CN111398253A - Atmosphere-adjustable L IBS signal enhancement device and heavy metal detection method - Google Patents
Atmosphere-adjustable L IBS signal enhancement device and heavy metal detection method Download PDFInfo
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Abstract
The invention provides an atmosphere adjustable L IBS signal enhancement device and a heavy metal detection method, wherein the device comprises a solid pulse laser, a light path system, a single gas cylindrical gas chamber, an optical fiber collector, a spectrometer and a controller, the light path system is connected with the solid pulse laser, the single gas cylindrical gas chamber is arranged corresponding to the light path system, the optical fiber collector is arranged corresponding to the single gas cylindrical gas chamber, the spectrometer is connected with the optical fiber collector, the controller is respectively connected with the spectrometer and the solid pulse laser, the spectrometer determines laser induced breakdown spectrum information according to light signals received by the optical fiber collector, the controller determines L IBS spectrum information according to the received laser induced breakdown spectrum information, the capacity of generating plasma by a sample to be detected through laser ablation is provided with single gas environment atmosphere with different pressures, the input quantity of gas and the proportion of air are adjusted according to detection requirements, the pressure is adjusted, the IBS spectrum information of L is enhanced, and the accuracy of determining the heavy metal content is improved.
Description
Technical Field
The invention relates to the technical field of L IBS spectral information detection, in particular to an atmosphere adjustable L IBS signal enhancement device and a heavy metal detection method.
Background
With human activities such as industrial, agricultural and urban pollution, the heavy metal content in the environment is continuously accumulated. Excessive heavy metal elements in an agricultural ecosystem not only can influence the physiological and biochemical processes of crops, but also can inhibit the growth of the crops to a certain extent to cause cell death, and can enter animals and human bodies through the transmission of a food chain to cause serious health problems. Taking rice as an example, the photosynthetic product of functional leaves of rice provides over 80% contribution to the yield of rice grains, and is an important organ for forming the grains. Because rice plants have the characteristic of strong absorption of heavy metals such as Cd, Cu and the like, the heavy metals can be accumulated in rice leaves and fruits due to low-degree heavy metal pollution, and finally the toxic rice is formed. As for the heavy metal cadmium (Cd), Cd has carcinogenic, mutagenic, and teratogenic hazards to the human body, interferes with calcium regulation in biological systems, and also causes renal failure and chronic anemia. Therefore, the rapid detection of the heavy metal elements in the object to be detected is beneficial to judging the heavy metal condition in the object to be detected and the contact environment of the object to be detected, and has important significance for grain safety and environmental safety supervision.
As an effective metal element detection technology, a laser induced breakdown spectroscopy (L ase induced breakdown spectroscopy, L IBS) technology ablates a sample to be detected by using high-energy laser pulses, laser plasmas with extremely high temperature and brightness are instantaneously generated on the surface of the sample, the plasma spectra correspond to substance elements one by one, and a certain quantitative relation exists.
Compared with other fields, the L IBS technology is more challenging in detection application in the environmental and agricultural fields, mainly because the components of samples such as soil, plants and the like are complex and have large differences, and a complex matrix effect is finally formed. L IBS-generated plasma spectrum contains thousands of variable information, which not only contains emission lines and continuous background information of target elements, but also contains matrix information corresponding to complex matrixes, how to improve L IBS quantitative analysis performance on trace elements is continuously a hotspot field of research.
Disclosure of Invention
Based on the above, the invention aims to provide an atmosphere-adjustable L IBS signal enhancement device and a heavy metal detection method, which can enhance L IBS spectral information and improve the accuracy of heavy metal content determination by changing the atmosphere environment of plasma.
To achieve the above object, the present invention provides an atmosphere adjustable L IBS signal enhancement apparatus comprising:
a solid-state pulse laser for generating laser light;
the optical path system is connected with the solid pulse laser and is used for transmitting laser;
the single gas cylindrical gas chamber is arranged corresponding to the light path system and is used for providing a uniform single gas atmosphere environment for the sample to be detected;
the optical fiber collector is arranged corresponding to the single gas cylindrical gas chamber and is used for receiving an optical signal generated in the plasma signal diffusion process; the plasma signal is generated based on the laser ablation of the sample to be detected;
the spectrometer is connected with the optical fiber collector and used for determining laser-induced breakdown spectroscopy information according to the optical signal received by the optical fiber collector;
and the controller is respectively connected with the spectrometer and the solid pulse laser, and is used for determining L IBS spectral information according to the received laser-induced breakdown spectral information, acquiring instrument parameters and generating a control instruction according to the instrument parameters to control the solid pulse laser to generate laser, wherein the instrument parameters comprise the distance from a lens in the optical path system to the surface of the sample to be detected and the laser energy.
