CN113155588A - Rapid automatic water quality detection system and method based on micro-fluidic - Google Patents

Rapid automatic water quality detection system and method based on micro-fluidic Download PDF

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Publication number
CN113155588A
CN113155588A CN202110521510.3A CN202110521510A CN113155588A CN 113155588 A CN113155588 A CN 113155588A CN 202110521510 A CN202110521510 A CN 202110521510A CN 113155588 A CN113155588 A CN 113155588A
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reagent
area
micro
digestion
sample
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武治国
杨伟光
潘凌
徐锦锋
张振扬
阮利民
周海涛
周勇
周久
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Wuhan Newfiber Optoelectronics Co Ltd
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Wuhan Newfiber Optoelectronics Co Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44Sample treatment involving radiation, e.g. heat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2200/00Solutions for specific problems relating to chemical or physical laboratory apparatus
    • B01L2200/10Integrating sample preparation and analysis in single entity, e.g. lab-on-a-chip concept

Abstract

The invention discloses a rapid automatic water quality detection system based on micro-fluidic, which comprises a micro-fluidic chip, wherein the micro-fluidic chip comprises a chip body, a sample adding area, a digestion detection area and a plurality of reagent areas are arranged on the chip body, a rotating shaft is arranged on the chip body, the sample adding area and the reagent areas are closer to the rotating shaft relative to the digestion detection area, the sample adding area and each reagent area are communicated with the digestion detection area through sample introduction channels, one-way valves are arranged at the communication positions of the digestion detection area and the sample introduction channels, the invention also discloses a rapid automatic water quality detection method based on micro-fluidic, the reagent is preset on the micro-fluidic chip, the micro-fluidic chip can be compatible with total phosphorus and total nitrogen, the main water quality indexes such as ammonia nitrogen, COD and the like creatively integrate the difficult problems of high-temperature closed digestion, step-by-step reaction, reagent presetting and the like on a small micro-fluidic chip.

Description

Rapid automatic water quality detection system and method based on micro-fluidic
Technical Field
The invention belongs to the field of water quality detection, and particularly relates to a rapid automatic water quality detection system based on micro-fluidic, and a rapid automatic water quality detection method based on micro-fluidic, which is suitable for micro-fluidic measurement of water quality indexes such as total phosphorus, total nitrogen, ammonia nitrogen, COD (chemical oxygen demand) and the like.
Background
The micro-fluidic technologies of the main indicators (total phosphorus, total nitrogen, ammonia nitrogen and COD) for water quality monitoring in the market at present are almost reusable chips and control fluids in the form of pump valves, such as CN108072648A, CN208537406 and the like, and have the following defects: the waste liquid still exists in a liquid form, and is not easy to treat, store and transport; the narrow micro-channel in the chip leads to the fact that the chip is inevitably blocked in the process of recycling; the on-site liquid reagent is limited to a shelf life of 1 month and cannot meet the requirements of unmanned and maintenance-free online long-term monitoring. Although a centrifugal microfluidic chip for detecting residual chlorine in water by a DPD spectrophotometry is introduced in CN110161026, the centrifugal microfluidic chip does not include total phosphorus, total nitrogen, ammonia nitrogen, COD and the like which have more urgent, more extensive and more complex water quality index requirements, and the chip design does not include more complex digestion and step-by-step processes.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a rapid automatic water quality detection system based on microfluidics, which comprises a microfluidic chip and a matched centrifugal microfluidic detector, wherein the microfluidic chip can detect indexes such as total phosphorus, total nitrogen, ammonia nitrogen, COD (chemical oxygen demand) and the like. The chip can be compatible with various indexes exceeding total phosphorus, total nitrogen, ammonia nitrogen, COD, DPD and the like. Also provides a rapid automatic water quality detection method based on micro-fluidic.
In order to achieve the purpose, the invention adopts the following technical measures:
the utility model provides a quick automatic water quality testing system based on it is micro-fluidic, including the micro-fluidic chip, the micro-fluidic chip includes the chip body, be provided with the application of sample district on the chip body, clear up the detection zone, first reagent district and second reagent district, be provided with the rotation axis on the chip body, application of sample district and reagent district are for clearing up the detection zone and be closer to the rotation axis, application of sample district and each reagent district all through injection channel with clear up the detection zone intercommunication, clear up detection zone and injection channel intercommunication department and be provided with the check valve.
The chip body is including the first chip layer that bonds in proper order, second chip layer and third chip layer, can be through optics level double faced adhesive tape, modes such as high temperature bond, reagent groove has been seted up on the second chip layer, it detects the groove to clear up, application of sample groove and introduction channel groove, first chip layer, third chip layer bonds behind second chip layer both sides, the reagent groove, it detects the groove to clear up, application of sample groove and introduction channel groove form the reagent district promptly, clear up the detection zone, application of sample district and introduction channel pipe, the application of sample mouth has been seted up to the part that first chip layer corresponds to the application of sample district.
The chip body is fan-shaped or circular, the sample adding area, the digestion detection area, the first reagent area and the second reagent area form a group of index areas, the microfluidic chip can comprise one or four independent index areas, and each microfluidic chip only carries out complete index test once. The radius range of the chip body is 1-10cm, and the thickness of the chip body is 0.2-2 cm; the preferred radius of the chip body is in the range of 2-6cm and the thickness of the chip body is 0.5-1.0 cm. The material of the micro-fluidic chip can be various transparent materials such as polyamide, polymethyl methacryl methyl ester, polycarbonate, polypropylene ethylene, acrylic acid, rubber, fluoroplastic, polydimethylsiloxane, epoxy resin, polyurethane, glass, quartz and the like.
