CN120084772A - A fluorescent in-situ detection device and method for groundwater pollutants - Google Patents
A fluorescent in-situ detection device and method for groundwater pollutants Download PDFInfo
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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Abstract
本发明公开了一种地下水污染物荧光原位检测装置及方法，装置包括：激发组件、荧光探测组件、浊度校正组件和竞争吸收校正组件；激发组件、浊度校正组件和竞争吸收校正组件围绕地下水监测位点采用环形结构布置，并处于同一水平面；同时，激发组件发射的光，既能够作为激发诱导待测样品产生荧光信号的光源，又能够作为竞争吸收校正组件的校正光源；荧光探测组件与激发组件垂直设置且处于不同水平面，以及荧光信号沿激发组件形成的激发光路垂直方向传播，荧光探测组件设置在荧光信号的传播方向上。本发明可以原位实时检测化工园区地下水苯类与酚类有毒有机污染物。
The present invention discloses a fluorescence in-situ detection device and method for groundwater pollutants, the device comprises: an excitation component, a fluorescence detection component, a turbidity correction component and a competitive absorption correction component; the excitation component, the turbidity correction component and the competitive absorption correction component are arranged in a ring structure around the groundwater monitoring site and are in the same horizontal plane; at the same time, the light emitted by the excitation component can be used as a light source for exciting and inducing the sample to be tested to generate a fluorescence signal, and can also be used as a correction light source for the competitive absorption correction component; the fluorescence detection component is arranged vertically with the excitation component and is in different horizontal planes, and the fluorescence signal propagates in the vertical direction of the excitation light path formed by the excitation component, and the fluorescence detection component is arranged in the propagation direction of the fluorescence signal. The present invention can detect benzene and phenol toxic organic pollutants in groundwater of chemical parks in real time in situ.
Description
Technical Field
The invention relates to the technical field of ultraviolet-induced fluorescence spectrum detection, in particular to a fluorescence in-situ detection device for groundwater pollutants.
Background
At present, the monitoring of underground water organic pollutants in a chemical industry park mainly depends on the traditional method of 'on-site sampling-laboratory analysis', such as the combined analysis of a full-automatic purging and trapping device and gas chromatography/mass spectrometry, and the method has the defects of time consumption in sampling, high difficulty in sample preservation, complex operation, loss of in-situ space-time information and the like. In addition, in-situ off-site monitoring methods such as portable chromatography, mass spectrometry, colorimetry, and the like have similar problems and may cause secondary environmental pollution. Therefore, there is a need to develop efficient in-situ monitoring methods and apparatus that overcome the above problems to achieve accurate and rapid monitoring of organic contaminants in groundwater.
As a nondestructive testing technology, the ultraviolet-induced fluorescence sensitivity is high, sample pretreatment is not needed, the response speed is high, and the method has great potential for in-situ monitoring of benzene and phenol pollutants in underground water of a chemical industry park. The fluorescence excitation wavelength range of benzene is usually between 250-280nm, and the fluorescence emission wavelength range is concentrated at about 270-350 nm. The fluorescence excitation wavelength range of phenols is usually 260-290nm, and the fluorescence emission wavelength range is 280-340nm, so that the fluorescence spectrum information of two main pollutants is obviously overlapped.
The in-situ fluorescence sensor for detecting benzene series abroad generally utilizes 255nm to excite benzene series, detects a fluorescence signal at 290nm, and realizes benzene series concentration measurement according to a measured signal value, wherein the problems comprise (1) that benzene and phenol pollutants coexist in a general chemical industry park, and phenol also has weaker 290nm fluorescence signal under 255nm excitation, and only one 255nm characteristic wavelength can not remove the influence of phenol on benzene series detection, and (2) suspended particles, sulfate, chloride and the like can cause light scattering and absorption in underground water of a chemical industry park with complex environment, weaken the intensity of benzene and phenol fluorescence signals, and influence the monitoring accuracy and reliability. The underground water of the chemical industry park has complex physical and chemical environment, when 255nm excitation and 290nm fluorescence in-situ detection are adopted to detect benzene series, partial interferents such as sulfate, chloride and the like can absorb excitation light near 255nm, so that the intensity of a fluorescence signal detected by a detector is reduced. In addition, suspended particles can cause scattering of light, weaken the intensity of benzene fluorescent signals and influence the accuracy and reliability of monitoring, and (3) the physical size limits the volume of the detection device because the diameter of a groundwater monitoring well is usually 5-10 cm. In the limited space, the excitation light source, the fluorescence detector and related optical elements are required to be reasonably arranged, and the prior art is difficult to meet the size requirement while ensuring the detection performance.