Optionally, the apparatus further comprises:
and the time delay integral generator is respectively connected with the controller and the spectrometer and is used for controlling the working time sequence of the spectrometer according to the time delay time and the integral time in the instrument parameters.
Optionally, the single gas cylindrical gas chamber comprises:
the gas storage tank is used for storing argon;
the gas splitter is connected with the gas storage tank through a pipeline and is used for splitting the argon gas in the gas storage tank;
the air chamber cabin is provided with a sample table and is used for placing the sample to be detected on the sample table and arranging the sample to be detected corresponding to the optical path system;
the gas transmission pipes are respectively connected with the gas splitter and the gas chamber and are used for transmitting the argon gas in the gas storage tank to the gas chamber, so that a uniform single gas atmosphere environment is provided for the sample to be detected;
and the vacuum pump is connected with the air chamber cabin through a pipeline and is used for vacuumizing the air chamber cabin.
Optionally, the single gas cylindrical gas chamber further comprises:
and the barometer is used for detecting the pressure in the air chamber cabin.
Optionally, the single gas cylindrical gas chamber further comprises:
and the first control valve is arranged on a pipeline between the gas splitter and the gas storage tank, is connected with the controller and is used for controlling the flow rate of the gas flowing out of the argon gas in the gas storage tank according to a control instruction generated by the controller.
Optionally, the single gas cylindrical gas chamber further comprises:
and the second control valve is arranged on a pipeline between the vacuum pump and the air chamber, is connected with the controller and is used for controlling the pumping flow rate of the vacuum pump according to a control instruction generated by the controller.
Optionally, the single gas cylindrical gas chamber further comprises:
and the gas outlet valve is arranged at the bottom of the side wall of the gas chamber cabin and is used for controlling the gas in the gas chamber cabin to flow out.
Optionally, the gas chamber is a cylinder with a height of 10cm and a diameter of 15cm, the top end of the cylinder is made of quartz glass, and the side surface and the bottom of the cylinder are made of stainless steel metal; the top end of the cylinder is provided with a plurality of air inlets, the number of the air inlets is the same as that of the gas transmission pipes, and the plurality of gas transmission pipes are inserted into the air chamber cabin through the air inlets.
The invention also provides a heavy metal detection method, which comprises the following steps:
determining a sample to be detected;
detecting the sample to be detected by using the signal enhancement device to obtain laser-induced breakdown spectroscopy information;
performing standard normal transformation processing on the laser-induced breakdown spectrum information to determine L IBS spectrum information;
establishing a multiple linear regression model of emission line intensity-heavy metal content;
inputting the L IBS spectral information into a multiple linear regression model to determine the true content of heavy metals.
Optionally, the establishing of the multiple linear regression model of emission line intensity-heavy metal content specifically includes:
obtaining a plurality of test set samples;
measuring the real content of heavy metal in each test set sample by adopting an inductively coupled plasma mass spectrometry;
detecting each test set sample by using the signal enhancement device to obtain laser-induced breakdown spectrum information corresponding to each test set sample;
performing standard normal transformation processing on the laser induced breakdown spectroscopy information corresponding to each test set sample to determine L IBS spectroscopy information corresponding to each test set sample;
screening characteristic wave bands which are related to heavy metals in L IBS spectra corresponding to the test set samples by adopting a variable screening partial least squares regression method;
selecting a plurality of emission spectral lines of heavy metals from a plurality of characteristic wave bands according to an NIST database;
and establishing a multiple linear regression model of emission line intensity-heavy metal content by adopting a multiple linear regression method, taking the emission lines of a plurality of heavy metals as input, and taking the real content of the heavy metals in each test set sample as output.
