On-site chlorinated organic staining fluorescence survey technique

CN117191749BActive Publication Date: 2026-09-01KUN SHAN UNIVERSITY +1
View PDF 2 Cites 0 Cited by

Patent Information

Application Number
CN202210611790.1
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2022-05-31
Publication Date
2026-09-01
Estimated Expiration
2042-05-31

AI Technical Summary

Technical Problem

[0003]然而,激光激发荧光的检测方法对于不具荧光特性的污染物(如三氯乙烯及四氯乙烯)并不适用,所以降低此检测方法的利用性

Benefits of technology

[0015]应用本发明的地下环境介质中的含氯有机物分布的调查方法,其中通过含有姜黄萃取物、红色油性色素及食品香精乳化液的荧光染料对地下环境介质进行染色处理,以使不具荧光特性的含氯有机物具备源自于荧光染料的荧光特性,从而使激光激发荧光检测方法可调查含氯有机物于地下环境介质中的分布。

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure CN117191749B_ABST
    Figure CN117191749B_ABST
Patent Text Reader

Abstract

This invention relates to a survey method for detecting the distribution of chlorinated organic compounds in underground environmental media. This method utilizes a fluorescent dye containing turmeric extract, red oily pigment, and food flavoring emulsion to stain the underground environmental media, thereby endowing the chlorinated organic compounds with fluorescent properties derived from the fluorescent dye. This allows a laser-excited fluorescence detection method to investigate the distribution of chlorinated organic compounds in underground environmental media.
Need to check novelty before this filing date? Find Prior Art

Description

Technical Field

[0001] This invention relates to a survey method for detecting the distribution of chlorinated organic compounds in underground environmental media, and more particularly to a survey method for detecting the distribution of non-fluorescent chlorinated organic compounds in underground environmental media. Background Technology

[0002] Traditional laser-excited fluorescence detection methods utilize laser light to excite a fluorescent analyte, causing it to emit fluorescence. The concentration of the analyte is then detected by the fluorescence intensity. Higher fluorescence intensity indicates a higher analyte concentration, and vice versa. This method offers high sensitivity even for trace amounts of analytes and is therefore widely used to detect pollutants and their distribution. Examples of pollutants include polycyclic aromatic hydrocarbons (PAHs) and fuel oils.

[0003] However, laser-excited fluorescence detection methods are not applicable to non-fluorescent pollutants (such as trichloroethylene and tetrachloroethylene), thus reducing the usability of this method. Therefore, there is an urgent need to develop a new detection method to overcome these shortcomings. Summary of the Invention

[0004] In view of the above-mentioned problems, one aspect of the present invention is to provide a method for investigating the distribution of chlorinated organic compounds in underground environmental media. This method utilizes a fluorescent dye containing turmeric extract, red oily pigment, and food flavoring emulsion to stain non-fluorescent chlorinated organic compounds, thereby giving them fluorescent properties and enabling the investigation of their distribution in underground environmental media.

[0005] According to one aspect of the present invention, a method for investigating the distribution of chlorinated organic compounds in underground environmental media is provided. In this method, the underground environmental media is dyed with a fluorescent dye to obtain a dyed environmental media containing chlorinated organic compounds. The fluorescent dye comprises 5 to 15% turmeric extract, 5 to 25% red oily pigment, 15 to 30% food flavoring emulsion, and the remainder being solvent, based on a 100% weight percentage of the fluorescent dye. Next, fluorescence measurement is performed on the dyed environmental media to obtain the distribution of chlorinated organic compounds in the underground environmental media. The fluorescence measurement utilizes an excitation light source to irradiate the dyed environmental media, and a detection element measures the fluorescence emitted by the irradiated dyed environmental media. The detection element uses a location on or inside the underground environmental media as the measurement starting point and measures the change in fluorescence intensity over a moving distance.

[0006] According to one embodiment of the present invention, the red oily pigment is an azo dye.