The invention patent with the publication number of CN107389644A discloses a rapid fluorescence quantification device, which comprises an excitation light source A, an excitation light source B and a fluorescence quantification device, wherein the excitation light source A is positioned at the left side of a sample tank, and the excitation light source B is positioned at the right side of the sample tank and is used for exciting fluorescent substances in a sample; the fluorescent detection unit A and the fluorescent detection unit B are respectively and vertically positioned at two sides of the sample groove and the excitation light path, are welded on a circuit board, are embedded in a light transmission channel, and can provide dual-band excitation light to realize free switching. The application technical field of the patent is biological detection, although the excitation light path and the detection light path are vertically arranged around a sample, the laser light path and the detection light path form a cross structure, a sample groove is positioned in the middle of the cross, and the laser light path and the detection light path are arranged on the same horizontal plane, so that the sectional area of the device is increased, and the device is difficult to descend into a well when the device is applied to a groundwater monitoring well.
Patent publication No. CN220340054U discloses a disc type multichannel optical detection system, in which the excitation light path and the detection light path are vertical, but the structural vertical is not the light path, and the fluorescence is vertical to the excitation light. In addition, the fluorescence in the opposite direction to the excitation light is measured in the patent, only the detection light path is deflected by the dichroic mirror, the volume size is reduced, and the fluorescence 90 degrees to the excitation light is not measured, so that the influence of the excitation light and scattered light is difficult to eliminate by the fluorescence measured by the light path.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the underground toxic organic pollutant detection device suitable for real-time correction of underground water monitoring well, turbidity and competitive absorption in a chemical industry park.
In order to solve the technical problems, the invention provides the following technical scheme:
The fluorescence in-situ detection device for groundwater pollutants comprises an excitation assembly 100, a fluorescence detection assembly 200, a turbidity correction assembly 300 and a competitive absorption correction assembly 400;
the excitation assembly 100, turbidity correction assembly 300, and competitive absorption correction assembly 400 are arranged in an annular configuration around the groundwater monitoring site 500 and are at the same level;
Meanwhile, the light emitted by the excitation assembly 100 can be used as a light source for exciting and inducing the sample to be detected to generate a fluorescent signal and can be used as a correction light source for the competitive absorption correction assembly 400;
The fluorescence detection assembly 200 is disposed vertically to the excitation assembly 100 and at different levels, and the fluorescence signal propagates in a direction perpendicular to an excitation light path formed by the excitation assembly 100, the fluorescence detection assembly 200 being disposed in a direction of propagation of the fluorescence signal.
The invention has the technical effects that the novel optical structural design is adopted, the fluorescence detection component and the excitation component are vertically arranged and are positioned at different horizontal planes, the fluorescence detection component is accurately arranged in the propagation direction of a fluorescence signal, and meanwhile, the fluorescence signal and an excitation light path formed by the excitation component are kept in a strict vertical relationship. The vertical crossed light path layout not only realizes the miniaturization of the device structure, but also utilizes the minimum physical characteristic of scattered light in the vertical direction, effectively reduces the interference of the scattering of the excitation light on the fluorescent signal, and improves the signal to noise ratio, thereby remarkably improving the accuracy and the reliability of the fluorescent detection of the groundwater pollutants while having a compact structural design.
Furthermore, the invention adopts a highly integrated annular layout design, forms a compact annular structure of the excitation component, the turbidity correction component and the competitive absorption correction component around the ground water monitoring site and is positioned on the same horizontal plane, simultaneously creatively realizes resource sharing, directly uses the excitation component as a light source of the competitive absorption correction component, and avoids the arrangement of redundant light sources. The annular integration and resource sharing design of the multifunctional assembly remarkably optimizes the space utilization rate, greatly reduces the size of the whole device, enables the device to be easily adapted to the narrow space limitation of a standard monitoring well, and solves the technical bottleneck that the equipment is too large in size and difficult to detect in a well.