The reagent in the reagent zone is coated by the reagent coating. The centrifugal rupture strength of the reagent envelopes in each reagent zone is different, or the centrifugal rupture strength of the reagent envelopes in part of the reagent zones is the same, or the centrifugal rupture strength of the reagent envelopes in each reagent zone is the same. The main component of the reagent coating is one or a mixture of a plurality of products such as PE, PP, PVC and the like. The reagent in the first reagent zone and the second reagent zone is respectively determined by the reagent envelope with the thickness of 0.01-0.5mm and the material. Preferably, the material of the reagent coating is PE, and the thickness is 0.01-0.1 mm. Thereby making the centrifugal rotation speed reach the centrifugal rotation speed R1When the reagent envelope in the first reagent zone is broken, the reagent in the reagent envelope in the first reagent zone flows out. When the centrifugal rotating speed reaches the centrifugal rotating speed R2(R1<R2) When the reagent envelope in the second reagent zone is broken, the reagent in the reagent envelope in the second reagent zone flows out.
The communicated part of the digestion detection area and the sample introduction channel is provided with a one-way valve. The material of check valve is materials such as elastic plastic or fluoroplastics thin slice of corrosion-resistant and high temperature, and check valve one end is fixed in the chip main part, and the check valve covers clears up detection zone and sampling channel intercommunication department, and this check valve can prevent that the steam that produces when high temperature is cleared up from getting into reagent district or excessive, but can be when adding the water sample, and during high-speed centrifugal force, the liquid reagent in the reagent district smoothly flows in and clears up the detection zone.
The width of the sample feeding channel connected with the corresponding first reagent zone with relatively small centrifugal rupture strength of the reagent capsule is larger than that of the sample feeding channel connected with the corresponding second reagent zone with relatively large centrifugal rupture strength of the reagent capsule. Thereby guaranteed under the centrifugal force of different rotational speeds that first reagent district and second reagent district reagent can pass through the capillary resistance of corresponding injection channel respectively. The chip sample introduction channel is of a rectangular structureThe rectangular height is equal to the thickness of the second chip layer and ranges from 1mm to 10mm, and the optimized height of the sample feeding channel is 5mm to 8 mm. The width of the sample feeding channel is 10-1000 μm, and preferably, the width of the sample feeding channel is 50-500 μm. Thereby making the centrifugal rotation speed reach the centrifugal rotation speed R1When the reagent flows out from the reagent pack in the first reagent zone, the capillary resistance of the sample feeding channel corresponding to the first reagent zone can be broken through, and the reagent fully enters the reaction detection zone. When the centrifugal rotating speed reaches the centrifugal rotating speed R2(R1<R2) When the reagent flows out from the reagent pack in the second reagent zone, the capillary resistance of the sample feeding channel corresponding to the second reagent zone can be broken through, and the reagent fully enters the digestion detection zone.
The utility model provides a quick automatic water quality testing system based on micro-fluidic, still includes detecting system, includes centrifugal base, electric heat module, cooling module, LED lamp source, photoelectric detection subassembly.
The centrifugal base is connected with the rotating shaft of the microfluidic chip, the electric heating module is tightly attached to the outside of the digestion detection area, the cooling module is close to the digestion detection area, and the LED lamp source and the photoelectric detection assembly are arranged on two sides of the digestion detection area. The centrifugal base can clamp the fan-shaped or circular micro-fluidic chip and other centrifugal micro-fluidic chips to provide different rotating speeds and centrifugal forces for the micro-fluidic chip; the electric heating module is tightly attached to a digestion tank detection area to provide high temperature for digestion of indexes such as total phosphorus, total nitrogen, COD and the like; the cooling module is close to a digestion pool detection area, and a fan cooling measure is started after digestion is finished; the LED lamp source and the photoelectric detection assembly are respectively arranged at two opposite sides of the digestion detection area, and the projection direction of the LED lamp source points to the photoelectric detection assembly along the detection section of the digestion detection area. The light emitted by the LED lamp source can pass through the digestion detection area, and the absorbance is calculated after the light is received by the photoelectric detection assembly, so that the concentration of total phosphorus, total nitrogen, ammonia nitrogen and COD in the water is obtained. The rotation speed of the micro-fluidic detector is 0-10000 rpm and is controlled by a servo motor. The wavelength of the LED light source comprises 220nm, 275nm, 700nm, 440nm or 600nm, the wavelength precision is +/-5 nm, and the preferred wavelength precision is +/-2 nm. The digestion heating temperature of the electric heating module exceeds 180 ℃, the error range is +/-2 ℃, and the preferred error range is +/-1 ℃.
