TWI860738B - Method for optically detecting distribution of chlorobenzene in subsurface of surroundings by dye assisted fluorescence image - Google Patents

Abstract

The present invention relates to a method for optically detecting a distribution of chlorobenzene in a subsurface of the surroundings by dye assisted fluorescence image. For enhancing sensitivity of the chlorobenzene by using a fluorescent detection, a dye mixture having a specific weight ratio between jasmine essence and honey essence is injected into a drilling hole in environmental matrices, such that the environmental matrices is stained and the chlorobenzene and the dye mixture form a fluorescent product. Immediately, an image-acquiring process is performed on the environmental matrices after stained, so as to obtain two-dimensional fluorescent images by using a probing device with an exciting light source and an image-acquiring element. The fluorescent product emits fluorescence after excited by the exciting light source, and creates luminous areas in the two-dimensional fluorescent images. Area ratios of the luminous areas in the two-dimensional fluorescent images can be analyzed to determine whether the chlorobenzene is present in the environmental matrices, thereby real-time detecting the distribution of the chlorobenzene in the environmental matrices.

Description

Method for detecting chlorobenzene in the local environment using dye-assisted fluorescent imaging

The present invention relates to a method for detecting chlorobenzene in the local environment by dye-assisted fluorescent imaging, and in particular to a method for detecting chlorobenzene in the local environment by dye-assisted fluorescent imaging using a natural blending dye.

Chlorobenzene is an important raw material in the chemical industry. It can be used to synthesize a variety of useful compounds and then manufacture many chemical products. Although chlorobenzene has the aforementioned advantages, it is biologically toxic. Therefore, when chlorobenzene leaks, especially when it diffuses into the environmental medium, it will cause great harm to organisms (including humans). Therefore, in order to grasp the initial leakage range of chlorobenzene, track the diffusion range of chlorobenzene after the leakage, and confirm whether chlorobenzene remains after cleaning, the investigation technology of dye-assisted fluorescent imaging detection of chlorobenzene in the local environment (specifically, the method used to detect the distribution of chlorobenzene in the local environmental medium) is being continuously studied.

In the known method of detecting the distribution of chlorobenzene in the local environmental medium, samples are taken from different positions (such as along different depths from the ground surface) in the local environmental medium, and the samples are pre-treated (such as extraction and purification) to obtain treated samples or extracts. Then, the concentration of chlorobenzene in the treated samples or extracts is detected by mass spectrometry to obtain the distribution of chlorobenzene in the local environmental medium.

However, these methods require complex sample pretreatment and use expensive instruments, making it difficult to detect the distribution of chlorobenzene in the local environmental medium in real time. In view of this, it is urgent to develop a new method for detecting the distribution of chlorobenzene in the local environmental medium to improve the above shortcomings.

In view of the above problems, one aspect of the present invention is to provide a method for detecting chlorobenzene in the local environment by dyeing assisted fluorescent imaging. This method uses a blended dye of jasmine essence and honey essence with a specific weight ratio to dye chlorobenzene so that the dyed chlorobenzene has fluorescent properties, thereby improving the sensitivity of detecting chlorobenzene by fluorescence, thereby instantly detecting the distribution of chlorobenzene in the local environmental medium.

According to one aspect of the present invention, a method for detecting chlorobenzene in the local environment by dyeing-assisted fluorescent image is proposed. First, a blended dye is provided, which is composed of jasmine essence, honey essence and propylene glycol solution. The weight ratio of jasmine essence to honey essence is 0.4 to 1.2. Next, a borehole is vertically drilled from the local environment medium. Then, the blended dye is poured into the borehole, and the local environment medium is dyed with the blended dye to obtain a dyed local environment medium, in which chlorobenzene and the blended dye form a fluorescent product. Thereafter, a detection device is inserted into the borehole, wherein the detection device includes an excitation light source and an image capture element electrically connected to the excitation light source. Next, the dyed local environment medium is irradiated with an excitation light source, and the dyed local environment medium is imaged and processed at multiple depths using an image capture element to obtain multiple two-dimensional fluorescent images, wherein one of these two-dimensional fluorescent images includes a fluorescent color-developing area, and the fluorescent color-developing area has an area ratio in the corresponding ones of these two-dimensional fluorescent images. Then, these two-dimensional fluorescent images are analyzed and processed to obtain distribution diagrams of these area ratios relative to these depths, wherein when one of these area ratios is not less than a threshold value, it is determined that chlorobenzene is distributed in the local environment medium at the depth corresponding to the corresponding ones of these area ratios.

