CN109115733A - The rapid detection method of soil sodium element based on conllinear double-pulse laser induced breakdown spectrum - Google Patents
The rapid detection method of soil sodium element based on conllinear double-pulse laser induced breakdown spectrum Download PDFInfo
- Publication number
- CN109115733A CN109115733A CN201811013888.7A CN201811013888A CN109115733A CN 109115733 A CN109115733 A CN 109115733A CN 201811013888 A CN201811013888 A CN 201811013888A CN 109115733 A CN109115733 A CN 109115733A
- Authority
- CN
- China
- Prior art keywords
- soil
- sodium element
- sodium
- sample
- pulse laser
- 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.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention discloses a kind of rapid detection methods of soil sodium element based on conllinear double-pulse laser induced breakdown spectrum, comprising: contains the soil sample of N number of na concn than mixed method preparation by multiple standards soil and its two-by-two etc.；Then the instrument parameter of dipulse LIBS system is optimized, and acquires the LIBS spectral line of soil tabletting sample；To spectroscopic data after pretreatment, select signal Na I 588.99nm, Na I 589.59nm at as input value, sodium element concentration establishes the Multivariable regressive analysis model that soil sample sodium content is predicted, prediction coefficient of determination R as output valve in sample2Reach 0.981.The present invention realizes the quick detection of sodium element content in soil, has the features such as easy to operate, at low cost；Simultaneously because the signal enhancing effect of conllinear dipulse, the detection accuracy of this method is higher, can provide reference to develop portable soil sodium element content detection instrument.
Description
Technical field
The present invention relates to soil nutrient elements detection techniques more particularly to a kind of induced with laser based on conllinear dipulse to hit
Wear the rapid detection method of the soil sodium element of spectrum.
Background technique
Soil nutrient elements are able to reflect the fertility of soil, influence crop yield and quality.Wherein, sodium element is a kind of strong
Power Cell revival agent can penetrate into rapidly in crop body after contacting with crop, and the plasm of cell is promoted to flow, and it is living to improve cell
Power, accelerates rooting rate, breaking dormancy, and enhancing development improves crop quality and yield.Soil sodium content is too low to be will affect
The normal growth and development of crop, sodium content is excessively high to destroy crop plant tissue and soil property.Therefore, sodium element in soil is determined
Amount detection has great significance for plant growth and Soil quality monitoring.Currently, in soil sodium element the side of predominantly detecting
Method has atomic absorption method, inductively coupled plasma mass spectrometry, the chemistry inspection such as inductively coupled plasma atomic emission spectrometry
Survey method needs to consume chemical reagent and carries out resolution processing to sample, to operator although the inspection accuracy of these methods is high
Professional degree require high, detection process is complicated, the period is longer, cannot achieve efficient, accurate, the real-time inspection of sodium element in soil
It surveys.
Laser induced breakdown spectrograph (Laser-Induced Breakdown Spectroscopy, LIBS) utilizes pulse
Laser ablation sample generates the specific spectral signal of plasma emission, passes through the light for the plasma emission that spectrometer obtains
The analysis of element composition and content in sample may be implemented in spectrum.But the problem of the higher always LIBS technology of Element detection limit.
Therefore, LIBS Signal Enhanced Technology becomes the focus of domestic and foreign scholars.LIBS signal enhancing skill based on conllinear dipulse
Art is that current effect is preferable, using more one of Signal Enhanced Technology.Using conllinear double-pulse laser induced breakdown spectrum skill
Art can fast and accurately obtain soil sodium content, be conducive to plant growth and Soil quality monitoring.
Summary of the invention
The invention discloses a kind of rapid detection method of soil nutrient elements, realizes and lured based on conllinear double-pulse laser
Quick detection of the breakdown spectral to soil sodium element is led, there is the features such as easy to operate, testing cost is low, and accuracy is high.