A rapid automatic total phosphorus detection method based on microfluidics comprises the following steps:
quantitatively transferring a water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into a sample adding area from a sample adding port, presetting a potassium persulfate digestion solution in a digestion detection area, presetting ascorbic acid in a first reagent area, and presetting an ammonium molybdate reagent in a second reagent area;
the centrifugal base drives the microfluidic chip to rotate centrifugally, and firstly, the microfluidic chip is driven to rotate at an initial rotating speed R0The sample feeding area and the potassium persulfate digestion solution in the digestion detection area are fully mixed through the sample feeding channel by reciprocating rotation,
then the digestion detection area is heated to 120 ℃ through an electric heating module, the temperature is reduced to room temperature by a cooling module after the temperature is kept for 20min,
subsequently driving the microfluidic chip at a first rotational speed R1The rotating speed is clockwise rotated, at the moment, a reagent envelope of the ascorbic acid preset in the first reagent zone is broken, the ascorbic acid flows into the digestion detection zone,
after 30 seconds, the micro-fluidic chip is driven to rotate at a second rotating speed R2The rotating speed rotates clockwise, at the moment, the reagent envelope of the ammonium molybdate reagent in the second reagent zone is broken, the ammonium molybdate reagent flows into the digestion detection zone,
stopping the centrifugal work of the micro-fluidic chip after the solution is uniformly mixed for 30 seconds,
standing for 15 min, detecting light with wavelength of 700nm emitted from the LED light source, reading out absorbance value by the photoelectric detection assembly, reading out total phosphorus content according to a preset calibration curve,
the second rotational speed R2 is greater than the first rotational speed R1, and the first rotational speed R1 is greater than the initial rotational speed R0.
A rapid automatic total nitrogen detection method based on micro-fluidic comprises the following steps:
quantitatively transferring a water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into a sample adding area from a sample adding port, presetting alkaline potassium persulfate in a digestion detection area, presetting a hydrochloric acid reagent in a first reagent area, and not filling any reagent in a second reagent area;
the centrifugal base drives the micro-fluidic chip to rotate centrifugally, firstly, the micro-fluidic chip rotates in a reciprocating way at an initial rotating speed R0 so as to ensure that a water sample in the sample adding area is fully mixed with alkaline potassium persulfate in the digestion detection area through the sample feeding channel,
then rapidly heating the digestion detection area to 125 ℃ through an electric heating module, keeping for 20min, then beginning to be cooled to room temperature by a cooling module,
then the micro-fluidic chip is driven to rotate clockwise at a first rotation speed R1, at the moment, a preset reagent envelope of the hydrochloric acid reagent in the first reagent zone is broken, the hydrochloric acid reagent flows into the digestion detection zone,
mixing uniformly after 30 seconds, stopping centrifugal work of the microfluidic chip, standing for 1 minute, detecting light with wavelength of 220nm and light with wavelength of 275nm emitted by the LED light source, reading out absorbance value by the photoelectric detection component, calculating, reading out total phosphorus content according to a preset calibration curve,
the first rotational speed R1 is greater than the initial rotational speed R0.
A rapid automatic ammonia nitrogen detection method based on micro-fluidic comprises the following steps:
quantitatively transferring a water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into a sample adding area from a sample adding port, digesting and presetting a color developing agent in the detection area, presetting a catalyst sodium nitroferricyanide in a first reagent area, and presetting alkaline sodium dichloroisocyanurate in a second reagent area;
the centrifugal base drives the micro-fluidic chip to rotate centrifugally, firstly, the micro-fluidic chip rotates in a reciprocating way at an initial rotating speed R0 so as to ensure that the water sample in the sample adding area is fully mixed with the color developing agent in the digestion detection area through the sample feeding channel,
and immediately driving the microfluidic chip to rotate clockwise at a first rotation speed R1, wherein the reagent envelope of the sodium nitroferricyanide preset in the first reagent zone is broken, and the sodium nitroferricyanide flows into the digestion detection zone.
And immediately driving the micro-fluidic chip to rotate clockwise at a second rotation speed R2, wherein the reagent envelope of the alkaline sodium dichloroisocyanurate in the second reagent zone is broken, and the alkaline sodium dichloroisocyanurate flows into the digestion detection zone.
After being uniformly mixed, the light source of the LED emits light with the wavelength of 700nm to be respectively detected, the photoelectric detection component reads out the absorbance value and reads out the content of ammonia nitrogen according to a preset calibration curve,
the second rotational speed R2 is greater than the first rotational speed R1, and the first rotational speed R1 is greater than the initial rotational speed R0.
A rapid automatic COD detection method based on micro-fluidic comprises the following steps:
quantitatively transferring the water sample to be detected from the sample adding port to the sample adding region by using a liquid transfer gun,
a digestion solution is preset in the digestion detection area, and no reagent is filled in the first reagent area and the second reagent area;
the centrifugal base drives the micro-fluidic chip to rotate centrifugally, firstly, the micro-fluidic chip rotates in a reciprocating way at an initial rotating speed R0 so as to ensure that a water sample in the sample adding area is fully mixed with a digestion solution in the digestion detection area through the sample feeding channel,
then rapidly heating the digestion detection area to 165 ℃ through an electric heating module, keeping for 10min, then beginning to be cooled to room temperature by a cooling module,
the LED light source emits light with the wavelength of 440nm or light with the wavelength of 600nm for detection, the photoelectric detection assembly reads out the absorbance value and calculates, and the COD content is read out according to a preset calibration curve.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the reagent to preset on the micro-fluidic chip, the micro-fluidic chip can be compatible with main water quality indexes such as total phosphorus, total nitrogen, ammonia nitrogen, COD and the like, and creatively integrates the difficult problems of high-temperature closed digestion, step-by-step reaction, reagent presetting and the like on a small micro-fluidic chip.
(2) The water quality detection is realized in a micro-scale mode, the water sample requirement and the reagent consumption are reduced, and the cost is reduced.
(3) The waste liquid amount is reduced by tens of times, the problem that the waste liquid of the conventional system is difficult to transport and treat is solved, and the threat to the environment is reduced.