According to one embodiment of the present invention, the weight ratio of jasmine essence to honey essence is 0.8 to 1.0.

According to one embodiment of the present invention, the concentration of propylene glycol in the propylene glycol solution is 30 weight percent to 100 weight percent.

According to another embodiment of the present invention, based on the usage of the blending dye being 100 weight percent, the usage of the propylene glycol solution is greater than 0 weight percent and equal to 80 weight percent.

According to another embodiment of the present invention, based on the usage of the blending dye being 100 weight percent, the usage of the propylene glycol solution is 40 weight percent to 80 weight percent.

According to another embodiment of the present invention, the rate of perfusion of the dye blend is 0.5 liters/meter to 2.0 liters/meter.

According to another embodiment of the present invention, the excitation light source is deep ultraviolet light.

According to another embodiment of the present invention, the wavelength of deep ultraviolet light is 270 nanometers to 280 nanometers.

According to one embodiment of the present invention, the distance between two adjacent depths is greater than 0 cm and less than 1 meter.

According to another embodiment of the present invention, the threshold value is 0.5 percent.

The method of using the dye-assisted fluorescent image to detect chlorobenzene in the local environment of the present invention uses a blended dye of jasmine essence and honey essence with a specific weight ratio to dye chlorobenzene so that the dyed chlorobenzene has fluorescent properties, thereby improving the sensitivity of detecting chlorobenzene by fluorescence, thereby instantly detecting the distribution of chlorobenzene in the local environmental medium.

100:Methods

110,120,130,140,150,160: Steps

In order to have a more complete understanding of the embodiments of the present invention and its advantages, please refer to the following description and the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are only for illustration purposes. The contents of the relevant drawings are described as follows: [Figure 1] is a flow chart of a method for detecting the distribution of chlorobenzene in an underground environmental medium according to an embodiment of the present invention.

[Figure 2] is a graph showing the relationship between the depth from the ground and the area ratio of the fluorescent color display area of the two-dimensional fluorescent image obtained by the detection method of an application example of the present invention.

[Figure 3] to [Figure 4] are two-dimensional fluorescent images captured at two depths from the ground based on the detection method of an application case in Figure 2.

The manufacture and use 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 variety of specific contexts. The specific embodiments discussed are for illustration only and are not intended to limit the scope of the present invention.

The dye-assisted fluorescent imaging method of the present invention for detecting chlorobenzene in the local environment is related to a method for detecting the distribution of chlorobenzene in underground environmental media, wherein chlorobenzene is dyed with a blended dye of jasmine essence and honey essence with a specific weight ratio so that the dyed chlorobenzene has fluorescent properties, thereby increasing the sensitivity to chlorobenzene and being able to detect the distribution of chlorobenzene in the local environmental medium in real time. The detection method is described in detail below.

Please refer to FIG. 1 . In the detection method 100 , a blending dye is provided, as shown in step 110 . The blending dye is composed of jasmine essence, honey essence and propylene glycol solution. Both jasmine essence and honey essence are food grade essences. In some embodiments, jasmine essence can be a commercial product produced by Baitai Company or Yuanxin Biotech Company or a combination thereof. Honey essence can be a commercial product produced by Baitai Company or Yongyuan Company or a combination thereof. However, the "jasmine essence" and "honey essence" referred to in the present invention are not limited to the jasmine essence and honey essence produced by the aforementioned companies, but can also be food grade jasmine essence and honey essence produced by other companies, but for the purpose of achieving the aforementioned "dyeing effect of parachlorobenzene".

As mentioned above, the weight ratio of jasmine essence to honey essence is 0.4 to 1.2. If this weight ratio does not fall within the aforementioned range, the dyeing effect of the blended dye composed of them on chlorobenzene is reduced, thereby reducing the sensitivity of detecting chlorobenzene by fluorescence. Preferably, the weight ratio of jasmine essence to honey essence can be selectively 0.8 to 1.0.

