KR20160120568A - THIN FILM FOR PASSIVE SAMPLER, PASSIVE SAMPER FOR MEASUREMENT OF BIOAVAILABLE PAHs, AND METHOD OF MANUFACTURING THEREOF - Google Patents
THIN FILM FOR PASSIVE SAMPLER, PASSIVE SAMPER FOR MEASUREMENT OF BIOAVAILABLE PAHs, AND METHOD OF MANUFACTURING THEREOF Download PDFInfo
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- KR20160120568A KR20160120568A KR1020150049796A KR20150049796A KR20160120568A KR 20160120568 A KR20160120568 A KR 20160120568A KR 1020150049796 A KR1020150049796 A KR 1020150049796A KR 20150049796 A KR20150049796 A KR 20150049796A KR 20160120568 A KR20160120568 A KR 20160120568A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2294—Sampling soil gases or the like
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
- G01N1/2205—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling with filters
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
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Abstract
Description
The present invention relates to a thin film for a passive sampler, a passive sampler and a method for producing the same, and more particularly to a method for measuring the concentration of bioavailable polycyclic aromatic hydrocarbons (PAHs) in a soil, a water system or a sediment, Is used to assess the degree of contamination of the environment by analyzing the concentration of the pollutant in the sampler after exposing it to the target environment for a certain period of time, A passive sampler for a passive sampler for measuring polycyclic aromatic hydrocarbons (PAHs) concentration, and a method of manufacturing the same.
Polycyclic aromatic hydrocarbons (PAHs) have recently been released from industrial sites and are exposed to various environmental media including soil. The EPA (Environmental Protection Agency) already recognizes the risks of PAHs and regulates 16 PAHs as poisonous substances, and recently regulated PAHs that are potentially toxic in Korea, potentially causing cancer Interest is increasing. Studies of bioavailability to regulate PAHs should be preceded. Traditionally, PAHs contamination studies in environmental media have been based on absolute concentrations in soils, rivers, or sediments. In general, the absolute concentration is evaluated by the total content extraction method using an organic solvent.
However, this method has a problem that it is difficult to evaluate the risk of pollutants on actual ecosystem. It is not easy to predict the pathway or reaction mechanism of contaminants in vivo, and there is no way yet to evaluate in vivo risk for more realistic assessment of contamination.
In order to measure the concentration of PAHs in environmental media, the concentration of organic matter in pore water must be measured. In this case, a large amount of soil sample is required and a lot of artificial working elements such as centrifugation and filtration are required.
In addition to the concentration assessment method for the regulation of PAHs, there is a method of using a DGT probe (diffusive gradient in thin film probe), which is an indirect concentration measuring device used in the in situ soil, (E.g., phosphorus (P)) and the like in the gel to evaluate the bioavailability. The absorber of DGT is similar to the absorption mechanism of organisms such as earthworms and plants, which can be used to assess bioavailability. In addition, since the thin film dispersion probe can be applied in situ without additional sampling, the measurement error can be greatly reduced due to the temporal change of the concentration of the pollutant in the actual environment. And monitoring at multiple points simultaneously. In addition, the thin-film dispersion probe has the advantage that the colloid component in the pore water can be essentially excluded in order to mount the filter.
Primarily, thin-film dispersion probes have been used only to assess small amounts of heavy metals in the water or sediment, particularly those that are prone to chemical changes. However, only a handful of researchers in the world have studied organic-thin-film dispersion probes (o-DGT probes, organic-DGT probes) to measure organic matter.
The conventional technology using such a thin film dispersion probe has not been activated in Korea so far, and there is no example in which it is filed in Korea registered patent. In addition, the related researches using thin film dispersion probes were applied to the measurement of heavy metal concentration in water (Hong Yong-seok, Journal of Korean Water Environment, 29, No. 5, 2013), application of biohazard assessment of heavy metals in soil (Rabindra Bade et (2005), Coastal Pollution Monitoring Methods (Choi, Man-Sik, Korea Basic Science Research Institute, Trend / Research Report, 2003). The need for a device for realistic pollution assessment is gradually increasing, and it is necessary to develop a technology to cope with this.
