CN111175229A - In-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water and application thereof - Google Patents

In-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water and application thereof Download PDF

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CN111175229A
CN111175229A CN202010062021.1A CN202010062021A CN111175229A CN 111175229 A CN111175229 A CN 111175229A CN 202010062021 A CN202010062021 A CN 202010062021A CN 111175229 A CN111175229 A CN 111175229A
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gel
situ detection
enrichment
detection device
image
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林坤德
袁东星
马明洁
顾兆阳
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Xiamen University
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Xiamen University
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    • 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
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Abstract

The invention discloses an in-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water and application thereof. The method adopts the gel technology to carry out in-situ enrichment and color development on Fe (II) and S (-II) in the sediment section pore water, utilizes a small-sized integrated section imager to obtain and store a color development image of the gel in situ, and returns the image to a laboratory for analyzing to obtain the concentration data of Fe (II) and S (-II). The method is convenient and quick, avoids the problems of sample pollution, Fe (II) and S (-II) oxidation and the like which possibly occur in the sampling and sample processing processes, has good application prospect, and realizes the in-situ detection of Fe (II) and S (-II) in the sediment section pore water.

Description

In-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water and application thereof
Technical Field
The invention belongs to the technical field of environmental monitoring, and particularly relates to an in-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water and application thereof.
Background
Sediment pore water is an important site and medium for material exchange of sediment with overlying water, and is rich in a plurality of important elements closely related to biogeochemical cycle and biological activity, most of which are iron and sulfur. The former plays a key role in the respiration, nitrogen fixation and photosynthesis of plants, and the latter is involved in the synthesis of proteins and vitamins. Both exist in the sediment pore water mainly in the reduced state, namely Fe (II) and S (-II). The conventional method for measuring Fe (II) and S (-II) in the sediment pore water is an ectopic analysis method, namely sampling and then bringing the sediment pore water back to a laboratory for analysis. The biggest defect of the method is that Fe (II) and S (-II) are easily oxidized in the processes of sampling, transportation and treatment. Therefore, the development of in-situ analysis methods capable of in-situ enrichment sampling and determination is of great significance for the biogeochemical research of iron and sulfur in the sediment pore water. However, the existing in-situ analysis methods and applications are still limited to in-situ enrichment or laboratory tests, and there is no real in-situ analysis method that can be used in the field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an in-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water.
The invention also aims to provide a method for detecting dissolved Fe (II) and S (-II) in sediment section pore water.
The principle of the invention is as follows: combining a gel color development technology and an imaging technology, carrying out in-situ enrichment and color development on Fe (II) and S (-II) in sediment section pore water through a gel sheet loaded with a color development agent, acquiring and storing a color development image in situ by using a small image sensor, obtaining an image pixel gray value by using image processing software, and finally calculating the concentration distribution of a target object according to a correction curve.
The technical scheme of the invention is as follows:
an in-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water comprises a shell, a gel enrichment and color development unit, an image acquisition unit and a control unit, wherein,
the shell comprises a lower shell with an upper opening and an upper cover, the upper cover is sealed on the upper opening of the lower shell, and the lower end of the lower shell is provided with a wedge-shaped insertion piece with a downward pointed end;
the gel enrichment chromogenic unit comprises a gel clamping mechanism and enrichment gel clamped in the gel clamping mechanism, the enrichment gel is formed by sequentially laminating a polyether sulfone filtering membrane, diffusion phase gel and enrichment phase gel, and chromogenic agents capable of reacting with dissolved Fe (II) and S (-II) and developing colors are loaded in the enrichment phase gel;
the image acquisition unit comprises a scanning component, a stepping motor, a synchronous belt linear transmission mechanism and two limit switches, wherein the scanning component is arranged on a synchronous belt of the synchronous belt linear transmission mechanism, the stepping motor drives the scanning component to move through the synchronous belt linear transmission mechanism, the two limit switches are arranged on two sides of the scanning component in the displacement direction and are electrically connected with the stepping motor, an image sensor of the scanning component is a linear array CCD sensor, and a storage medium used for storing images obtained by the linear array CCD sensor is arranged;
the gel of the gel enrichment color development unit is added and held the organization and locates on the sidewall of the lower shell, the image acquisition unit locates in the lower shell, its linear array CCD sensor of scanning assembly is just right above-mentioned sidewall in order to scan the image of enrichment gel in the gel fixture and store the image in the above-mentioned storage medium directly, the control unit and scanning assembly, step motor and two limit switches are all waterproof and electric to connect in order to control the opening of the step motor, scanning interval and displacement stroke of the scanning assembly.