(4) In the sample introduction channel, the heat transfer speed and the mass transfer speed are higher than those of the conventional system, and the reaction time or the analysis time is greatly shortened.
(5) The liquid reagent is wrapped by the reagent envelope, so that the preservation time of the common liquid reagent is greatly prolonged by 1 month.
(6) The water quality detection system can automatically complete closed digestion, sample liquid transfer, multi-step reaction, colorimetric measurement and the like within 35 minutes only by quantitatively adding a water sample to be detected through the one-step pipette gun, and other operations are not needed.
Drawings
FIG. 1 is a schematic structural diagram of a fan-shaped microfluidic chip,
fig. 2 is a schematic structural diagram of a circular microfluidic chip.
In the figure: 1-a microfluidic chip; 2-a chip body; 3-a sample addition zone; 4-digesting the detection zone; 5-a reagent zone; 6-a rotating shaft; 7-a sample introduction channel; 8-a one-way valve; 9-a sample addition port; 10-a digesting agent; 11-reagent.
Detailed Description
The invention will be described in further detail below to facilitate the understanding and practice of the invention by those skilled in the art, and it is to be understood that the description herein is merely illustrative and explanatory of the invention and is not restrictive thereof.
Example 1:
the utility model provides a quick automatic water quality testing system based on it is micro-fluidic, including micro-fluidic chip 1, micro-fluidic chip 1 includes chip body 2, be provided with on the chip body with the appearance district 3 that adds, clear up detection zone 4, and a plurality of reagent district 5, be provided with rotation axis 6 on the chip body 2, appearance district 3 and reagent district 5 are closer to rotation axis 6 for clearing up detection zone 4, appearance district 3 and each reagent district 5 all communicate with clearing up detection zone 4 through injection channel 7, it is provided with check valve 8 with injection channel 7 intercommunication department to clear up detection zone 4.
The reagent in the reagent zone 5 is coated by the reagent coating. The reagent envelopes of the reagent zones 5 have different rupture strengths at the centrifugal force, or some of the reagent envelopes of the reagent zones 5 have the same rupture strength at the centrifugal force, or the reagent envelopes of the reagent zones 5 have the same rupture strength at the centrifugal force.
The width of the sample feeding channel 7 connected with the corresponding reagent area 5 with the relatively small centrifugal rupture strength of the reagent envelope is larger than the width of the sample feeding channel 7 connected with the corresponding reagent area 5 with the relatively large centrifugal rupture strength of the reagent envelope. Thereby ensuring thatUnder the centrifugal force of different rotating speeds, the reagents in the first reagent zone and the second reagent zone can respectively pass through the capillary resistance of the corresponding sample feeding channels. The chip sample introduction channel is of a rectangular structure, the height of the rectangle is equal to the thickness of the second chip layer, the range is 1-10mm, and the optimized sample introduction channel is 5-8mm in height. The width of the sample feeding channel is 10-1000 μm, and preferably, the width of the sample feeding channel is 50-500 μm. Thereby making the centrifugal rotation speed reach the centrifugal rotation speed R1When the reagent flows out from the reagent pack in the first reagent zone, the capillary resistance of the sample feeding channel corresponding to the first reagent zone can be broken through, and the reagent fully enters the reaction detection zone. When the centrifugal rotating speed reaches the centrifugal rotating speed R2(R1<R2) When the reagent flows out from the reagent pack in the second reagent zone, the capillary resistance of the sample feeding channel corresponding to the second reagent zone can be broken through, and the reagent fully enters the digestion detection zone.
The chip body 2 may be in the form of a disc, a sector, or other centrifugable form.
The micro-fluidic chip 1 can be compatible with various indexes exceeding total phosphorus, total nitrogen, ammonia nitrogen, COD, DPD and the like. Wherein the reagents except the digestion solution are packaged and prefabricated by reagent envelopes.
When the micro-fluidic chip 1 is used as a total phosphorus chip, a potassium persulfate digestion solution is preset in the digestion detection area 4, a reducing agent ascorbic acid is preset in the first reagent area 5, and a color developing agent (sulfuric acid, ammonium molybdate and potassium antimony tartrate) is preset in the second reagent area 5;
when the micro-fluidic chip 1 is used as a total nitrogen chip, a digestion solution (alkaline potassium persulfate) is preset in the digestion detection area 4, dilute hydrochloric acid is preset in the first reagent area 5, and no reagent is filled in the second reagent area 5;
when the micro-fluidic chip 1 is used as an ammonia nitrogen chip, a color developing agent (sodium salicylate-potassium sodium tartrate) is preset in the digestion detection area 4, a catalyst sodium nitroferricyanide is preset in the first reagent area 5, and alkaline sodium dichloroisocyanurate is preset in the second reagent area 5;
when the microfluidic chip 1 is used as a COD chip, a digestion solution (sulfuric acid-silver sulfate-mercury sulfate) is preset in the digestion detection area 4, and no reagent is filled in the first reagent area 5 and the second reagent area 5.
The reagent in the reagent zone 5 is coated and prefabricated through a reagent coating, and when the micro-fluidic chip 1 is subjected to high-speed centrifugation and reaches a set rotating speed R1, the reagent coating in the first reagent zone 5 is broken, and the built-in reagent flows out; when the micro-fluidic chip 1 is centrifuged at a high speed to reach the set rotation speed R2 (R1< R2), the reagent envelope in the second reagent zone 5 is broken, and the built-in reagent will flow out.