Optionally, the determining a sample to be detected specifically includes:
selecting plants to be detected with the same growth vigor;
carrying out various gradient CdCl on the plant to be detected2Solution stress treatment;
and collecting the plants to be detected after a set day, and carrying out cleaning, drying, grinding, sieving and tabletting treatment on the plants to be detected to obtain samples to be detected.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
the invention provides an atmosphere adjustable L IBS signal enhancement device and a heavy metal detection method, wherein the device comprises a solid pulse laser, a light path system, a single gas cylindrical air chamber, an optical fiber collector, a spectrometer and a controller, the light path system is connected with the solid pulse laser, the single gas cylindrical air chamber is arranged corresponding to the light path system, the optical fiber collector is arranged corresponding to the single gas cylindrical air chamber, the spectrometer is connected with the optical fiber collector, the controller is respectively connected with the spectrometer and the solid pulse laser, the spectrometer determines laser induced breakdown spectrum information according to light signals received by the optical fiber collector, the controller determines L IBS spectrum information in a map form according to the received laser induced breakdown spectrum information, the device provides the capacity of single gas environment atmosphere with different pressures for generating plasma by a sample to be detected through laser ablation, adjusts the input quantity of gas and the proportion of air according to detection requirements, adjusts the pressure, enhances L IBS spectrum information and improves the accuracy of heavy metal content determination.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, 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 only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic structural diagram of a signal enhancement apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of the upper and lower surfaces of a single gas chamber in a signal enhancement device according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a signal enhancement device according to an embodiment of the present invention;
FIG. 4 is a flowchart of a heavy metal detection method according to an embodiment of the present invention;
the device comprises a solid pulse laser 1, a solid pulse laser 2, an optical path system 3, a single gas cylindrical gas chamber 4, an optical fiber collector 5, a spectrometer 6, a delay integral generator 7, a lead wire 8, a controller 3-1, a gas storage tank 3-2, a first control valve 3-3, a gas splitter 3-4, a gas transmission pipe 3-5, a gas inlet 3-6, a sample stage 3-7, a gas chamber 3-8, a top end 3-9, a barometer 3-10, a second control valve 3-11 and a vacuum pump.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide an atmosphere adjustable L IBS signal enhancement device and a heavy metal detection method, which can enhance L IBS spectral information and improve the accuracy of heavy metal content determination by changing the atmosphere environment of plasma.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Fig. 1 is a schematic structural diagram of a signal enhancement device according to an embodiment of the present invention, and as shown in fig. 1, the present invention provides an atmosphere adjustable L IBS signal enhancement device, which includes a solid pulse laser 1, an optical path system 2, a single gas cylindrical gas chamber 3, an optical fiber collector 4, a spectrometer 5 and a controller 8, where the optical path system 2 is connected to the solid pulse laser 1, the single gas cylindrical gas chamber 3 is disposed corresponding to the optical path system, the optical fiber collector 4 is disposed corresponding to the single gas cylindrical gas chamber 3, the spectrometer 5 is connected to the optical fiber collector 4 through a wire 7, and the controller 8 is connected to the spectrometer 5 and the solid pulse laser 1 through a wire 7.
The solid pulse laser device 1 is used for generating laser, the optical path system 2 is used for transmitting laser, the single gas cylindrical gas chamber 3 is used for providing a uniform single gas atmosphere environment for a sample to be detected, the optical fiber collector 4 is used for receiving optical signals generated in a plasma signal diffusion process, the plasma signals are generated based on laser ablation of the sample to be detected, the spectrometer 5 is used for determining laser induced breakdown spectrum information according to the optical signals received by the optical fiber collector 4, the controller 8 is used for determining spectrum form L IBS spectrum information according to the received laser induced breakdown spectrum information, the controller 8 is further used for obtaining instrument parameters and generating control instructions according to the instrument parameters to control the solid pulse laser device 1 to generate laser, and the instrument parameters comprise the distance between a lens in the optical path system 2 and the surface of the sample to be detected and laser energy.
As an embodiment, the apparatus of the present invention further comprises:
and the time delay integral generator 6 is respectively connected with the controller 8 and the spectrometer 5 through a lead 7 and is used for controlling the working time sequence of the spectrometer 5 according to the time delay time and the integral time in the instrument parameters.