In a preferred embodiment of the present invention, the lower housing includes an upper cavity and a lower cavity separated by a partition, the upper opening is disposed in the upper cavity, the stepping motor and the corresponding cable are disposed in the upper cavity, and the scanning assembly, the synchronous belt linear transmission mechanism and the two limit switches are disposed in the lower cavity.
Preferably, the edge of the upper opening is circumferentially provided with an annular sealing gasket clamping groove, the upper cover is provided with at least two first waterproof connector mounting holes communicated with the upper opening, a sealing gasket is arranged in the annular sealing gasket clamping groove, the upper cover compresses the sealing gasket in the annular sealing gasket clamping groove through a bolt and covers the upper opening so as to realize the sealing cover between the upper cover and the upper opening, and the at least two first waterproof connector mounting holes are used for mounting first waterproof connectors.
Still further preferably, the first waterproof joint is a panel type waterproof female joint of M13.
In a preferred embodiment of the invention, the side wall of the lower cavity is provided with a maintenance opening, and the maintenance opening is provided with a detachable watertight plug.
In a preferred embodiment of the present invention, the gel holding mechanism comprises a transparent bottom plate and a holding upper cover,
the bottom plate is provided with an enriched gel placing position, the edge of the enriched gel placing position is circumferentially provided with an annular groove in a concave mode,
the clamping upper cover is provided with an enriched gel sampling window, the edge of the enriched gel sampling window is provided with an annular boss in a protruding way in the circumferential direction, the enriched gel sampling window is opposite to the enriched gel placing position, the shape and the size of the annular boss are matched with the annular groove,
the enrichment gel of bottom plate is located to the enrichment gel and is placed the position, and the centre gripping upper cover is located on the transparent bottom plate through the PP screw lid.
Further preferably, the transparent bottom plate is a side wall of the lower casing.
In a preferred embodiment of the present invention, the control unit includes a waterproof housing, and an STM32F103C8T6 single chip microcomputer and a stepping motor driver disposed in the waterproof housing, the STM32F103C8T6 single chip microcomputer is electrically connected to the power supply and the scanning assembly, and is electrically connected to the stepping motor through the stepping motor driver, and the waterproof housing is provided with at least two second waterproof connector mounting holes for mounting the second waterproof connectors.
Further preferably, the second waterproof joint is a panel type waterproof female joint of M13.
The other technical scheme of the invention is as follows:
a method for detecting dissolved Fe (II) and S (-II) in sediment section pore water comprises the following steps:
(1) selecting different enrichment phase gels and diffusion phase gels according to the detected Fe (II) and S (-II);
(2) arranging the enriched phase gel, the diffused phase gel and the polyether sulfone filtering membrane in a gel clamping mechanism of the in-situ detection device as claimed in any one of claims 1 to 9, and adjusting the scanning time interval of the image acquisition unit through a control unit;
(3) the in-situ detection device is arranged on the site until the gel enrichment and color development unit is completely sunk into the sediment or reaches a selected depth, and the control unit is arranged on the shore;
(4) starting the in-situ detection device, controlling the scanning assembly to scan and image the enriched gel at set time intervals through the control unit, and directly storing the obtained image in the storage medium;
(5) after the in-situ detection device is distributed on site for a specified time, the in-situ detection device is closed, recovered and cleaned, and then the in-situ detection device is taken back to a laboratory;
(6) reading the Image in the storage medium in a laboratory, converting the Image from a three-channel color Image into RGB three single-channel gray level images by using Image-J software, and performing subsequent analysis by using the gray level value of at least one channel of the RGB three single channels according to the principle that the higher the concentration of Fe (II) and S (-II) is, the longer the enrichment time is, and the smaller the gray level value of the obtained Image is.
The invention has the beneficial effects that:
1. the method adopts the gel technology to carry out in-situ enrichment and color development on Fe (II) and S (-II) in the sediment section pore water, utilizes a small-sized integrated section imager to obtain and store a color development image of the gel in situ, and returns the image to a laboratory for analyzing to obtain the concentration data of Fe (II) and S (-II).