The reagent coating film (sealing plastic film) is one or a mixture of a plurality of products such as PE film, PP film, PVC film and the like. The reagent in the first reagent zone and the second reagent zone is respectively determined by the reagent envelope with the thickness of 0.01-0.5mm and the material. Preferably, the material of the reagent coating is PE, and the thickness is 0.01-0.1 mm. Thereby making the centrifugal rotation speed reach the centrifugal rotation speed R1When the reagent envelope in the first reagent zone is broken, the reagent in the reagent envelope in the first reagent zone flows out. When the centrifugal rotating speed reaches the centrifugal rotating speed R2(R1<R2) When the reagent envelope in the second reagent zone is broken, the reagent in the reagent envelope in the second reagent zone flows out.
The chip body 2 may be made of various transparent materials, such as polyamide, polymethacrylic methyl ester, polycarbonate, polypropylene, acrylic, rubber, fluoroplastic, polydimethylsiloxane, epoxy resin, polyurethane, glass, quartz, etc.
Chip body 2 is including the first chip layer that bonds in proper order, second chip layer and third chip layer, can be through optics level double faced adhesive tape, modes such as high temperature bond, reagent groove has been seted up on the second chip layer, it detects the groove to clear up, application of sample groove and introduction channel groove, first chip layer, third chip layer bonds behind second chip layer both sides, the reagent groove, it detects the groove to clear up, application of sample groove and introduction channel groove form reagent district 5 promptly, it detects the area 4 to clear up, application of sample district 3 and introduction channel 7, the application of sample mouth has been seted up to first chip layer corresponding to application of sample district 3's part.
It is provided with check valve 8 with each injection channel 7 intercommunication department to clear up detection zone 4, the material of check valve is materials such as elastic plastic or fluoroplastics thin slice of corrosion-resistant and high temperature, check valve one end is fixed in the chip main part, check valve covers and clears up detection zone and injection channel intercommunication department, steam that can prevent when high temperature to clear up the production gets into reagent district 5 or is excessive through adding appearance district 3, but can be when the centrifugation is rotatory, the water sample is added to adding appearance district 3, reagent in the reagent district 5 can be smoothly through corresponding injection channel and the 8 inflow of check valve clear up detection zone 4.
The chip body 2 is in a fan shape or a circular shape, the sample adding area, the digestion detection area, the first reagent area and the second reagent area form a group of index areas, the chip body can comprise one or four independent index areas, and each microfluidic chip only carries out complete index test once. The radius range of the chip body 2 is 1-10cm, and the thickness is 0.2-2 cm; the radius of the chip body 2 is preferably in the range of 2-6cm, and the thickness of the chip body 2 is 0.5-1.0 cm.
A rapid automatic water quality detection system based on micro-fluidic, which also comprises a detection system, comprising a centrifugal base, an electric heating module, a cooling module, an LED lamp source and a photoelectric detection component,
the centrifugal base is connected with the rotating shaft 6 of the microfluidic chip 1, drives the rotating shaft 6 to rotate, further drives the microfluidic chip 1 to rotate, and provides different rotating speeds and centrifugal forces for the microfluidic chip 1.
The electric heating module is tightly attached to the outside of the digestion detection area 4, and provides high temperature for digestion of indexes such as total phosphorus, total nitrogen, COD and the like.
The cooling module is close to and clears up detection zone 4, starts the cooling module after clearing up and implements the cooling measure, can select for use fan etc..
LED lamp source, photoelectric detection subassembly set up and digesting 4 contralateral sides in detection zone, and the light that the LED lamp source sent can pass and digest detection zone 4 to calculate and obtain absorbance via photoelectric detection subassembly receipt back, and then obtain the concentration of total phosphorus, total nitrogen, ammonia nitrogen, COD in the aquatic.
The centrifugal base drives the micro-fluidic chip 1 to rotate at a speed of 0-6000 rpm.
The wavelengths of the LED light source include 220nm, 275nm, 700nm, 440nm and 600nm, with a wavelength accuracy of 5nm, preferably 2 nm.
The heating temperature of the electric heating module exceeds 180 ℃, the error range is +/-2 ℃, and the preferred error range is +/-1 ℃.
The rotating speed of the micro-fluidic detector matched with the micro-fluidic chip is 0-10000 rpm and is controlled by a servo motor. The digestion heating temperature of the electric heating module exceeds 180 ℃, the error range is +/-5 ℃, and the preferred error range is +/-1 ℃.
Example 2:
a rapid automatic total phosphorus detection method based on microfluidics utilizes the rapid automatic water quality detection system based on microfluidics in embodiment 1, and comprises the following steps:
quantitatively transferring 200 mu L of water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into a sample adding area 3 from a sample adding port, presetting a potassium persulfate digestion solution in a digestion detection area 4, presetting a reducing agent ascorbic acid in a first reagent area 5, and presetting a color developing agent (ammonium molybdate reagent) in a second reagent area 5; the centrifugal base drives the microfluidic chip 1 to rotate centrifugally, firstly, the microfluidic chip 1 rotates back and forth at an initial rotating speed R0, so that a water sample in the sample adding area 3 is fully mixed with a potassium persulfate digestion solution in the digestion detection area 4 through the sample introduction channel 7, then the digestion detection area 4 is rapidly heated to 120 ℃ through the electric heating module, and the temperature is reduced to room temperature by the temperature reduction module (temperature reduction fan) after the temperature is maintained for 20 min. Then the micro-fluidic chip 1 is driven to rotate clockwise at a first rotation speed R1, at this time, the reagent envelope of the reducing agent ascorbic acid preset in the first reagent zone 5 is broken, and the reducing agent flows into the digestion detection zone 4. After 30 seconds, the micro-fluidic chip 1 is driven to rotate clockwise at a second rotation speed R2, at the moment, the reagent envelope of the color developing agent (ammonium molybdate reagent) in the second reagent zone 5 is broken, and the color developing agent flows into the digestion detection zone 4. And stopping the centrifugal work of the microfluidic chip 1 after the solution is uniformly mixed for another 30 seconds, standing for 15 minutes, detecting light with the wavelength of 700nm emitted by the LED light source, reading the absorbance value by the photoelectric detection assembly, and reading the total phosphorus content according to a preset calibration curve. The second rotational speed R2 is greater than the first rotational speed R1, and the first rotational speed R1 is greater than the initial rotational speed R0.