In one embodiment of the present invention, the excitation assembly 100 includes an LED light source 110, a collimator lens 120, an optical filter 130, and a focusing lens 140;
the LED light source I110 with adjustable wave band emits excitation light, the generated excitation light is collimated by the collimating lens I120, stray light is filtered by the optical filter I130, and finally the excitation light is focused to the underground water monitoring site 500 by the focusing lens I140 to form an excitation light path;
the excitation assembly 100 is provided with a plurality of groups, each group of excitation assemblies 100 having the same structure.
In an embodiment of the present invention, the fluorescence detection assembly 200 includes a window 210, a second collimating lens 220, a second filter 230, a second focusing lens 240, a light shielding diaphragm 250, and a fluorescence detector 260 sequentially disposed along the propagation direction of the fluorescence signal.
The fluorescence detection device has the technical effects that the fluorescence detection assembly is arranged in the direction strictly perpendicular to the excitation light path by adopting the carefully optimized optical path design, and the optical elements are sequentially arranged along the propagation direction of the fluorescence signal. The structure not only realizes the miniaturization of the device, but also aims at the severe requirement of underground water detection scenes on high sensitivity, effectively reduces the incidence angle of light rays through the collimating lens and prevents fluorescence from blue shift, the focusing lens accurately gathers signals, and the light shielding diaphragm further filters stray light. The multiple optical filtering combination design remarkably improves the signal collection efficiency, reduces stray light interference to the greatest extent, ensures that high-quality fluorescent signals can be obtained in complex groundwater environment, and achieves the purpose of high-sensitivity in-situ detection.
In one embodiment of the present invention, the fluorescent detection assemblies 200 are provided with two groups, and the two groups of fluorescent detection assemblies 200 are symmetrically arranged with the groundwater monitoring site 500 as a center;
and, the fluorescence receiving wavelength bands of the fluorescence detectors 260 in the two sets of fluorescence detection assemblies 200 are different.
In one embodiment of the present invention, the window 210 is in a convex shape, wherein the small opening of the convex window 210 faces the light source, the large caliber faces the fluorescence detector 260, and the ratio of the small caliber to the large caliber is 0.2-1;
two focusing lenses 240 are arranged side by side.
In one embodiment of the present invention, the turbidity correction assembly 300 comprises a turbidity light source assembly 310 and a turbidity detection assembly 320, wherein the turbidity detection assembly 320 comprises a collimating lens IV 321, a filter IV 322, a focusing lens IV 323 and a photodiode IV 324;
the transmitted light emitted by the turbidity light source assembly 310 does not generate fluorescent signals on the sample to be detected, and the transmitted light emitted by the turbidity light source assembly 310 is formed into parallel light beams through the collimating lens IV 321, passes through the optical filter IV 322 and the focusing lens IV 323, and is focused on the photodiode IV 324.
In an embodiment of the present invention, the turbidity light source assembly 310 includes a second LED light source 311, a third collimator lens 312, a third filter 313, and a third focusing lens 314;
The transmitted light emitted by the second LED light source 311 with adjustable wave band sequentially passes through the third collimating lens 312, the third optical filter 313 and the third focusing lens 314 and irradiates the underground water monitoring site 500 and is simultaneously received by the turbidity detection assembly 320.
In one embodiment of the present invention, the competitive absorbent calibration assembly 400 includes a competitive absorbent probe assembly 410;
The competitive absorption detection assembly 410 includes a fifth collimator lens 411, a fifth filter 412, a fifth focusing lens 413, and a second photodiode 414;
the excitation light of the excitation assembly 100 excites the sample to be detected to generate a fluorescent signal, and meanwhile, the transmission light of the excitation light passes through the collimating lens five 411 to form a parallel light beam, and then passes through the optical filter five 412 and the focusing lens five 413 to form a parallel light beam which is focused on the photodiode two 414.
In one embodiment of the present invention, the competitive absorbent probe assembly 410 is provided with multiple sets, and the number of competitive absorbent probe assemblies 410 matches the number of excitation assemblies 100 and the wavelength bands used.
