CN115308173A - Categorised detection device of sea water oil spilling - Google Patents
Categorised detection device of sea water oil spilling Download PDFInfo
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- CN115308173A CN115308173A CN202210820877.XA CN202210820877A CN115308173A CN 115308173 A CN115308173 A CN 115308173A CN 202210820877 A CN202210820877 A CN 202210820877A CN 115308173 A CN115308173 A CN 115308173A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N21/65—Raman scattering
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
- G01N35/00584—Control arrangements for automatic analysers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
Abstract
The invention discloses a seawater oil spill classification detection device, which belongs to the technical field of multispectral measurement and comprises an automatic circulation platform, an optical detection system and an automatic control unit; collecting seawater containing oil spill by an automatic circulation platform, and sending the seawater sample and the constant-temperature mixed liquid of the seawater and the nano material into a cuvette in a time-sharing manner; the optical detection system utilizes a laser light source capable of exciting a fluorescence signal to irradiate the seawater sample injection in the cuvette so as to excite the fluorescence signal and collect the fluorescence signal to generate fluorescence spectrum data; or a laser light source capable of exciting Raman optical signals is used for irradiating the constant-temperature mixed liquid in the cuvette so as to excite the Raman optical signals and collect the Raman optical signals to generate Raman spectrum data; and the automatic control unit receives the fluorescence spectrum data and the Raman spectrum data and executes the seawater oil spill classification detection process. The device can improve the speed and the accuracy of the classification detection of the spilled oil, realize the in-situ detection of the seawater and solve the problem of difficult tracing of the spilled oil.
Description
The application is a divisional application with the application date of 2022, 5 and 23, the application number of 202210559319.2, and the name of the invention being 'device and method for classifying and detecting seawater spilled oil by using spectral analysis technology'.
Technical Field
The invention belongs to the technical field of multispectral measurement, and particularly relates to a device for classifying and detecting seawater oil spill by using a spectral analysis technology.
Background
With the rise of offshore oil exploration and exploitation, offshore oil leakage and oil carrier oil leakage accidents frequently occur, so that a large amount of oil and various types of oil products flow into the ocean, and the ocean environment is seriously polluted. As the supervision of the produced crude oil and the finished oil generally belong to different law enforcement departments, when oil pollutants appear in the seawater, the type of the spilled oil needs to be judged firstly, and then the relevant law enforcement departments are determined according to the type of the spilled oil for supervision management and tracing. Therefore, the classification detection of seawater oil spill is necessary for some law enforcement departments. Meanwhile, the seawater spilled oil is quickly and accurately classified, and the efficient development of the marine oil stain removing work is facilitated.
At the present stage, aiming at the detection and classification of petroleum and various oil products thereof, the most common methods are liquid chromatography and gas chromatography, the methods need to sample oil spill in seawater and send the oil spill to a laboratory, and classification detection work of the oil product is completed by using large-scale equipment in the laboratory, so that the method not only has long time consumption and high cost, but also has poor timeliness, and thus the later period tracing is difficult.
Disclosure of Invention
The invention aims to provide a device for classifying and detecting seawater oil spill by using a spectral analysis technology, which combines a fluorescence spectrum and a Raman spectrum to improve the efficiency and the accuracy of the classification and detection of the seawater oil spill.
In order to achieve the technical purpose, the invention adopts the following technical scheme to realize:
a kind of sea water spilled oil classification detection device, including automatic circulation platform, optical detection system and automatic control unit; wherein the content of the first and second substances,
the automatic circulation platform is used for collecting seawater containing oil spill, mixing the seawater with a nano material required by surface enhanced Raman spectrum detection at constant temperature, and sending the seawater sample introduction and the constant-temperature mixed liquid into a cuvette at different times so as to perform fluorescence spectrum detection and Raman spectrum detection respectively;
the optical detection system utilizes a laser light source capable of exciting a fluorescence signal to irradiate seawater sample injection in the cuvette so as to excite the fluorescence signal and collect the fluorescence signal to generate fluorescence spectrum data; or a laser light source capable of exciting Raman optical signals is used for irradiating the constant-temperature mixed liquid in the cuvette so as to excite the Raman optical signals and collect the Raman optical signals to generate Raman spectrum data; it includes:
the fluorescence light path system comprises a fluorescence laser light source, a first collimating lens, a first narrow-band filter, a first converging lens, a second collimating lens, a first long-wavelength-pass filter, a second converging lens and a fluorescence detector; the device comprises a fluorescent laser light source, a first narrow-band light filter, a first converging lens, a cuvette and a second converging lens, wherein the fluorescent laser light source is used for emitting 360nm laser light, processing the laser light into parallel light through the first collimating lens, emitting the parallel light to the first narrow-band light filter, converging the parallel light to the cuvette through the first converging lens after stray light outside 360nm is eliminated, and irradiating seawater containing oil spill in the cuvette to excite a fluorescent signal; the second collimating lens collects the fluorescence signals and emits the fluorescence signals to the long-wavelength-pass filter as parallel light so as to filter out interference light of non-fluorescence signals, and then the fluorescence signals are converged to the fluorescence detector through the second converging lens to realize the collection of fluorescence spectrum data;
the Raman optical path system comprises a differential Raman laser, a third collimating lens, a short-wave-pass dichroic mirror, a second narrow-band optical filter, a third narrow-band optical filter, a first long-wave-pass dichroic mirror, a third converging lens, a second long-wave-pass dichroic mirror, a second long-wave-pass optical filter, a fourth converging lens and a Raman detector; the differential Raman laser is used for emitting 785nm and 830nm laser light, processing the laser light into parallel light through a third collimating lens and then emitting the parallel light to a short-wave dichroic mirror, and the short-wave dichroic mirror transmits the 785nm laser light and reflects the 830nm laser light to form two laser light beam shunt transmission; the 785nm laser is filtered by the second narrow-band filter to remove stray light beyond 785nm, and then is emitted to the first long-wavelength-pass dichroic mirror; the laser light with the wavelength of 830nm is filtered by a third narrow-band filter to remove stray light except for the wavelength of 830nm, and then is reflected to the first long-wavelength-pass dichroic mirror by a second long-wavelength-pass dichroic mirror; the first long-wavelength-pass dichroic mirror reflects 785nm laser and transmits 830nm laser, two beams of the 785nm laser and the two beams of the 830nm laser are converged to the cuvette through the third converging lens to irradiate the constant-temperature mixed liquid in the cuvette, and two paths of Raman optical signals of 785nm and 830nm are excited; the two paths of Raman optical signals are transmitted to a second long-wavelength-pass optical filter through a third converging lens, a first long-wavelength-pass dichroic mirror and a second long-wavelength-pass dichroic mirror respectively to filter out non-Raman optical signals smaller than 830nm, and the non-Raman optical signals are converged to a Raman detector through a fourth converging lens to realize the acquisition of Raman spectrum data;