The specific technical solution of the present invention is as follows:
A kind of rapid detection method of the soil sodium element based on conllinear double-pulse laser induced breakdown spectrum, including step
It is rapid:
1) soil sample containing sodium of N number of gradient is made, and press sheet compression is made, sodium element concentration is denoted as Y in sample；
2) X is denoted as using the LIBS spectroscopic data of double-pulse laser acquisition soil sample containing sodium；
3) sodium element pair is found out in conjunction with wavelength and the one-to-one relationship of element according to LIBS spectroscopic data X data and curves
The wavelength answered；
4) LIBS spectroscopic data X is pre-processed, pretreated data be X1, extracted in X1 in step 3)
The corresponding spectroscopic data X2 of sodium element wavelength；Gained spectroscopic data (X2, Y) is drawn in the ratio of 2:1 using X-Y co-occurrence matrix method
It is divided into modeling collection and forecast set；
5) respectively to model the X2 concentrated as input, Y is to export, establish in soil sample sodium element concentration with it is corresponding
The multivariate linear regression analysis model of LIBS the intensity of spectral line:
Y=0.0037X1+0.0006X2+0.2947
Wherein, Y is the actual content of sodium element in sample, X1、X2588.99nm respectively corresponding with sodium element,
The signal strength of 589.59nm；
The Quantitative Analysis Model that X2 in forecast set is brought into foundation obtains the prediction concentrations of sodium element in sample.
In step 1), it is mixed with the soil sample containing sodium using weight such as different soils, sodium element is dense in soil
Degree is respectively 22.57mgg-1、14.13mg·g-1、6.14mg·g-1、12.88mg·g-1、14.06mg·g-1、9.03mg·
g-1。
In the technical program, six kinds of soil of preparation soil sample containing sodium are respectively Inner Mongol Hangjin Rear Banner saline-alkali soil
(GBW07447), Zhejiang Province Xiangshan East Sea Tidal Flat Sediments (GBW7452), Yangjiang city's South Beach deposit
(GBW7453), Shaanxi Province's Luochuan Loess (GBW7454), Anhui Wu He Sediments from Huaihe River (GBW7455), Jiangsu Province Zhangjiagang are clear
River deposit (GBW7456).
In step 1), soil sample containing sodium is made to the rectangular press sheet compression of equal-specification, every tablet quality is 0.5g, each
Gradient prepares 3 tabletting samples.
In step 2), the parameter of laser induced breakdown spectrograph is optimized, obtained optimized parameter are as follows: the first beam
Laser energy is 25mJ；Second beam laser energy is 75mJ；Optical maser wavelength is 532nm；Delay time is 6us；The time of integration is
10us, pulse spacing 1.2us.Under the conditions of optimized parameter, the average signal-to-noise ratio of 2 spectral line single pulse signals of sodium element in sample
(ratio of signal and noise) is minimum to have reached 155.59, and the average signal-to-noise ratio of dipulse signal is minimum to have reached 310.14, letter
It number can obviously be distinguished with noise.
In step 4), noise reduction process is carried out using small wave converting method, small echo odd function is db4, and the number of plies is set as 3.
In step 4), sample is divided using SPXY method (X-Y co-occurrence matrix method).First institute when specific method
Some samples all regard modeling collection candidate samples as, then using two farthest vectors of the method choice Euclidean distance of iteration into
Enter modeling collection, until selecting required number of samples.Its range formula is as follows:
Wherein, dxy(m, n) is Euclidean distance, dx(m, n) is spectrum intervals, dy(m, n) is physicochemical property characteristic distance.
The present invention uses SPXY method when sample divides, while considering the spectral signature and physicochemical property feature of sample,
The predictive ability of model can be improved.
In step 5), according to the characteristic wavelength that U.S.'s NIST atomic spectra database and pilot system are demarcated, for building
The main feature spectral line of the sodium element of formwork erection type are as follows: Na I 588.99nm, Na I589.59nm.
Compared with the existing technology, the invention has the advantages that:
(1) quantitative detection of soil sodium element is realized.
(2) detection of soil sodium element is carried out using the LIBS technology based on conllinear dipulse, there is easy to operate, cost
The features such as low, quickly, efficiently and accurately.It is complicated effectively to overcome traditional detection method program, higher cost is big etc. to sample broke
Disadvantage.
(3) representative sodium element wavelength has been selected, the exploitation of portable sensor instrument is conducive to.
Detailed description of the invention
Fig. 1 is the Multivariable regressive analysis model prediction result of soil sample sodium element concentration.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be described in detail, but the present invention is not limited to this.