As an embodiment, the single gas cylindrical gas cell 3 of the present invention comprises: 3-1 parts of a gas storage tank, 3-3 parts of a gas splitter, 3-7 parts of a gas chamber cabin with a sample table 3-6, 3-4 parts of a plurality of gas transmission pipes and 3-11 parts of a vacuum pump; the gas splitter 3-3 is connected with the gas storage tank 3-1 through a pipeline, a plurality of gas transmission pipes 3-4 are respectively connected with the gas splitter 3-3 and the gas chamber 3-7, the vacuum pump 3-11 is connected with the gas chamber 3-7 through a pipeline, the vacuum pump 3-11 is connected with the controller 8 through a lead 7, the sample to be detected is placed on the sample stage 3-6, and the sample to be detected is arranged corresponding to the optical path system 2; the optical fiber collector 4 and the normal line of the sample stage 3-6 are arranged at an angle of 45 degrees.
The gas storage tank 3-1 is used for storing argon; the gas splitter 3-3 is used for splitting the argon gas in the gas storage tank 3-1; the plurality of gas transmission pipes 3-4 are used for transmitting the argon gas in the gas storage tank 3-1 to the gas chamber cabin 3-7, so that a uniform single gas atmosphere environment is provided for the sample to be detected; the vacuum pump 3-11 is used for vacuumizing the air chamber 3-7.
As an embodiment, the single gas cylindrical gas cell 3 of the present invention further comprises:
a barometer 3-9 for detecting the pressure in said air chamber compartment 3-7.
As an embodiment, the single gas cylindrical gas cell 3 of the present invention further comprises:
the first control valve 3-2 is arranged on a pipeline between the gas splitter 3-3 and the gas storage tank 3-1, is connected with the controller 8, and is used for controlling the flow rate of argon flowing out of the gas storage tank 3-1 according to a control instruction generated by the controller 8; the first control valve 3-2 is a control valve with a flow meter for detecting the volume of the gas flowing out.
As an embodiment, the single gas cylindrical gas cell 3 of the present invention further comprises:
and the second control valve 3-10 is arranged on a pipeline between the vacuum pump 3-11 and the air chamber 3-7, is connected with the controller 8, and is used for controlling the flow rate of vacuum pumping of the vacuum pump 3-11 according to a control command generated by the controller 8.
As an embodiment, the single gas cylindrical gas cell 3 of the present invention further comprises:
and the gas outlet valve is arranged at the bottom of the side wall of the air chamber 3-7 and is used for controlling the gas in the air chamber 3-7 to flow out.
As shown in fig. 2, the gas chamber 3-7 is a cylinder with a height of 10cm and a diameter of 15cm, the top end 3-8 of the cylinder is made of quartz glass, and the side surface and the bottom are made of stainless steel metal; the quartz glass has light transmittance of more than 99%; a plurality of gas inlets 3-5 are arranged at the top end 3-8 of the cylinder, the number of the gas inlets 3-5 is the same as that of the gas transmission pipes 3-4, and the plurality of gas transmission pipes 3-4 are inserted into the gas chamber 3-7 through the gas inlets 3-5; the air inlets 3-5 are uniformly arranged on the circumference of the top end 3-8 of the air chamber cabin 3-7, which is 4cm away from the circle center, the bottom of the air chamber cabin 3-7 is provided with a sample table 3-6, and the sample table 3-6 is fixed at the circle center position of the bottom of the air chamber cabin 3-7 by a movable buckle.
Fig. 3 is a schematic structural diagram of a signal enhancement device according to an embodiment of the present invention, as shown in fig. 3:
setting the instrument parameters: after the solid pulse laser 1, the spectrometer 5 and the delay integral generator 6 are started in sequence, the controller 8 is started until the instrument is stable; the instrument parameters included a delay time of 3 mus, an integration time of 9 mus, a lens to sample surface distance of 98mm and laser energy of 80 mJ.
Obtaining a uniform single gas atmosphere environment: firstly, the controller 8 starts the vacuum pump 3-11 and the second control valve 3-10 to vacuumize the air chamber 3-7, and the pressure in the air chamber 3-7 is observed from the barometer 3-9; opening 4 channel switches of the gas splitter 3-3, opening the first control valve 3-2 and the control valve on the gas tank, setting the required gas flow rate, introducing argon gas into the gas chamber 3-7, and enabling 4 uniform gas inlets 3-5 to be beneficial to obtaining a uniform single gas atmosphere environment.