It is an object of the present invention to provide a passive sampler thin film capable of quickly and accurately assessing contamination by PAHs of soil, water or sediments through analysis of bioavailable concentrations.
Another object of the present invention is to provide a method for producing the thin film.
It is still another object of the present invention to provide a passive sampler comprising the thin film.
It is still another object of the present invention to provide a method of manufacturing the passive sampler.
A passive sampler thin film for measuring the bioavailable polycyclic aromatic hydrocarbons (PAHs) concentration in soil, water or sediment for one purpose of the present invention comprises an agarose gel and a poly (2,6- Diphenylphenylene oxide). ≪ / RTI >
In one embodiment, the thin film may be formed of a mixed solution in which 0.1 to 1.0 g of the porous beads are mixed with 20 to 200 mL of the agarose gel solution.
A method for manufacturing a passive sampler thin film for measuring the concentration of bioavailable polycyclic aromatic hydrocarbons (PAHs) in soil, water or sediments for another purpose of the present invention comprises the steps of mixing poly (2,6-diphenylphenylene Oxide) to prepare a mixed solution, and gelling the mixed solution to form a thin film.
For another purpose of the present invention, a passive sampler for measuring bioavailable polycyclic aromatic hydrocarbons (PAHs) concentrations in soil, aquatic or sediment comprises a lower base, an agarose gel and an agarose gel A second thin film formed on the first thin film, the second thin film including an agarose gel, and a second thin film formed on the second thin film, the first thin film including a resin gel containing porous beads of poly (2,6-diphenylphenylene oxide) dispersed therein, A membrane filter disposed on the second thin film, and an upper cap coupled to the lower base such that the first thin film, the second thin film, and the membrane filter are fixed on the lower base.
In one embodiment, the first thin film may be formed of a mixed solution in which 0.0005 g to 0.05 g of the porous beads are dispersed in 1 mL of the agarose gel solution.
In one embodiment, the first thin film may be formed of a mixed solution containing 0.1 to 1.0 g of the porous beads in 20 to 200 mL of agarose gel solution.
In another aspect of the present invention, there is provided a method of manufacturing a passive sampler, comprising: forming a first thin film by gelling a mixed solution in which porous beads of poly (2,6-diphenylphenylene oxide) are dispersed in an agarose gel solution; , Sequentially laminating the first thin film, the second thin film including the agarose gel, and the membrane filter formed of the polymer on the lower base, and assembling the lower base disposed up to the membrane filter with the upper cap do.
In one embodiment, the mixed solution may be dispersed with 0.0005 g to 0.05 g of the porous beads per 1 mL of the agarose gel solution.
In one embodiment, the thickness of the first thin film may be 0.05 cm to 0.1 cm.
According to the thin film, the passive sampler for passive sampler and the manufacturing method thereof for measuring the bioavailable polycyclic aromatic hydrocarbons (PAHs) concentration in the soil, water or sediment according to the present invention, the thin film for passive sampler has high Absorbing ability. In particular, passive samplers containing thin films for passive samplers have high PAHs absorption capacity in representative phenanthrene and pyrene contaminated soils of PAHs.
This suggests the possibility of in situ analysis of PAHs contaminated soils and may provide a way to indirectly predict the bioavailable concentrations in PAHs contaminated soils.
1 is an exploded perspective view illustrating a passive sampler according to the present invention.
FIG. 2 is a photograph for explaining a state where the lower base and the upper cap of FIG. 1 are coupled.
3 is a photograph for explaining an apparatus and a method for forming the first thin film and the second thin film of the passive sampler.
4 is a photograph showing a state in which a passive sampler according to the present invention is applied to a soil in a laboratory environment.