[0007] According to another embodiment of the present invention, the solvent includes an oily solvent and an aqueous solvent.

[0008] According to another embodiment of the present invention, the underground environmental medium includes soil, silt, rocks and / or stone.

[0009] According to another embodiment of the present invention, the chemical structure of the chlorinated organic compound includes at least one alkenyl group.

[0010] According to another embodiment of the present invention, at least one substituent of the alkenyl group is a chlorine atom.

[0011] According to another embodiment of the present invention, the excitation wavelength of the excitation light source is 250 nm to 350 nm.

[0012] According to another embodiment of the present invention, the detection wavelength of the detection element is 300nm to 550nm.

[0013] According to another embodiment of the present invention, prior to the dyeing treatment, the investigation method further includes an infusion step, which includes infusing fluorescent dye into the surface and / or interior of the underground environmental medium.

[0014] According to another embodiment of the present invention, the infusion rate of the infusion step is from 0.5 L / m to 2.0 L / m.

[0015] The method for investigating the distribution of chlorinated organic compounds in underground environmental media according to the present invention involves staining the underground environmental media with a fluorescent dye containing turmeric extract, red oily pigment and food flavor emulsion, so that the chlorinated organic compounds that do not have fluorescent properties acquire fluorescent properties derived from the fluorescent dye, thereby enabling the laser-excited fluorescence detection method to investigate the distribution of chlorinated organic compounds in underground environmental media. Attached Figure Description

[0016] To gain a more complete understanding of the embodiments and advantages of the present invention, please refer to the following description and the accompanying drawings. It must be emphasized that the various features are not depicted to scale and are for illustrative purposes only. The relevant drawings are explained below: Figure 1 A flowchart illustrating a method for investigating the distribution of chlorinated organic compounds in underground environmental media according to an embodiment of the present invention.

[0017] Figure 2 A flowchart illustrating a method for investigating the distribution of chlorinated organic compounds in underground environmental media according to a specific embodiment of the present invention.

[0018] Figure 3 To illustrate the relationship between the location depth and fluorescence intensity according to an embodiment of the present invention. Detailed Implementation

[0019] The investigation and application of embodiments of the present invention are discussed in detail below. However, it is understood that the embodiments provide many applicable inventive concepts that can be implemented in a wide variety of specific contexts. The specific embodiments discussed are for illustrative purposes only and are not intended to limit the scope of the invention.

[0020] Please see Figure 1 A method for investigating the distribution of chlorinated organic compounds in underground environmental media 100 utilizes a fluorescent dye containing turmeric extract, red oily pigment, and food flavoring emulsion to stain the underground environmental media, so that the chlorinated organic compounds have the fluorescent properties derived from the fluorescent dye, thereby enabling the laser-excited fluorescence detection method to investigate the distribution of chlorinated organic compounds in underground environmental media.

[0021] Besides imparting fluorescent properties to chlorinated organic compounds, the selection of fluorescent dyes should also consider their compatibility with chlorinated organic compounds to promote mixing and accelerate staining, thereby facilitating in-situ detection of their distribution. Furthermore, the permeability of fluorescent dyes to underground environmental media should also be considered to allow for rapid penetration and immediate staining of the chlorinated organic compounds. This permeability can be determined by the properties of the fluorescent dye (such as hydrophobicity and viscosity).

[0022] The aforementioned staining treatment utilizes fluorescent dyes on the underground environmental medium to obtain a stained environmental medium, as shown in operation 110. In some embodiments, the chlorinated organic compound may include chlorinated alkanes having 1 to 3 carbon atoms, or chlorinated ethylene compounds. For example, dichloroethane, carbon tetrachloride, and chlorinated ethylene compounds such as dichloroethylene, trichloroethylene, and tetrachloroethylene. Preferably, the chemical structure of the chlorinated organic compound contains at least one alkenyl group, which can react with components of the fluorescent dye having active functional groups (such as alkenyl and azo groups) to further enhance the staining effect. More preferably, at least one substituent of the alkenyl group is a chlorine atom to accelerate the staining reaction, thereby facilitating the on-site detection of the distribution of the chlorinated organic compound. After the aforementioned chlorinated organic compound is stained, a stained chlorinated organic compound is generated. This stained chlorinated organic compound can emit fluorescence upon excitation for subsequent fluorescence detection.

