CN108169092B - Online detection device and method for heavy metals and isotopes of atmospheric particulates - Google Patents
Online detection device and method for heavy metals and isotopes of atmospheric particulates Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 57
- 238000001514 detection method Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 19
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- 238000001228 spectrum Methods 0.000 claims abstract description 29
- 238000002347 injection Methods 0.000 claims abstract description 16
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- 238000005192 partition Methods 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 15
- 239000008277 atmospheric particulate matter Substances 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000001561 resonance enhanced multiphoton ionisation spectroscopy Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 6
- 238000000608 laser ablation Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 238000001269 time-of-flight mass spectrometry Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000004451 qualitative analysis Methods 0.000 claims description 4
- 238000004445 quantitative analysis Methods 0.000 claims description 4
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- 238000012545 processing Methods 0.000 claims description 3
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- 241000282414 Homo sapiens Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/06—Investigating concentration of particle suspensions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/06—Investigating concentration of particle suspensions
- G01N15/075—Investigating concentration of particle suspensions by optical means
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Abstract
The invention discloses an atmosphere particulate heavy metal and isotope online detection device and method thereof, wherein the atmosphere particulate heavy metal and isotope online detection device comprises a vacuum cavity, the vacuum cavity is divided into a spectrum cavity and an ionization cavity by a partition plate, an ionization cavity sample injection small hole is formed in the middle of the partition plate, a sample injection pipeline penetrates through one end of the vacuum cavity and a pulse valve is arranged at one end of the sample injection pipeline, which is positioned in the vacuum cavity, a first laser beam and a second laser beam action area are arranged in the spectrum cavity and are positioned at one side of the pulse valve, a fiber spectrometer collecting probe is arranged at the upper sides of the first laser beam and the second laser beam action area, a mass spectrometer flying tube is horizontally arranged in the ionization cavity, a mass spectrometer ion lens group is arranged at one end of the mass spectrometer flying tube, the position of the mass spectrometer ion lens group corresponds to the ionization cavity sample injection small hole, a third laser beam action area is positioned in the mass spectrometer ion lens group, and a MCP detector is arranged at the other end of the mass spectrometer flying tube. The invention greatly improves the accuracy, sensitivity and comprehensiveness of detecting the heavy metal elements of the particulate matters.
Description
Technical Field
The invention relates to an on-line detection device and a method thereof, in particular to an on-line detection device and a method for heavy metals and isotopes of atmospheric particulates.
Background
The atmospheric environment is related to the death of human beings, and enough researches indicate that the atmospheric particulates contain various toxic heavy metal elements such as lead, cadmium, mercury, copper, antimony, zinc and the like. Most of these heavy metals exist in isotopes, and the ratio of isotopic abundance is one of the important ways to study the source of the same. In the example of lead, there are four stable isotopes in nature, namely 204 Pb、 206 Pb、 207 Pb and 208 pb. The isotope abundance ratio information is generally unchanged by the chemical and physical changes it undergoes. This makes it possible to identify and distinguish different plastic sources of lead by using the isotopic abundance ratio of lead as a kind of "fingerprint" of lead-containing substance. The isotope abundance ratio of lead from different plastic sources is different, and scientists can study the source of lead pollution and the contribution of the lead pollution of the atmospheric particulates according to different lead isotope abundance ratios in the atmospheric particulates. Therefore, high-precision online detection of heavy metals and isotopes of the atmospheric particulates is very important.
The current detection accuracy of the online detection mass spectrometer of the atmospheric particulates is lower mainly because the prior art only obtains the mass number information of the substances in the atmospheric particulates, but does not obtain the atomic emission spectrum information of the atmospheric particulates at the same time,the analysis accuracy is not high, and accurate detection cannot be realized. Meanwhile, the prior art adopts a multi-component simultaneous detection technology, such as a UV single photon photoionization technology, and can realize the simultaneous detection of multi-component substances contained in the particulate matters, but can not carry out selective high-sensitivity detection on trace heavy metal elements, and has lower sensitivity, especially when the concentration of the atmospheric particulate matters is lower, the trace heavy metal can not be detected. In addition, the prior art adopts laser ablation to seriously damage the structure of the substance before detection by mass spectrometry, and the original heavy metal substance structure (such as PbO, pbNO) can not be obtained by mass spectrometry 3 ，PbSO 4 ) Information.
