CN102279171B - Method for promoting sensitivity of metal pollutants in water in laser breakdown spectrum detection - Google Patents
Method for promoting sensitivity of metal pollutants in water in laser breakdown spectrum detection Download PDFInfo
- Publication number
- CN102279171B CN102279171B CN 201110207663 CN201110207663A CN102279171B CN 102279171 B CN102279171 B CN 102279171B CN 201110207663 CN201110207663 CN 201110207663 CN 201110207663 A CN201110207663 A CN 201110207663A CN 102279171 B CN102279171 B CN 102279171B
- Authority
- CN
- China
- Prior art keywords
- solid carrier
- testing liquid
- liquid sample
- laser
- breakdown spectrum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for promoting sensitivity of metal pollutants in water in laser breakdown spectrum detection. According to the method, a thin to-be-measured liquid film is formed on the surface of a solid carrier by a to-be-measured liquid sample in an atomized form, so as to convert the measurement for the to-be-measured liquid sample into the analysis for the solid carrier, thereby realizing the measurement for metal elements in the water. According to the method provided by the invention, the complex sample preparation is unnecessary, the stability of laser plasma measurement is promoted, the influence of water drop sputtering is eliminated, the emission life of a laser plasma is prolonged, the emission power of a laser plasma spectral line is promoted, the limit of detection of the analyzed elements is greatly promoted, and the influence of residues of the analyzed liquid sample is avoided. The method provided by the invention is suitable for various analyses of the elements in the liquid sample, in which a laser induced breakdown spectrum process is taken as an analysis means.
Description
Technical field
The present invention relates to the laser spectral analysis field, be specially a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity.
Background technology
The LIBS technology is to act on sample surfaces after utilizing short-pulse laser to focus on to produce high-temperature plasma; Before the plasma cooling; The atom that is excited, ion and molecule will produce the plasma emission spectral line of elemental composition characteristic, through receiving plasma spectrometry and element-specific line strength being analyzed to carry out the quantitative measurment of constituent content.System's composition and principle that LIBS is measured are as shown in Figure 1.System is made up of Laser emission assembly, optics receiving unit and probe assembly etc.The laser that laser instrument sends acts on sample surfaces and produces laser plasma after catoptron, condenser lens focus on; By reception optical fiber the laser plasma signal is transferred to spectrometer and carry out beam split; And carry out the conversion of photosignal by detector; Get into data Collection & Processing System then and carry out data acquisition process, power supply and control system provide the power supply of laser instrument and detector and logical sequence and the trigger pip of surveying control.
For water body metal pollutant LIBS measuring system; Very faint with acting directly on the laser plasma signal that produces in the water body after the laser beam focusing; Be difficult to realize effective detection; The method of more employing is that the laser beam after focusing on is acted on water surface, forms the laser plasma of high temperature, high heat, thereby carries out the measurement of spectrum.At present; The problem that exists has: 1., since high-octane laser beam act in the water surface to the laser plasma forming process; With the influence that produces the water droplet sputter, severe contamination the laser focusing diversing lens receive the optical fiber coupled lens with optics, make laser plasma generation efficient and spectrographic detection efficient seriously reduce; The laser repeat function repeatedly after, to such an extent as to can't realize effective measurement of water body metal pollutant spectrum of laser plasma; 2., the stability of spectral measurement receives the influence of systematic parameter (like pulsed laser energy, beam emissions system stability etc.), environmental baseline (like environment temperature, pressure etc.) and measurement component uniformity; Usually improve the measuring accuracy of spectrum with increase laser pulse number raising signal intensity and with the multiple averaging measurement; Or use external reference to do normalization and handle, like the fluctuation of Laser Measurement energy; For the forming process of laser induced plasma, said method is obviously not enough, and the measurement stability that how to improve spectrum also becomes the essential step of high accuracy analysis; 3., in the water body the lasting launch time of laser plasma shorter, have only hundreds of nanosecond usually, and element spectral line intensity a little less than, how prolonging laser plasma emission lifetime and enhanced line emissive porwer is the another key that improves ultimate analysis sensitivity.
Summary of the invention
The purpose of this invention is to provide a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity, to solve the low problem of sensitivity that the direct measurement of LIBS technology fluid sample exists in the prior art.
In order to achieve the above object, the technical scheme that the present invention adopted is:
A kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity is characterized in that: at first the testing liquid sample is atomized; Secondly the testing liquid sample after will atomizing forms the testing liquid film attached to solid carrier surface; Adopt the LIBS technology that the solid carrier that the surface is attached with the testing liquid film is surveyed at last, obtain metallic pollution species and content in the testing liquid sample.
Described a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity is characterized in that: said solid carrier preferred structure is stable, the solid that hardness is strong.
Described a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity, it is characterized in that: said solid carrier composition is single, the preferred high simple substance of purity.