The invention also provides a fluorescence in-situ detection method for the groundwater pollutants, which is applied to the fluorescence in-situ detection device for the groundwater pollutants and comprises the following steps:
The fluorescence characteristic signal is obtained by taking the excitation wavelength of the excitation component 100 and the fluorescence receiving wavelength received by the fluorescence detection component 200 as fluorescence characteristic signals, and meanwhile, the absorbance received by the competitive absorption correction component 400 and the transmitted light at the excitation wavelength of the excitation component 100 are taken as competitive absorption correction signals;
the transmitted light wavelength emitted by the turbidity correction assembly 300 and the received turbidity are used as turbidity correction signals;
And taking the fluorescence characteristic signal, the competitive absorption correction signal and the turbidity correction signal as input characteristic sets of a trained multiple linear regression model, and outputting the model to obtain the concentration of the pollutant.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts a highly optimized optical system design, and realizes the unification of the accuracy of the fluorescence detection of the groundwater pollutants and the miniaturization of the device. The core innovation is that the annular LED light source structure is adopted, so that multi-wavelength excitation capability is provided, excitation requirements of different pollutants such as benzene series, phenols and the like are met, the volume of the device is remarkably reduced, and the device can smoothly enter a standard monitoring well for in-situ detection. The light path system is carefully designed, the light shielding diaphragms which are strategically arranged effectively inhibit stray light interference and improve signal purity, and the combination of the collimating lens and the optical filter which are precisely matched ensures that only light with target wavelength is used for sample excitation, thereby greatly improving fluorescent signal quality. Meanwhile, the invention integrates a multiple correction mechanism, effectively eliminates interference of water body particles on fluorescent signals by adopting a 860nm wavelength transmission light detection technology, realizes competitive absorption correction by 255nm, 265nm and 275nm wavelength transmission light detection, comprehensively improves the accuracy and reliability of organic pollutant fluorescence detection in complex groundwater environment, and provides a high-efficiency and compact technical scheme for monitoring groundwater pollution in real time.
The invention can accurately compensate the problems of fluorescence signal attenuation caused by competitive absorption of substances such as ions in groundwater to excitation light and turbidity scattering caused by suspended particles. The real-time correction technology enables the system to accurately calculate the actual concentration of organic pollutants such as phenols, benzenes and the like in complex and changeable groundwater environments, and the data reliability of in-situ monitoring is remarkably improved. Particularly in a low-concentration pollutant detection scene, the unique optical design and correction algorithm of the invention greatly improves the selective capture efficiency and detection sensitivity of benzene and phenol fluorescent signals, reduces the detection limit to ppb level, and provides high-precision and high-reliability technical support for early warning and trace pollutant monitoring of groundwater pollution.
Drawings
FIG. 1 is a schematic diagram of a fluorescence in-situ detection device for groundwater pollutants according to an embodiment of the invention.
FIG. 2 is a schematic diagram of an excitation assembly and a fluorescence detection assembly according to an embodiment of the present invention.
FIG. 3 is a schematic diagram of a turbidity calibration assembly according to an embodiment of the present invention.
FIG. 4 is a schematic diagram of a competitive absorbent calibration assembly according to an embodiment of the present invention.
FIG. 5 is a flow chart of a fluorescence in-situ detection method for groundwater pollutants according to an embodiment of the invention.
Reference numerals illustrate:
100—an excitation assembly;
110-an LED light source I, 120-a collimating lens I, 130-an optical filter I, 140-a focusing lens I;
200-a fluorescence detection assembly;
210-window, 220-second collimating lens, 230-second optical filter, 240-second focusing lens, 250-shading diaphragm and 260-fluorescence detector;
300—turbidity correction assembly;
310, a turbidity light source assembly, 311, a LED light source II, 312, a collimating lens III, 313, an optical filter III and 314, and a focusing lens III;
320-turbidity detection component, 321-collimating lens IV, 322-optical filter IV, 323-focusing lens IV, 324-photodiode I;
400-competitive absorbent correction assembly;
410-competitive absorption detection component, 411-collimating lens five, 412-optical filter five, 413-focusing lens five, 414-photodiode two;
500—groundwater monitoring site.
Detailed Description
In order to facilitate the understanding of the technical scheme of the present invention by those skilled in the art, the technical scheme of the present invention will be further described with reference to the accompanying drawings.
The terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Referring to fig. 1 and 2, the present invention provides a fluorescence in-situ detection device for groundwater pollutants, which includes an excitation assembly 100, a fluorescence detection assembly 200, a turbidity calibration assembly 300 and a competitive absorption calibration assembly 400. The excitation assembly 100, the turbidity calibration assembly 300 and the competitive absorption calibration assembly 400 are arranged in a ring-shaped structure around the groundwater monitoring site 500 and are in the same horizontal plane, and meanwhile, the light emitted by the excitation assembly 100 can be used as a light source for exciting and inducing a sample to be tested to generate a fluorescent signal and can be used as a calibration light source of the competitive absorption calibration assembly 400. The fluorescence detection assembly 200 is disposed vertically to the excitation assembly 100 and at different levels, and the fluorescence signal propagates in a direction perpendicular to an excitation light path formed by the excitation assembly 100, the fluorescence detection assembly 200 being disposed in a direction of propagation of the fluorescence signal.
In one embodiment of the present invention, the excitation assembly 100 includes an LED light source 110, a collimator lens 120, an optical filter 130, and a focusing lens 140.
In this embodiment, the first band-adjustable LED light source 110 emits excitation light, the generated excitation light is collimated by the first collimating lens 120, stray light is filtered by the first filter 130, and finally the excitation light is focused to the groundwater monitoring site 500 by the first focusing lens 140 to form an excitation light path.
In this embodiment, taking detection of benzene and phenol pollutants in groundwater as an example, the excitation assembly 100 is used for efficiently collecting deep ultraviolet light emitted by the first LED light source 110, and irradiating the deep ultraviolet light to the groundwater monitoring site 500 at a specific exit angle after collimation and filtering. The excitation assembly 100 employs deep ultraviolet LEDs arranged in a ring configuration to generate excitation light and form an excitation light path that is focused onto the groundwater monitoring site 500 to excite the sample to generate a fluorescent signal.
In this embodiment, the excitation modules 100 are provided with multiple groups, and each group of excitation modules 100 has the same structure. In this embodiment, the excitation assembly 100 is provided with three groups, and the first LED light sources 110 in each group of excitation assemblies 100 respectively emit light of 255nm, 265nm and 275nm, and the light source intensity of each first LED light source 110 can be controlled independently, so that excitation light with different wavelengths excites benzene and phenol characteristic fluorescence.
In an embodiment of the present invention, the fluorescent detection assembly 200 sequentially includes a window 210, a second collimating lens 220, a second optical filter 230, a second focusing lens 240, a light shielding diaphragm 250, and a fluorescent detector 260 along the fluorescent signal propagation direction, and the fluorescent signal is sent to the fluorescent detector 260 and converted into an analyzable electrical signal.
The fluorescence detection assemblies 200 are provided with two groups, and the two groups of fluorescence detection assemblies 200 are symmetrically arranged with the groundwater monitoring site 500 as the center. And, the fluorescence receiving wavelength bands of the fluorescence detectors 260 in the two sets of fluorescence detection assemblies 200 are different, in this embodiment, the difference is that one side fluorescence receiving wavelength is 290nm and the other side fluorescence receiving wavelength is 310nm.
In this embodiment, the window 210 is in a convex shape, the small opening of the convex window 210 faces the light source, and the large aperture faces the fluorescence detector 260. And the ratio of the small caliber to the large caliber is 0.2-1, so that the receiving efficiency of fluorescent signals emitted from the sample is effectively enhanced.
In this embodiment, the second focusing lens 240 is disposed side by side, so that the focal length is shorter and the optical path size is reduced. A light shielding diaphragm 250 is further included in the fluorescence detection light path for filtering out non-target light in the fluorescence detection light path, optimizing beam quality, and ensuring maximum capture of fluorescence emitted from groundwater monitoring site 500.
In this embodiment, the fluorescence detection assembly 200 is used to collect weak fluorescence signals from benzene and phenol organic contaminants at the 500 th site of the groundwater monitoring site.