And L IBS spectral information of a sample is obtained, namely the sample table 3-6 is movably buckled and taken down from the bottom of the gas chamber 3-7, the sample to be detected is arranged and then is fixed at the bottom of the gas chamber 3-7 again, the solid pulse laser 1 is started to generate 532nm laser, the 532nm laser reaches the surface of the sample in the gas chamber 3-7 through the optical path system 2, the rice leaf sample is ablated by the laser to generate plasma, an optical signal generated in the plasma diffusion process is collected by the optical fiber collector 4, the optical fiber collector 4 transfers the optical signal to the spectrometer 5, and the laser induced breakdown spectral information processed by the spectrometer 5 is transmitted to spectral information collection software of the controller 8 to obtain L IBS spectral information.
The gas flow rate of the gas storage tank 3-1 is required to be more than 6ml/min under the condition of uniform gas atmosphere, after the gas is continuously introduced for 10min, the barometer 3-9 displays that the gas pressure is 1000P, and then subsequent experiments are carried out.
The L IBS spectral information of the sample to be detected is acquired, which requires that the focal point of the optical fiber collector 4 coincides with the focal point of the solid pulse laser 1 generated by the lens in the optical path system 2, and must penetrate through the quartz glass of the gas chamber 3-7 to avoid the signal being blocked by the stainless steel body on the side wall.
Fig. 4 is a flowchart of a heavy metal detection method according to an embodiment of the present invention, and as shown in fig. 4, the present invention further provides a heavy metal detection method, where the method includes:
step S1: and determining a sample to be detected.
Step S2: after instrument parameters of the signal enhancement device are set, detecting the sample to be detected by using the signal enhancement device to obtain laser-induced breakdown spectroscopy information; the delay time is set to be 3 mu s, the integration time is set to be 9 mu s, the distance from the lens to the surface of the sample is 98mm, the laser energy is 80mJ, and the gas flow rate is 6 ml/min.
And step S3, performing standard normal transformation processing on the laser-induced breakdown spectrum information to determine L IBS spectrum information.
Step S4: and establishing a multiple linear regression model of emission line intensity-heavy metal content.
And step S5, inputting the L IBS spectral information into a multiple linear regression model to determine the true content of the heavy metal.
The individual steps are discussed in detail below:
step S1: determining a sample to be detected, specifically comprising:
step S11: and selecting the plants to be detected with the same growth vigor.
Step S12: carrying out various gradient CdCl on the plant to be detected2Solution stress treatment; stressing CdCl of the plant to be detected2The solution had a total of 5 gradients, 0. mu.M, 5. mu.M, 30. mu.M, 70. mu.M and 100. mu.M, respectively, for 5 gradients.
Step S13: collecting the plant to be detected after a set day, and carrying out cleaning, drying, grinding, sieving and tabletting treatment on the plant to be detected to obtain a sample to be detected; with 20mM Na2Cleaning the plant to be detected with EDTA and distilled water, drying in an oven at 80 deg.C, rapidly pulverizing in an automatic grinding apparatus at frequency of 60Hz for 80s, tabletting to obtain plant with a mass of 0.20g and length, width and height of 10 × 10-10 × 2 mm.
Step S4: establishing a multiple linear regression model of emission line intensity-heavy metal content, which specifically comprises the following steps:
step S41: a plurality of test set samples are obtained.
Step S42: and measuring the real content of the heavy metal in each test set sample by adopting an inductively coupled plasma mass spectrometry.
Step S43: and detecting each test set sample by using the signal enhancement device to obtain the laser-induced breakdown spectroscopy information corresponding to each test set sample.
And step S44, performing standard normal transformation processing on the laser-induced breakdown spectroscopy information corresponding to each test set sample to determine L IBS spectroscopy information corresponding to each test set sample.
And S45, screening characteristic wave bands which are related to heavy metals in L IBS spectra corresponding to the test set samples by adopting a variable screening partial least squares regression method.
Step S46: and selecting a plurality of emission lines of the heavy metal from the plurality of characteristic wave bands according to the NIST database.
Step S47: and establishing a multiple linear regression model of emission line intensity-heavy metal content by adopting a multiple linear regression method, taking the emission lines of a plurality of heavy metals as input, and taking the real content of the heavy metals in each test set sample as output.