5 is a photograph showing a state in which a passive sampler according to the present invention is applied to each of the soil contaminated with PAHs at different concentrations.
6 is a photograph of the first thin film produced using the apparatus of FIG.
7 and 8 are graphs showing the amount of contaminants accumulated in the first thin film with time.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the term "comprises" or "having ", etc. is intended to specify that there is a feature, step, operation, element, part or combination thereof described in the specification, , &Quot; an ", " an ", " an "
Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
1 is an exploded perspective view illustrating a passive sampler according to the present invention.
Referring to FIG. 1, a
The first
The resin gel may be prepared by mixing the agarose gel solution and the porous beads homogeneously to prepare a mixed solution, applying the mixed solution, and then gelating. The "agarose gel solution" is a solution for forming an agarose gel, which means a state before gelation. It is preferable that the porous beads include 0.0005 g to 0.05 g per 1 mL of the agarose gel solution. If the content of the porous beads is less than 0.0005 g per 1 mL of the agarose gel solution, adsorption of polycyclic aromatic hydrocarbons (PAHs) by the resin gel does not substantially take place, and the content of the porous beads per mL of the agarose gel solution If it is more than 0.05 g, it is difficult to homogeneously mix the porous beads in the agarose gel solution. At this time, the concentration of the agarose gel solution may be 1.5%.
On the other hand, the thickness of the first
The
A first
The
The first
FIG. 2 is a photograph for explaining a state where the lower base and the upper cap of FIG. 1 are coupled.
Referring to FIG. 2 together with FIG. 1, a
3 is a photograph for explaining an apparatus and a method for forming the first thin film and the second thin film of the passive sampler.
3 (a) is a front view of the manufacturing apparatus, (b) is a photograph taken at an angle of 45 degrees from the front, and FIG. 3 (c) is a side view of the manufacturing apparatus.
Referring to Fig. 3, the manufacturing apparatus includes a pair of glass plates and spacers (white tubular members in Fig. 3) interposed between the glass plates. The spacers are disposed at each of the three edges of the glass plates except for the injection port into which the solution is injected and the thicknesses of the first thin film and the second thin film can be determined by the height of the spacers. In order to fix the pair of glass plates to the spacers, a clamp can be used as at least two fixing members. In the case of installing the spacers, a fixing rubber (yellow tubular member in Fig. 3) can be used.
Each of the first thin film and the second thin film is formed by injecting a mixed solution or an agarose gel solution described in FIG. 1 between a pair of glass plates through an injection port of the apparatus described in FIG. 3, gelling the mixed solution or agarose gel solution, Followed by separation and cutting.
FIG. 4 is a photograph showing a state in which a passive sampler according to the present invention is applied to soil in a laboratory environment, and FIG. 5 is a photograph showing a state in which a passive sampler according to the present invention is applied to each soil contaminated with PAHs having different concentrations .
Referring to FIG. 4, the
Referring to FIG. 5, the
Hereinafter, the method of manufacturing the passive sampler according to the present invention, the characteristics of the first thin film (resin gel), and the evaluation method of the PAHs contamination degree in the soil, water or sediments according to the present invention, This will be described in detail.
Example 1: Manufacture of a passive sampler
(1) Preparation of mixed solution
First, a 1.5% agarose gel solution was prepared. The agarose gel solution was prepared by measuring the amount of agarose to fit the ratio, placing it in a beaker with ultrapure water, stirring it with a stirring magnet, and heating it to 100 ° C or higher. While the agarose gel solution was boiling and transparent, 0.1 g of Tenax ® TA beads was added to 20 mL of agarose gel solution while stirring with a stirring magnet to prepare a homogeneous mixed solution.