In this embodiment, 6 fluorescence characteristic signals are obtained in total by a combination of 3 excitation wavelengths and 2 fluorescence receiving wavelengths. Further, the ratio calculation is performed on the 6 fluorescence characteristic signals two by two, and 15 additional ratio signals are generated. The 6 raw fluorescence signature signals and 15 ratio signals are integrated into a column of data as an input signature set. Based on a multiple linear regression model, the model is trained by using benzene and phenol samples with known concentrations, and a quantitative relationship between fluorescence characteristic signals and pollutant concentrations is established. And analyzing the fluorescence characteristic signals through a trained multiple linear regression model to realize quantitative detection of benzene and phenol pollutants.
Referring to fig. 1 to 4, in an embodiment of the present invention, the apparatus further provides an efficient detection light path for fluorescence of groundwater organic matters, which can correct turbidity and competitive absorption interference in real time.
In one embodiment of the present invention, turbidity correction assembly 300 includes turbidity light source assembly 310 and turbidity detection assembly 320.
In the present embodiment, the turbidity light source assembly 310 includes a second LED light source 311, a third collimator lens 312, a third filter 313, and a third focusing lens 314. The transmitted light emitted by the second LED light source 311 with adjustable wave band sequentially passes through the third collimating lens 312, the third optical filter 313 and the third focusing lens 314 and irradiates the underground water monitoring site 500 and is simultaneously received by the turbidity detection assembly 320. Wherein, the transmitted light emitted by the turbidity light source assembly 310 does not generate fluorescent signal to the sample to be tested.
In this embodiment, the turbidity detection assembly 320 includes a fourth collimating lens 321, a fourth filter 322, a fourth focusing lens 323, and a first photodiode 324. The transmitted light from the turbidity light source assembly 310 is formed into a parallel beam by the collimating lens four 321, and then is focused on the photodiode one 324 by the optical filter four 322 and the focusing lens four 323. The light intensity value of the transmitted light detected by the first photodiode 324 is used for calculating the turbidity value of the water body, and the turbidity condition of the underground water is reflected in real time.
In this embodiment, turbidity values are determined from transmitted light intensities at groundwater monitoring sites 500 for turbidity disturbances. The specific implementation manner is that when the LED light source II 311 emitting 860nm wavelength works, the photodiode I324 synchronously detects the light intensity change of 860nm transmitted light. Because suspended particles in the water body can produce scattering effect on light, the higher the turbidity of the water body is, the lower the transmitted light intensity is, so the turbidity value of the water body can be calculated by measuring the attenuation degree of the transmitted light.
Referring to fig. 1, 2 and 4, in an embodiment of the invention, the competitive absorption calibration assembly 400 includes a competitive absorption detection assembly 410, and the competitive absorption detection assembly 410 includes a collimator lens 411, a filter lens 412, a focusing lens 413 and a photodiode 414.
In this embodiment, when the excitation light of the excitation assembly 100 excites the sample to be measured to generate a fluorescent signal, the transmitted light of the excitation light passes through the collimating lens five 411 to form a parallel beam, and then passes through the optical filter five 412 and the focusing lens five 413 to form a parallel beam and focus on the photodiode two 414.
In the present embodiment, the competitive absorption detection assembly 410 is provided with a plurality of sets, and the number of competitive absorption detection assemblies 410 matches the number of excitation assemblies 100, and the wavelength bands used match. It can be understood that, while the competitive absorption detection component 410 is also provided with three groups of substances excited by the first LED light source 110 with wavelengths of 255nm, 265nm and 275nm, the transmitted light of 3 excitation lights respectively passes through the collimating lens 411 of each group to form parallel light beams, then respectively enters the 255nm optical filters five 412, the 265nm optical filters five 412 and the 275nm optical filters five 412, passes through the focusing lens five 413 of each group, finally enters the second photodiode 414 of each group, measures the light intensity value of the transmitted light, calculates the absorbance according to the transmitted light intensity under different wavelengths, and reflects the absorption condition of sulfate, chloride and the like in the water body on the excitation light.