the automatic control unit is used for receiving the fluorescence spectrum data and the Raman spectrum data and executing the following seawater oil spill classification detection process:
performing spectrum smoothing and denoising processing on the fluorescence spectrum data to obtain a smooth fluorescence spectrum;
performing baseline correction on the smooth fluorescence spectrogram, and removing a local baseline;
picking up the peak value of the fluorescence spectrogram after the local base line is removed, and picking up the spectral positions and intensities of all characteristic peaks;
comparing the spectral position and intensity of the picked characteristic peak with the fluorescent spectrum of gasoline and diesel oil to identify whether the spilled oil is gasoline or diesel oil;
when the spilled oil is not gasoline or diesel oil, performing spectrum smoothing denoising treatment on Raman spectrum data to obtain a smooth Raman spectrum chart;
performing baseline correction on the smooth Raman spectrogram, and removing a local baseline;
picking up the peak value of the Raman spectrogram without the local base line, and picking up the spectral positions and intensities of all characteristic peaks;
comparing the spectral position and intensity of the picked characteristic peak with the Raman spectrum of the polycyclic aromatic hydrocarbon type characteristics of the crude oil and the finished oil, and identifying the polycyclic aromatic hydrocarbon type contained in the oil spill;
and identifying the type of the oil spill according to the types of the polycyclic aromatic hydrocarbons contained in the oil spill and the content ratio of various polycyclic aromatic hydrocarbons.
In some embodiments of the present application, the automated circulation platform comprises:
a first three-way valve, wherein a first gating port of the first three-way valve is used for sampling the nanometer material, and a second gating port of the first three-way valve is used for accessing a pipeline cleaning solution;
a first gating port of the second three-way valve is communicated with a common port of the first three-way valve;
the water inlet of the constant-temperature mixing circulating pipe is communicated with the common port of the second three-way valve;
a first gating port of the third three-way valve is used for sampling seawater containing spilled oil, and a second gating port of the third three-way valve is communicated with a water outlet of the constant-temperature mixing circulating pipe;
the water inlet of the peristaltic pump is communicated with the common port of the third three-way valve;
a common port of the fourth three-way valve is communicated with a water outlet of the peristaltic pump, a first gating port of the fourth three-way valve is communicated with a second gating port of the second three-way valve, and a second gating port of the fourth three-way valve is communicated with the cuvette;
in the process of classifying and detecting the seawater oil spill, the automatic control unit executes the following control process on the automatic circulation platform:
controlling the common port of the third three-way valve to be communicated with a first gating port of the third three-way valve, controlling the common port of the fourth three-way valve to be communicated with a second gating port of the fourth three-way valve, starting the peristaltic pump, and pumping the seawater containing the spilled oil into the cuvette for fluorescence spectrum detection;
controlling the common port of the first three-way valve, the second three-way valve and the fourth three-way valve to be communicated with the first gating port of the third three-way valve, controlling the common port of the third three-way valve to be communicated with the second gating port of the third three-way valve, and pumping the nano material into the constant-temperature mixed circulation pipe;
controlling the common port of the second three-way valve to be communicated with a second gating port of the second three-way valve, controlling the common port of the third three-way valve to be communicated with a first gating port of the third three-way valve, and pumping a certain amount of seawater containing spilled oil;
controlling a common port of the third three-way valve to be communicated with a second gating port of the third three-way valve to form a mixing loop, and fully mixing the seawater and the nano material through the constant-temperature mixing loop pipe and keeping the constant temperature to form constant-temperature mixed liquid;
controlling a common port of the fourth three-way valve to be communicated with a second gating port of the fourth three-way valve, and pumping the constant-temperature mixed liquid into the cuvette for Raman spectrum detection;
after Raman spectrum detection is finished, controlling the common port of the first three-way valve to be communicated with the second gating port of the first three-way valve, controlling the common ports of the second three-way valve and the fourth three-way valve to be communicated with the first gating port of the first three-way valve, and pumping pipeline cleaning liquid into a pipeline of the automatic circulation platform;
controlling a common port of the second three-way valve to be communicated with a second gating port of the second three-way valve to form a cleaning loop, and cleaning a pipeline of the automatic circulation platform;
and controlling a common port of the fourth three-way valve to be communicated with a second gating port of the fourth three-way valve to clean the cuvette.
Compared with the prior art, the invention has the advantages and positive effects that:
the seawater oil spill classification detection device provided by the invention adopts the fluorescence spectrum to identify gasoline and diesel oil, adopts the Raman spectrum to identify crude oil, fuel oil and light oil, adopts a differential Raman mode to eliminate fluorescence interference in the Raman spectrum, realizes accurate pickup of the position and intensity of a characteristic peak by performing smooth denoising, baseline correction and peak value pickup on the fluorescence spectrum and the Raman spectrum, solves the problem that the oil product identification is easy to generate errors due to inaccurate estimation of the position of the characteristic peak, and improves the accuracy of the seawater oil spill classification detection.
The seawater oil spill classification detection device combines fluorescence spectrum detection and Raman spectrum detection on the basis of an automatic circulation platform, adopts an automatic control strategy to realize complete mixing and constant temperature control of nano materials and seawater oil spill required by the Raman spectrum detection, and realizes the automatic cleaning function of a circulation pipeline, so that the whole process from seawater sampling, mixing, oil spill excitation, optical signal acquisition, spectrum processing to oil spill classification identification can be automatically completed, the speed and the accuracy of oil spill classification detection are improved, in-situ detection can be realized on seawater, and the problem of difficulty in tracing the oil spill is solved.