Furthermore, based on the usage of the blending dye being 100 weight percent, the usage of the propylene glycol solution can be selected to be greater than 0 weight percent and equal to 80 weight percent, 40 weight percent to 80 weight percent, or 50 weight percent to 75 weight percent, so as to facilitate the blending dye to penetrate into the local environmental medium for dyeing, thereby improving the dyeing effect of the blending dye on chlorobenzene.

In some embodiments, the concentration of propylene glycol in the propylene glycol solution can be selected to be greater than 0 weight percent to 100 weight percent, preferably 30 weight percent to 100 weight percent, and more preferably 50 weight percent to 100 weight percent, so as to facilitate the blending dye to penetrate into the local environmental medium for dyeing, thereby improving the dyeing effect of the blending dye on chlorobenzene.

After step 110, a borehole is drilled vertically downward from the local environmental medium, as shown in step 120. In some embodiments, a penetration device can be used to drill vertically downward from the surface of the environmental medium (such as along the depth from the ground) to form a borehole. The penetration device can be one commonly used by those with ordinary knowledge in the technical field to which the present invention belongs. The formed borehole can be filled with the blending dye described later and penetrated into the detection device described later. As can be understood by those with ordinary knowledge in the technical field to which the present invention belongs, the borehole can be a hole of various sizes and shapes, and can be adjusted according to the shape of the detection device.

After step 120, the blended dye is poured into the drill hole, and the blended dye is used to dye the local environmental medium to obtain the dyed local environmental medium, as shown in step 130. In some embodiments, the local environmental medium may be, for example, a solid substance. In some specific examples, the local environmental medium may selectively include soil, sand and/or stone. As understood by those with ordinary knowledge in the technical field to which the present invention belongs, soil, sand and stone can be distinguished according to particle size. For example, the particle size of soil is smaller, the particle size of sand is second, and the particle size of stone is larger.

The method of perfusion of the blending dye can be as known to those with ordinary knowledge in the technical field to which the present invention belongs. For example, in some embodiments, the blending dye contained in the dye tank can be selectively pumped into the drill hole of the local environmental medium by a pump. In some specific examples, the perfusion rate can be selectively 0.5 liters/meter to 2.0 liters/meter, so as to save the blending dye while retaining the detection sensitivity of chlorobenzene. In other embodiments, the blending dye can selectively flow into the drill hole by gravity to save energy.

It should be noted that the "injection rate" referred to herein in the present invention refers to the volume of the mixed dye injected for each meter of the distance along the depth of the local environment medium (the unit is liter). The mixed dye contains a propylene glycol solution, which can make the mixed dye easily penetrate into the interior of the local environment medium. Therefore, when the mixed dye is injected into the drill hole, once the mixed dye contacts the inner wall of the drill hole (i.e., a part of the local environment medium), it will immediately penetrate into the interior of the local environment medium to dye. Therefore, the injection rate does not substantially affect the effect of the mixed dye on chlorobenzene dyeing. However, an appropriate injection rate (such as 0.5L/m to 2.0L/m) can avoid injecting too much blending dye into the drill hole of the local environmental medium. Excess blending dye may flow to the bottom of the drill hole, which will waste the blending dye.

When chlorobenzene is distributed in the local environmental medium, chlorobenzene will be dyed by the blending dye to form dyed chlorobenzene, i.e., a fluorescent product. Therefore, after dyeing, the local environmental medium contains dyed chlorobenzene. This dyed chlorobenzene has fluorescent properties and can scatter (or emit) fluorescence under the irradiation of an excitation light source, thereby increasing the sensitivity of detecting chlorobenzene by fluorescence.

After step 130, the detection device is inserted into the drill hole, as shown in step 140. The detection device includes an excitation light source and an image capture element electrically connected to the excitation light source.

After step 140, the dyed local environment medium is irradiated with an excitation light source, and the dyed local environment medium is imaged at a plurality of depths using an image capture element to obtain a plurality of two-dimensional fluorescent images, as shown in step 150. In detail, the excitation light source is used to irradiate the dyed local environment medium so that the dyed chlorobenzene contained in the environment medium scatters fluorescence, so the excitation light source must be able to generate light of a wavelength that can excite the chlorobenzene after dyeing with the blended dye, such as deep ultraviolet light. In some embodiments, the wavelength of the light generated by the excitation light source can be selectively 270nm to 280nm, and preferably 275nm. In addition, a specific example of an excitation light source may be a light-emitting diode (LED) bulb.