The water sample to be tested adopts 200 mu L of total phosphorus standard use solution with total phosphorus of 0mg/L, 0.04mg/L, 0.08mg/L, 0.24mg/L, 0.4mg/L, 0.8mg/L and 1.2mg/L respectively, and the standard curve of the total phosphorus is measured and shown in Table 1.
Table 1 Total phosphorus standard curve chart obtained by measurement
Total phosphorus standard solution mg/L 0 0.04 0.08 0.24 0.4 0.8 1.2
Absorbance of the solution 0.0021 0.0265 0.0612 0.1765 0.2398 0.4952 0.740
Example 3:
a rapid automatic total nitrogen detection method based on microfluidics utilizes the rapid automatic water quality detection system based on microfluidics in embodiment 1, and comprises the following steps:
quantitatively transferring 200 mu L of water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into a sample adding region 3 from a sample adding port, presetting a digestion solution (alkaline potassium persulfate) in a digestion detection region 4, presetting a hydrochloric acid reagent in a first reagent region 5, and not filling any reagent in a second reagent region 5; the centrifugal base drives the microfluidic chip 1 to rotate centrifugally, firstly, the microfluidic chip 1 rotates back and forth at an initial rotating speed R0, so that a water sample in the sample adding region 3 is fully mixed with digestion liquid in the digestion detection region 4 through the sample introduction channel 7, then the digestion detection region 4 is rapidly heated to 125 ℃ through the electric heating module, and the temperature is reduced to room temperature by the temperature reduction module (temperature reduction fan) after being maintained for 20 min. And then the micro-fluidic chip 1 is driven to rotate clockwise at a first rotation speed R1, at the moment, the reagent envelope of the hydrochloric acid reagent preset in the first reagent zone 5 is broken, and the reducing agent flows into the digestion detection zone 4. And after 30 seconds, uniformly mixing, stopping the centrifugal work of the microfluidic chip 1, standing for 1 minute, detecting light with wavelength of 220nm and light with wavelength of 275nm emitted by the LED light source, reading an absorbance value by the photoelectric detection assembly, calculating, and reading the total phosphorus content according to a preset calibration curve, wherein the first rotating speed R1 is greater than the initial rotating speed R0.
The water sample to be detected adopts 200 mu L of total nitrogen standard use solution with total nitrogen of 0mg/L, 0.4mg/L, 1mg/L, 2mg/L, 6.0mg/L and 14.0mg/L respectively. The standard curve of total nitrogen is shown in Table 2.
Table 2 Total nitrogen standard curve chart obtained by measurement
Total nitrogen standard solution mg/L 0 0.4 1.0 2.0 6.0 14.0
Ar 0.0032 0.0251 0.0585 0.1059 0.3458 0.8120
Example 4:
a rapid automatic ammonia nitrogen detection method based on microfluidics utilizes the rapid automatic water quality detection system based on microfluidics in embodiment 1 to perform ammonia nitrogen detection:
quantitatively transferring 200 mu L of water sample to be detected from a sample adding port to a sample adding region 3 by using a liquid transferring gun, and pre-arranging a color developing agent (sodium salicylate-potassium sodium tartrate) in a digestion detection region 4, a catalyst sodium nitroferricyanide in a first reagent region 5, and alkaline sodium dichloroisocyanurate in a second reagent region 5; the centrifugal base drives the microfluidic chip 1 to rotate centrifugally, firstly, the microfluidic chip 1 rotates in a reciprocating mode at an initial rotating speed R0, so that a water sample in the sample adding area 3 is fully mixed with a color developing agent in the digestion detection area 4 through the sample introduction channel 7, then, the microfluidic chip 1 is immediately driven to rotate clockwise at a first rotating speed R1, at the moment, a reagent envelope of sodium nitrosoferricyanide preset in the first reagent area 5 is broken, and the sodium nitrosoferricyanide flows into the digestion detection area 4. Immediately driving the micro-fluidic chip 1 to rotate clockwise at a second rotation speed R2, wherein the reagent envelope of the alkaline sodium dichloroisocyanurate in the second reagent zone 5 is broken, and the alkaline sodium dichloroisocyanurate flows into the digestion detection zone 4. After the mixture is uniformly mixed, the light of 700nm wavelength emitted by the LED light source is respectively detected, the photoelectric detection assembly reads out the absorbance value and reads out the ammonia nitrogen content according to a preset calibration curve, the second rotating speed R2 is greater than the first rotating speed R1, and the first rotating speed R1 is greater than the initial rotating speed R0.