Other features and advantages of the present invention will become more apparent from the detailed description of the embodiments of the present invention when taken in conjunction with the accompanying drawings.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an overall architecture diagram of an embodiment of an automatic circulation platform in a seawater oil spill classification detection device according to the present invention;
FIG. 2 is an overall structure diagram of an embodiment of an optical detection system in the device for classifying and detecting seawater oil spill according to the present invention;
FIG. 3 is a process flow diagram of one embodiment of a method for seawater oil spill classification detection;
FIG. 4 is a smoothed fluorescence spectrum obtained by smoothing and denoising original fluorescence spectrum data;
FIG. 5 is a spectrum obtained by baseline correction of the smoothed fluorescence spectrum shown in FIG. 4;
in the figure, 10, cuvette; 11. a first three-way valve; 12. a second three-way valve; 13. a third three-way valve; 14. a fourth three-way valve; 15. a constant temperature mixing circulation pipe; 16. a peristaltic pump; 21. a fluorescent laser light source; 22. a first collimating lens; 23. a first narrow-band filter; 24. a first condenser lens; 25. a second collimating lens; 26 a first long wavelength pass filter; 27. a second condenser lens; 28. a fluorescence detector; 31. a differential Raman laser; 32. a third collimating lens; 33. a short wave pass dichroic mirror; 34. a second narrow band filter; 35. a mirror; 38. a third narrow-band filter; 36. a first long-wavelength-pass dichroic mirror; 37. a third condensing lens; 39. a second long-wavelength-pass dichroic mirror; 40. a second long-wavelength pass filter; 41. a fourth condensing lens; 42. a Raman detector.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
It should be noted that in the description of the present invention, the terms "front", "back", etc. indicating directions or positional relationships are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the devices or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and "fourth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Furthermore, it should be noted that in the description of the present invention, the terms "connected" and "connected" should be interpreted broadly unless explicitly stated or limited otherwise. For example, it may be a fixed connection, a detachable connection or an integral connection; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
An important characteristic of offshore oil spill is that an accident is sudden, and a small amount of oil spill cannot be found quickly and accurately, so that later-period tracing is difficult. Based on this, this embodiment has designed an automatic circulation analysis platform to combine spectroscopy means, realize the unmanned on duty, the quick analysis survey in oil spilling scene, provide the basis for the quick trace back and the accurate classification of marine oil spilling accident.
The spectroscopic analysis technique can measure the oils in seawater, but the single spectroscopic analysis technique cannot achieve accurate classification determination with high sensitivity. An important characteristic of seawater oil spill is that the oil spill contains multiple polycyclic aromatic hydrocarbons, and the polycyclic aromatic hydrocarbons have fluorescence and Raman characteristics. For gasoline and diesel, the fluorescent characteristic peaks of polycyclic aromatic hydrocarbons contained in the gasoline and the diesel are obviously distinguished, and whether the oil spill is the gasoline or the diesel can be identified through the positions of the characteristic peaks of a fluorescent spectrum. In crude oil, fuel oil, light oil and the like, the fluorescence characteristic peaks of some polycyclic aromatic hydrocarbons contained in the crude oil, the fuel oil, the light oil and the like overlap, so that the types of the spilled oil cannot be accurately distinguished by only using a fluorescence spectrum. However, the positions of the raman characteristic peaks of the polycyclic aromatic hydrocarbons of the oil spill are different, so that the quantification and the qualification of different polycyclic aromatic hydrocarbons can be realized by measuring the peak positions and the intensities of the raman characteristic peaks, and the type of the oil spill can be identified.
Based on this, in this embodiment, on the automatic circulation analysis platform, the fluorescence spectrum technology and the raman spectrum technology are jointly applied to the classification detection of the oil spilling pollutants, which not only can save manpower and improve the efficiency and accuracy of the classification detection of the oil spilling, but also can make up for the defects of a laboratory method and a single spectrum analysis method, and becomes a new method for rapidly detecting the organic pollutants in the environment.
Since fluorescence interference is usually accompanied when measuring the raman spectrum, which affects the accuracy of the raman measurement result, the present embodiment employs the differential raman spectroscopy technology to remove the fluorescence interference, so as to complete the accurate measurement of the raman spectrum.
Based on the design concept, the present embodiment firstly designs a set of seawater oil spill classification detection apparatus to support in-situ detection of seawater oil spill, and specifically includes an automatic circulation platform, an optical detection system, an automatic control unit, and other main components.
The functions to be completed by the automatic circulation platform of the embodiment mainly include:
(1) Collecting seawater containing oil spill, wherein the seawater can be collected in situ on site, or collected in a laboratory;
(2) Sending the collected seawater into a cuvette for fluorescence spectrum detection;
(3) Mixing collected seawater with nano materials (such as gold nano particle solution) required for Raman spectrum detection at constant temperature, and then sending the constant-temperature mixed liquid into a cuvette for Raman spectrum detection;
(4) And automatically cleaning the circulation pipeline and the cuvette.
To achieve the above function, as shown in fig. 1, the present embodiment is mainly configured with four three-way valves 11 to 14 (defined as a first three-way valve 11, a second three-way valve 12, a third three-way valve 13, and a fourth three-way valve 14, respectively), a thermostatic mixing loop 15, and a peristaltic pump 16 in the automatic loop stage.
The first port NC1 of the first three-way valve 11 is used for injecting nano materials required by Raman spectrum detection, the second port NO1 is used for accessing pipeline cleaning liquid, and the common port COM1 is connected with the first port NC2 of the second three-way valve 12.
The second port NO2 of the second three-way valve 12 communicates with the first port NC4 of the fourth three-way valve 14, and the common port COM2 of the second three-way valve 12 communicates with the water inlet of the thermostatic mixing loop pipe 15.
The first port NC3 of the third three-way valve 13 is used for feeding seawater containing spilled oil, the second port NO3 is communicated with the water outlet of the constant-temperature mixing circulating pipe 15, and the common port COM3 of the third three-way valve 13 is communicated with the water inlet of the peristaltic pump 16.
The common port COM4 of the fourth three-way valve 14 is communicated with the water outlet of the peristaltic pump 16, and the second selection port NO4 of the fourth three-way valve 14 is communicated with the cuvette 10, as shown in fig. 2.
In this embodiment, the cuvette 10 is preferably a corrosion-resistant quartz cuvette, the lower end is a sample inlet and communicates with the second port NO4 of the fourth three-way valve 14, and the upper end is a sample outlet, so that gas interference can be effectively avoided.
As a preferred embodiment, the normally closed ports of the four three-way valves 11 to 14 may be used as the first selective port, and the normally open port may be used as the second selective port, so as to simplify the control flow and avoid frequent switching control of the valve body.
