CN113504275B - Device and method for quickly measuring BOD - Google Patents
Device and method for quickly measuring BOD Download PDFInfo
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- CN113504275B CN113504275B CN202110826301.XA CN202110826301A CN113504275B CN 113504275 B CN113504275 B CN 113504275B CN 202110826301 A CN202110826301 A CN 202110826301A CN 113504275 B CN113504275 B CN 113504275B
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- 239000000945 filler Substances 0.000 claims abstract description 39
- 235000015097 nutrients Nutrition 0.000 claims abstract description 30
- 230000036284 oxygen consumption Effects 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 46
- 229910052760 oxygen Inorganic materials 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 46
- 239000000126 substance Substances 0.000 claims description 20
- 238000005259 measurement Methods 0.000 claims description 8
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- 238000001514 detection method Methods 0.000 abstract description 30
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- C12M23/00—Constructional details, e.g. recesses, hinges
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- C12M23/06—Tubular
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- C12M25/00—Means for supporting, enclosing or fixing the microorganisms, e.g. immunocoatings
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- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/30—Means for regulation, monitoring, measurement or control, e.g. flow regulation of concentration
- C12M41/32—Means for regulation, monitoring, measurement or control, e.g. flow regulation of concentration of substances in solution
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- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
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Abstract
The application provides a device and a method for quickly measuring BOD, wherein the device for quickly measuring BOD comprises a flow channel, a carrier tube and a filler, the carrier tube array is arranged on the inner side of the flow channel, the filler is filled in the carrier tube, the carrier tube is used for loading nutrients and the filler is used for loading microorganisms, the surfaces of the carrier tube and the filler are loaded with nutrients, the carrier tube and the filler are inoculated with microorganisms by water samples to be detected and cultured, different calibration samples of known BOD are adopted for detection after the culture is finished, curve fitting is carried out according to the dissolved oxygen consumption value obtained by detection and the corresponding BOD value, the formula of the fitting curve is an empirical formula, the water sample to be detected is detected, and the BOD value can be obtained by substituting the empirical formula after the dissolved oxygen consumption value is obtained, so that the detection is completed. The application provides a faster and more reasonable BOD detection device and detection method, and has good application prospect.
Description
Technical Field
The application relates to the technical field of environmental monitoring, in particular to a device and a method for quickly measuring BOD.
Background
The BOD measurement in the market at present mainly adopts a laboratory five-day method and a microbial film rapid measurement method, the laboratory five-day method is the most strict from the purposes and principles, however, the laboratory five-day method has very high requirements on the operation level of laboratory operators, the timeliness of samples and the effectiveness of storage, the measurement time is long, the influence of the precision of dissolved oxygen electrodes on the result is large, the measurement range is small, and the deviation of the measurement result is enlarged due to the error caused by dilution in the operation process, so that the laboratory five-day method has great difficulty in practical application.
The microbial film rapid determination method is a BOD determination method which has been developed in recent years, has high determination speed and simple operation, overcomes the defects of a five-day method, but the microbial film used in the method is prepared in advance, microorganisms contained in the microbial film are not derived from a water sample to be detected, so that the microbial film does not accord with the definition of BOD, the degradation capability of the microorganisms contained in the water body to be detected on organic matters in the water body cannot be illustrated through the degradation capability of other microorganisms, and the detected BOD by the microbial film method has deviation.
Disclosure of Invention
In view of the above, the application provides a device and a method for rapidly measuring BOD, which are more reasonable in principle and have higher detection speed.
The technical scheme of the application is realized as follows: the application provides a device for quickly measuring BOD, which comprises a flow channel, a carrier tube and a filler, wherein the carrier tube array is arranged on the inner side of the flow channel, the filler is filled in the carrier tube, the carrier tube is used for loading nutrients, and the filler is used for loading microorganisms.
On the basis of the technical scheme, the water inlet dissolved oxygen electrode and the water outlet dissolved oxygen electrode are preferably further included, the water inlet dissolved oxygen electrode is arranged on the inner side of the water inlet end of the flow channel, and the water outlet dissolved oxygen electrode is arranged on the inner side of the water outlet end of the flow channel.