(2) Production of first thin film (resin gel)
As shown in FIG. 3, three spacers made of 0.075 cm thick plastic were sandwiched between two glass plates. The mixed solution prepared above was poured between the glass plates with one side (injection port) not fixed with a spacer so as not to create a maximum gap. The mixed solution was allowed to stand at room temperature (about 25 ° C) until it hardened, and then cut into a 2.5 cm diameter cutter made of stainless steel to prepare a first thin film (resin gel). At this time, the thickness of the first thin film (resin gel) was 0.75 cm. The produced first thin film (resin gel) was photographed, and the results are shown in Fig.
6 is a photograph of the first thin film produced using the apparatus of FIG.
Referring to FIG. 6, the agarose gel is gelled to form a matrix of a transparent thin film as a whole, and Tenax ® TA beads uniformly dispersed in the matrix can be identified.
(3) Production of second thin film (diffusion gel)
3 was prepared and a second thin film (diffusion gel) was prepared through substantially the same procedure as that for forming the first thin film (resin gel) using a 1.5% agarose gel solution. At this time, the thickness of the second thin film (diffusion gel) was 0.05 cm.
(4) Assembly process
The lower base and upper cap of the type shown in Figure 2 were purchased from DGT Research (UK, UK). A first thin film (resin gel) and a second thin film (diffusion gel) prepared above were sequentially laminated on a lower base, and a PTFE filter (Polytetrafluoroethylene filter) having a thickness of 0.1 cm, a diameter of 2.5 cm and a pore size of 0.45 탆, (Purchased from Chmlab group, Inc., Spain) was placed on a second membrane (diffusion gel) as a membrane filter, and then the upper cap was covered to prepare a passive sampler according to Example 1 of the present invention.
Manufacture of PAHs contaminated soil
The amount of 20% of soil to be contaminated among natural soil sieved with 2 mm sieve was first put into a glass bottle. Phenanthrene (> 96%, purchased from Sigma Chemical Co, USA) was dissolved in acetone (Acetone,> 99.8%, Merck, USA) as solvent and dissolved in acetone Phenanthrene solutions with concentrations of 62.5, 125, 250 and 500 mg / kg of phenanthrene were prepared, each of the phenanthrene solutions was added to a vial containing 20% of soil, and a quantity corresponding to 80% of uncontaminated soil And mixed with a tumbler (Tumbler, 15 rpm) for 1 day. After the mixing process, acetone was volatilized for 16 hours in the dark to produce PAHs contaminated soil contaminated with phenanthrene.
Pyrene solutions with pyrene concentrations of 62.5, 125, 250 and 500 mg / kg were prepared using Pyrene (> 95%, purchased from Sigma-Aldrich, Inc., USA) PAHs contaminated soils with different concentrations of pyrene were prepared.
Measurement of adsorption efficiency of 1st thin film (resin gel)
Adsorption efficiency was measured in PAHs solution to confirm the practical use of the first thin film (resin gel). Specifically, the first thin film (resin gel) prepared above was placed in a 125 mL Erlenmeyer flask together with 80 mL of the PAHs solution and subjected to adsorption reaction in a shaker (200 rpm) for 24 hours. The adsorption efficiency of the first thin film (resin gel) was measured by analyzing the remaining PAHs concentration in the PAHs solution extracted from the first thin film (resin gel) after the adsorption reaction.
In Equation 1, f e means the ratio of the eluted resin gel to the first thin film (resin gel).
[Formula 1]
Diffusion coefficient measurement of first thin film (resin gel)
In order to evaluate the concentration of PAHs extracted with the first thin film (resin gel) of the passive sampler, a gel diffusion coefficient was required, and the measurement was made as follows.