The water sample to be detected adopts total ammonia nitrogen standard use solutions with total ammonia nitrogen of 0mg/L, 0.3mg/L, 0.6mg/L, 1.2mg/L, 1.8mg/L and 2.4mg/L respectively. The standard curve of the measured ammonia nitrogen is shown in table 3.
Table 3 ammonia nitrogen standard curve chart
Ammonia nitrogen standard solution mg/L 0 0.3 0.6 1.2 1.8 2.4
Absorbance of the solution 0.0050 0.0745 0.1485 0.2984 0.4341 0.6120
Example 5:
a rapid automatic COD detection method based on micro-fluidic utilizes the rapid automatic water quality detection system based on micro-fluidic in the embodiment 1 to carry out COD detection:
quantitatively transferring 200 mu L of water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into the sample adding region 3 from the sample adding port, presetting a digestion solution (sulfuric acid-silver sulfate-mercuric sulfate) in the digestion detection region 4, and not filling any reagent in the first reagent region 5 and the second reagent region 5; the centrifugal base drives the microfluidic chip 1 to rotate centrifugally, firstly, the microfluidic chip 1 rotates back and forth at an initial rotating speed R0, so that a water sample in the sample adding region 3 is fully mixed with digestion liquid in the digestion detection region 4 through the sample introduction channel 7, then the digestion detection region 4 is rapidly heated to 165 ℃ through the electric heating module, and the temperature of the digestion detection region 4 is reduced to room temperature through the temperature reduction module (temperature reduction fan) after the temperature is maintained for 10 min. The LED light source emits light with the wavelength of 440nm or light with the wavelength of 600nm for detection, the photoelectric detection assembly reads out the absorbance value and calculates, and the COD content is read out according to a preset calibration curve.
The water sample to be tested adopts total COD standard use solutions with COD of 0mg/L, 0.4mg/L, 1.0mg/L, 2mg/L, 6mg/L and 14mg/L respectively. The measured COD standard curve is shown in Table 4.
Table 4 COD standard curve chart obtained by measurement
COD standard solution mg/L 0 10 20 50 100 200
Ar 0.0062 0.0451 0.0856 0.1748 0.3312 0.6525
It should be noted that the specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (10)

1. The utility model provides a quick automatic water quality testing system based on it is micro-fluidic, including micro-fluidic chip (1), a serial communication port, micro-fluidic chip (1) is including chip body (2), be provided with on the chip body with appearance district (3), clear up detection zone (4), and a plurality of reagent district (5), be provided with rotation axis (6) on chip body (2), it is closer to rotation axis (6) for clearing up detection zone (4) to add appearance district (3) and reagent district (5), it all communicates with clearing up detection zone (4) through injection channel (7) to add appearance district (3) and each reagent district (5), it is provided with check valve (8) with injection channel (7) intercommunication department to clear up detection zone (4).
2. The micro-fluidic based rapid automatic water quality detection system of claim 1, wherein the reagent in the reagent zone (5) is coated by a reagent envelope.
3. The micro-fluidic based rapid automatic water quality detection system according to claim 2, wherein the centrifugal rupture strength of the reagent envelopes of each reagent zone (5) is different or the centrifugal rupture strength of the reagent envelopes of some reagent zones (5) is the same or the centrifugal rupture strength of the reagent envelopes of each reagent zone (5) is the same.
4. The micro-fluidic based rapid automatic water quality detection system according to claim 2, wherein the width of the sample injection channel (7) connected to the corresponding reagent zone (5) with the relatively small rupture strength of the reagent capsule centrifugal force is larger than the width of the sample injection channel (7) connected to the corresponding reagent zone (5) with the relatively large rupture strength of the reagent capsule centrifugal force.
5. The rapid automatic water quality detection system based on micro-fluidic according to claim 1, characterized in that a one-way valve (8) is arranged at the communication position of the digestion detection area (4) and the sample injection channel (7).
6. The micro-fluidic based rapid automatic water quality detection system of claim 1, further comprising a detection system comprising a centrifugal base, an electric heating module, a cooling module, an LED lamp source, and a photoelectric detection assembly,
the centrifugal base is connected with a rotating shaft (6) of the microfluidic chip (1), the electric heating module is tightly attached to the outside of the digestion detection area (4), the cooling module is close to the digestion detection area (4), and the LED lamp source and the photoelectric detection assembly are arranged on two sides of the digestion detection area (4).
7. A rapid automatic total phosphorus detection method based on microfluidics, which utilizes the rapid automatic water quality detection system based on microfluidics of claim 6, is characterized by comprising the following steps:
quantitatively transferring a water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into a sample adding area (3) from a sample adding port, presetting a potassium persulfate digestion solution in a digestion detection area (4), presetting ascorbic acid in a first reagent area (5), and presetting an ammonium molybdate reagent in a second reagent area (5);
the centrifugal base drives the microfluidic chip (1) to rotate centrifugally, firstly, the microfluidic chip (1) rotates in a reciprocating manner at an initial rotating speed R0 so as to ensure that a water sample in the sample adding area (3) is fully mixed with a potassium persulfate digestion solution in the digestion detection area (4) through the sample introduction channel (7),
then the digestion detection area (4) is heated to 120 ℃ through an electric heating module, the temperature is reduced to room temperature through a cooling module after the temperature is kept for 20min,
then the micro-fluidic chip (1) is driven to rotate clockwise at a first rotation speed R1, at the moment, a reagent envelope of the ascorbic acid preset in the first reagent area (5) is broken, the ascorbic acid flows into the digestion detection area (4),
after 30 seconds, the micro-fluidic chip (1) is driven to rotate clockwise at a second rotation speed R2, at the moment, the reagent envelope of the ammonium molybdate reagent in the second reagent zone (5) is broken, the ammonium molybdate reagent flows into the digestion detection zone (4),
the centrifugal work of the micro-fluidic chip (1) is stopped after the solution is uniformly mixed for 30 seconds,
standing for 15 min, detecting light with wavelength of 700nm emitted from the LED light source, reading out absorbance value by the photoelectric detection assembly, reading out total phosphorus content according to a preset calibration curve,
the second rotational speed R2 is greater than the first rotational speed R1, and the first rotational speed R1 is greater than the initial rotational speed R0.