On the basis of the technical scheme, the carrier tube is preferably made of porous adsorption materials, such as activated carbon, alumina ceramics, coral sand, zeolite, volcanic rock and the like.
On the basis of the above technical solution, preferably, the filler is one or more of natural fibers, artificial fibers and synthetic fibers, such as carbon fibers, polyurethane fibers, rayon and rayon.
Still more preferably, the length direction of the carrier tube is parallel to the length direction of the flow channel.
The application also provides a detection method of the device for quickly measuring BOD. The method comprises the following steps:
s1, loading nutrient substances in a carrier tube and loading the nutrient substances on the surface of a filler;
step S2, inoculating microorganisms in the water sample to be detected to the surfaces of the carrier tube and the filler, and culturing the microorganisms until the growth of the microorganisms is stable;
s3, detecting different BODs by using the BOD rapid measuring device with the stable microorganisms obtained in the step S2, and obtaining an empirical formula between the BOD and the dissolved oxygen consumption value;
and S4, monitoring the water sample to be detected by using the BOD rapid measuring device with the stable microorganisms obtained in the step S2, and calculating the BOD of the water sample to be detected according to the dissolved oxygen consumption value and an empirical formula.
On the basis of the above technical solution, preferably, in step S1, the method for loading the nutrient substance in the carrier tube includes a step of immersing the carrier tube in a solution of the nutrient substance, and the method for loading the nutrient substance on the surface of the filler includes a step of immersing the filler in the solution of the nutrient substance.
On the basis of the above technical solution, preferably, in step S2, the method for culturing the microorganism and determining that the microorganism is stable in growth includes: and (3) introducing a water sample to be detected into the flow channel, carrying out oxygen supply treatment on the water sample to be detected, detecting the difference value of the dissolved oxygen of the water body at the inlet and the outlet of the flow channel, and judging that the microorganism has grown stably when the fluctuation of the difference value of the dissolved oxygen is not more than 5% within 5min and the value of the dissolved oxygen at the water outlet continuously drops after stopping the oxygen supply treatment on the water sample.
Based on the above technical solution, preferably, in step S3, the method for obtaining the empirical formula includes respectively inputting standard water samples of at least three different BODs to have stabilityIn the device for rapidly measuring BOD of microorganism, when fluctuation of dissolved oxygen difference value within 5min is not more than 5%, recording dissolved oxygen consumption value, obtaining at least three groups of different dissolved oxygen consumption values and corresponding BOD values according to y=ax 2 And (3) performing curve fitting by adopting a least square method, wherein the dissolved oxygen consumption value is taken as the parameter input of x, the BOD value is taken as the parameter input of y, and a, b and c are all parameters of a fitted curve expression.
Compared with the prior art, the device and the method for quickly measuring BOD have the following beneficial effects:
(1) Compared with the prior art, the device can realize faster BOD detection, meanwhile, the microorganism in the water sample to be detected is adopted to carry out water body dissolved oxygen consumption, and the obtained BOD detection value is more close to the definition of BOD, so that the result is more accurate and reliable, a nested channel structure is adopted in the device, the space between the flow channel and the carrier tube provides the flow channel for the water body, the carrier tube provides nutrient substances for the growth of the microorganism, the filler provides attachment points and places for the growth of the microorganism and can also provide nutrient substances, the structural design is reasonable, the water body and the microorganism can be contacted quickly and effectively, and the detection efficiency is improved;
(2) The whole device can be reused, and microbial groups of different water bodies can be obtained in an in-situ culture mode, so that the device can be used for BOD detection of corresponding water bodies;
(3) And detecting by adopting a calibration sample to obtain an original parameter, performing curve fitting according to the original parameter to obtain an empirical formula, and predicting a detection result by using the empirical formula to be more rapid and reliable.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an isometric view of an apparatus for BOD rapid determination of the present application;
FIG. 2 is an exploded view of the device for rapid BOD determination of the present application.
In the figure: 1-flow channel, 2-carrier tube, 3-filler, 4-water-inlet dissolved oxygen electrode and 5-water-outlet dissolved oxygen electrode.
Detailed Description
The following description of the embodiments of the present application will clearly and fully describe the technical aspects of the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to fall within the scope of the present application.