[0023] The underground environmental medium of this invention is not particularly limited, but its primary purpose is to allow chlorinated organic compounds to be distributed therein. Therefore, as those skilled in the art will understand, the underground environmental medium is not dissolved by chlorinated organic compounds. In some embodiments, the underground environmental medium may comprise soil, silt, rocks and / or stones, or other solid environmental media. In these embodiments, the investigation method 100 can detect the distribution of chlorinated organic compounds, such as pollutants, in the environmental medium, thereby revealing the spread of pollutants or tracing their source.

[0024] In detail, based on a 100% by weight percentage of the fluorescent dye, the fluorescent dye comprises 5% to 15% by weight of turmeric extract, 5% to 25% by weight of red oily pigment, 15% to 30% by weight of food flavoring emulsion, and the balance being solvent. If the fluorescent dye does not contain the aforementioned components, chlorinated organic matter in the underground environmental medium treated with the fluorescent dye will not have good fluorescent properties, and therefore its distribution in the underground environmental medium cannot be effectively detected.

[0025] In some embodiments, turmeric extract can be obtained by extracting the rhizomes of turmeric using water, alcohols, and / or other organic solvents. For example, the composition of the turmeric extract may include curcumin, demethoxycurcumin, didemethoxycurcumin, dihydrocurcumin, and hexahydrocurcumin. When the amount of this turmeric extract is 5% by weight, this amount can significantly improve the staining effect on chlorinated organic compounds; for example, by comparing the fluorescence intensity of trichloroethylene before and after staining, the fluorescence signal intensity can be significantly increased.

[0026] Furthermore, if the amount of turmeric extract used is less than 5% by weight, the insufficient amount of turmeric extract will reduce the staining effect of the fluorescent dye on chlorinated organic compounds. Conversely, if the amount of turmeric extract used is greater than 15% by weight, the excessive amount of turmeric extract will increase the generation of fluorescence noise and interfere with the detection of chlorinated organic compounds. Preferably, the amount of turmeric extract used is 10% by weight.

[0027] In some embodiments, the red oily pigment is an azo dye, which has an azo group and can therefore react with chlorinated organic compounds having an alkenyl group, thereby improving the dyeing effect.

[0028] Table 1 below shows the staining effects of common food flavorings and turmeric powder on chlorinated organic matter in soil. Two grams of sandy soil containing 0.2 mL of trichloroethylene were used for staining with 0.2 mL of food flavoring or turmeric powder. The fluorescence intensity was measured after irradiating the soil with a 308 nm laser (the fluorescence intensity was measured in the 350 nm to 500 nm fluorescence band using an additive method). The increase in fluorescence intensity after staining was calculated as a percentage, using the pre-staining fluorescence intensity as a baseline.

[0029] Table 1

[0030] Furthermore, if the amount of red oily dye used is less than 5% by weight, too little red oily dye will reduce the staining effect of the fluorescent dye on chlorinated organic compounds. Conversely, if the amount of red oily dye used is greater than 25% by weight, too much red oily dye will increase the generation of fluorescence noise and interfere with the detection of chlorinated organic compounds. Preferably, the amount of red oily dye used can be between 10% and 20% by weight.