The functions to be performed by the optical detection system of the present embodiment mainly include:
(1) Irradiating seawater sample injection in the cuvette by using a laser light source capable of exciting a fluorescence signal to excite the fluorescence signal and collect the fluorescence signal to generate fluorescence spectrum data;
(2) And irradiating the constant-temperature mixed liquid in the cuvette by using a laser light source capable of exciting Raman optical signals so as to excite the Raman optical signals and collect the Raman optical signals to generate Raman spectrum data.
To achieve the above function, this embodiment is mainly provided with a fluorescence optical path system and a raman optical path system in the optical detection system, as shown in fig. 2. The fluorescence light path system mainly comprises a fluorescence laser light source 21, a first collimating lens 22, a first narrow-band filter 23, a first converging lens 24, a second collimating lens 25, a first long-wave pass filter 26, a second converging lens 27 and a fluorescence detector 28. The raman optical path system mainly includes a differential raman laser 31, a third collimating lens 32, a short-wave pass dichroic mirror 33, a second narrow-band filter 34, a reflecting mirror 35, a third narrow-band filter 38, a first long-wave pass dichroic mirror 36, a third converging lens 37, a second long-wave pass dichroic mirror 39, a second long-wave pass filter 40, a fourth converging lens 41, and a raman detector 42.
The fluorescent laser light source 21 preferably adopts an ultra-high brightness LED light source, the spectral range is 355nm to 365nm, the divergence angle is 60 degrees, and the optical power is 0.5W. This embodiment will be described by taking a laser beam of 360nm as an example. The ultra-high brightness 360nm laser with the power of 0.5W can effectively excite a detected object to emit a fluorescence signal, and the divergence angle of 60 degrees can meet the requirement of a subsequent lens on light collimation treatment.
The first collimating lens 22 is located behind the fluorescent laser light source 21 (the front and the back are defined by the transmission direction of the light), and is configured to collimate the laser light of 360nm emitted by the fluorescent laser light source 21, so as to implement parallel emission of the light beam and ensure that the light is transmitted in parallel in the optical fiber.
The first narrow-band filter 23 is located behind the first collimating lens 22, and is used for eliminating stray light with a wavelength of 360nm and monochromaticity of exciting light, and effectively avoiding the problems of complex fluorescent signals, difficulty in distinguishing and the like caused by wide-spectrum excitation.
The first converging lens 24 is located behind the first narrow-band filter 23 and is used for converging 360nm laser into the quartz cuvette 10, and the seawater containing oil spilling is excited by the small-spot high-energy 360nm laser to ensure that the oil spilling emits a fluorescent signal.
The second collimating lens 25 is used to collect the excited fluorescence signal. Since the excited fluorescence signal is scattered light without a specific direction, a lens with a specific focal length and diameter is required to collect the fluorescence signal so that the fluorescence signal passes through the first long-wavelength pass filter 26 as parallel light as possible to filter out stray light.
The first long-wave pass filter 26 is located behind the second collimating lens 25 and is used for filtering stray light except for fluorescent signals. The fluorescent signal is often accompanied by reflected light of 360nm and other interference light, and the interference of the other light on the fluorescent detection can be filtered by adopting a long-wave pass filter.
The second converging lens 27 is located behind the first long-wave pass filter 26, and is used for converging the fluorescence signal to the fluorescence detector 28, so that the fluorescence is effectively detected by the fluorescence detector 28.
In this embodiment, the fluorescence detector 28 may be a spectrometer selectively used for detecting fluorescence signals, and the spectral range is 200nm to 600nm, and is mainly used for receiving fluorescence signals and performing photoelectric conversion, so as to output fluorescence spectrum data.
The differential raman laser 31 preferably adopts a 785nm/830nm differential raman laser, that is, the laser can emit laser with two wavelengths of 785nm and 830nm, the line width is 0.1nm at most, the maximum output power is 600mW, the output optical fiber interface FC/PC is externally connected with an optical fiber, so as to ensure the light output efficiency and facilitate the collimation processing of the light by a rear lens.
The third collimating lens 32 is located behind the differential raman laser 31, and is used for collimating the laser light and emitting the light beam in parallel.
And the short-wave dichroic mirror 33 is positioned behind the third collimating lens 32, is placed at an angle of 45 degrees, and is used for transmitting 785nm laser light and reflecting 830nm laser light to realize the shunt transmission of the two laser beams.
The second narrow-band filter 34 is located behind the short-wave-pass dichroic mirror 33, and is used for transmitting 785nm laser and filtering stray light except the 785nm laser, so that monochromaticity of light beams is realized, and the requirement of Raman signal excitation is met.
The reflector 35 is located behind the second narrowband filter 34, is disposed at an angle of 45 degrees, and is used for reflecting 785nm laser light to realize steering of a light path, so as to shorten the length of the light path and realize backward detection.
The first long-wave-pass dichroic mirror 36 is located below the reflecting mirror 35, is placed at an angle of 45 degrees, and is used for reflecting 785nm laser, transmitting Raman light larger than 785nm, realizing steering of 785nm laser beams, and filtering stray light in collected Raman signals.
The third converging lens 37 is located between the first long-wave-pass dichroic mirror 36 and the quartz cuvette 10, and is used for converging 785nm laser light and 830nm laser light to form small light spots so as to improve the energy of the light beam in unit area, and the two laser beams can excite the constant-temperature mixed liquid in the cuvette to emit Raman scattering light. Meanwhile, the device is also used for collecting Raman scattering light generated by excitation of the two beams of laser light, so that the Raman scattering light passes through a subsequent optical device as parallel light as possible, and stray light is filtered.
The third narrow-band filter 38 is used for transmitting the 830nm laser beam reflected by the short-wave-pass dichroic mirror 33, and filtering stray light except for 830nm, so as to realize monochromaticity of the light beam and meet the requirement of raman light signal excitation.
The second long-wavelength dichroic mirror 39 is placed at an angle of 45 degrees, the laser with the wavelength of 830nm is reflected to the first long-wavelength dichroic mirror 36, and is transmitted to the third converging lens 37 through the first long-wavelength dichroic mirror 36, so that the constant-temperature mixed liquid in the cuvette 10 is irradiated by the laser with the wavelength of 830nm with small light spots and high energy, and the Raman scattering light with the wavelength of 830nm is excited.