As shown in fig. 1, in combination with fig. 2, the device for rapid BOD measurement of the present application comprises a flow channel 1, wherein the flow channel 1 is used for providing a flow space of a water sample to be detected, so that the water sample to be detected can be in sufficient contact with cultured microorganisms in the space to consume nutrients and oxygen, and the specific flow channel can be a cavity with an inlet and an outlet or a tube structure.
The inner measuring array of the flow channel 1 is provided with a plurality of carrier pipes 2, the carrier pipes 2 are of tubular structures, the carrier pipes 2 are made of porous materials and have good adsorption capacity, and particularly, the carrier pipes 2 can be made of activated carbon, alumina ceramics, coral sand, zeolite, volcanic rock and other materials, and nutrient substances are adsorbed, so that nutrient substances are provided for attached microorganisms before and during BOD detection, meanwhile, the carrier pipes can also provide attachment points for the growth of the microorganisms, the specific surface area of the porous materials is large, the porous materials can be more efficiently contacted with dissolved oxygen in a water body in unit time, and the absorption and consumption capacities of the dissolved oxygen are improved, so that the accuracy of BOD detection is indirectly improved.
The inner side of the carrier tube 2 is filled with a filler 3, the filler 3 mainly serving to provide attachment points for the growth of microorganisms, and at the same time the filler 3 can also serve to absorb reserve nutrients, thereby enabling the rapid and efficient growth of microorganisms, and in particular, the filler 3 is preferably one or more of natural fibers, artificial fibers and synthetic fibers, the specific surface area of the fibers being large, being able to support more microorganisms, while part of the fiber material can provide characteristic groups to increase affinity with microorganisms, such as carbon fibers and the like, and the fiber material can also form porous materials after stacking, thereby increasing the loading capacity, enabling the loading of nutrients and the loading of microorganisms.
For attaching the nutrient substances to the carrier tube 2 and the filler 3, a soaking treatment mode may be adopted, specifically, the carrier tube 2 may be soaked in a mixed solution of a nutrient solution and a growth promoter for 10-24 hours, or the filler may be soaked in the nutrient solution for 1-6 hours.
As a preferred embodiment, the length direction of the carrier tube 2 is parallel to the length direction of the flow channel 1, at this time, the water sample to be detected flowing through the flow channel 1 is more fully contacted with the filler 3, so that the consumption of dissolved oxygen by the microorganisms attached to the filler 3 is promoted, the detection amount is changed more greatly, and the error is reduced.
The water inlet dissolved oxygen electrode 4 is arranged on the inner side of the water inlet end of the flow channel 1, the water outlet dissolved oxygen electrode 5 is arranged on the inner side of the water outlet end of the flow channel 1, and the two electrodes are respectively used for detecting the dissolved oxygen of the water sample to be detected flowing into the flow channel 1 and the dissolved oxygen of the water sample to be detected flowing out of the flow channel 1, so that basic parameters are provided for BOD detection.
Specifically, the application also provides a detection method of the device for rapidly determining BOD, by adopting the method, the time period of BOD detection can be shortened, and compared with a microbial film method, the detection result is more reasonable and is more similar to the real BOD value, and the method specifically comprises the following steps:
firstly, the surface of the carrier tube 2 is loaded with nutrient substances and necessary growth promoters, and the surface of the filler 3 is also loaded with nutrient substances;
then, the filler 3 is filledFilling the carrier tube 2 filled with the filler 3, installing the carrier tube 2 filled with the filler 3 in the flow channel 1, introducing a water sample to be detected with constant flow rate into the flow channel 1 through a water inlet end, enabling primary microorganisms in the water sample to adhere to the surfaces of the carrier tube 2 and the filler 3 in the process of flowing through the carrier tube 2 and the filler 3, enabling nutrients adsorbed on the surfaces of the filler 3 and the carrier tube 2 to promote the growth of the microorganisms until the microorganisms grow to a stable state, enabling the microbial population not to continue growing, and enabling stable dissolved oxygen consumption, at the moment, inputting calibration samples with different BODs into a BOD rapid measuring device, detecting the dissolved oxygen consumption under the stable state, adopting at least three groups of calibration samples with different BODs, thereby obtaining correlation data between the at least three groups of BODs and the dissolved oxygen consumption, taking the dissolved oxygen consumption as parameter input of x, taking a BOD value as parameter input of y, and taking BOD value as parameter input of y according to a quadratic function y=ax 2 And performing curve fitting on +bx+c by adopting a least square method, wherein a is a coefficient of a quadratic term, b is a coefficient of a primary term, and c is a coefficient of a constant term, and obtaining an empirical formula between BOD and a dissolved oxygen consumption value after fitting.