2. The method is convenient and quick, avoids the problems of sample pollution, Fe (II) and S (-II) oxidation and the like which possibly occur in the sampling and sample processing processes, has good application prospect, and realizes the in-situ detection of Fe (II) and S (-II) in the sediment section pore water.
3. The invention can not only carry out in-situ detection on the dissolved Fe (II) and S (-II) in the pore water of the section of the sediment, but also can be horizontally placed on the sediment to carry out in-situ detection on the dissolved Fe (II) and S (-II) on the surface layer of the sediment
Drawings
Fig. 1 is a schematic perspective view of an in-situ detection apparatus according to the present invention.
Fig. 2 is an exploded perspective view of the upper cover of the in-situ detection apparatus according to the present invention.
Fig. 3 is a schematic perspective view of an image capturing unit of the in-situ detection apparatus according to the present invention.
Fig. 4 is a schematic perspective view of the upper clamping cover of the gel clamping mechanism of the in-situ detection apparatus of the present invention.
FIG. 5 is an exploded perspective view of the gel holding mechanism of the in-situ detection device according to the present invention.
FIG. 6 is a graph showing the results of the experiment in example 2 of the present invention.
FIG. 7 is a graph showing the results of the experiment in example 3 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
As shown in figure 1, an in-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water comprises a transparent shell 1, a gel enrichment and color development unit 2, an image acquisition unit 3 and a control unit 4, wherein,
the transparent shell 1 comprises a lower shell 10 with an upper opening and an upper cover 11, wherein the lower shell 10 is made of transparent materials, the upper cover 11 is arranged on the upper opening of the lower shell 10 in a sealing manner, and the lower end of the lower shell 10 is provided with a wedge-shaped insertion piece 13 with a downward pointed end;
as shown in fig. 4 and 5, the gel enrichment and color development unit 2 comprises a gel clamping mechanism 21 and an enrichment gel clamped in the gel clamping mechanism 21, wherein the enrichment gel is formed by sequentially laminating a polyethersulfone filter membrane (0.45 μm, in-situ filtering pore water to obtain a dissolved target substance and prevent a particulate matter from interfering detection), a diffusion phase gel and an enrichment phase gel, and the enrichment phase gel is loaded with a color development agent capable of reacting with dissolved Fe (II) and S (-II) and developing color;
as shown in fig. 3, the image capturing unit 3 includes a scanning assembly 30 (resolution (number of dots per inch) is 300-2400), a stepping motor 31, a synchronous belt linear transmission mechanism 32, and two limit switches 33, the scanning assembly 30 is disposed on a synchronous belt of the synchronous belt linear transmission mechanism 32, the stepping motor 31 drives the scanning assembly 30 to move through the synchronous belt linear transmission mechanism 32, the two limit switches 33 are disposed on two sides of the scanning assembly 30 in the moving direction and electrically connected to the stepping motor 31, the image sensor of the scanning assembly 30 is a linear array CCD sensor, and is provided with a storage medium for storing an image obtained by the linear array CCD sensor;
the gel of the gel enrichment and color development unit 2 is added and held the organization and locates on the sidewall of the lower body 10, the image acquisition unit 3 locates in lower body 10, its linear array CCD sensor of the scanning assembly 30 is just facing the above-mentioned sidewall in order to scan the enriched gel picture in the gel clamping mechanism 21, and store the picture in the above-mentioned storage medium directly, the control unit 4 and scanning assembly 30, step motor 31 and two limit switches 33 are all waterproof and electric to connect in order to control the start of the step motor 31, scanning interval and displacement stroke of the scanning assembly 30.
Preferably, the lower housing 10 includes an upper cavity 102 and a lower cavity 103 separated by a partition 101, the upper opening is disposed in the upper cavity 102, the stepping motor 31 and the corresponding cable are disposed in the upper cavity 102, and the scanning assembly 30, the synchronous belt linear transmission mechanism 32 and the two limit switches 33 are disposed in the lower cavity 103; as shown in fig. 2, preferably, an annular sealing gasket slot 104 is circumferentially disposed at an edge of the upper opening, the upper cover 11 is provided with at least two first waterproof connector mounting holes 105 communicating with the upper opening, a sealing gasket 106 is disposed in the annular sealing gasket 106 slot 104, the upper cover 11 presses the sealing gasket 106 into the annular sealing gasket 106 slot 104 by bolts and covers the upper opening to achieve sealing between the upper cover 11 and the upper opening, and the at least two first waterproof connector mounting holes 105 are used for mounting first waterproof connectors (M13 panel type waterproof female connectors);
the sidewall of the lower chamber 103 is provided with a maintenance opening, which is provided with a detachable watertight plug (not shown).