In this embodiment, the second photodiode 414 is used to detect the transmitted light from the first 255nm, 265nm, 275nm LED source 110, and the absorbance is measured after the transmitted light is transmitted through the lens assembly in the competitive absorption detection assembly 410. The fluorescence signal is corrected based on the measured absorbance values to eliminate the effect of competing absorption on fluorescence intensity. The specific correction method comprises the following steps of measuring absorbance of water samples with different turbidity at 255nm, 265nm and 275nm through experiments, simultaneously measuring fluorescent signals of phenols and benzene compounds through a standard method, and establishing a quantitative relation model between the absorbance and the fluorescent signals. In the detection process, the transmitted light intensity of three wavelengths is recorded in real time, the absorbance value A 255、A265、A275 is calculated, and meanwhile, the turbidity data of the water sample is obtained.
In the embodiment, light rays with the wavelengths of 860nm, 255nm, 265nm and 275nm are used for detecting scattered light and transmitted light in a water sample, turbidity data and absorbance data of the water sample are obtained, and real-time correction is performed on the attenuation of a fluorescent signal caused by the light rays, so that the excitation light and the fluorescent signal are ensured to be accurate. And quantitatively calculating the concentration of benzene series and phenol compounds in the underground water according to the corrected multi-wavelength fluorescence signal data and a trained multiple linear regression model.
Referring to fig. 1 to 4, in one embodiment of the present invention, the configuration and materials of the collimating lenses in the excitation assembly 100, the fluorescence detection assembly 200, the turbidity correction assembly 300, and the competitive absorption correction assembly 400 are optimized for the purpose of minimizing light loss and improving beam quality. Specifically, the material of the collimator lens is, for example, quartz or sapphire.
In the present embodiment, the focusing lenses in the excitation assembly 100, the fluorescence detection assembly 200, the turbidity correction assembly 300, and the competitive absorption correction assembly 400 are designed as high-precision optical assemblies capable of focusing excitation light to a minute area with high efficiency.
In this embodiment, the design of the window 210 and the shutter 250 is optimized for the purpose of improving the quality and accuracy of the fluorescent signal received from the sample.
In one embodiment, the fluorescence detector 260 is selected to be variable depending on the application requirements, including a photomultiplier tube PMT or a silicon photodiode SiPD, for the purpose of optimizing signal capture and conversion efficiency.
Referring to fig. 1 to 5, the present invention further provides a fluorescence in-situ detection method for groundwater pollutants, which is applied to the fluorescence in-situ detection device for groundwater pollutants, and includes:
the excitation wavelength of the excitation assembly 100 and the fluorescence receiving wavelength received by the fluorescence detection assembly 200 are used as fluorescence characteristic signals. And simultaneously uses the absorbance received by the competitive absorption correction assembly 400 and the transmitted light at the excitation wavelength of the excitation assembly 100 as the competitive absorption correction signal.
The transmitted light wavelength emitted by the turbidity correction assembly 300 and the received turbidity are used as turbidity correction signals.
And taking the fluorescence characteristic signal, the competitive absorption correction signal and the turbidity correction signal as input characteristic sets of a trained multiple linear regression model, and outputting the model to obtain the concentration of the pollutant.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
The above-described embodiments merely represent embodiments of the invention, the scope of the invention is not limited to the above-described embodiments, and it is obvious to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (10)
1. The fluorescence in-situ detection device for the groundwater pollutants is characterized by comprising an excitation assembly (100), a fluorescence detection assembly (200), a turbidity correction assembly (300) and a competitive absorption correction assembly (400);
The excitation assembly (100), the turbidity correction assembly (300) and the competitive absorption correction assembly (400) are arranged in an annular structure around the groundwater monitoring site (500) and are in the same horizontal plane;
Meanwhile, the light emitted by the excitation assembly (100) can be used as a light source for exciting and inducing a sample to be detected to generate a fluorescent signal and can be used as a correction light source for the competitive absorption correction assembly (400);
The fluorescence detection assembly (200) is vertically arranged with the excitation assembly (100) and is in different horizontal planes, and fluorescence signals are transmitted along the vertical direction of an excitation light path formed by the excitation assembly (100), and the fluorescence detection assembly (200) is arranged in the transmission direction of the fluorescence signals.
2. The in-situ fluorescence detection device for groundwater pollutants according to claim 1, wherein the excitation assembly (100) comprises an LED light source I (110), a collimating lens I (120), an optical filter I (130) and a focusing lens I (140);
The LED light source I (110) with adjustable wave band emits excitation light, the generated excitation light is collimated by the collimating lens I (120), stray light is filtered by the optical filter I (130), and finally the excitation light is focused to the underground water monitoring site (500) by the focusing lens I (140) to form an excitation light path;
The excitation components (100) are provided with a plurality of groups, and the structures of the excitation components (100) in each group are identical.