A kind of rapid detection method of the soil sodium element based on conllinear double-pulse laser induced breakdown spectrum, comprising:
(1) sample preparation.The pedotheque purchase that this research uses is in the standard soil sample of the China Measures Institute, and six kinds
Soil is respectively Inner Mongol Hangjin Rear Banner saline-alkali soil (GBW07447), Zhejiang Province Xiangshan East Sea Tidal Flat Sediments (GBW7452), wide
East saves Yangjiang City South Beach deposit (GBW7453), Shaanxi Province's Luochuan Loess (GBW7454), Anhui Wu He Sediments from Huaihe River
(GBW7455), Jiangsu Province Zhangjiagang Chengjiang deposit (GBW7456).It is more dense in order to be obtained using existing six kinds of soil
Gradient is spent, is mixed to get the sodium element soil-like containing 21 concentration gradients two-by-two using six kinds and six kinds of pedotheque equivalent
This.The concentration of sodium element is respectively as follows: 22.57mgg in 6 kinds of standard soil samples-1、14.13mg·g-1、6.14mg·g-1、
12.88mg·g-1、14.06mg·g-1、9.03mg·g-1.Being fabricated to specification using tablet press machine (10MPa pressure continues 30s) is
10mm × 10mm × 2mm square sample, every tablet quality are 0.5g.Each concentration prepares 3 samples, and 63 soil pressures are obtained
Piece sample is for testing.
(2) the LIBS spectral signal of collecting sample.Laboratory apparatus preheating 30min is reached into stable state before experiment.
According to the first beam laser energy 25mJ, the second beam laser energy 75mJ, optical maser wavelength 532nm, delay time 6us, the time of integration
10us, the pulse spacing, 1.2us was configured instrument parameter.Sample is placed in displacement platform, adjustment programme sets displacement platform
Movement routine, open laser, recall two beam laser, guarantee to hit laser under the conditions of the impact position of two beam laser is consistent
The different points of 16 originally that draw a design, each point accumulation 5 spectral signals of acquisition.
(3) according to original LIBS spectroscopic data (X) curve, in conjunction with U.S.'s NIST atomic spectra database and pilot system mark
Fixed characteristic wavelength finds out the main feature spectral line of sodium element are as follows: Na I588.99nm, Na I 589.59nm.
(4) wavelet transformation noise reduction carried out to original LIBS spectroscopic data (X), be averaging pretreatment, process is pretreated
Data are denoted as X1, extracted in X1 with 3) in the corresponding spectroscopic data of sodium element wavelength, be denoted as X2.Using SPXY method according to
The ratio of 2:1 divides sample, obtains modeling collection 42, sample, 21, forecast set sample.
(5) it is established polynary time according to the content of sodium element in the peak strength of the sodium element spectral line in modeling collection X2 and sample
Return analysis model:
Y=0.0037X1+0.0006X2+0.2947
Wherein, Y is the actual content of sodium element in sample, X1、X2588.99nm respectively corresponding with sodium element,
The signal strength of 589.59nm
Bring the peak strength of sodium element spectral line in forecast set into sodium element concentration that regression analysis model is predicted, such as
Shown in Fig. 1.The result shows that sodium element content and corresponding conllinear dipulse LIBS the intensity of spectral line linear dependence are preferable, prediction
The fitting coefficient of determination R of collection2Reach 0.981.The above results show that method of the invention can be realized the quick of sodium in soil
Quantitative detection can provide reference for plant growth and Soil quality monitoring, have a good application prospect.
The foregoing is merely preferable implementation examples of the invention, are not intended to restrict the invention, it is all in spirit of that invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of rapid detection method of the soil sodium element based on conllinear double-pulse laser induced breakdown spectrum, feature exist
In, comprising steps of
1) soil sample containing sodium of N number of gradient is made, and press sheet compression is made, sodium element concentration is denoted as Y in sample；
2) X is denoted as using the LIBS spectroscopic data of double-pulse laser acquisition soil sample containing sodium；
3) it is corresponding to find out sodium element in conjunction with wavelength and the one-to-one relationship of element according to LIBS spectroscopic data X data and curves
Wavelength；
4) LIBS spectroscopic data X is pre-processed, pretreated data are X1, are extracted in X1 and sodium member in step 3)
The corresponding spectroscopic data X2 of plain wavelength；It is by the ratio cut partition of 2:1 by gained spectroscopic data (X2, Y) using X-Y co-occurrence matrix method
Modeling collection and forecast set；
5) respectively to model the X2 concentrated as input, Y is output, establishes sodium element concentration in soil sample and composes with corresponding LIBS
The multivariate linear regression analysis model of line intensity:
Y=0.0037X1+0.0006X2+0.2947
Wherein, Y is the actual content of sodium element in sample, X1、X2588.99nm, 589.59nm respectively corresponding with sodium element
Signal strength；
The Quantitative Analysis Model that X2 in forecast set is brought into foundation obtains the prediction concentrations of sodium element in sample.