Disclosure of Invention
The invention aims to solve the technical problem of providing an on-line detection device and method for heavy metals and isotopes of atmospheric particulates, and the accuracy, sensitivity and comprehensiveness of detecting heavy metal elements of the particulates are improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
an atmosphere particulate matter heavy metal and isotope on-line measuring device thereof which characterized in that: the device comprises a vacuum cavity, wherein the vacuum cavity is divided into a spectrum cavity and an ionization cavity by a partition plate, an ionization cavity sample injection small hole is formed in the middle of the partition plate, a sample injection pipeline penetrates through one end of the vacuum cavity and is arranged at one end of the sample injection pipeline, which is positioned in the vacuum cavity, a pulse valve is arranged at one side of the pulse valve, a first laser beam and a second laser beam action area are arranged in the spectrum cavity, a fiber spectrometer collecting probe is arranged at the upper side of the first laser beam and the second laser beam action area, a mass spectrometer flying tube is horizontally arranged in the ionization cavity, a mass spectrometer ion lens group is arranged at one end of the mass spectrometer flying tube and corresponds to the ionization cavity sample injection small hole, a third laser beam action area is positioned in the mass spectrometer ion lens group, and a MCP detector is arranged at the other end of the mass spectrometer flying tube.
Further, a first molecular pump is arranged on the lower side of the spectrum cavity.
Further, the ionization cavity downside is provided with second molecular pump and third molecular pump, and second molecular pump and third molecular pump set up respectively at ionization cavity downside both ends.
Further, the ion lens group of the mass spectrometer comprises a telescope system and a lens, wherein the telescope system is composed of two convex lenses with focal lengths of 9cm and 3cm respectively, the distance between the two convex lenses is 12cm, the lens is arranged at the rear side of the telescope system, and the focal length of the lens is 3cm to focus a beam after the telescope system is contracted.
Further, the mass spectrometer flight tube adopts a grid metal tube, and the mesh design of the grid is about 1mm.
The method of the on-line detection device for the heavy metals and the isotopes of the heavy metals in the atmospheric particulates is characterized by comprising the following steps:
step one: firstly, obtaining a real-time atmospheric particulate sample through an atmospheric particulate online sampling system, and then selecting atmospheric particulate with different particle diameters to enter a detection system through a particulate diameter measuring and selecting system;
step two: after entering a detection system, firstly, based on a near infrared NIR (near infrared) online detection technology, obtaining functional group information of atmospheric particulates, rapidly obtaining main component information of the particulates and chemical forms possibly existing in heavy metals, and completing primary component measurement and component prediction;
step three: the method comprises the steps of enabling an atmospheric particulate matter sample to enter a spectrum cavity under the blowing of carrier gas, enabling the atmospheric particulate matter sample to enter the vacuum cavity in a pulse mode through a pulse valve, enabling the particulate matter to be in a plasma state under the focusing effect of a 1064nm first laser beam generated by a pulse YAG laser, collecting LIBS spectrum of the atmospheric particulate matter by using an optical fiber spectrometer, transmitting data into a data processing system, and rapidly analyzing to obtain multicomponent heavy metal element distribution in the atmospheric particulate matter;
step four: locking the heavy metal of interest, generating tunable laser by adopting YAG laser pumping dye in the experiment to obtain plasma generated by focusing a second laser beam on the action of the first laser beam, generating LIF spectrum, and realizing accurate qualitative and quantitative analysis of metal elements in the particulate matters through the obtained LIF spectrum;
step five: after YAG laser ablation, the structure of the atmospheric particulates is destroyed, most of the contained substances exist in a gas form, and enter an ionization chamber under the action of carrier gas, and at the moment, a third laser beam is adopted to carry out REMPI resonance enhanced multiphoton ionization on the gas entering the ionization chamber, so that high-quality resolution detection of resonance excitation type TOFMS is realized, and isotope distribution and abundance information of heavy metal elements in the atmospheric particulates are selectively obtained.
In the fourth step, the output wavelength of the second laser beam is the resonance wavelength of the heavy metal element of interest, and the dye laser outputs the resonance wavelength corresponding to different heavy metals aiming at different heavy metals obtained by LIBS spectrum analysis generated by YAG laser action, so that the content of different heavy metals is accurately analyzed on line.
Further, in the fifth step, the third laser beam is the same as the second laser beam for generating the LIF spectrum, and is obtained by beam splitting by a beam splitter.