8. A rapid automatic total nitrogen detection method based on microfluidics, which utilizes the rapid automatic water quality detection system based on microfluidics of claim 6, is characterized by comprising the following steps:
quantitatively transferring a water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into a sample adding area (3) from a sample adding port, presetting alkaline potassium persulfate in a digestion detection area (4), presetting a hydrochloric acid reagent in a first reagent area (5), and not filling any reagent in a second reagent area (5);
the centrifugal base drives the microfluidic chip (1) to rotate centrifugally, firstly, the microfluidic chip (1) rotates in a reciprocating manner at an initial rotating speed R0 so as to ensure that a water sample in the sample adding area (3) is fully mixed with alkaline potassium persulfate in the digestion detection area (4) through the sample introduction channel (7),
then the digestion detection area (4) is rapidly heated to 125 ℃ through an electric heating module, the temperature is reduced to the room temperature by a cooling module after the temperature is kept for 20min,
then the micro-fluidic chip (1) is driven to rotate clockwise at a first rotation speed R1, at the moment, a preset reagent envelope of the hydrochloric acid reagent in the first reagent zone (5) is broken, the hydrochloric acid reagent flows into the digestion detection zone (4),
after 30 seconds, the mixture is uniform, the centrifugal work of the microfluidic chip (1) is stopped, after the mixture is kept stand for 1 minute, the LED light source emits light with the wavelength of 220nm and light with the wavelength of 275nm to be detected, the photoelectric detection component reads out the absorbance value and calculates, and the total phosphorus content is read out according to a preset calibration curve,
the first rotational speed R1 is greater than the initial rotational speed R0.
9. A rapid automatic ammonia nitrogen detection method based on microfluidics, which utilizes the rapid automatic water quality detection system based on microfluidics of claim 6, is characterized by comprising the following steps:
quantitatively transferring a water sample to be detected by using a liquid transfer gun, injecting the water sample to be detected into a sample adding area (3) from a sample adding port, presetting a color developing agent in a digestion detection area (4), presetting a catalyst sodium nitroferricyanide in a first reagent area (5), and presetting alkaline sodium dichloroisocyanurate in a second reagent area (5);
the centrifugal base drives the microfluidic chip (1) to rotate centrifugally, firstly, the microfluidic chip (1) rotates in a reciprocating way at an initial rotating speed R0 so as to ensure that a water sample in the sample adding area (3) is fully mixed with a color developing agent in the digestion detection area (4) through the sample introduction channel (7),
then immediately driving the micro-fluidic chip (1) to rotate clockwise at a first rotation speed R1, wherein the reagent envelope of the sodium nitroferricyanide preset in the first reagent zone (5) is broken, the sodium nitroferricyanide flows into the digestion detection zone (4),
then the micro-fluidic chip (1) is driven to rotate clockwise at a second rotation speed R2, at the moment, the reagent envelope of the alkaline sodium dichloroisocyanurate in the second reagent zone (5) is broken, the alkaline sodium dichloroisocyanurate flows into the digestion detection zone (4),
after being uniformly mixed, the light source of the LED emits light with the wavelength of 700nm to be respectively detected, the photoelectric detection component reads out the absorbance value and reads out the content of ammonia nitrogen according to a preset calibration curve,
the second rotational speed R2 is greater than the first rotational speed R1, and the first rotational speed R1 is greater than the initial rotational speed R0.
10. A rapid automatic COD detection method based on micro-fluidic, which utilizes the rapid automatic water quality detection system based on micro-fluidic of claim 6, is characterized by comprising the following steps:
quantitatively transferring the water sample to be detected from the sample adding port to the sample adding area (3) by using a liquid transfer gun,
digestion solution is preset in the digestion detection area (4), and no reagent is filled in the first reagent area (5) and the second reagent area (5);
the centrifugal base drives the microfluidic chip (1) to rotate centrifugally, firstly, the microfluidic chip (1) rotates in a reciprocating manner at an initial rotating speed R0 so as to ensure that a water sample in the sample adding area (3) is fully mixed with a digestion solution in the digestion detection area (4) through the sample introduction channel (7),
then the digestion detection area (4) is rapidly heated to 165 ℃ through an electric heating module, the temperature is reduced to room temperature by a cooling module after the temperature is kept for 10min,
the LED light source emits light with the wavelength of 440nm or light with the wavelength of 600nm for detection, the photoelectric detection assembly reads out the absorbance value and calculates, and the COD content is read out according to a preset calibration curve.
CN202110521510.3A 2021-05-13 2021-05-13 Rapid automatic water quality detection system and method based on micro-fluidic Pending CN113155588A (en)

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