The third converging lens 37 collects raman scattered light of 785nm and 830nm, processes the raman scattered light into parallel light, and sequentially transmits through the first long-wavelength-pass dichroic mirror 36 and the second long-wavelength-pass dichroic mirror 39. The first and second long-pass dichroic mirrors 36 and 39 have a characteristic of transmitting raman light, and transmit the two raman lights to the second long-pass filter 40.
The second long wavelength pass filter 40 is used to filter out non-raman light, mainly to eliminate the influence of 785nm and 830nm reflected light on raman detection.
The fourth converging lens 41 is located behind the second long-wave pass filter 40, and is configured to converge the raman light to the raman detector 42, so that the raman light is effectively detected by the raman detector 42.
In this embodiment, the raman detector 42 may be selected from a spectrometer for raman signal detection with a raman shift range of 150cm -1 ~3500cm -1 The Raman spectrum data acquisition device is mainly used for receiving Raman signals and performing photoelectric conversion, and output of Raman spectrum data is achieved.
As a preferred embodiment, raman detection is preferably performed using Surface Enhanced Raman Spectroscopy (SERS). The use of surface enhanced raman spectroscopy to detect oil spill contaminants is often accompanied by the generation of fluorescence. The fluorescence signal is stronger than the raman signal, which can cause the raman signal to be submerged in the fluorescence and prevent the useful raman signal from being extracted. The fluorescence signal of the oil spilling pollutant is not obviously shifted when the Raman spectrum is excited by laser with the wavelengths of 785nm and 830nm, and the spectral characteristic peak of the Raman spectrum shifts along with the exciting light and keeps a certain position relation with the exciting light. Therefore, the difference between the oil spilling Raman characteristic spectrum excited by the laser with the wavelength of 785nm and the oil spilling Raman characteristic spectrum excited by the laser with the wavelength of 830nm is reduced, so that the Raman spectrum information with fluorescence eliminated can be obtained, and the Raman detection accuracy can be improved.
The automatic control unit is mainly used for controlling the switching of the passages of four three-way valves 11-14 in the automatic circulation platform and the on-off control of a constant-temperature mixing circulation pipe 15 and a peristaltic pump 16; meanwhile, the on-off time sequence of the fluorescence laser source 21 and the differential raman laser 31 in the optical detection system is controlled, and the fluorescence spectrum data and the raman spectrum data output by the fluorescence detector 28 and the raman detector 42 are received, so as to perform the classification detection of the seawater oil spill.
The following describes the seawater oil spill classification detection method proposed in this embodiment in detail with reference to the seawater oil spill classification detection device shown in fig. 1 and fig. 2.
Firstly, fluorescence detection is carried out on collected seawater containing spilled oil, and the method specifically comprises the following steps:
the automatic control unit firstly controls the communication of the common port COM3 of the third three-way valve 13 in the automatic circulation platform with the first port NC3, controls the communication of the common port COM4 of the fourth three-way valve 14 with the second port NO4 of the third three-way valve, starts the peristaltic pump 16, and pumps the seawater containing oil spilling into the cuvette 10 for about 10s for fluorescence spectrum detection.
The automatic control unit starts the fluorescence laser light source 21 in the optical detection system to emit 380nm laser, and starts the fluorescence detector 28 to collect the fluorescence signal excited by the seawater oil spill, so as to generate fluorescence spectrum data.
The automatic control unit collects the fluorescence spectrum data output by the fluorescence detector 28 and performs the following processing procedures, as shown in fig. 3:
s301, performing spectrum smoothing and denoising processing on the fluorescence spectrum data to obtain a smooth fluorescence spectrum.
Since the collected fluorescence spectrum contains much noise, if the fluorescence information is directly extracted, the noise will affect the extraction effect. In the embodiment, the smoothing and denoising processing for the fluorescence spectrum data can adopt Savitzky-Golay polynomial smoothing, and spectrum denoising is realized through weighted average.
The specific process is as follows: carrying out convolution operation on the collected spectral data P [ n ] and the smoothing weight vector W [ n ], wherein the formula is as follows:
wherein n is i Is the ith spectral data; z is the total number of the spectral data, and m is an integer of z/2; w j Is a smooth weight factor; e [ n ]]The effect of the smoothing is shown in fig. 4 (in fig. 4, the abscissa indicates the spectral position and the ordinate indicates the light intensity) for the smoothed spectral data.
And S302, performing baseline correction on the smooth fluorescence spectrogram and removing a local baseline.
In this embodiment, the fluorescence dark background spectrum may be first obtained, and then the fluorescence dark background spectrum is subtracted from the smoothed fluorescence spectrogram to obtain a fluorescence spectrogram with the local baseline removed, thereby completing the baseline calibration.
The basic process of baseline calibration is:
first, the baseline curve B [ n ] of the spectrum is sought]The method is to use the original spectrum data P [ n ]]And spectral data E [ n ] smoothed by Savitzky-Golay polynomial]Is analyzed in comparison, i.e. for P n i ]And E [ n ] i ]Comparing, and combining the smaller value of the two to generate a baseline curve B [ n ]]；
Secondly, making a difference between the original spectrum data P [ n ] and the generated baseline data, and adopting a trapezoidal method to calculate the integral to form a new matrix C [ n ];
next, a search is made for conditions C [ n ] that are simultaneously satisfied i-1 ]< C[n i-2 ]、C[n i-1 ]< C[n i ]Point n of i-1 Extracting B [ n ] i-1 ]Generating a minimum baseline B min [n]；
Finally, the raw spectral data P [ n ]]And B min [n]Making difference to obtain spectrum data D [ n ] after base line correction]. The effect graph after the baseline correction is shown in fig. 5 (in fig. 5, the abscissa represents the spectral position and the ordinate represents the light intensity).
S303, picking up the peak value of the fluorescence spectrogram without the local base line, and picking up the spectral positions and intensities of all characteristic peaks.
In this embodiment, the smoothed and baseline corrected spectral data can be expressed as:
D[n]={n 1 , n 2 , n 3 ,…,n z }。
to pick up the characteristic peaks in the fluorescence spectrum, the following characteristic peak picking process can be adopted:
spectral data D [ n ]]Every 5 adjacent data points in the data set constitute a set of data, which can be denoted as A k {n i-2 , n i-1 , n i , n i+1 , n i+2 In which n is i Represents the light intensity at spectral coordinate i, i.e., peak height;
5 data points in each group of data are sorted in an ascending order;
if three adjacent groups of data A k-1 、A k 、A k+1 In (A) k-1 Ascending spectral coordinates of (A) k Disorder of spectral coordinates of A k+1 The spectrum coordinate of A is reduced in order, then A is k The position is determined as the characteristic peak position.