[0031] The food flavoring emulsion comprises honey flavoring, jasmine flavoring, pineapple flavoring, and propylene glycol. Propylene glycol is used only as a solvent to dissolve the three flavorings, and its amount is the minimum required for them to be miscible. In one specific example, this amount may be, but is not limited to, less than 0.05 times the weight of the food flavoring emulsion. The food flavoring emulsion can adjust the viscosity of the fluorescent dye and its permeability to underground environmental media. If the amount of food flavoring emulsion is less than 15% by weight, the fluorescent dye diffuses too quickly, leaving insufficient time for the chlorinated organic matter to be dyed. Conversely, if the amount of food flavoring emulsion is greater than 30% by weight, the viscosity of the fluorescent dye is too high, and the fluorescent dye is not easily filled into the underground environmental media, thus failing to effectively dye the chlorinated organic matter. Preferably, the amount of food flavoring emulsion is 20% to 30% by weight.

[0032] The solvent is used to dissolve the aforementioned components of the fluorescent dye and helps to adjust the hydrophobicity and permeability of the fluorescent dye to underground environmental media. For example, it improves the compatibility of the fluorescent dye with chlorinated organic compounds (e.g., by having similar hydrophobicity to chlorinated organic compounds) to facilitate the penetration of the fluorescent dye into the underground environmental media and the uniform mixing of the two. In some embodiments, the solvent may comprise an oil-based solvent and an aqueous solvent. Specifically, the oil-based solvent may comprise edible blended oils, propylene glycol, and glycerin, and the aqueous solvent may comprise ethanol and water.

[0033] In some embodiments, the edible blended oil is a mixture of at least two edible oils. There are no particular limitations on the type and amount of the edible blended oil used in this invention, as long as the purpose is to enable the fluorescent dye obtained therefrom to penetrate and stain underground environmental media. For example, the edible blended oil may contain at least two of vegetable oils such as canola oil, sunflower oil, palm oil, olive oil, and soybean oil. Preferably, the oil is liquid at room temperature. In some specific examples, based on a 100% by weight percentage of the fluorescent dye, the amount of edible blended oil may be from 0.1% to 0.5% by weight.

[0034] Please refer to the following: Figure 1 Following operation 110, fluorescence measurements were performed on the stained environmental medium to obtain the distribution of chlorinated organic compounds in the underground environmental medium, as shown in operation 120. For details, please refer to [link to relevant documentation]. Figure 2In some embodiments, the investigation method 200 may sequentially perform drilling step 210, injection step 220, staining treatment 230 and fluorescence measurement 240.

[0035] In drilling step 210, a penetration device is used to drill through the underground environmental medium contaminated with chlorinated organics to form a borehole or channel. Then, a priming element, such as a pump, is used to prime fluorescent dye into the borehole or channel through a conduit. In some specific examples, the priming rate in priming step 220 can be from 0.5 L / m to 2.0 L / m to ensure that the fluorescent dye is smoothly and uniformly injected into the borehole or channel and penetrates into the underground environmental medium, immediately generating stained chlorinated organics, thereby achieving on-site fluorescence detection.

[0036] Then, fluorescent dyes are used to stain chlorinated organic compounds in the underground environmental medium 230 to generate stained chlorinated organic compounds. Next, a detection element is used to detect the fluorescence of the stained chlorinated organic compounds. The detection element includes an excitation light source module, an emission light detection module, a window, an optical fiber signal line, an oscilloscope, and a computer.

[0037] In some embodiments, the excitation source of the excitation light source module can generate excitation light, such as light with a wavelength of 250 nm to 350 nm. After irradiating the staining environment medium with the excitation light, the stained chlorinated organic matter inside the staining environment medium emits fluorescence. The fluorescence is measured using a radiation detection module. In some embodiments, the detection wavelength of the detection module can be 300 nm to 550 nm, which can be adjusted according to the fluorescence emitted by the stained chlorinated organic matter.