3. The groundwater contaminant fluorescence in-situ detection device of claim 1, wherein the fluorescence detection assembly (200) is sequentially provided with a window (210), a second collimating lens (220), a second optical filter (230), a second focusing lens (240), a light shielding diaphragm (250) and a fluorescence detector (260) along a fluorescence signal propagation direction.
4. A groundwater contaminant fluorescence in situ detection apparatus according to claim 3, wherein the fluorescence detection assemblies (200) are arranged in two groups, and the two groups of fluorescence detection assemblies (200) are symmetrically arranged with the groundwater monitoring site (500) as a center;
And fluorescence receiving wavelength bands of the fluorescence detectors (260) in the two sets of fluorescence detection assemblies (200) are different.
5. The in-situ fluorescence detection device for groundwater pollutants according to claim 3, wherein the window (210) is in a convex shape, wherein a small opening of the convex window (210) faces the light source, a large caliber faces the fluorescence detector (260), and the ratio of the small caliber to the large caliber is 0.2-1;
Two focusing lenses (240) are arranged side by side.
6. The groundwater contaminant fluorescence in situ detection device of claim 1, wherein the turbidity correction assembly (300) comprises a turbidity light source assembly (310) and a turbidity detection assembly (320), wherein the turbidity detection assembly (320) comprises a collimating lens four (321), a filter four (322), a focusing lens four (323), and a photodiode one (324);
The transmitted light emitted by the turbidity light source assembly (310) does not generate fluorescent signals on a sample to be detected, and the transmitted light emitted by the turbidity light source assembly (310) passes through the collimating lens IV (321) to form parallel light beams, passes through the filter IV (322) and the focusing lens IV (323) and is focused on the photodiode IV (324).
7. The groundwater contaminant fluorescence in situ detection device of claim 6, wherein the turbidity light source assembly (310) comprises a second LED light source (311), a third collimating lens (312), a third optical filter (313), and a third focusing lens (314);
The transmitted light emitted by the LED light source II (311) with adjustable wave band sequentially passes through the collimating lens III (312), the optical filter III (313) and the focusing lens III (314) and irradiates to the underground water monitoring site (500) and is simultaneously received by the turbidity detection assembly (320).
8. The groundwater contaminant fluorescence in situ detection device of claim 1, wherein the competitive absorption correction assembly (400) includes a competitive absorption detection assembly (410);
the competitive absorption detection component (410) comprises a collimating lens five (411), a filter five (412), a focusing lens five (413) and a photodiode two (414);
The excitation light of the excitation component (100) is excited to induce a sample to be detected to generate a fluorescent signal, and meanwhile, the transmission light of the excitation light passes through a collimating lens five (411) to form a parallel light beam, and then passes through a light filter five (412) and a focusing lens five (413) to form the parallel light beam and focus on a photodiode two (414).
9. The in-situ groundwater contaminant fluorescence detection device of claim 8, wherein the competitive absorption detection assembly (410) is provided with a plurality of groups, and the number of competitive absorption detection assemblies (410) is matched with the number of excitation assemblies (100) and the used wave bands are matched.
10. A method for in-situ detection of groundwater pollutants by fluorescence, which is characterized in that the in-situ detection device for groundwater pollutants by fluorescence according to any one of claims 1-9 is applied, and comprises the following steps:
The fluorescence characteristic signal is obtained by using the excitation wavelength of the excitation component (100) and the fluorescence receiving wavelength received by the fluorescence detection component (200), and the absorbance received by the competitive absorption correction component (400) and the transmitted light at the excitation wavelength of the excitation component (100) are used as the competitive absorption correction signal;
taking the wavelength of the transmitted light emitted by the turbidity correction assembly (300) and the received turbidity as turbidity correction signals;
And taking the fluorescence characteristic signal, the competitive absorption correction signal and the turbidity correction signal as input characteristic sets of a trained multiple linear regression model, and outputting the model to obtain the concentration of the pollutant.
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