In a 250 mL Erlenmeyer flask made with a wide inlet with the same diameter as the top cap of the passive sampler, 80 mL of the phenanthrene solution and the pyrene solution used to make the PAHs artificially contaminated soil were added. The upper cap of the passive sampler manufactured above was fitted to fit the inlet of the flask, and then fixed with parafilm and rubber band. The Erlenmeyer flask equipped with a fixed passive sampler was inverted and reacted in a shaker (200 rpm, 25 ° C) for 1, 2, 5, 10, 16, 24, 36 and 48 hours. The number of repetitions per each hour was 3. The first thin film (resin gel) harvested at each reaction time was harvested and added to a mixed solution of 3 mL of acetone and hexane (volume ratio) of 1: 1. Ultrasonic washing machine (Branson 8510, trade name, USA) Respectively. The extraction procedure was repeated three times. The extracted solution was concentrated using a concentrator (Cheilmin Tech Co., Ltd., Korea) and 1.5 mL of dichloromethane was used as a final solvent. The final solution was purified on a 35-60 mesh silica gel (purchased from Sigma-Aldrich (USA), mesh Silica gel) and analyzed by GC-MS (Agilent Technologies, USA). The amount of contaminants accumulated in the first thin film (resin gel) was calculated by applying
[Formula 2]
M represents the amount (unit: mg) of the contaminant accumulated in the first thin film (resin gel), C e represents the concentration of the contaminant extracted in the solvent (unit: mg / mL). Where V e is the volume of the solvent for extracting means (in mL) and, V g is a first thin film bulk of the (resin gel) by the product of cross-sectional area and thickness (in mL) of a first thin film (resin gel) . If V g is 2-3% of V e , V g can be ignored. In addition, f e represents the adsorption efficiency of the resin gel obtained from Equation 1. The M values obtained in the equation (2) are plotted in graphs for each hour (1, 2, 5, 10, 16, 24, 36, 48 hours), and the results are shown in FIG. 7 and FIG.
7 and 8 are graphs showing the amount of contaminants accumulated in the first thin film with time. FIG. 7 is a graph of phenanthrene and FIG. 8 is a graph of pyrene. FIG.
7, the slope of the phenanthrene graph is 0.2364, and the slope of the phenylene graph of FIG. 8 is 0.0224. Using this slope, the diffusion coefficient ( D ) is calculated according to the following equation (3).
[Formula 3]
7 and 8, and Δg is the thickness of the diffusion layer plus the thickness of the second thin film (diffusion gel) (0.05 cm) plus the thickness of the membrane filter (0.01 cm) . C represents the concentration (unit: μg / mL) of the solution present at the interface with the passive sampler. A represents the surface area (3.14 cm 2 ) at which the passive sampler is actually exposed. The diffusion coefficients D (cm 2 / s) of phenanthrene and pyrene derived from Equation 3 were 1.7776 × 10 -6 and 1.6844 × 10 -7 , respectively.
Comparison of Concentration in PAHs Contaminated Soil and Concentration Absorbed by Passive Sampler
Phenanthrene and pyrene, respectively, were determined as shown in
[Formula 4]
In
The results are shown in Tables 1 and 2. Table 1 shows the concentration of phenanthrene and Table 2 shows the concentration of pyrene.
Soil concentration
(mg / kg)
(mg / L)
(mL)
(μg)
(μg / L)
Soil concentration
(mg / kg)
(mg / L)
(mL)
(μg)
(μg / L)
Referring to Table 1 and Table 2, it can be confirmed that PAHs of organic materials such as phenanthrene and pyrene can be measured using the first thin film (resin gel) included in the passive sampler of the present invention. This suggests the possibility of in situ analysis of soil contaminated with PAHs, thus providing a method for indirectly predicting bioavailable concentrations in PAHs contaminated soil.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims. It can be understood that it is possible.
300:
130: Membrane filter 210: Lower base
220: upper cap
Claims (9)
An agarose gel, and a porous bead of poly (2,6-diphenylphenylene oxide) dispersed in the agarose gel.
Thin film for passive sampler.
Wherein the porous beads are formed by mixing 0.1 to 1.0 g of the porous beads in 20 to 200 mL of the agarose gel solution.
Thin film for passive sampler.
And gelling the mixed solution to form a thin film.