[0038] When measuring fluorescence, the excitation light source module uses a predetermined location on or inside the surface of the underground environmental medium as the measurement starting point and measures the change in fluorescence intensity within a predetermined moving distance. In some embodiments, the predetermined moving distance can be a vertical distance (such as depth). For example, using the factory ground (the surface of the underground environmental medium) as a reference point, a drilling machine is used to drill 30 meters down from the ground to form a borehole. When a fluorescent dye comes into contact with trichloroethylene in the soil, the fluorescent dye stains the trichloroethylene, making the stained trichloroethylene fluorescent. The ultraviolet light generated by the excitation light source irradiates the stained trichloroethylene through an optical fiber signal line and a window of a probe inserted into the borehole. The resulting fluorescence is then transmitted through the window and via the optical fiber signal line to the detection element. The fluorescence intensity is displayed on an oscilloscope, and a computer records the change in fluorescence intensity with depth. Since the fluorescence intensity is positively correlated with the concentration of chlorinated organic compounds, the distribution of chlorinated organic compounds 30 meters down from the ground can be determined based on the change in fluorescence intensity with depth.

[0039] In some applications, within a geological site contaminated with chlorinated organic compounds (COCs), the investigation method according to the present invention allows for the detection of COCs at a single location to obtain a graph showing the relationship between depth and fluorescence intensity at that location. Analysis of this graph then reveals the distribution of COCs with depth at that location. In other applications, COCs can be detected at multiple locations to obtain graphs showing the relationship between depth and fluorescence intensity at these locations. Analysis of these graphs then reveals the distribution of COCs, thereby identifying the initial location of the contamination and the extent of its spread. Furthermore, the results of the aforementioned investigations can provide users with a reference for designing the removal or remediation of COC contamination.

[0040] The following examples illustrate the application of the present invention, but are not intended to limit the invention. Those skilled in the art can make various modifications and refinements without departing from the spirit and scope of the invention.

[0041] Methods for investigating the distribution of chlorinated organic compounds Example The method for investigating the distribution of chlorinated organic compounds in this embodiment involves first drilling the soil contaminated with trichloroethylene and cis-1,2-dichloroethylene, then injecting fluorescent dye from the bottom of the borehole upwards at an injection rate of 1.5 L / m, using the ground as the starting point for measurement, and recording the fluorescence intensity according to the depth. The aforementioned fluorescent dye comprises 10% by weight of turmeric extract, 20% by weight of red oily pigment, 20% by weight of food flavoring emulsion, and 50% by weight of solvent. The solvent contains 0.3% by weight of edible blended oil, and the remainder is a mixture of propylene glycol, ethanol, and water. The weight ratio of propylene glycol, ethanol, and water is adjusted to ensure uniform mixing of the other components. During fluorescence measurement, the soil is irradiated with laser light at a wavelength of 308 nm, and fluorescence at wavelengths of 350±20 nm, 400±20 nm, 450±20 nm, and 500±20 nm is collected from the soil. The fluorescence intensity is plotted vertically and plotted against the fluorescence intensity. Figure 3 In addition, after completing the fluorescence detection of the distribution of chlorinated organic matter, soil samples were collected from the drilled underground environmental medium according to the drilling depth.

[0042] Evaluation method The following three experiments are used to compare the results of the survey method in the embodiments to evaluate the accuracy of the survey method. The survey method of the embodiments is considered accurate when the results of all the experiments match the results of the embodiments.

[0043] 1. Dye shaking test The dye shaking test uses a dye (trade name: Oil-Red-O) mixed with a soil sample. This dye stains trichloroethylene and cis-1,2-dichloroethylene, so soil samples contaminated with these pollutants will appear red. This red color is visible to the naked eye, thus indicating the presence of the pollutants in the soil sample.

[0044] 2. Soil pollutant concentration analysis Soil pollutant concentration analysis was performed according to the volatile organic compound detection method (method number NIEA M711.04C). The concentration of volatile organic compounds in soil samples was analyzed by gas chromatography-mass spectrometry (GC-MS) to determine whether the aforementioned pollutants were present in the soil samples.