And finally, inputting the water sample to be detected into a BOD rapid measuring device from the water inlet end, detecting the consumption of the dissolved oxygen in a stable state, substituting the consumption of the dissolved oxygen into an empirical formula, and calculating to obtain a BOD value, wherein the obtained BOD value is the target detection value.
The method has the advantages that the detection speed is higher, and the adopted microorganisms come from the water sample to be detected, so that the adaptability to the water sample to be detected is better, and compared with the method which uses the immobilized bacterial film, the detection result of the method is more accurate and reliable.
In the specific embodiment, in the detection process, the water sample to be detected is supplemented with dissolved oxygen into the water body through the oxygen bubbling equipment before entering the BOD rapid determination device, so that the saturation of the dissolved oxygen is ensured.
In a specific embodiment, the method for judging whether the detection state is stable is to judge the difference value of the dissolved oxygen in the water body at the water inlet and the water outlet of the flow channel 1, and judge that the microorganism has grown stably if the value of the dissolved oxygen at the water outlet continuously drops when the fluctuation value of the dissolved oxygen difference value within 5min is not more than 5% and the operation of supplementing the dissolved oxygen at the water inlet of the flow channel 1 is stopped.
In the above embodiment, when the difference in dissolved oxygen does not fluctuate widely within a certain time range, it can be judged that the consumption of dissolved oxygen by microorganisms is approaching to steady, at this time, it can be judged that the growth state of microorganisms is approaching to steady, but it is still impossible to judge whether there is a sufficient amount of microorganism population, if there is no microorganism population, the consumption of dissolved oxygen can reach steady, but the consumption value approaches to 0, and it is unambiguous for BOD detection, in order to eliminate such possibility, the present application judges whether the condition of continuous consumption of dissolved oxygen occurs by stopping oxygen supply in the water body at the water inlet, if the condition occurs, the dissolved oxygen at the water outlet rapidly drops, it can be judged that there is a sufficient amount of microorganisms, and if not, it can be judged that there is a sufficient amount of microorganisms.
Alternatively, the method for judging whether the detection state is stable further comprises the step of observing the state of the bacterial film on the surfaces of the carrier tube 2 and the filler 3 through a scanning electron microscope, so as to judge whether the bacterial film grows stably.
As another alternative, the method for judging whether the detection state is stable further includes performing OD600 detection on the water sample discharged from the flow channel 1, and judging whether the absorbance reaches the preset requirement.
In the BOD rapid determination device, the flow channel 1 can preferably adopt a circular pipeline structure, the carrier pipes 2 of the flow channel 1 adopt a pipe body with smaller diameter, and as a preferred implementation mode, the carrier pipes 2 are arranged in the flow channel 1 in parallel and tightly, at the moment, the carrier pipes 2 are arranged on the inner side of the flow channel 1 in a honeycomb shape, the surface area provided by the carrier pipes 2 is larger, the stored nutrient substances are more, the volume of the filled filling material 3 is larger, so that more spaces for microorganism growth and adhesion can be provided, the BOD detection range is determined according to the quantity of microorganisms, and meanwhile, when the structure is adopted, the contact efficiency of water flowing through the flow channel 1 with microorganisms is higher, and the dissolved oxygen consumption speed is improved, so that the BOD detection speed is higher.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (5)
1. A device for rapid BOD determination, characterized by comprising a flow channel (1), a carrier tube (2) and a filler (3), wherein the array of carrier tubes (2) is arranged inside the flow channel (1), the filler (3) is filled in the carrier tube (2), the carrier tube (2) is used for loading nutrients, and the filler (3) is used for loading microorganisms; the carrier tube (2) is made of porous adsorption materials; the filler (3) is one or more of natural fiber, artificial fiber and synthetic fiber; the length direction of the carrier tube (2) is parallel to the length direction of the flow channel (1); the water inlet dissolved oxygen electrode (4) and the water outlet dissolved oxygen electrode (5) are further included, the water inlet dissolved oxygen electrode (4) is arranged on the inner side of the water inlet end of the flow channel (1), and the water outlet dissolved oxygen electrode (5) is arranged on the inner side of the water outlet end of the flow channel (1).