Described a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity, it is characterized in that: said solid carrier is a solid graphite.
Described a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity is characterized in that: do not comprise in the said solid carrier preferred component in the testing liquid sample the solid of the metal component that will survey.
Described a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity is characterized in that: the testing liquid sample after the atomizing attached to the solid carrier before, need to solid carrier surface clean, polishing.
Described a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity; It is characterized in that: adopt testing liquid sample effect after the water droplet atomizer will atomize on solid carrier surface, make testing liquid sample after the atomizing attached to solid carrier surface formation testing liquid film.
The present invention is through forming thin testing liquid film with atomised form on solid carrier surface with the testing liquid sample; When adopting the LIBS technology to survey; Laser beam after the focusing directly affacts solid carrier surface and produces laser plasma, carries out the measurement of the contained metallic element of testing liquid sample thus.The present invention is applicable to that all are the analysis of metallic element in the fluid sample of analysis means with the LIBS technology.Compared with prior art, advantage of the present invention is following:
(1) high-octane focussed laser beam is directly affacted solid carrier surface, eliminated the influence of drop sputter, avoided laser focusing diversing lens and optics to receive the optical fiber coupled lens in the measuring process and received pollution problems.
(2) than the testing liquid sample; The solid carrier has relatively low laser breakdown threshold value; Be easy to realize that induced with laser optics punctures; And the solid carrier has long laser plasma emission lifetime, has prolonged the laser plasma launch time of surperficial testing liquid film.
(3) high temperature that produces in the solid carrier breakdown process, high thermal laser plasma are that the formation of surperficial testing liquid film plasma provides initiating electron density, have further strengthened the emissive porwer of element spectral line.
(4) constituent content and characteristic are known in the solid carrier; With a certain elemental characteristic spectral line of emission in the solid carrier is the normalization processing that normative reference is carried out measured element spectral line; Can eliminate the influence to measurement result such as systematic parameter (like pulsed laser energy, beam emissions system stability etc.), environmental baseline (like environment temperature, pressure etc.) and the variation of testing liquid sample characteristics of for example, improve the stability of spectral measurement;
(5) through drop sputter influence is removed, the raising of spectrum stability prolongs the emission lifetime of laser plasma, and strengthens by analytical element spectral line emissive porwer, has improved by the sensitivity of analytical element and detectability;
(6) utilize after the laser pulse effect the cleaning function on solid carrier surface, avoided pollution, therefore different testing liquid sample analysis has been eliminated by the residual influence of analytic sample solid carrier surface.
Description of drawings
Fig. 1 is the measuring system schematic diagram of LIBS technology.
Embodiment
A kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity at first atomizes the testing liquid sample; Secondly the testing liquid sample after will atomizing forms the testing liquid film attached to solid carrier surface; Adopt the LIBS technology that the solid carrier that the surface is attached with the testing liquid film is surveyed at last, obtain metallic pollution species and content in the testing liquid sample.
In the present invention, the selection of solid carrier is extremely important for being analyzed testing liquid sample element.Select the solid carrier should to follow principle following:
(1) has structural stability preferably, the change that is not easy to after the laser action that surface oxidation takes place or produces the structure of matter.
(2) have stronger hardness, be not easy to after the laser action form big pit, in order to avoid influence is to follow-up Analysis of measuring on its surface.
(3) solid carrier composition is single, and purity is high, can guarantee laser action after the solid carrier element spectral line of emission little to being disturbed by analytical element, and can be as standard normalization processing;
(4) in the solid carrier no testing liquid sample the element that will analyze, to reduce by the influence of testing liquid sample constituent content.
The generation of solid carrier surface testing liquid film: according in the testing liquid sample the element that will analyze, confirm suitable solid carrier, to solid carrier surface clean, polishing.Use the solid carrier surface of testing liquid sample effect after cleaning, polishing after the water droplet atomizer will atomize, produce the testing liquid film of micron dimension.
Specific embodiment:
The demand quick to the water body weight metallic element, that multielement detects simultaneously, having selected with graphite is the solid carrier, in the laboratory, elements such as water body weight metallic element Cr, Cd, Pb, Zn, Ni is measured and is analyzed.1., eliminated to act directly on the influence of water droplet sputter on the water surface result shows:; 2., do inner normalization with the spectral line of emission of C element in the graphite and handle, reduced the influence of systematic parameter, environmental baseline and sample characteristics of for example to measurement result, improved the stability of spectral measurement; 3., prolonged the laser plasma emission lifetime, extend to 2100ns by the 700ns that directly affacts the water surface; 4., line strength has improved nearly 10 times; 5., the detectability of each element has also improved 2-5 doubly.