[0045] 3. Experiment with photoionization detection (PID) The photoionization detection test uses a photoionization detector to screen soil samples for volatile organic compounds in order to determine whether the aforementioned pollutants are present in the soil samples.

[0046] Table 2

[0047] "X" indicates that no contaminants were detected, and "O" indicates that contaminants were detected.

[0048] "%RE" represents the relative percentage intensity, which is the sum of the fluorescence intensities at 350nm, 400nm, 450nm, and 500nm.

[0049] Please refer to Table 2 and Figure 3 Table 2 shows Figure 3 The results were measured at two depths. According to the investigation results of the distribution of chlorinated organic compounds in the example, chlorinated organic compounds exhibited a high-intensity fluorescence peak at depths of 8.75 m to 9.00 m. This result is consistent with the results of the dye shaking test, soil pollutant concentration analysis, and photoionization detection test. Furthermore, the soil pollutant concentration analysis results are higher than the soil pollution control standards (the control standard for trichloroethylene is 60 mg / Kg, and the control standard for cis-1,2-dichloroethylene is 7 mg / Kg). Therefore, the investigation method for the distribution of chlorinated organic compounds in the example is accurate.

[0050] In summary, the method for investigating the distribution of chlorinated organic compounds in underground environmental media of the present invention utilizes a fluorescent dye containing turmeric extract, red oily pigment, and food flavoring emulsion to stain the underground environmental media, thereby causing non-fluorescent chlorinated organic compounds to acquire fluorescent properties derived from the fluorescent dye, thus enabling the laser-excited fluorescence detection method to investigate the distribution of chlorinated organic compounds in underground environmental media.

[0051] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Those skilled in the art to which this invention pertains can make various modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the claims.

[0052] [Symbol Explanation] 100, 200: Method 110, 120: Operation 210, 220: Steps 230: Processing 240: Measurement.

Claims

1. A method for investigating the distribution of chlorinated organic matter in underground environmental media, characterized in that, Include: The underground environmental medium is dyed with a fluorescent dye to obtain a dyed environmental medium containing a chlorinated organic compound, wherein the chlorinated organic compound is a chlorinated substituted alkane with 1 to 3 carbon atoms, or a chlorinated substituted ethylene compound, and the fluorescent dye comprises, based on 100% by weight, the following: 5% to 15% by weight of turmeric extract; 5% to 25% by weight of red oily pigment; Food flavoring emulsions ranging from 15% to 30% by weight; and The remaining solvent; and Fluorescence measurement is performed on the dyed environmental medium to obtain the distribution of the chlorinated organic compound in the underground environmental medium. The fluorescence measurement is performed by irradiating the dyed environmental medium with an excitation light source and measuring the fluorescence emitted by the dyed environmental medium after irradiation with a detection element. The detection element takes the position on the surface or inside the underground environmental medium as the measurement starting point and measures the change in fluorescence intensity within the moving distance.

2. The survey method according to claim 1, characterized in that, The red oily pigment is an azo dye.

3. The survey method according to claim 1, characterized in that, The solvent includes both oil-based and water-based solvents.

4. The survey method according to claim 1, characterized in that, The underground environment includes soil, silt, rocks and / or stones.

5. The survey method according to claim 1, characterized in that, The chemical structure of this chlorinated organic compound contains at least one alkenyl group.

6. The survey method according to claim 5, characterized in that, At least one substituent of the alkenyl group is a chlorine atom.

7. The survey method according to claim 1, characterized in that, The excitation wavelength of this excitation source is 250 nm to 350 nm.

8. The survey method according to claim 1, characterized in that, The detection wavelength of this detection element is from 300nm to 550nm.

9. The survey method according to claim 1, characterized in that, Prior to the dyeing treatment, the investigation method also includes an infusion step, which involves infusing the fluorescent dye into the surface and / or interior of the underground environmental medium.

Citation Information

Patent Citations

  • Application of curcumin to detection of hypochlorous acid

    CN103926230A

  • Vital stain

    US20160041100A1