Compared with the prior art, the invention has the following advantages and effects:
(1) The invention can simultaneously acquire the atomic spectrum (LIBS spectrum and LIF spectrum) and the mass number (TOFMS) two-dimensional fingerprint information of the heavy metal elements in the atmospheric particulate matters, and obtain high-precision detection of the heavy metal elements in the atmospheric particulate matters. The description is as follows: the spectral lines of many elements are very close and almost coincide, for example, in the case that the spectral line of Fe is very close to the spectral line of Pb, a low-resolution spectrometer cannot distinguish whether the element is Fe or Pb, so that the elements contained in the low-resolution spectrometer are difficult to accurately calibrate only through spectral detection, and researchers in the spectrum field know that many spectral data calibration can give more than two possible results; at the same time, judging the species by mass number alone is also inaccurate, and the laser ablated species exist in molecular form, e.g. for 208 The mass number of Pb element is 208amu, and there are hundreds of molecules with mass numbers equal to 208amu, and it is definitely not accurate to detect the kind of element by using only the mass number as a criterion. The method skillfully combines the atomic spectrum and the mass number two-dimensional fingerprint information, and can greatly improve the high accuracy of heavy metal online detection.
(2) The heavy metal concentration of the atmospheric particulates is very low, the signal is unstable, and the low concentration detection is difficult to realize under the condition of low online detection sampling rate. For example, for Pb element in the particulate matters, the LIF spectrum technology can be used for realizing low-concentration qualitative and quantitative analysis, and the TOFMS detection technology based on REMPI technology can be used for realizing accurate analysis of low-concentration isotope abundance.
(3) Because the prior art destroys the structural information of the original particulate matters after laser ablation of the sample, the invention provides that after the particulate matters are collected, the functional group information of the atmospheric particulate matters is firstly obtained based on a Near Infrared (NIR) on-line detection technology, and the main component information of the particulate matters and the chemical forms possibly existing in heavy metals can be rapidly obtained through the information, so that the primary component measurement and the component prediction are completed.
(4) The smart light path design ensures that the system for multidimensional detection only needs one pulse YAG laser, and three lasers needed by measurement are all from the same laser, which is beneficial: the stability of the whole system is high, the influence of the fluctuation of the laser on the test result is consistent, the fluctuation amplitude of the signals in the three test processes is consistent, and the calibration is easy; the second laser beam and the third laser beam are all required to have the same resonance wavelength of a certain heavy metal element, and only one tuning is needed to realize two sets of resonance tests, so that the complexity of use is greatly reduced; meanwhile, as only one laser is needed, the production cost of the invention for further industrialization can be greatly reduced; the integration and portability of the instrument are high.
Drawings
FIG. 1 is a schematic diagram of an on-line detection device for heavy metals and isotopes of atmospheric particulates according to the present invention.
Fig. 2 is a flow chart of the method for on-line detection of heavy metals and isotopes of atmospheric particulates according to the present invention.
Fig. 3 is a schematic diagram of an optical path system of the on-line detection method for the heavy metals and isotopes of the atmospheric particulates.
Description of the embodiments
The present invention will be described in further detail by way of examples with reference to the accompanying drawings, which are illustrative of the present invention and not limited to the following examples.
As shown in fig. 1, the online detection device for heavy metals and isotopes of atmospheric particulates comprises a vacuum cavity, wherein the vacuum cavity is divided into a spectrum cavity 10 and an ionization cavity 11 by a partition plate, an ionization cavity sample injection small hole 5 is formed in the middle of the partition plate, a sample injection pipeline 1 passes through one end of the vacuum cavity, a pulse valve 2 is arranged at one end of the sample injection pipeline 1, a first laser beam and a second laser beam action area 4 are arranged in the spectrum cavity 10 and are positioned at one side of the pulse valve 2, a fiber spectrometer collecting probe 3 is arranged at the upper side of the first laser beam and the second laser beam action area 4, a mass spectrometer flight tube 8 is horizontally arranged in the ionization cavity 11, a mass spectrometer ion lens group 7 is arranged at one end of the mass spectrometer flight tube 8, the position of the mass spectrometer ion lens group 7 corresponds to that of the ionization cavity sample injection small hole 5, a third laser beam action area 6 is positioned in the mass spectrometer ion lens group 7, and an MCP detector 9 is arranged at the other end of the mass spectrometer flight tube 8.