For example, the following steps are carried out: suppose pair A 8 、A 9 、A 10 Three groups of data are obtained after ascending order arrangement:
A 8 {2643 742 ，2784 743 ，2832 744 ，2903 745 ，2923 746 }
A 9 {3000 751 ，3115 748 ，3220 747 ，3314 750 ，3423 749 }
A 10 {2822 752 ，2713 753 ，2590 754 ，2345 755 ，2212 756 }。
wherein A is 8 The spectral coordinates of (a) are in ascending order 9 The spectral coordinates of (A) are out of order 10 The spectral coordinates of (2) are in descending order, and therefore, A can be judged 9 Is the position of one characteristic peak.
S304, comparing the spectral position and the intensity of the picked characteristic peak with the fluorescent spectrum of the gasoline and the diesel to identify whether the oil spill is the gasoline or the diesel. If the gasoline or diesel is adopted, executing the detection process of the concentration of the spilled oil, namely, skipping to the step S311; otherwise, classifying and identifying the seawater oil spill by adopting a Raman detection technology.
The method for carrying out Raman detection on the collected seawater containing the spilled oil specifically comprises the following steps:
firstly, the automatic control unit controls the common ports COM1, COM2 and COM4 of the first three-way valve 11, the second three-way valve 12 and the fourth three-way valve 14 in the automatic circulation platform to be respectively communicated with the first port selection NC1, NC2 and NC4 of the automatic circulation platform, controls the common port COM3 of the third three-way valve 13 to be communicated with the second port selection NO3 of the automatic circulation platform, pumps the nano material required by Raman spectrum detection into the constant-temperature mixing circulation tube 15, and realizes the sample injection of the nano material, wherein the time is about 10s.
And then, the automatic control unit controls the common port COM2 of the second three-way valve 12 to be communicated with the second port NO2 of the second three-way valve, controls the common port COM3 of the third three-way valve 13 to be communicated with the first port NC3 of the third three-way valve, and pumps a certain amount of seawater containing spilled oil to realize the sample introduction of the seawater sample. The pumping amount of the seawater sample can be adjusted by controlling the sample introduction time of the seawater sample, so that the requirement of Raman spectrum detection is met.
Then, the automatic control unit controls the common port COM3 of the third three-way valve 13 to be communicated with the second selection port NO3 of the third three-way valve to form a mixing loop, so that the seawater sample and the nano material are fully mixed through the constant-temperature mixing circulating pipe 15 and are kept at a constant temperature to form a constant-temperature mixed liquid. The mixing time was about 30s.
Finally, the automatic control unit controls the common port COM4 of the fourth three-way valve 14 to be communicated with the second port NO4 of the fourth three-way valve, and the constant-temperature mixed liquid is pumped into the quartz cuvette 10 for about 10 seconds to perform raman spectrum detection.
The automatic control unit starts the differential raman laser 31 in the optical detection system to emit laser with the wavelength of 785nm and 830nm, and starts the raman detector 42 to collect two paths of raman optical signals excited by seawater oil spill so as to generate two groups of raman spectrum data.
The automatic control unit collects the raman spectrum data output by the raman detector 42 and performs the following processes, as shown in fig. 3:
s305, differentiating the acquired Raman characteristic spectrum of 785nm and the acquired Raman characteristic spectrum of 830nm to obtain Raman spectrum data after fluorescence elimination, namely differential surface enhanced Raman spectrum data.
S306, performing spectrum smoothing and denoising processing on the differential surface enhanced Raman spectrum data to obtain a smooth SERS spectrogram.
In this embodiment, the spectral smoothing and denoising process may be performed on the differential surface enhanced raman spectrum data by using the same method for performing the spectral smoothing and denoising process on the fluorescence spectrum data, that is, by using a Savitzky-Golay polynomial smoothing process, and the specific method may be referred to in step S301.
And S307, performing baseline correction on the smoothed SERS spectrogram, and removing a local baseline.
In this embodiment, the same method for performing baseline correction on the smoothed SERS spectrogram can be adopted, and the specific process is shown in step S302.
S308, picking up the peak value of the SERS spectrogram without the local base line, and picking up the spectral positions and intensities of all characteristic peaks.
In this embodiment, the same method for performing peak picking on the SERS spectrogram after removing the local baseline can be adopted, and the specific process may be as shown in step S303.
S309, comparing the spectral position and the intensity of the picked characteristic peak with the Raman spectrum of the polycyclic aromatic hydrocarbon type characteristics of the crude oil and the finished oil, and identifying the polycyclic aromatic hydrocarbon type contained in the oil spill.
S310, identifying the type of the oil spill according to the types of the polycyclic aromatic hydrocarbons contained in the oil spill and the content ratio of various types of polycyclic aromatic hydrocarbons.
In the embodiment, the type of the oil spill can be judged according to the ratio of five polycyclic aromatic hydrocarbons, namely naphthalene, phenanthrene, anthracene, fluoranthene and pyrene. The specific process is as follows:
extracting the peak heights of characteristic peaks corresponding to five substances of naphthalene, phenanthrene, anthracene, fluoranthene and pyrene in the polycyclic aromatic hydrocarbon;
calculating the sum of the peak heights of the five substances to form a total peak height;
calculating the ratio of the sum of the peak heights of the characteristic peaks corresponding to the naphthalene and the phenanthrene to the total peak height;
if the ratio of the naphthalene to the phenanthrene is higher than 20%, judging the oil to be light oil;
if the ratio of the naphthalene to the phenanthrene is 10-20%, judging to be fuel oil;
and if the ratio of the naphthalene and the phenanthrene is less than 10%, judging the crude oil.
And S311, detecting the concentration of the spilled oil.
Because a linear relation exists between the characteristic peak in the spectrogram and the sample concentration, quantitative detection of oil spill can be realized by utilizing a multivariate linear regression analysis method.