The specific method for detecting the accumulation amount of heavy metal cadmium in the rice leaves by using the device comprises the following steps:
step S1: cultivating rice leaf plants, selecting plants with the same growth vigor, and performing different CdCl2Treating the solution under stress, collecting samples after 20 days, cleaning, quickly drying, grinding, sieving and tabletting to obtain samples to be detected; CdCl of stressed rice leaf plants2The solution has 5 gradients of 0. mu.M, 5. mu.M, 30. mu.M, 70. mu.M and 100. mu.M; with 20mM Na2Washing a rice leaf sample with EDTA and distilled water in sequence, drying the sample in an oven at 80 ℃, rapidly crushing the sample in an automatic grinding instrument at the frequency of 60Hz for 80s, wherein the mass of a pressed sample is 0.20g, and the length, width and height of the pressed sample are 10 × 10 × 2 mm.
And step S2, after setting instrument parameters of the signal enhancement device, acquiring laser-induced breakdown spectroscopy data X of the sample to be detected in the step 1 by using a L IBS instrument (figure 3), wherein the instrument parameters comprise delay time of 3 mu S, integration time of 9 mu S, distance between a lens and the surface of the sample of 98mm, laser energy of 80mJ and gas flow rate of 6 ml/min.
And step S3, performing standard normal transformation processing on the laser-induced breakdown spectrum information X to obtain L IBS spectrum information X1.
Step S4: establishing a multivariate linear regression model of the cadmium element emission line intensity-cadmium element content of the sample;
and step S5, inputting the L IBS spectral information into a multivariate linear regression model of the cadmium element emission line intensity-cadmium element content of the sample to determine the true content of the heavy metal cadmium element.
Step S4: establishing a multivariate linear regression model of the cadmium element emission line intensity-cadmium element content of the sample, which specifically comprises the following steps:
step S41: and measuring the real content y of the heavy metal cadmium element in each test set sample by adopting an inductively coupled plasma mass spectrometry.
And S42, screening the characteristic wave band X which is related to the rice leaf Cd in the L IBS spectral information X1 corresponding to each test set sample by adopting a variable screening partial least squares regression method.
Step S43: according to the NIST database, 3 emission spectral lines of cadmium elements are positioned from the characteristic wave band x, and the recording spectral lines are Cd II 214.56nm, Cd II 226.50nm and Cd I228.83 nm.
Step S44: adopting a multiple linear regression method, and respectively using the emission line intensities of cadmium elements as I214，I226，I228Establishing a multivariate linear regression model of the cadmium element emission line intensity-cadmium element content of the sample by taking the true value y of the cadmium element content as an input vector and taking the true value y of the cadmium element content as an output vector: yd-0.6109I 214-0.1286I226+0.2313I228410.8372, the correlation R value reaches 0.983.
Compared with the prior art, the invention has the following advantages:
(1) the single gas column-shaped gas chamber is added, the capacity of providing single gas environment atmosphere with different pressure intensities for plasma generated by a laser ablation sample is provided, the input quantity of gas and the proportion of air are regulated according to detection requirements, the pressure intensity is regulated, and L IBS spectral information is enhanced and the accuracy of determining the heavy metal content is improved by changing the atmosphere environment of the plasma.
(2) The atmosphere adjustable signal enhancement device disclosed by the invention has the characteristics of no contact with strong acid and alkali reagents, simplicity and rapidness in operation, low cost and the like.
(3) The four uniformly distributed air inlets are arranged in the cylindrical air chamber, so that a uniform single gas atmosphere environment can be quickly obtained in the cylindrical air chamber.
(4) The strength and stability of L IBS spectral information are improved by using the air chamber cabin, and the accuracy and sensitivity of quantitative detection of heavy metal content are improved.
(5) The signal enhancement device is utilized to realize the rapid, accurate and large-batch detection of the heavy metal elements.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. An ambiance-tunable L IBS signal enhancement apparatus, the apparatus comprising:
a solid-state pulse laser for generating laser light;
the optical path system is connected with the solid pulse laser and is used for transmitting laser;
the single gas cylindrical gas chamber is arranged corresponding to the light path system and is used for adjusting the sample to be detected and providing a uniform single gas atmosphere environment;
the optical fiber collector is arranged corresponding to the single gas cylindrical gas chamber and is used for receiving an optical signal generated in the plasma signal diffusion process; the plasma signal is generated based on the laser ablation of the sample to be detected;
the spectrometer is connected with the optical fiber collector and used for determining laser-induced breakdown spectroscopy information according to the optical signal received by the optical fiber collector;
and the controller is respectively connected with the spectrometer and the solid pulse laser, and is used for determining L IBS spectral information according to the received laser-induced breakdown spectral information, acquiring instrument parameters and generating a control instruction according to the instrument parameters to control the solid pulse laser to generate laser, wherein the instrument parameters comprise the distance from a lens in the optical path system to the surface of the sample to be detected and the laser energy.