A specific example of the aforementioned image capture element may be a camera, which may have a complementary metal oxide semiconductor (CMOS) sensor to improve its sensitivity to the scattered fluorescence of dyed chlorobenzene. There is no special restriction on the setting of the parameters of the image capture element in the image processing, but the purpose is to achieve or promote the aforementioned "blending dyes to improve the sensitivity of detecting chlorobenzene".

During the image acquisition process, the dyed local environment medium is irradiated with an excitation light source. As mentioned above, when chlorobenzene is distributed in the local environment medium, the chlorobenzene will be dyed by the blending dye to become dyed chlorobenzene (i.e., fluorescent product), and the dyed chlorobenzene will scatter fluorescence under the irradiation of the excitation light source. This fluorescence produces a fluorescent color-developing area in a two-dimensional fluorescent image. Preferably, the image capture element can be selectively equipped with a filter to filter out other background interference or the light of the aforementioned excitation light source, and only allow the fluorescence scattered by the dyed chlorobenzene to enter the sensor in the image capture element to enhance the sensitivity to chlorobenzene.

The dyed local environment medium can be imaged along the depth direction of the local environment medium (i.e., images are captured facing the wall of the drill hole), and these two-dimensional fluorescent images correspond to different depths of the local environment medium. Specifically, the interval between two adjacent depths can be determined according to the size of the two-dimensional fluorescent image, the preset depth of the local environment medium to be detected, and the time of image processing. In some embodiments, continuous imaging can be adopted, that is, there is no interval between two adjacent depths. In other embodiments, two adjacent depths can be selectively separated by more than 0 cm and no more than 1 meter to efficiently capture images, and these two-dimensional fluorescent images can still reflect the distribution of chlorobenzene in the local environment medium.

After step 150, these two-dimensional fluorescent images are analyzed and processed, as shown in step 160. Specifically, commercially available image analysis and processing software can be used, and the area ratio of the fluorescent color display area of the corresponding two-dimensional fluorescent image can be obtained based on the area of the corresponding one of these two-dimensional fluorescent images. Then, a relationship diagram between the area ratio of the fluorescent color display area and the depth from the ground is plotted to obtain a distribution diagram of the area ratio relative to the depth.

As mentioned above, since the fluorescent coloring area is generated by the fluorescence scattered by the dyed chlorobenzene after excitation. When the area ratio is not less than the threshold value, it is determined that chlorobenzene is distributed in the local environmental medium at this depth, that is, it is contaminated by chlorobenzene. Generally speaking, the threshold value can be established based on the type of local environmental medium (such as soil, sand and/or stone), the composition of the blending dye, and the type of image capture element. Specifically, in some embodiments, the threshold value may be not less than 0.5 percentage. In other embodiments, the threshold value may be not less than 2.0 percentage.

The following examples are used to illustrate the application of the present invention, but they are not intended to limit the present invention. Anyone familiar with this art can make various changes and modifications without departing from the spirit and scope of the present invention.

Fluorescence detection of chlorobenzene distribution in simulated environmental media

Example 1

In a darkroom, the blended dye of Example 1 and the contaminated sand (the content of chlorobenzene in the sand is 5 weight percent) are dyed to obtain dyed sand, wherein the volume ratio of the blended dye to the contaminated sand is 5 weight percent to 10 weight percent. Then, the dyed sand is irradiated with light of a wavelength of 275nm, and the dyed sand is photographed using a camera with a CMOS sensor to obtain a two-dimensional fluorescent image, the imaging magnification of which is 1 times, and the two-dimensional fluorescent image is rectangular. Then, the two-dimensional fluorescent image is analyzed and processed to identify the fluorescent color development area of each two-dimensional fluorescent image, and the area ratio of the fluorescent color development area is obtained based on the area of the corresponding two-dimensional fluorescent image.