The specific process is as follows:
if the identified oil spill is gasoline or diesel oil, extracting all characteristic peak intensities in the fluorescence spectrogram;
if the identified oil spill is crude oil, fuel oil or light oil, extracting all characteristic peak intensities in the Raman spectrogram;
calculating the oil spill concentration using the following multiple linear regression model:
y=b 0 +b 1 x 1 + b 2 x 2 +…+ b r x r +e；
wherein y represents the oil spill concentration; x is the number of 1 ，x 2 ，…，x r Representing the intensities of r characteristic peaks extracted from a fluorescence spectrogram or a Raman spectrogram, wherein r is the total number of the characteristic peaks; e is a random error term; b 0 Is a constant term; b 1 ，b 2 ，…，b r Is a regression coefficient, wherein b 1 Is x 2 ，x 3 ，…，x r At the time of fixation, x 1 The effect of each increment of one unit on y, i.e. x 1 Partial regression coefficients for y; in the same way, b 2 Is x 1 ，x 3 ，…，x r At the time of fixation, x 2 The effect of each increment of one unit on y, i.e. x 2 Partial regression coefficients for y; b is a mixture of r Is x 1 ，x 2 ，…，x r-1 At the time of fixation, x r The effect of each increment of one unit on y, i.e. x r Partial regression coefficients for y.
Therefore, the functions of classification and identification of the seawater oil spill and concentration detection are realized.
It should be noted that the detection of characteristic peaks is an initial step of the fluorescence-raman spectroscopy data analysis, the position of the characteristic peaks cannot be accurately estimated, problems may occur in identifying potential oils, and erroneous predictions may result. Therefore, it is very important to accurately estimate peak parameters such as the position of the characteristic peak, the peak height (light intensity), and the like. In the peak detection procedure, the three steps of spectrum smoothing, baseline correction and peak picking are adopted, so that the accuracy of characteristic peak picking can be improved, and the accuracy of classification and identification of seawater oil spill and concentration detection is further improved.
After the raman spectrum detection is finished, the automatic control unit controls the common port COM1 of the first three-way valve 11 to be communicated with the second port NO1, controls the common ports COM2 and COM4 of the second three-way valve 12 and the fourth three-way valve 14 to be communicated with the first port NC2 and NC4 of the automatic control unit, and pumps the pipeline cleaning liquid into the pipeline of the automatic circulation platform. The pumping amount of the pipeline cleaning liquid is adjusted by controlling the pumping time.
After pumping a proper amount of pipeline cleaning liquid, the automatic control unit controls the communication between the common port COM2 of the second three-way valve 12 and the second selective port NO2 thereof to form a cleaning loop, and the pipeline of the automatic loop platform is automatically cleaned.
Then, the automatic control unit controls the common port COM4 of the fourth three-way valve 14 to communicate with the second port NO4, and cleans the quartz cuvette 10.
Therefore, the automatic cleaning work of the pipeline of the automatic circulation platform is completed, and preparation is made for the next oil spill sampling and detection work.
Of course, the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and embellishments can be made without departing from the principle of the present invention, and these should also be regarded as the protection scope of the present invention.
Claims (7)
1. The utility model provides a categorised detection device of sea water oil spilling which characterized in that includes:
the automatic circulation platform is used for collecting seawater containing oil spill, mixing the seawater with a nano material required by surface enhanced Raman spectrum detection at constant temperature, and sending the seawater sample introduction and the constant-temperature mixed liquid into a cuvette at different times so as to perform fluorescence spectrum detection and Raman spectrum detection respectively;
the optical detection system irradiates seawater sample injection in the cuvette by utilizing a laser light source capable of exciting a fluorescence signal so as to excite the fluorescence signal and collect the fluorescence signal to generate fluorescence spectrum data; or a laser light source capable of exciting Raman optical signals is used for irradiating the constant-temperature mixed liquid in the cuvette so as to excite the Raman optical signals and collect the Raman optical signals to generate Raman spectrum data; it includes:
-a fluorescence light path system comprising a fluorescence laser light source, a first collimating lens, a first narrow band filter, a first converging lens, a second collimating lens, a first long-wavelength pass filter, a second converging lens and a fluorescence detector; the fluorescence laser light source is used for emitting laser of 360nm, processing the laser into parallel light through the first collimating lens, emitting the parallel light to the first narrow-band optical filter, eliminating stray light beyond 360nm, converging the parallel light to the cuvette through the first converging lens, and irradiating seawater containing oil spilling in the cuvette to excite a fluorescence signal; the second collimating lens collects the fluorescence signal and emits the fluorescence signal to the long-wavelength-pass filter as parallel light so as to filter out interference light of a non-fluorescence signal, and the interference light is converged to the fluorescence detector through the second converging lens to realize the collection of fluorescence spectrum data;
-a raman optical path system comprising a differential raman laser, a third collimating lens, a short-wave pass dichroic mirror, a second narrow-band filter, a third narrow-band filter, a first long-wave pass dichroic mirror, a third converging lens, a second long-wave pass dichroic mirror, a second long-wave pass filter, a fourth converging lens and a raman detector; the differential Raman laser is used for emitting 785nm and 830nm laser, processing the laser into parallel light through a third collimating lens and emitting the parallel light to a short-wave-pass dichroic mirror, and the short-wave-pass dichroic mirror transmits the 785nm laser light and reflects the 830nm laser light to form two laser light branches for transmission; the 785nm laser is filtered by the second narrow-band filter to remove stray light beyond 785nm, and then is emitted to the first long-wavelength-pass dichroic mirror; the laser light with the wavelength of 830nm is filtered by a third narrow-band filter to remove stray light except for the wavelength of 830nm, and then is reflected to the first long-wavelength-pass dichroic mirror by a second long-wavelength-pass dichroic mirror; the first long-wavelength-pass dichroic mirror reflects 785nm laser and transmits 830nm laser, two beams of the 785nm laser and the two beams of the 830nm laser are converged to the cuvette through the third converging lens to irradiate the constant-temperature mixed liquid in the cuvette, and two paths of Raman optical signals of 785nm and 830nm are excited; the two paths of Raman optical signals are transmitted to a second long-wavelength-pass optical filter through a third converging lens, a first long-wavelength-pass dichroic mirror and a second long-wavelength-pass dichroic mirror respectively to filter out non-Raman optical signals smaller than 830nm, and the non-Raman optical signals are converged to a Raman detector through a fourth converging lens to realize the acquisition of Raman spectrum data;
an automatic control unit which receives the fluorescence spectrum data and the Raman spectrum data and executes the following seawater oil spill classification detection process:
performing spectrum smoothing and denoising processing on the fluorescence spectrum data to obtain a smooth fluorescence spectrum diagram;
performing baseline correction on the smooth fluorescence spectrogram, and removing a local baseline;
picking up the peak value of the fluorescence spectrogram after the local baseline is removed, and picking up the spectral positions and intensities of all characteristic peaks;
comparing the spectral position and intensity of the picked characteristic peak with the fluorescent spectrum of gasoline and diesel oil to identify whether the spilled oil is gasoline or diesel oil;
when the spilled oil is not gasoline or diesel oil, performing spectrum smoothing denoising treatment on Raman spectrum data to obtain a smooth Raman spectrum chart;
performing baseline correction on the smooth Raman spectrogram, and removing a local baseline;
picking up the peak value of the Raman spectrogram without the local base line, and picking up the spectral positions and intensities of all characteristic peaks;
comparing the spectral position and intensity of the picked characteristic peak with the Raman spectrum of the polycyclic aromatic hydrocarbon type characteristics of the crude oil and the finished oil, and identifying the polycyclic aromatic hydrocarbon type contained in the oil spill;
and identifying the type of the oil spill according to the types of the polycyclic aromatic hydrocarbons contained in the oil spill and the content ratio of various polycyclic aromatic hydrocarbons.