2. The apparatus for ambience-tunable L IBS signal enhancement according to claim 1, further comprising:
and the time delay integral generator is respectively connected with the controller and the spectrometer and is used for controlling the working time sequence of the spectrometer according to the time delay time and the integral time in the instrument parameters.
3. The atmosphere tunable L IBS signal enhancing apparatus of claim 1, wherein the single gas cylinder plenum comprises:
the gas storage tank is used for storing argon;
the gas splitter is connected with the gas storage tank through a pipeline and is used for splitting the argon gas in the gas storage tank;
the air chamber cabin is provided with a sample table and is used for placing the sample to be detected on the sample table and arranging the sample to be detected corresponding to the optical path system;
the gas transmission pipes are respectively connected with the gas splitter and the gas chamber and are used for transmitting the argon gas in the gas storage tank to the gas chamber, so that a uniform single gas atmosphere environment is provided for the sample to be detected;
and the vacuum pump is connected with the air chamber cabin through a pipeline and is used for vacuumizing the air chamber cabin.
4. The atmosphere tunable L IBS signal enhancing apparatus of claim 3, wherein the single gas cylinder plenum further comprises:
and the barometer is used for detecting the pressure in the air chamber cabin.
5. The atmosphere tunable L IBS signal enhancing apparatus of claim 3, wherein the single gas cylinder plenum further comprises:
and the first control valve is arranged on a pipeline between the gas splitter and the gas storage tank, is connected with the controller and is used for controlling the flow rate of the gas flowing out of the argon gas in the gas storage tank according to a control instruction generated by the controller.
6. The atmosphere tunable L IBS signal enhancing apparatus of claim 3, wherein the single gas cylinder plenum further comprises:
and the second control valve is arranged on a pipeline between the vacuum pump and the air chamber, is connected with the controller and is used for controlling the pumping flow rate of the vacuum pump according to a control instruction generated by the controller.
7. The atmosphere tunable L IBS signal enhancing apparatus of claim 3, wherein the single gas cylinder plenum further comprises:
and the gas outlet valve is arranged at the bottom of the side wall of the gas chamber cabin and is used for controlling the gas in the gas chamber cabin to flow out.
8. The atmosphere adjustable L IBS signal enhancement device of claim 3, wherein the gas chamber is a cylinder with a height of 10cm and a diameter of 15cm, the top of the cylinder is made of quartz glass, the side and bottom of the cylinder are made of stainless steel metal, a plurality of gas inlets are arranged on the top of the cylinder, the number of the gas inlets is the same as that of the gas transmission pipes, and the gas transmission pipes are inserted into the gas chamber through the gas inlets.
9. A method for detecting heavy metals, the method comprising:
determining a sample to be detected;
detecting the sample to be detected by using the signal enhancement device of any one of claims 1 to 8 to obtain laser-induced breakdown spectroscopy information;
performing standard normal transformation processing on the laser-induced breakdown spectrum information to determine L IBS spectrum information;
establishing a multiple linear regression model of emission line intensity-heavy metal content;
inputting the L IBS spectral information into a multiple linear regression model to determine the true content of heavy metals.
10. The method for detecting heavy metals according to claim 9, wherein the establishing of the multiple linear regression model of emission line intensity-heavy metal content specifically comprises:
obtaining a plurality of test set samples;
measuring the real content of heavy metal in each test set sample by adopting an inductively coupled plasma mass spectrometry;
detecting each test set sample by using the signal enhancement device of any one of claims 1-8 to obtain laser-induced breakdown spectroscopy information corresponding to each test set sample;
performing standard normal transformation processing on the laser induced breakdown spectroscopy information corresponding to each test set sample to determine L IBS spectroscopy information corresponding to each test set sample;
screening characteristic wave bands which are related to heavy metals in L IBS spectra corresponding to the test set samples by adopting a variable screening partial least squares regression method;
selecting a plurality of emission spectral lines of heavy metals from a plurality of characteristic wave bands according to an NIST database;
and establishing a multiple linear regression model of emission line intensity-heavy metal content by adopting a multiple linear regression method, taking the emission lines of a plurality of heavy metals as input, and taking the real content of the heavy metals in each test set sample as output.
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