A method for the preparation of thin films for passive samplers for the determination of bioavailable polycyclic aromatic hydrocarbons (PAHs) in soil, water or sediments.
A first thin film disposed on the lower base and comprising a resin gel comprising agarose gel and porous beads of poly (2,6-diphenylphenylene oxide) dispersed in the agarose gel;
A second thin film formed on the first thin film and including an agarose gel;
A membrane filter disposed on the second thin film and formed of a polymer; And
And an upper cap coupled to the lower base such that the first thin film, the second thin film, and the membrane filter are fixed on the lower base,
Passive sampler for measuring bioavailable polycyclic aromatic hydrocarbons (PAHs) concentrations in soil, aquatic or sediment.
The first thin film
Wherein the porous beads are formed of a mixed solution in which 0.0005 g to 0.05 g of the porous beads are dispersed in 1 ml of the agarose gel solution.
Passive sampler for measuring bioavailable polycyclic aromatic hydrocarbons (PAHs) concentrations in soil, aquatic or sediment.
The first thin film
Wherein the porous beads are formed by mixing 0.1 to 1.0 g of the porous beads in 20 to 200 mL of the agarose gel solution.
Passive sampler for measuring bioavailable polycyclic aromatic hydrocarbons (PAHs) concentrations in soil, aquatic or sediment.
Sequentially stacking the first thin film, the second thin film including the agarose gel, and the membrane filter formed of the polymer on the lower base; And
Assembling the lower base disposed up to the membrane filter with the upper cap.
A method for the preparation of passive samplers for the determination of bioavailable polycyclic aromatic hydrocarbons (PAHs) concentrations in soil, aquatic or sediment.
The mixed solution
0.0005 g to 0.05 g of the porous beads are dispersed in 1 mL of the agarose gel solution.
A method for the preparation of passive samplers for the determination of bioavailable polycyclic aromatic hydrocarbons (PAHs) concentrations in soil, aquatic or sediment.
Wherein the thickness of the first thin film is 0.05 cm to 0.1 cm.
A method for the preparation of passive samplers for the determination of bioavailable polycyclic aromatic hydrocarbons (PAHs) concentrations in soil, aquatic or sediment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102394285B1 (en) | 2021-10-01 | 2022-05-04 | 주식회사 한국수산해양공학연구소 | Apparatus for sampling nutrients and contaminants in pore water of river and lake sediments |
| CN115541565A (en) * | 2022-09-22 | 2022-12-30 | 中国石油大学(北京) | Detection device and method for heavy metal bioavailability |
| KR102507441B1 (en) | 2022-11-16 | 2023-03-09 | 주식회사 한국수산해양공학연구소 | Remotely Operated Vehicle With the Function of Pollutant Sampling |
| CN116593415A (en) * | 2023-07-18 | 2023-08-15 | 延津县兴鑫农业种植专业合作社 | Dynamic detection device and method for soil heavy metal remediation |
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2015
- 2015-04-08 KR KR1020150049796A patent/KR20160120568A/en active Search and Examination
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102394285B1 (en) | 2021-10-01 | 2022-05-04 | 주식회사 한국수산해양공학연구소 | Apparatus for sampling nutrients and contaminants in pore water of river and lake sediments |
| CN115541565A (en) * | 2022-09-22 | 2022-12-30 | 中国石油大学(北京) | Detection device and method for heavy metal bioavailability |
| KR102507441B1 (en) | 2022-11-16 | 2023-03-09 | 주식회사 한국수산해양공학연구소 | Remotely Operated Vehicle With the Function of Pollutant Sampling |
| CN116593415A (en) * | 2023-07-18 | 2023-08-15 | 延津县兴鑫农业种植专业合作社 | Dynamic detection device and method for soil heavy metal remediation |
| CN116593415B (en) * | 2023-07-18 | 2023-10-03 | 延津县兴鑫农业种植专业合作社 | Dynamic detection device and method for soil heavy metal remediation |
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