Examples 2 to 12 and Comparative Examples 1 to 8

The detection methods of Examples 2 to 12 and Comparative Examples 1 to 8 are performed in the same steps as Example 1. The difference is that Examples 2 to 12 and Comparative Examples 1 to 8 change the blending dye, environmental medium and/or pollutant. The specific conditions and detection results of the aforementioned Examples 1 to 12 and Comparative Examples 1 to 8 are shown in Tables 1 and 2 below.

Comparison Examples 9 to 17

The detection method of Comparative Examples 9 to 17 is carried out in the same steps as Example 1. The difference is that the flavors of the dyes are changed in Comparative Examples 9 to 17, wherein Comparative Examples 9 to 17 use taro flavor, brown sugar flavor, rose flavor, milk flavor, chocolate flavor, vanilla flavor, strawberry flavor, pineapple flavor and banana flavor respectively. The area ratio of the fluorescent coloring area of the uncontaminated and contaminated sand detected by the aforementioned Comparative Examples 9 to 17 is 0.0% to 0.1%.

According to the detection results of Examples 1 to 12 and Comparative Examples 1 to 8, compared with other pollutants (such as trichloroethylene and tetrachloroethylene), the detection method using a blended dye with jasmine essence and honey essence is selective for chlorobenzene.

Furthermore, according to the detection results of Examples 1 to 12 and Comparative Examples 9 to 17, compared with other food-grade flavors, the blended dye containing jasmine flavor and honey flavor has a better sensitivity to chlorobenzene.

Fluorescent detection of chlorobenzene distribution in local environmental media

Application Examples

Weigh 25 weight percent of jasmine essence, 25 weight percent of honey essence and 50 weight percent of propylene glycol and mix them evenly to prepare a dye blend. Then, use a drill to drill a hole underground, and sequentially inject the dye blend and insert the detection device into the drill hole to obtain dyed soil. The injection rate of the dye blend is 1 liter/meter, and the detection device is equipped with an LED light and a camera with a CMOS sensor.

The LED lamp emits light with a wavelength of 275nm to illuminate the dyed soil. Starting from the ground, the dyed soil is imaged vertically downward using a camera (i.e., the image is captured facing the wall of the drill hole) to obtain multiple two-dimensional fluorescent images, wherein the image acquisition magnification is 1 times, and the image is acquired once every 15 mm, and the shape of the two-dimensional fluorescent image is rectangular (as shown in Figures 3 and 4). Subsequently, the two-dimensional fluorescent image is analyzed and processed using commercially available image analysis and processing software (such as the image analysis software image-Pro 10 provided by Zhonghui Technology Co., Ltd.), and the fluorescent color display area of each two-dimensional fluorescent image is identified to obtain the area ratio of the fluorescent color display area. Next, Figure 2 is plotted with depth as the horizontal axis and the area ratio of the fluorescent color rendering area as the vertical axis, and the specific results are shown in Table 3 below.

In addition, corresponding to the depth, multiple soil samples were collected from the underground environment, and these soil samples were detected using the following two tests to compare the results of the fluorescent detection method of the above application case, and then evaluate the accuracy of the fluorescent detection method of the application case. When the results of the fluorescent detection method of the application case are consistent with the results of these tests, the fluorescent detection method of the application case is accurate.

1. Dye shaking test

The dye shaking test uses red oil dye mixed with soil samples. This dye will dye chlorobenzene, so soil samples contaminated with chlorobenzene will have red stains. The opposite is true. Therefore, whether the soil sample is contaminated with chlorobenzene can be judged by whether the soil sample is stained red.

2. Gas chromatography-mass spectrometry analysis test

The gas chromatography-mass spectrometry analysis test is based on the volatile organic compound detection method (method number NIEA M711.04C), using gas chromatography-mass spectrometry (GC-MS) to detect chlorobenzene in soil samples to determine whether the soil samples are contaminated with chlorobenzene, with a chlorobenzene concentration of 75 mg/kg (75 mg of chlorobenzene per kilogram of soil sample) as the threshold value.

Please refer to Figures 2 to 4 and Table 3. Figure 2 shows the relationship between the area ratio of the fluorescent color display area of the two-dimensional fluorescent image obtained by the detection method of the application case and the depth from the ground, and Figures 3 and 4 are two-dimensional fluorescent images captured at depths of 0.76 meters and 2.94 meters respectively. The X-axis and Z-axis shown in Figures 3 and 4 respectively represent the imaged borehole wall in the direction perpendicular to the depth and in the direction parallel to the depth.