2. The method for detecting a device for rapid BOD determination according to claim 1, comprising the steps of:
s1, loading nutrient substances in a carrier pipe (2) and loading the nutrient substances on the surface of a filler (3);
step S2, inoculating microorganisms in a water sample to be detected to the surfaces of the carrier tube (2) and the filler (3), and culturing the microorganisms until the microorganisms grow stably;
s3, detecting different BODs by using the BOD rapid measuring device with the stable microorganisms obtained in the step S2, and obtaining an empirical formula between the BOD and the dissolved oxygen consumption value;
and S4, monitoring the water sample to be detected by using the BOD rapid measuring device with the stable microorganisms obtained in the step S2, and calculating the BOD of the water sample to be detected according to the dissolved oxygen consumption value and an empirical formula.
3. The method for detecting a device for rapid BOD determination according to claim 2, wherein in step S1, the method for loading the carrier tube (2) with the nutrient substance comprises immersing the carrier tube (2) in a solution of the nutrient substance, and the method for loading the filler (3) with the nutrient substance comprises immersing the filler (3) in a solution of the nutrient substance.
4. The method for detecting a device for rapid BOD measurement according to claim 2, wherein in step S2, the method for culturing the microorganism and judging the growth stability of the microorganism comprises: and (3) introducing a water sample to be detected into the flow channel, carrying out oxygen supply treatment on the water sample to be detected, detecting the difference value of the dissolved oxygen of the water body at the inlet and the outlet of the flow channel (1), and judging that the microorganism has grown stably when the fluctuation of the difference value of the dissolved oxygen is not more than 5% within 5min and the value of the dissolved oxygen at the water outlet continuously drops after stopping the oxygen supply treatment on the water sample.
5. The method for detecting a device for rapid BOD measurement according to claim 2, wherein in step S3, the method for obtaining an empirical formula comprises inputting standard water samples of at least three different BODs, respectively, into a BOD rapid measurement device having stable microorganisms, recording dissolved oxygen consumption values when fluctuation of the dissolved oxygen difference value within 5min does not exceed 5%, obtaining at least three different sets of dissolved oxygen consumption values, and corresponding BOD values, according to y=ax 2 And (3) performing curve fitting by adopting a least square method, wherein the dissolved oxygen consumption value is taken as the parameter input of x, the BOD value is taken as the parameter input of y, and a, b and c are all parameters of a fitted curve expression.
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CN112213459A (en) * | 2020-09-09 | 2021-01-12 | 清华大学 | Biochemical oxygen demand micro-fluidic detection device and method based on bacterial microcapsules |
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US4149936A (en) * | 1977-09-14 | 1979-04-17 | Corning Glass Works | High surface low volume fungal biomass composite |
CN1300268A (en) * | 1998-03-31 | 2001-06-20 | 三星工程株式会社 | Waste water treatment method for removing organic matter and nitrogen, carrier used thereof and method for manufacturing the carrier |
JP2003340480A (en) * | 2002-05-29 | 2003-12-02 | Mitsubishi Rayon Co Ltd | Microbial cell immobilization support, method for producing the same and method for treating waste water using the same |
CN202083662U (en) * | 2011-05-06 | 2011-12-21 | 湖北博凡生物科技有限公司 | Online tester for biochemical oxygen demand BOD |
CN102798650A (en) * | 2012-08-29 | 2012-11-28 | 中国科学院长春应用化学研究所 | Method and device for detecting biochemical oxygen demand |
CN112213459A (en) * | 2020-09-09 | 2021-01-12 | 清华大学 | Biochemical oxygen demand micro-fluidic detection device and method based on bacterial microcapsules |
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