The lower side of the spectroscopic cavity 10 is provided with a first molecular pump 12. The ionization chamber 11 is provided with a second molecular pump 13 and a third molecular pump 14 at the lower side, and the second molecular pump 13 and the third molecular pump 14 are respectively arranged at two ends of the ionization chamber 11 at the lower side. Because the instrument directly adopts the pollutant to enter the ionization cavity during detection, the speed requirement of the ionization cavity vacuumizing of the mass spectrometer is very high, in the design, the ionization cavity is provided with two high-pumping-speed molecular pumps, and meanwhile, the following special settings are made on the device: the mass spectrometer flight tube 8 adopts a grid metal tube, the mesh design of the grid is about 1mm, the working efficiency (grounding electric field) of the flight tube can be completely ensured, the sample injection substances of the ionization cavity can be conveniently and rapidly extracted by the molecular pump, the vacuum degree of the ionization cavity is improved, the average free path of detected ions is further increased, and the detection resolution of mass spectrum is further improved.
In order to improve the detection efficiency of the gas sample, the intensity of the laser beams after focusing is improved by adopting an ion lens group of a mass spectrometer, and the three laser beams are focused in the following way before the action: firstly, carrying out beam compression on a laser beam through a first telescope system (two convex lenses with focal lengths of 9cm and 3cm are combined together and the distance is 12 cm), so that the radius of a light spot is reduced to one third of the original radius; and then a lens with the focal length of 3cm is used for focusing the condensed light beam to act on the substance.
As shown in fig. 2 and 3, a method for an on-line detection device for heavy metals and isotopes of atmospheric particulates comprises the following steps:
step one: firstly, obtaining a real-time atmospheric particulate sample through an atmospheric particulate online sampling system, and then selecting atmospheric particulate with different particle diameters to enter a detection system through a particulate diameter measuring and selecting system;
step two: after entering a detection system, firstly, obtaining functional group information of atmospheric particulates based on a near infrared NIR (near infrared ray) online detection technology, and rapidly obtaining main component information of the particulates and chemical forms possibly existing in heavy metals through the information to finish primary component measurement and component prediction;
step three: the atmospheric particulate matter sample enters the spectrum cavity under the blowing of carrier gas, enters the vacuum cavity in a pulse mode through the pulse valve, and is in a plasma state under the focusing effect of a 1064nm first laser beam generated by the pulse YAG laser (laser ablation), the LIBS spectrum of the atmospheric particulate matter is collected by adopting an optical fiber spectrometer, and the data are transmitted into the data processing system, so that the multicomponent heavy metal element distribution in the atmospheric particulate matter can be rapidly analyzed and obtained.
Step four: the method is characterized in that heavy metals such as Pb elements are locked, tunable laser is generated by pumping dye through YAG laser in an experiment, a second laser beam with the output wavelength of 283.31nm (the resonance wavelength of Pb elements) is obtained and focused on plasma generated by the action of the first laser beam, LIF spectrum with the wavelength of 405.78nm is generated, and accurate qualitative and quantitative analysis of the Pb elements in the particulate matters can be realized under the condition of extremely low Pb concentration through the obtained LIF spectrum. The above description is given by taking Pb as an example, and different heavy metals are obtained by LIBS spectrum analysis generated by YAG laser action, and dye lasers need to output resonance wavelengths corresponding to different heavy metals, so that accurate online analysis is performed on the content of different heavy metals.
Step five: after YAG laser ablation, the structure of the atmospheric particulates is destroyed, most of the contained substances exist in a gas form and enter an ionization chamber under the action of carrier gas, and at the moment, a third laser beam is adopted to carry out REMPI resonance enhanced multiphoton ionization on the gas entering the ionization chamber, so that high-quality resolution detection of resonance excitation type TOFMS is realized, and isotope distribution and abundance information of heavy metal elements in the atmospheric particulates are selectively obtained. For example, here for lead element, the wavelength output is chosen to be 283.31nm, detected with (1+1) REMPI, and the third laser beam required is identical to the second laser beam producing the LIF spectrum, obtained by spectroscopic analysis by a spectroscope.
The foregoing description of the invention is merely exemplary of the invention. Various modifications or additions to the described embodiments may be made by those skilled in the art to which the invention pertains or in a similar manner, without departing from the spirit of the invention or beyond the scope of the invention as defined in the appended claims.