2. The apparatus for classifying and detecting seawater oil spill according to claim 1, wherein in the Raman spectrum detection process,
the automatic control unit controls the differential Raman laser to emit laser with the wavelength of 785nm and the wavelength of 830nm, and the laser respectively irradiates the constant-temperature mixed liquid in the cuvette to excite Raman optical signals belonging to 785nm and Raman optical signals belonging to 830 nm;
the Raman detector collects Raman optical signals belonging to 785nm and Raman optical signals belonging to 830nm to respectively form a Raman characteristic spectrum belonging to 785nm and a Raman characteristic spectrum belonging to 830 nm;
and the automatic control unit performs difference on the Raman characteristic spectrum to which the wavelength of 785nm belongs and the Raman characteristic spectrum to which the wavelength of 830nm belongs to obtain Raman spectrum data after fluorescence is eliminated.
3. The seawater oil spill classification detection device according to claim 1, wherein the automatic control unit performs spectral denoising by weighted average using a Savitzky-Golay polynomial smoothing algorithm in performing smoothing denoising processing on the raman spectral data and the fluorescence spectral data.
4. The seawater oil spill classification detecting device according to claim 3, wherein the automatic control unit performs the following baseline correction process:
the raw spectral data P [ n ]]And spectral data E [ n ] smoothed by Savitzky-Golay polynomial]Is comparatively analyzed, i.e. for P n i ]And E [ n ] i ]Comparing, and combining the smaller value of the two to generate a baseline curve B [ n ]]；
Making difference between the original spectrum data and the generated baseline data, and adopting a trapezoidal method to calculate integration to form a new matrix Cn;
searching for simultaneous satisfaction of condition C [ n ] i-1 ]< C[n i-2 ]、C[n i-1 ]< C[n i ]Point n of i-1 Extracting B [ n ] i-1 ]Generating a minimum baseline B min [n]；
The raw spectral data P [ n ]]And B min [n]Making difference to obtain spectrum data D [ n ] after base line correction]。
5. The seawater oil spill classification detection device according to claim 1, wherein the automatic control unit adopts the following characteristic peak picking process in the process of picking up the peak of the Raman spectrogram and the fluorescence spectrogram:
representing denoised and baseline-corrected spectral data as D [ n ]]={n 1 , n 2 , n 3 ,…,n z };
Every 5 adjacent data points in the spectrum data are combined into a group of data, and the data is marked as A k {n i-2 , n i-1 , n i , n i+1 , n i+2 In which n is i Representing the light intensity at spectral coordinate i;
5 data points in each group of data are sorted in an ascending order;
if three adjacent groups of data A k-1 、A k 、A k+1 In (A) k-1 Ascending spectral coordinates of (A) k Disorder of spectral coordinates of A k+1 The spectrum coordinate of A is reduced in order, then A is k The position is determined as the characteristic peak position.
6. The apparatus according to claim 1, wherein the automatic control unit identifies the type of oil spill according to the types of polycyclic aromatic hydrocarbons and the content ratios of the polycyclic aromatic hydrocarbons, and comprises:
extracting the peak heights of characteristic peaks corresponding to five substances of naphthalene, phenanthrene, anthracene, fluoranthene and pyrene in the polycyclic aromatic hydrocarbon;
calculating the sum of the peak heights of the five substances to form a total peak height;
calculating the ratio of the sum of the peak heights of the characteristic peaks corresponding to the naphthalene and the phenanthrene to the total peak height;
if the ratio of the naphthalene to the phenanthrene is higher than 20%, judging the oil to be light oil;
if the ratio of the naphthalene to the phenanthrene is 10-20%, judging to be fuel oil;
and if the ratio of the naphthalene and the phenanthrene is less than 10%, judging the crude oil.
7. The seawater oil spill classification detection apparatus according to any one of claims 1 to 6, wherein the automatic control unit performs an oil spill concentration detection process after identifying the oil spill type, comprising:
if the oil spill is gasoline or diesel oil, extracting all characteristic peak intensities in a fluorescence spectrogram;
if the oil spill is not gasoline or diesel oil, extracting all characteristic peak intensities in the Raman spectrogram;
calculating the oil spill concentration using the following multiple linear regression model:
y=b 0 +b 1 x 1 + b 2 x 2 +…+ b r x r +e；
wherein y represents the oil spill concentration; x is the number of 1 ，x 2 ，…，x r Representing the intensities of r characteristic peaks extracted from a fluorescence spectrogram or a Raman spectrogram, wherein r is the total number of the characteristic peaks; b 0 Is a constant term; b 1 ，b 2 ，…，b r Is a regression coefficient; e is a random error term.
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| CN101692045B (en) * | 2009-10-28 | 2011-04-27 | 广西工学院 | Multi-wavelength excitation-based fluorescence elimination method for Raman spectrum |
| CN101923649B (en) * | 2010-06-22 | 2013-01-09 | 中国海洋大学 | Oil spill type recognition method based on fluorescence spectrum |
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