Preferably, as shown in fig. 4 and 5, the gel holding mechanism 21 includes a transparent bottom plate 210 and a holding upper cover 211, the transparent bottom plate 210 being a side wall of the lower housing 10;
the bottom plate is provided with a gel-enriched placing position 2101, the edge of the gel-enriched placing position 2101 is circumferentially provided with an annular groove 2102 in a concave way,
the holding cover 211 has an enriched gel sampling window 2111, an annular boss 2112 is protruded from the edge of the enriched gel sampling window 2111 in the circumferential direction, the enriched gel sampling window 2111 faces the enriched gel placement position 2101, the annular boss 2112 is fitted to the annular groove 2102 in the shape and size,
the enriched gel is arranged at an enriched gel placing position 2101 of the bottom plate, and the clamping upper cover 211 is arranged on the transparent bottom plate 210 through a PP screw cover;
preferably, the control unit 4 includes a waterproof case 40 and an STM32F103C8T6 single chip microcomputer and a driver of a stepping motor 31 which are arranged in the waterproof case 40, the STM32F103C8T6 single chip microcomputer is electrically connected with the power supply and the scanning assembly 30, and is electrically connected with the stepping motor 31 through the driver of the stepping motor 31, and the waterproof case 40 is provided with at least two second waterproof joint mounting holes 401 for mounting second waterproof joints (M13 panel type waterproof female heads).
Further preferably, the control unit 4 comprises a 24V, 5Ah lithium battery, an STM32F103C8T6 single chip microcomputer and two dc-dc buck-boost circuits. The working voltage of the STM32F103C8T6 single chip microcomputer is 3.3V, the working voltage of the controller of the stepping motor 31 is 18-40V, therefore, a direct current-direct current buck-boost module is required to be respectively connected in series between the lithium battery and the two electrical devices, the output voltage of the regulating module is respectively 3.3V and 24V, and the power is supplied to the single chip microcomputer and the driver of the stepping motor 31 so as to meet different power consumption requirements of the single chip microcomputer and the driver of the stepping motor 31. Because the battery discharges continuously in the working process, the voltage is reduced gradually, and the series voltage increasing and decreasing module can also keep the output voltage stable, so that the instrument operates stably.
The control unit 4 is in waterproof electric connection with the scanning assembly 30, the stepping motor 31 and the two limit switches 33 through a digital signal transmission cable 5 with M13 panel type waterproof male heads at two ends.
Further preferably, an infrared remote control relay is additionally connected between the lithium battery and the electrical equipment for convenient control, and an infrared remote controller is matched. The infrared ray can pass through the transparent sealing box cover to control the start and the close of the image probe.
The use method of the in-situ detection device of the embodiment comprises the following steps:
(1) selecting different enrichment phase gel, diffusion phase gel and polyether sulfone filtering membranes according to detected Fe (II) and S (-II);
(2) arranging the enriched phase gel, the diffused phase gel and the polyether sulfone filtering membrane in a gel clamping mechanism 21 of the in-situ detection device of the embodiment, and adjusting the scanning time interval of the image acquisition unit 3 through a control unit 4;
(3) the in-situ detection device is arranged on site until the gel enrichment and color development unit 2 is completely sunk into the sediment or reaches a selected depth, and the control unit 4 is arranged on the shore;
(4) starting the in-situ detection device, controlling the scanning assembly 30 to scan and image the enriched gel at set time intervals through the control unit 4, and directly storing the obtained image in the storage medium;
(5) after the in-situ detection device is distributed on site for a specified time, the in-situ detection device is closed, recovered and cleaned, and then the in-situ detection device is taken back to a laboratory;
(6) reading the Image in the storage medium in a laboratory, converting the Image from a three-channel color Image into three RGB single-channel gray images by using Image-J software, and performing subsequent analysis by using the gray value of a G channel according to the principle that the higher the concentration of Fe (II) and S (-II), the longer the enrichment time and the smaller the gray value of the obtained Image.