Claims (5)
1. The method is characterized in that the online detection device of the heavy metal and the isotopes of the heavy metal of the atmospheric particulates comprises a vacuum cavity, the vacuum cavity is divided into a spectrum cavity and an ionization cavity by a partition plate, an ionization cavity sample injection small hole is formed in the middle of the partition plate, a sample injection pipeline penetrates through one end of the vacuum cavity and is provided with a pulse valve at one end of the sample injection pipeline, a first laser beam action area and a second laser beam action area are arranged in the spectrum cavity and are positioned at one side of the pulse valve, a fiber spectrometer collecting probe is arranged at the upper side of the first laser beam action area and the second laser beam action area, a mass spectrometer flight tube is horizontally arranged in the ionization cavity, a mass spectrometer ion lens group is arranged at one end of the mass spectrometer flight tube and corresponds to the ionization cavity small hole, a third laser beam action area is positioned in the mass spectrometer ion lens group, and a MCP detector is arranged at the other end of the mass spectrometer flight tube; a first molecular pump is arranged at the lower side of the spectrum cavity; the ionization cavity is provided with a first molecular pump and a second molecular pump at the lower side, and the first molecular pump and the second molecular pump are respectively arranged at two ends of the lower side of the ionization cavity;
comprises the following steps:
step one: firstly, obtaining a real-time atmospheric particulate sample through an atmospheric particulate online sampling system, and then selecting atmospheric particulate with different particle diameters to enter a detection system through a particulate diameter measuring and selecting system;
step two: after entering a detection system, firstly, based on a near infrared NIR (near infrared) online detection technology, obtaining functional group information of atmospheric particulates, rapidly obtaining main component information of the particulates and chemical forms possibly existing in heavy metals, and completing primary component measurement and component prediction;
step three: the method comprises the steps of enabling an atmospheric particulate matter sample to enter a spectrum cavity under the blowing of carrier gas, enabling the atmospheric particulate matter sample to enter the vacuum cavity in a pulse mode through a pulse valve, enabling the particulate matter to be in a plasma state under the focusing effect of a 1064nm first laser beam generated by a pulse YAG laser, collecting LIBS spectrum of the atmospheric particulate matter by using an optical fiber spectrometer, transmitting data into a data processing system, and rapidly analyzing to obtain multicomponent heavy metal element distribution in the atmospheric particulate matter;
step four: locking the heavy metal of interest, generating tunable laser by adopting YAG laser pumping dye in the experiment to obtain plasma generated by focusing a second laser beam on the action of the first laser beam, generating LIF spectrum, and realizing accurate qualitative and quantitative analysis of metal elements in the particulate matters through the obtained LIF spectrum;
step five: after YAG laser ablation, the structure of the atmospheric particulates is destroyed, most of the contained substances exist in a gas form, and enter an ionization chamber under the action of carrier gas, and at the moment, a third laser beam is adopted to carry out REMPI resonance enhanced multiphoton ionization on the gas entering the ionization chamber, so that high-quality resolution detection of resonance excitation type TOFMS is realized, and isotope distribution and abundance information of heavy metal elements in the atmospheric particulates are selectively obtained.
2. The method of the on-line detection device for heavy metals and isotopes of atmospheric particulates according to claim 1, wherein: in the fourth step, the output wavelength of the second laser beam is the resonance wavelength of the interested heavy metal element, and different heavy metals are obtained by LIBS spectrum analysis aiming at the YAG laser effect, and the dye laser outputs the resonance wavelengths corresponding to different heavy metals, so that the accurate online analysis is performed on the content of different heavy metals.
3. The method of the on-line detection device for heavy metals and isotopes of atmospheric particulates according to claim 2, wherein: in the fifth step, the third laser beam is the same as the second laser beam generating the LIF spectrum, and is obtained by spectroscopic analysis by a spectroscope.
4. The method of the on-line detection device for heavy metals and isotopes of atmospheric particulates according to claim 1, wherein: the ion lens group of the mass spectrometer comprises a telescope system and a lens, wherein the telescope system is composed of two convex lenses with focal lengths of 9cm and 3cm respectively, the distance between the two convex lenses is 12cm, the lens is arranged at the rear side of the telescope system, and the focal length of the lens is 3cm to focus a beam after beam shrinking of the telescope system.
5. The method of the on-line detection device for heavy metals and isotopes of atmospheric particulates according to claim 1, wherein: the mass spectrometer flight tube adopts a grid metal tube, and the mesh of the grid is designed to be 1mm.
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