Furthermore, Table 3 shows the judgment results at three different depths in Figure 2. When the area ratio of the fluorescent coloring area is not less than 0.5%, the local environmental medium is judged to be contaminated by chlorobenzene, and vice versa.

In the application case, chlorobenzene was detected to be distributed at depths of 2.5~3.5 meters and 3.5~4.5 meters underground. These determination results are consistent with the determination results of the dye shaking test, gas chromatography-mass spectrometry analysis test and photoionization detection test. Therefore, the detection method of the application case can accurately detect the distribution of chlorobenzene in the local environmental medium.

In summary, the dye-assisted fluorescent imaging method of the present invention for detecting chlorobenzene in the local environment uses a blended dye of jasmine essence and honey essence with a specific weight ratio to enhance the sensitivity of fluorescent detection of chlorobenzene, thereby instantly detecting the distribution of chlorobenzene in the local environmental medium.

Although the present invention has been disclosed in the form of implementation as above, it is not intended to limit the present invention. Anyone with common knowledge in the technical field to which the present invention belongs can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be subject to the scope of the patent application attached hereto.

100:Methods

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Claims (9)

A method for detecting chlorobenzene in a local environment by dyeing-assisted fluorescent imaging comprises: providing a blended dye composed of jasmine essence, honey essence and propylene glycol solution, wherein a weight ratio of the jasmine essence to the honey essence is 0.4 to 1.2, and a concentration of propylene glycol in the propylene glycol solution is 30 weight percent to 100 weight percent; vertically drilling a borehole from a local environment medium; pouring the blended dye into the borehole, and dyeing the local environment medium with the blended dye to obtain a dyed local environment medium, wherein chlorobenzene and the blended dye form a fluorescent product; inserting a detection device into the borehole, wherein the detection device comprises: an excitation light source; and an image A capture element is electrically connected to the excitation light source; the excitation light source is used to illuminate the dyed local environment medium, and the image capture element is used to perform an image capture process on the dyed local environment medium at multiple depths to obtain multiple two-dimensional fluorescent images, wherein one of the two-dimensional fluorescent images includes a fluorescent color development area, and the fluorescent color development area has an area ratio in the one of the two-dimensional fluorescent images; and the two-dimensional fluorescent images are analyzed and processed to obtain a distribution diagram of the area ratios relative to the depths, wherein when one of the area ratios is not less than a threshold value, it is determined that the chlorobenzene is distributed in the local environment medium at one of the depths corresponding to the one of the area ratios. The method for detecting chlorobenzene in the local environment by dye-assisted fluorescent imaging as described in claim 1, wherein the weight ratio of the jasmine essence to the honey essence is 0.8 to 1.0. The method of dye-assisted fluorescent imaging for detecting chlorobenzene in the local environment as described in claim 1, wherein the amount of the blended dye used is 100 weight percent, and the amount of the propylene glycol solution used is greater than 0 weight percent and equal to 80 weight percent. The method of dye-assisted fluorescent imaging for detecting chlorobenzene in the local environment as described in claim 1, wherein the amount of the blended dye used is 100 weight percent and the amount of the propylene glycol solution used is 40 weight percent to 80 weight percent. A method for detecting chlorobenzene in the local environment by dye-assisted fluorescent imaging as described in claim 1, wherein the injection rate of the mixed dye is 0.5 liters/meter to 2.0 liters/meter. A method for detecting chlorobenzene in the local environment by dye-assisted fluorescent imaging as described in claim 1, wherein the excitation light source is a deep ultraviolet light. A method for detecting chlorobenzene in the local environment by dye-assisted fluorescent imaging as described in claim 6, wherein a wavelength of the deep ultraviolet light is 270 nanometers to 280 nanometers. A method for detecting chlorobenzene in the local environment by dye-assisted fluorescent imaging as described in claim 1, wherein the distance between two adjacent depths is greater than 0 cm and no greater than 1 meter. A method for detecting chlorobenzene in the local environment by dye-assisted fluorescent imaging as described in claim 1, wherein the threshold value is 0.5 percent.