Claims (4)
1. a method that improves laser breakdown spectrum water body metal pollutant detection sensitivity is characterized in that: at first the testing liquid sample is atomized; Secondly the testing liquid sample after will atomizing forms the testing liquid film attached to solid carrier surface; Adopt the LIBS technology that the solid carrier that the surface is attached with the testing liquid film is surveyed at last, obtain metallic pollution species and content in the testing liquid sample; Said solid carrier has structural stability preferably, stronger hardness, composition is single, purity high and do not have the testing liquid sample the element that will analyze.
2. a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity according to claim 1, it is characterized in that: said solid carrier is a solid graphite.
3. a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity according to claim 1; It is characterized in that: the testing liquid sample after the atomizing attached to the solid carrier before, need to solid carrier surface clean, polishing.
4. a kind of method that improves laser breakdown spectrum water body metal pollutant detection sensitivity according to claim 1; It is characterized in that: adopt testing liquid sample effect after the water droplet atomizer will atomize on solid carrier surface, make testing liquid sample after the atomizing attached to solid carrier surface formation testing liquid film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110207663 CN102279171B (en) | 2011-07-22 | 2011-07-22 | Method for promoting sensitivity of metal pollutants in water in laser breakdown spectrum detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110207663 CN102279171B (en) | 2011-07-22 | 2011-07-22 | Method for promoting sensitivity of metal pollutants in water in laser breakdown spectrum detection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102279171A CN102279171A (en) | 2011-12-14 |
| CN102279171B true CN102279171B (en) | 2012-12-05 |
Family
ID=45104739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110207663 Active CN102279171B (en) | 2011-07-22 | 2011-07-22 | Method for promoting sensitivity of metal pollutants in water in laser breakdown spectrum detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102279171B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103411930B (en) * | 2013-07-26 | 2015-06-03 | 中国科学院安徽光学精密机械研究所 | Laser-induced breakdown spectrometry continuous detection device and method for heavy metal of water body |
| CN103604782A (en) * | 2013-11-22 | 2014-02-26 | 天津陆海石油设备系统工程有限责任公司 | Solid sample element analyzer based on laser technology |
| CN103884689B (en) * | 2014-01-04 | 2016-11-23 | 青岛大学 | A kind of induced with laser list drop punctures the method and apparatus of detection |
| CN104596995A (en) * | 2014-12-25 | 2015-05-06 | 北京农业智能装备技术研究中心 | Device and method for measuring chlorine elements in water in real time |
| WO2016154509A1 (en) * | 2015-03-26 | 2016-09-29 | Dover Photonics Llc | Preparation of fluid samples for laser induced breakdown spectroscopy and/or imaging analysis |
| CN106198492A (en) * | 2016-07-26 | 2016-12-07 | 浙江大学 | A kind of method utilizing microalgae LIBS signal detection heavy metal in water lead contamination degree |
| CN106680227A (en) * | 2017-02-20 | 2017-05-17 | 绍兴文理学院 | Spectrum analysis system and spectrum analysis method for component detection |
| CN108195823B (en) * | 2017-12-11 | 2021-03-12 | 中国科学院光电研究院 | Laser-induced breakdown spectroscopy detection system |
| CN108195824B (en) * | 2017-12-11 | 2021-07-06 | 中国科学院光电研究院 | Laser-induced breakdown spectroscopy detection system |
| CN109406541A (en) * | 2018-11-22 | 2019-03-01 | 深圳供电局有限公司 | A kind of device and method detecting the filth of external insulation equipment surface metal |
| CN109884035B (en) * | 2019-02-25 | 2021-10-01 | 广东朗研科技有限公司 | Detection device, detection method and anti-counterfeiting detection method for sample to be detected |
| CN112595704A (en) * | 2020-12-11 | 2021-04-02 | 华中科技大学 | Method and system for detecting halogen elements in fluid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2170022B2 (en) * | 2000-11-22 | 2003-10-16 | Univ Madrid Complutense | NEW METHOD OF ANALYSIS OF CHEMICAL, METAL AND NON-METAL ELEMENTS, IN LIQUIDS BY LASER ABLATION PRIOR TO FREEZING THE SAMPLE. |
| EP1482302A1 (en) * | 2002-04-19 | 2004-12-01 | Energy Research Company | Apparatus and method for in situ, real time measurements of properties of liquids |
| CN101694469A (en) * | 2009-11-12 | 2010-04-14 | 中国海洋大学 | Guiding deposition strengthening method for detecting ions in water through laser-induced breakdown spectroscopy |
-
2011