Example 2
The in-situ detection device is the same as the embodiment 1, and comprises the following specific steps:
(1) washing the surface of a transparent shell 1 of the in-situ detection device by using ultrapure water, sequentially placing an enrichment phase gel, a diffusion phase gel and a cleaned polyether sulfone filter membrane (0.45 mu m) on a transparent bottom plate 210 of a gel clamping mechanism 21, covering a cover 11 plate, and fastening the periphery by using PP screws; and tightly coating the in-situ detection device with a plastic film to prevent the enriched phase gel from being polluted.
(2) When the gel enrichment and color development unit 2 is laid on site, the plastic film is removed, and the in-situ detection device is inserted into the sediment in a lake until the gel enrichment and color development unit 2 is completely immersed into the sediment or reaches a selected depth; the upper chamber 102 is left on the sediment or in overlying water and the control unit 4 is placed on shore.
(3) And starting the in-situ detection device, and scanning the enriched-phase gel by the scanning component 30 every 75 s.
(4) After the cloth is placed for 1h, the in-situ detection device is closed; and (5) recovering the in-situ detection device, cleaning silt on the surface of the in-situ detection device, and bringing the silt back to the laboratory.
(5) And reading the image data of the memory card in the in-situ detection device, and performing data processing and quantitative analysis. The detection result is shown in fig. 6, wherein a is an imaging diagram of the enriched phase gel of the in-situ detection device after being deployed; b is the vertical distribution of Fe (II) concentration in pore water corresponding to A.
The preparation method of the enriched phase gel comprises the following steps: weighing 3g of acrylamide, placing the acrylamide into a 50mL clean small bottle made of polyethylene terephthalate, adding 8mL of methanol, adding 4g of fully ground C18 solid-phase extraction filler after the acrylamide is completely dissolved, and uniformly mixing to avoid C18 caking. Then 0.1g of methylenebisacrylamide, 260. mu.L of 10% (v/v) ammonium persulfate solution and 10mL of ultrapure water were added in this order. The solution was shaken to avoid the formation of bubbles. Pouring the gel solution into a U-shaped mold, reacting at room temperature for 1h, and molding. Carefully taking out the gel sheet, placing in ultrapure water, soaking for 24h, and replacing ultrapure water for 2-3 times during the soaking process to wash away residual reagent on the surface and fully expand the gel. Storing in ultrapure water at room temperature for use, and storing for more than 7 days. Before use, the gel sheet is placed in 0.01mol/L phenanthroline solution to be soaked for more than 1h, so that the phenanthroline is fully attached to the gel; taking out the gel sheet, simply washing and soaking in ultrapure water for 10h, replacing ultrapure water for 1-2 times during the process, and washing out the phenanthroline which is not attached to the gel. The gel sheet was cut into a desired shape, and the area having pores and granular C18 was avoided as much as possible in order to ensure uniformity of gel properties. The enriched phase gel is stored in ultrapure water at room temperature, and the enriched phase gel attached with the phenanthroline needs to be used within 3 days.
The preparation method of the diffusion phase gel comprises the following steps: 30g of acrylamide and 0.6g of methylene bisacrylamide were sequentially weighed, dissolved in 182g of ultrapure water, and stored in a polyethylene bottle, and the solution was stored at 4 ℃ for 4 months. 10mL of the solution was taken out and placed in a 50mL clean vial made of polyethylene terephthalate, 70. mu.L of 10% (v/v) ammonium persulfate solution was added, and 25. mu. L N, N, N, N ', N' -tetramethylethylenediamine solution was added and mixed gently to prepare a dispersed phase gel solution. Pouring the gel solution into a U-shaped mold, reacting at room temperature for 1h, and molding. Thereafter, the gel sheet was taken out and placed in ultrapure water to be soaked for 24 hours, during which time the ultrapure water was replaced 2 to 3 times to wash away the reagent remaining on the surface and to sufficiently swell the gel. Finally, the gel sheet was cut into a desired shape and stored at room temperature in NaNO at a concentration of 0.01mol/L3The solution is ready for use.
Example 3
The in-situ detection device is the same as the embodiment 1, and comprises the following specific steps:
(1) washing the surface of a transparent shell 1 of the in-situ detection device by using ultrapure water, sequentially placing an enrichment phase gel, a diffusion phase gel and a cleaned polyether sulfone filter membrane (0.45 mu m) on a transparent bottom plate 210 of a gel clamping mechanism 21, covering a cover 11 plate, and fastening the periphery by using PP screws; and tightly coating the in-situ detection device with a plastic film to prevent the enriched phase gel from being polluted.
