial river water once a certain period. The activity of sulfated microorganisms in the microbial reaction tank is periodically determined by measuring EC and pH to increase the activity of EC. Periodically monitor EC changes per unit time.

  The water sample is then diluted using artificial river water (test water stock solution (%): 0, 0.5, 5, 10, 25, 50, 85, 100). Dilute the water sample in a batch reactor, and use sulfur particles less than 1 mm in diameter and prepare a fixed volume in each reactor. It is preferable to wrap the inlet with aluminum foil so that moisture does not evaporate.

   Incubate at 150 rpm using a shaking incubator maintained at 30 ° C to supply oxygen. PH and EC were measured at 6 and 12 hours after the start of the experiment. Based on the change in EC, the inhibition of sulfated microorganisms is calculated and the toxicity is determined by calculating the EC50 and TU (Toxicity Unit) values using TOXCALC software.

12 to 14 are diagrams showing a process of calculating the degree of inhibition (%) and the TU, and Equations 1 and 2 below are equations for calculating the TU and the degree of degradation (%).

Here, TU of Equation 1 is the toxicity unit (toxicity unit) and EC50 means the concentration of toxic substances that the microorganism is 50% inhibited, EC _12h forcontrol of Equation 2 EC after 12 hours of non-toxic artificial river water Change, EC _12h forsample, refers to the change in EC after 12 hours of sample. The following equation can calculate the inhibition factor (Inhibition factor) can be drawn based on this. Toxicity can be determined by calculating EC50 and TU (Toxicity Unit) values using TOXCALC software from FIG. 13.

On the other hand, Figure 15 is a chart showing the composition of the minerals used in the artificial river water production.

As described above, the microbial toxicity detection apparatus according to the present invention includes a second measurement unit on the outside of the microbial reaction tank to prevent the influence of air bubbles generated when the air and the water sample are supplied. As a result, more stable and reliable experimental results can be obtained.

In addition, when the pH of the water sample is high or the alkalinity is high, the acid control unit is supplied with an acidic substance or an alkaline substance in advance to adjust the water sample to an appropriate pH range in which the sulfated microorganism can survive and then supply it to the microbial reactor. This reduces the activity of the sulfated microorganisms by the pH of the water sample can determine the correct toxicity.

 In addition, the auxiliary microbial reaction tank is provided to assist the microbial reaction tank to be used when the activity of the sulfated microorganisms in the microbial reaction tank is inhibited, or can be used to supplement the sulfated microorganisms immediately can run the experiment continuously.

The embodiment of the ecotoxicity detection apparatus using the sulfated microorganism of the present invention described above is merely exemplary, and those skilled in the art to which the present invention pertains have various modifications and equivalent examples. You can see that it is possible. Therefore, it will be understood that the present invention is not limited to the forms mentioned in the above detailed description. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims. It is also to be understood that the invention includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

10: microbial toxicity detector 100: microbial reaction tank
110: reaction vessel body 120: inlet
130: air supply port 140: discharge port
150: shield plate 151: opening
200: first measuring unit 210: first measuring tank
220: first pH measuring unit 230: first EC measuring unit
300: second measuring unit 310: second measuring tank
311: communication hole 320: pH measuring unit
330: EC measuring unit 400: raw water supply unit
410: first supply pipe 411: first supply pump
420: second supply pipe 421: second supply pump
500: pH control tank 600: control unit
700 dilution tank

Claims (10)

A microbial reaction tank having an inlet and an outlet through which a water sample is introduced and discharged, the sulfated microorganisms are supported, and sulfur particles and oxygen are sulfate-ionized by the sulfated microorganisms;
A first measuring unit provided at the inlet side and having a first pH measuring unit and a first EC measuring unit for measuring pH and electrical conductivity of the water sample;
The upper part of the microbial reaction tank is an independent space partitioned from the microbial reaction tank so as not to be affected by the air bubbles due to the aeration of air, and an opening portion is provided so that the water sample in which the sulfate ion is generated inside the microbial reaction tank is introduced into the independent space. A second measuring unit formed in the independent space and having a second pH measuring unit and a second EC measuring unit for measuring pH and electrical conductivity of the water sample in which sulfate ions introduced into the opening are generated;
And a control unit comparing the measured values of the first measurement unit and the second measurement unit to determine whether the water sample is toxic.
The opening part is formed on the side of the microbial reaction tank, the second measuring unit further comprises a second measuring tank coupled to the outer surface of the microbial reaction tank in which the opening is formed,
And the second pH measuring unit and the second EC measuring unit are provided in the second measuring tank.
delete delete The method of claim 1,
It is provided on one side of the inlet to supply acidic material to the water sample supplied to the microbial reaction tank ecological toxicity using a sulfated microorganism, characterized in that it further comprises a pH control tank to adjust the pH of the water sample to the reference range. Detector. The method of claim 1,
It is provided on one side of the inlet to supply nutrients to the water sample supplied to the microbial reaction tank ecological toxicity using sulfated microorganisms, characterized in that it further comprises a nutrient element supply tank to maintain the activity of the sulfated microorganisms Detector. The method of claim 4, wherein
It further comprises at least one auxiliary microbial reaction tank is provided on one side of the microbial reaction tank, the active sulfated microorganisms,
In the absence of the activity of sulfated microorganisms in the microbial reactor, the water sample is supplied to the auxiliary microbial reactor or the sulfur particles loaded with the microorganisms can be taken out and used in another microbial reactor to determine the toxicity of the water sample. Ecotoxicity detection device using sulfated microorganisms. The method of claim 6,
The auxiliary microbial reactor is an ecotoxicity detection device using sulfated microorganisms, characterized in that the operation by supplying only the minimum water and the minimum air while determining the toxicity of the water sample using the microbial reaction tank. The method of claim 4, wherein
It is provided on one side of the microbial reaction tank by receiving a water sample and a diluted water sample alternately with the microbial reaction tank using a microbial reaction tank characterized in that it further comprises a secondary microbial reaction tank to determine whether the water sample is toxic. Ecotoxicity Detector. The method of claim 4, wherein
Having at least two microbial reaction tanks, the water sample and the diluted water sample are alternately supplied to each microbial reaction tank to determine whether the water sample is toxic from the increase rate according to the time of electrical conductivity after operation in batch. Toxicity detection device using sulfur particles, characterized in that. 10. The method of claim 9,
The control unit dilutes the artificial river water in the water sample in several stages and reacts for a predetermined time to determine whether the water sample is toxic by a batch method of calculating the EC50 value and the degree of inhibition (%) by Equation 1 and Equation 2 below. Toxicity detection device using sulfur particles, characterized in that judging.
[Equation 1]

[Equation 2]

Here, in Equation 1, TU is the toxicity unit (toxicity unit), EC50 means the concentration of the toxic substance that the microorganism is 50% inhibited, EC _12h forcontrol means EC change after 12 hours of non-toxic artificial river water EC _12h forsample means the change in EC after 12 hours of the sample.

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