2. the quick detection side of the soil sodium element as described in claim 1 based on conllinear double-pulse laser induced breakdown spectrum
Method, which is characterized in that in step 1), be mixed with the soil sample containing sodium, sodium in soil using weight such as different soils
The concentration of element is respectively as follows: 22.57mgg-1、14.13mg·g-1、6.14mg·g-1、12.88mg·g-1、14.06mg·g-1、9.03mg·g-1。
3. the quick detection side of the soil sodium element as claimed in claim 2 based on conllinear double-pulse laser induced breakdown spectrum
Method, which is characterized in that in step 1), soil sample containing sodium is made to the rectangular press sheet compression of equal-specification, every tablet quality is
0.5g, each gradient prepare 3 tabletting samples.
4. the quick detection side of the soil sodium element as described in claim 1 based on conllinear double-pulse laser induced breakdown spectrum
Method, which is characterized in that in step 2), the parameter of laser induced breakdown spectrograph is optimized, obtained optimized parameter are as follows:
First beam laser energy is 25mJ；Second beam laser energy is 75mJ；Optical maser wavelength is 532nm；Delay time is 6us；Integral
Time is 10us, pulse spacing 1.2us.
5. the quick detection side of the soil sodium element as described in claim 1 based on conllinear double-pulse laser induced breakdown spectrum
Method, which is characterized in that in step 4), noise reduction process is carried out using small wave converting method, small echo odd function is db4, and the number of plies is set
It is 3.
6. the quick detection side of the soil sodium element as described in claim 1 based on conllinear double-pulse laser induced breakdown spectrum
Method, which is characterized in that in step 4), when being divided using X-Y co-occurrence matrix method to sample, by all soil-likes containing sodium
This all regards modeling collection candidate samples as, is then modeled using two farthest vectors of the method choice Euclidean distance of iteration to entering
Collection, until selecting required number of samples；Its range formula is as follows:
Wherein, dxy(m, n) is Euclidean distance, dx(m, n) is spectrum intervals, dy(m, n) is physicochemical property characteristic distance.
7. the quick detection side of the soil sodium element as described in claim 1 based on conllinear double-pulse laser induced breakdown spectrum
Method, which is characterized in that in step 5), according to the characteristic wavelength that U.S.'s NIST atomic spectra database and pilot system are demarcated,
For establishing the main feature spectral line of the sodium element of model are as follows: Na I 588.99nm, Na I 589.59nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811013888.7A CN109115733A (en) | 2018-08-31 | 2018-08-31 | The rapid detection method of soil sodium element based on conllinear double-pulse laser induced breakdown spectrum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811013888.7A CN109115733A (en) | 2018-08-31 | 2018-08-31 | The rapid detection method of soil sodium element based on conllinear double-pulse laser induced breakdown spectrum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109115733A true CN109115733A (en) | 2019-01-01 |
Family
ID=64861574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811013888.7A Pending CN109115733A (en) | 2018-08-31 | 2018-08-31 | The rapid detection method of soil sodium element based on conllinear double-pulse laser induced breakdown spectrum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109115733A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104020143A (en) * | 2014-06-09 | 2014-09-03 | 江西农业大学 | Method for quickly detecting benzopyrene content of edible oil based on collinear double-pulse LIBS (Laser-induced Breakdown Spectroscopy) technique |
| US20140368819A1 (en) * | 2013-06-12 | 2014-12-18 | Applied Research Associates, Inc. | Methods for Detecting Parasites, Viruses, Bacteria and Drugs in Human and Animal Blood and Cerebral Spinal Fluid, Using Laser-Induced Breakdown Spectroscopy |
| CN105092540A (en) * | 2015-06-16 | 2015-11-25 | 江西农业大学 | Method and device for rapid and high-precision detection of content of heavy metal lead in edible oil |
| CN106290309A (en) * | 2016-09-16 | 2017-01-04 | 天津大学 | Device is detected based on LIBS portable variable depth heavy metal content in soil |
| CN107966430A (en) * | 2017-10-18 | 2018-04-27 | 深圳市芭田生态工程股份有限公司 | A kind of method for being used to quickly detect fertilizer nutrient content |
-
2018
- 2018-08-31 CN CN201811013888.7A patent/CN109115733A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140368819A1 (en) * | 2013-06-12 | 2014-12-18 | Applied Research Associates, Inc. | Methods for Detecting Parasites, Viruses, Bacteria and Drugs in Human and Animal Blood and Cerebral Spinal Fluid, Using Laser-Induced Breakdown Spectroscopy |
| CN104020143A (en) * | 2014-06-09 | 2014-09-03 | 江西农业大学 | Method for quickly detecting benzopyrene content of edible oil based on collinear double-pulse LIBS (Laser-induced Breakdown Spectroscopy) technique |
| CN105092540A (en) * | 2015-06-16 | 2015-11-25 | 江西农业大学 | Method and device for rapid and high-precision detection of content of heavy metal lead in edible oil |
| CN106290309A (en) * | 2016-09-16 | 2017-01-04 | 天津大学 | Device is detected based on LIBS portable variable depth heavy metal content in soil |
| CN107966430A (en) * | 2017-10-18 | 2018-04-27 | 深圳市芭田生态工程股份有限公司 | A kind of method for being used to quickly detect fertilizer nutrient content |
Non-Patent Citations (1)
| Title |
|---|
| 吕阳阳: "共线双脉冲及单脉冲激光诱导击穿光谱技术对土壤中营养元素检测对比研究", 《中国优秀硕士学位论文全文数据库 农业科技辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103983595B (en) | A kind of water turbidity calculation method processed based on ultraviolet-visible spectrum | |
| CN109030428A (en) | The rapid detection method of soil potassium element based on conllinear double-pulse laser induced breakdown spectrum | |
| CN103674789A (en) | Atmospheric particulate real-time source analytic method based on single-particle mass spectrums | |
| CN105486655B (en) | The soil organism rapid detection method of model is intelligently identified based on infrared spectroscopy | |
| CN103698255A (en) | Real-time analytic method for atmospheric particle source | |
| CN106290309A (en) | Device is detected based on LIBS portable variable depth heavy metal content in soil | |
| CN111488926B (en) | Soil organic matter determination method based on optimization model | |
| CN105445218B (en) | The method for building up of middle infrared spectrum rapeseed protein content detection adaptive model | |
| CN104596957A (en) | Estimation method for content of copper in soil on basis of visible-light near-infrared spectrum technology | |
| CN105044050A (en) | Rapid quantitative analysis method for metallic elements in crop straw | |
| CN103983617A (en) | Improved laser probe quantitative analysis method based on wavelet transform | |
| CN108872198A (en) | The effect of fertilizer cadmium detection method of laser induced breakdown spectroscopy based on ar gas environment | |
| CN104730042A (en) | Method for improving free calibration analysis precision by combining genetic algorithm with laser induced breakdown spectroscopy | |
| CN101836561B (en) | Model for predicating yield of castor beans planted in coastal saline soil and construction method and application thereof | |
| CN102507512A (en) | On-line in situ detecting method for infrared-ultraviolet double pulse laser induced breakdown spectroscopy | |
| Limoges et al. | Long-term hydrological changes in the northeastern Gulf of Mexico (ODP-625B) during the Holocene and late Pleistocene inferred from organic-walled dinoflagellate cysts | |
| CN109187498A (en) | The rapid detection method of soil calcium constituent based on conllinear double-pulse laser induced breakdown spectrum | |
| CN107655918B (en) | Method and device for determining soil heavy metal energy spectrum range | |
| Fu et al. | Calibration methods of laser-induced breakdown spectroscopy | |
| Mingjing et al. | A novel strategy for quantitative analysis of soil pH via laser-induced breakdown spectroscopy coupled with random forest | |
| Li et al. | In situ simultaneous quantitative analysis multi-elements of archaeological ceramics via laser-induced breakdown spectroscopy combined with machine learning strategy | |
| CN104931475A (en) | Method for detecting total heavy metal content in medicinal materials | |
| CN108872199A (en) | The rapid detection method of soil magnesium elements based on conllinear double-pulse laser induced breakdown spectrum | |
| CN109001186A (en) | The rapid detection method of soil manganese element based on conllinear double-pulse laser induced breakdown spectrum | |
| Li et al. | New record of the green algal fossil Proterocladus and coexisting microfossils from the Meso-Neoproterozoic Diaoyutai Formation in southern Liaoning, North China |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190101 |
|
| RJ01 | Rejection of invention patent application after publication |