(2) When the gel enrichment and color development unit 2 is laid on site, the plastic film is removed, and the in-situ detection device is inserted into the sediment in a lake until the gel enrichment and color development unit 2 is completely immersed into the sediment or reaches a selected depth; the upper chamber 102 is left on the sediment or in overlying water and the control unit 4 is placed on shore.
(3) And starting the in-situ detection device, and scanning the enriched-phase gel by the scanning component 30 every 75 s.
(4) After the cloth is laid for 2 hours, the in-situ detection device is closed; and (5) recovering the in-situ detection device, cleaning silt on the surface of the in-situ detection device, and bringing the silt back to the laboratory.
(5) And reading the image data of the memory card in the in-situ detection device, and performing data processing and quantitative analysis. The detection result is shown in fig. 7, wherein a is an imaging diagram of the enriched phase gel of the in-situ detection device after being deployed; b is the vertical distribution of S (-II) concentration in pore water corresponding to A.
The preparation method of the enriched phase gel comprises the following steps: 10mL of the gel stock solution was put in a small bottle made of polyethylene terephthalate, and 80. mu.L of AgNO with a concentration of 1.0mol/L was added to each bottle3Mixing the solutions, adding 0.40mL KI solution with 0.20mol/L degree, shaking, adding 30 μ L10% (v/v) (NH)4)282O8And (3) rapidly and uniformly mixing the solution and 25 mu LN, N, N, N ', N' -tetramethylethylenediamine solution to obtain an enriched-phase gel preparation mixed solution. After standing at normal temperature for 45-60min, the gel layer is carefully taken out and soaked in ultrapure water for 24h, during which time the ultrapure water is replaced 3-4 times to remove unreacted reagents and to fully swell the gel. After the soaking, the gel sheet is cut into a desired shape and stored in ultrapure water at room temperature for later use. Avoiding light as much as possible in the process of preparation and preservation.
The preparation method of the diffusion phase gel comprises the following steps: 10mL of the dispersed phase gel stock solution is weighed and placed in a 50mL clean vial made of polyethylene terephthalate, 70 mu L of 10% (v/v) ammonium persulfate solution is added, 25 mu L of LN, N, N, N ', N' -tetramethylethylenediamine solution is added, and the dispersed phase gel solution is prepared by gentle mixing. Pouring the gel solution into a U-shaped mold, reacting at room temperature for 1h, and molding. Thereafter, the gel sheet was taken out and placed in ultrapure water to be soaked for 24 hours, during which time the ultrapure water was replaced 2 to 3 times to wash away the reagent remaining on the surface and to sufficiently swell the gel. Finally, the gel sheet was cut into a desired shape and stored at room temperature in NaNO at a concentration of 0.01mol/L3The solution is ready for use.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (10)

1. An in-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water is characterized in that: comprises a shell, a gel enrichment and color development unit, an image acquisition unit and a control unit, wherein,
the shell comprises a lower shell with an upper opening and an upper cover, the upper cover is sealed on the upper opening of the lower shell, and the lower end of the lower shell is provided with a wedge-shaped insertion piece with a downward pointed end;
the gel enrichment and color development unit comprises a gel clamping mechanism and an enrichment gel clamped in the gel clamping mechanism, the enrichment gel is formed by sequentially laminating a filtering membrane, a diffusion phase gel and an enrichment phase gel, and a color development agent capable of reacting with dissolved Fe (II) and S (-II) and developing color is loaded in the enrichment phase gel;
the image acquisition unit comprises a scanning component, a stepping motor, a synchronous belt linear transmission mechanism and two limit switches, wherein the scanning component is arranged on a synchronous belt of the synchronous belt linear transmission mechanism, the stepping motor drives the scanning component to move through the synchronous belt linear transmission mechanism, the two limit switches are arranged on two sides of the scanning component in the displacement direction and are electrically connected with the stepping motor, an image sensor of the scanning component is a linear array CCD sensor, and a storage medium used for storing images obtained by the linear array CCD sensor is arranged;
the gel of the gel enrichment color development unit is added and held the organization and locates on the sidewall of the lower shell, the image acquisition unit locates in the lower shell, its linear array CCD sensor of scanning assembly is just facing the above-mentioned sidewall in order to scan the picture of the enrichment gel in the gel fixture, and store the picture in the above-mentioned storage medium directly, the control unit and scanning assembly, step motor and two limit switches are all waterproof and electric to connect in order to control the opening of the step motor, scanning interval and displacement stroke of the scanning assembly.
2. The in-situ detection apparatus of claim 1, wherein: the lower shell comprises an upper cavity and a lower cavity which are separated by a partition plate, the upper opening is formed in the upper cavity, the stepping motor and the corresponding cable are arranged in the upper cavity, and the scanning assembly, the synchronous belt linear transmission mechanism and the two limit switches are arranged in the lower cavity.
3. The in-situ detection apparatus of claim 2, wherein: the edge circumference of upper shed is equipped with an annular seal gasket draw-in groove, the upper cover is equipped with two at least first water joint mounting holes of intercommunication upper shed, and a seal gasket is located in above-mentioned annular seal gasket draw-in groove, and the upper cover compresses tightly seal gasket in this annular seal gasket draw-in groove through the bolt to the upper shed is located in order to realize that the sealed lid between upper cover and the upper shed is established to the lid, and two at least first water joint mounting holes are used for installing first water joint.
4. The in-situ detection apparatus of claim 3, wherein: the model of the first waterproof joint is an M13 panel type waterproof female joint.
5. The in-situ detection apparatus according to any one of claims 2 to 4, wherein: the lateral wall of cavity is equipped with a maintenance mouth down, and this maintenance mouth is equipped with a detachable watertight end cap.
6. The in-situ detection apparatus of claim 1, wherein: the gel clamping mechanism comprises a transparent bottom plate and a clamping upper cover,
the bottom plate is provided with an enriched gel placing position, the edge of the enriched gel placing position is circumferentially provided with an annular groove in a concave mode,
the clamping upper cover is provided with an enriched gel sampling window, the edge of the enriched gel sampling window is provided with an annular boss in a protruding way in the circumferential direction, the enriched gel sampling window is opposite to the enriched gel placing position, the shape and the size of the annular boss are matched with the annular groove,
the enrichment gel of bottom plate is located to the enrichment gel and is placed the position, and the centre gripping upper cover is located on the transparent bottom plate through the PP screw lid.
7. The in-situ detection apparatus of claim 6, wherein: the transparent bottom plate is a side wall of the lower shell.
8. The in-situ detection apparatus of claim 1, wherein: the control unit includes a waterproof case and locates an STM32F103C8T6 singlechip and a step motor driver in this waterproof case, this STM32F103C8T6 singlechip and power and the scanning subassembly electricity is connected to be connected with step motor electricity through the step motor driver, be equipped with at least two second water joint mounting holes on the waterproof case in order to install the second water joint.
9. The in-situ detection apparatus of claim 8, wherein: the model of the second waterproof joint is an M13 panel type waterproof female joint.
10. A method for detecting dissolved Fe (II) and S (-II) in sediment section pore water is characterized in that: the method comprises the following steps:
(1) selecting different enrichment phase gel, diffusion phase gel and filtering membrane according to the detected Fe (II) and S (-II);
(2) installing the enriched phase gel, the diffused phase gel and the filtering membrane in the gel clamping mechanism of the in-situ detection device as claimed in any one of claims 1 to 9, and adjusting the scanning time interval of the image acquisition unit through the control unit;
(3) the in-situ detection device is arranged on the site until the gel enrichment and color development unit is completely sunk into the sediment or reaches a selected depth, and the control unit is arranged on the shore;
(4) starting the in-situ detection device, controlling the scanning assembly to scan and image the enriched gel at set time intervals through the control unit, and directly storing the obtained image in the storage medium;
(5) after the in-situ detection device is distributed on site for a specified time, the in-situ detection device is closed, recovered and cleaned, and then the in-situ detection device is taken back to a laboratory;
(6) reading the Image in the storage medium in a laboratory, converting the Image from a three-channel color Image into RGB three single-channel gray images by using Image-J software, and performing subsequent analysis by using the gray value of at least one channel of the RGB three single channels according to the principle that the higher the concentration of Fe (II) and S (-II), the longer the enrichment time and the smaller the gray value of the obtained Image.
CN202010062021.1A 2020-01-19 2020-01-19 In-situ detection device for dissolved Fe (II) and S (-II) in sediment section pore water and application thereof Pending CN111175229A (en)

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