- 2011-07-22 CN CN 201110207663 patent/CN102279171B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2170022B2 (en) * | 2000-11-22 | 2003-10-16 | Univ Madrid Complutense | NEW METHOD OF ANALYSIS OF CHEMICAL, METAL AND NON-METAL ELEMENTS, IN LIQUIDS BY LASER ABLATION PRIOR TO FREEZING THE SAMPLE. |
| EP1482302A1 (en) * | 2002-04-19 | 2004-12-01 | Energy Research Company | Apparatus and method for in situ, real time measurements of properties of liquids |
| CN101694469A (en) * | 2009-11-12 | 2010-04-14 | 中国海洋大学 | Guiding deposition strengthening method for detecting ions in water through laser-induced breakdown spectroscopy |
Non-Patent Citations (6)
| Title |
|---|
| Chen.ZJ,et.al.Sensitive detection of metals in water using laser-induced breakdown spectroscopy on wood sample substrates.《APPLIED OPTICS 》.2010,第49卷(第13期),C87-C94. |
| Determination of sub—ppm levels of boron in ground water samples by laser induced breakdown spectroscopy;Sarkar. A,et.al;《 MICROCHIMICA ACTA》;20100228;第168卷(第1-2期);65-69 * |
| Sarkar. A,et.al.Determination of sub—ppm levels of boron in ground water samples by laser induced breakdown spectroscopy.《 MICROCHIMICA ACTA》.2010,第168卷(第1-2期),65-69. |
| Sensitive detection of metals in water using laser-induced breakdown spectroscopy on wood sample substrates;Chen.ZJ,et.al;《APPLIED OPTICS 》;20100501;第49卷(第13期);C87-C94 * |
| 超声波雾化辅助液体样品激光诱导击穿光谱技术研究;钟石磊等;《光谱学与光谱分析》;20110630;第31卷(第6期);1458-1462 * |
| 钟石磊等.超声波雾化辅助液体样品激光诱导击穿光谱技术研究.《光谱学与光谱分析》.2011,第31卷(第6期),1458-1462. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102279171A (en) | 2011-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102279171B (en) | Method for promoting sensitivity of metal pollutants in water in laser breakdown spectrum detection | |
| Hilbk-Kortenbruck et al. | Analysis of heavy metals in soils using laser-induced breakdown spectrometry combined with laser-induced fluorescence | |
| Cahoon et al. | Quantitative analysis of liquids from aerosols and microdrops using laser induced breakdown spectroscopy | |
| US6008897A (en) | Method and apparatus for materials analysis by enhanced laser induced plasma spectroscopy | |
| Rodriguez-Celis et al. | Laser induced breakdown spectroscopy as a tool for discrimination of glass for forensic applications | |
| Burakov et al. | Quantitative analysis of alloys and glasses by a calibration-free method using laser-induced breakdown spectroscopy | |
| US20200300770A1 (en) | Portable laser induced breakdown spectroscopy systems | |
| Gonzaga et al. | A compact and low cost laser induced breakdown spectroscopic system: Application for simultaneous determination of chromium and nickel in steel using multivariate calibration | |
| CN102262075B (en) | Method for measuring elemental concentration through laser-induced breakdown spectroscopy based on spectrophotometry | |
| Sarkar et al. | Determination of thorium and uranium in solution by laser-induced breakdown spectrometry | |
| CN101620183A (en) | Photoelectric double-pulse laser induced breakdown spectrograph and spectral analysis method | |
| CN110088600B (en) | Laser-induced breakdown spectroscopy system and method, and detection system and method thereof | |
| Zoriy et al. | Determination of uranium isotopic ratios in biological samples using laser ablation inductively coupled plasma double focusing sector field mass spectrometry with cooled ablation chamber | |
| CN108169092A (en) | Atmospheric particulates heavy metal and its isotope on-line water flushing devices and methods therefor | |
| Cheung et al. | Single-shot elemental analysis of liquids based on laser vaporization at fluences below breakdown | |
| Zheng et al. | Near real-time measurement of carbonaceous aerosol using microplasma spectroscopy: Application to measurement of carbon nanomaterials | |
| CN110057795B (en) | Spectrum detection method and device for breakdown ionization of femtosecond plasma | |
| Álvarez-Trujillo et al. | Preliminary studies on stand-off laser induced breakdown spectroscopy detection of aerosols | |
| Evans et al. | Atomic spectrometry update: review of advances in atomic spectrometry and related techniques | |
| Chen et al. | The parameter optimization of lasers' energy ratio of the double-pulse laser induced breakdown spectrometry for heavy metal elements in the soil | |
| Kurniawan et al. | Quantitative hydrogen analysis of zircaloy-4 using low-pressure laser plasma technique | |
| Hegazy et al. | Laser-induced breakdown spectroscopy: technique, new features, and detection limits of trace elements in Al base alloy | |
| CN111289497B (en) | Transient-state laser-induced breakdown spectroscopy detection system | |
| Bernardoni et al. | Set-up of a multi wavelength polar photometer for off-line absorption coefficient measurements on 1-h resolved aerosol samples | |
| CN201449373U (en) | Photoelectric double-pulse laser induced breakdown spectrometer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |