CN106124481A - One is suitable to milk powder multicomponent heavy metal lossless detection method - Google Patents

One is suitable to milk powder multicomponent heavy metal lossless detection method Download PDF

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Publication number
CN106124481A
CN106124481A CN201610257937.6A CN201610257937A CN106124481A CN 106124481 A CN106124481 A CN 106124481A CN 201610257937 A CN201610257937 A CN 201610257937A CN 106124481 A CN106124481 A CN 106124481A
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heavy metal
milk powder
spectral line
concentration
metal element
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赵超
陈达
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Zhejiang Da Da Technology Co., Ltd.
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Tianjin Zhiqiao Data Technology Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718—Laser microanalysis, i.e. with formation of sample plasma

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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Optics & Photonics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • General Health & Medical Sciences (AREA)
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  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The present invention relates to one and be suitable to milk powder multicomponent heavy metal lossless detection method, the method for every kind of heavy metal element to be analyzed, detection method is: determine the best features analysis spectral line of this Heavy Metallic Elements；Gather the LIBS often organizing standard milk powder print, comprise wavelength and signal strength information, utilize the principle that the signal intensity of feature analysis spectral line is linear with corresponding heavy metal element concentration, concentration P of this Heavy Metallic Elements is carried out curve fitting with the relation of feature analysis the intensity of spectral line W；For powdered milk sample to be measured, it is compressed into milk powder print, gathers the LIBS of milk powder print；Infer in powdered milk sample and whether contain corresponding heavy metal element；Obtain concentration P of this Heavy Metallic Elements.The present invention can realize simple, quick, the Non-Destructive Testing of heavy metal.The present invention can simply, quickly, nondestructively measure the grain graininess of material.

Description

One is suitable to milk powder multicomponent heavy metal lossless detection method
Technical field
The invention belongs to milk powder Determination Method of Heavy Metal Contamination field, particularly relate to a kind of based on LIBS Multicomponent heavy metal lossless detection method.
Background technology
In recent years, along with the raising of people's living standard, the attention rate of food safety is constantly risen by the public, and milk powder peace Complete as the conspicuous contradiction in food safety, cause the highest attention of the whole society.In the various potential risks of milk powder, with much money Belong to and pollute the serious infringement that human body can be caused accumulation property, it has also become the key object that milk powder safety controls.Therefore, Development of Novel Detection means, to realize the quick detection of contents of heavy metal elements in milk powder, becomes the hot research class in present food security field Topic.
Along with the aggravation of mankind's activity, the heavy metal pollution that the approach such as commercial production, pesticide residues and domestic sewage causes Situation is more serious, and the safe edible of milk powder is caused serious threat.Existing milk powder heavy metal analysis technology mainly has atom Absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS), ICP-AES (ICP-AES) and Inductively coupled plasma mass spectrometries (ICP-MS) etc., these are mostly ripe laboratory method, have detection limit low, sensitive Degree is high, high repeatability and other advantages, but generally requires loaded down with trivial details sample pretreatment process, there is apparatus expensive, operates complexity, to people Member wants the shortcoming such as high.Under the food safety situation of China's current rigorous, it is low that existing detection technique is difficult to meet great amount of samples The requirement of cost rapid screening, is also limited by the human and material resources condition that China is current, it is difficult to spread simultaneously.Therefore, send out Open up heavy metal Fast Detection Technique in new and effective milk powder extremely urgent.
In various heavy metal analysis technology, LIBS have measuring speed element fast, complete analyze simultaneously, Sample pretreatment simply waits outstanding advantage, and sample can directly carry out Non-Destructive Testing, has in the milk product detections such as milk powder Huge application potential.
Summary of the invention
It is an object of the invention to provide a kind of quickly, simple and can detect simultaneously multi-component milk powder heavy metal without Damage detection method.Technical scheme is as follows:
One is suitable to milk powder multicomponent heavy metal lossless detection method, and the method is for every kind of heavy metal to be analyzed unit Element, uses the steps to detect:
(1) the best features analysis spectral line of this Heavy Metallic Elements is determined；
(2) it is pressed into standard milk powder print by organizing the different milk powder standard sample of this Heavy Metallic Elements content more；
(3) gather the LIBS of often group standard milk powder print, comprise wavelength and signal strength information, utilize The principle that the signal intensity of feature analysis spectral line is linear with corresponding heavy metal element concentration, to this Heavy Metallic Elements Concentration P carries out curve fitting with the relation of feature analysis the intensity of spectral line W；
(4) for powdered milk sample to be measured, it is compressed into milk powder print, gathers the laser-induced breakdown light of milk powder print Spectrum, comprises wavelength and signal strength information；
(5) for heavy metal element to be analyzed, according to its best features analysis spectral line wavelength, the laser at milk powder print lures Lead the feature spectral peak demarcating this heavy metal element corresponding in breakdown spectral, by the presence or absence of feature spectral peak i.e. deducibility milk powder sample Whether product contain corresponding heavy metal element；
(6) if existing, extracting the intensity level of feature spectral peak extreme higher position, according to the relation of (3) matching, obtaining this kind of huge sum of money Belong to concentration P of element.
Present invention heavy metal detection method based on LIBS, according to the feature launched by heavy metal element The signal intensity of analysis spectral line and the linear relationship of concentration of element, it is achieved simple, quick, the Non-Destructive Testing of heavy metal, it is possible to Realize multi-component detecting simultaneously.
Accompanying drawing explanation
Fig. 1 is a kind of based on LIBS the milk powder multicomponent heavy metal Non-Destructive Testing side that the present invention provides The flow chart of method.
Fig. 2 is Pb I 405.78nm, the Cr I 425.43nm feature spectral peak demarcated in the spectrogram that the present invention provides.
Fig. 3 is the Pb concentration of element that provides of the present invention and Pb I 405.78nm the intensity of spectral line fitting result, is used for measuring school Quasi-coefficient a1And b1。
Fig. 4 is the Cr concentration of element that provides of the present invention and Cr I 425.43nm the intensity of spectral line fitting result, is used for measuring school Quasi-coefficient a2And b2。
Fig. 5 is the application Pb concentration of element that obtains of internal standard method that provides of the present invention and the intensity of spectral line ratio fitting result, uses In measuring calibration factor a1inAnd b1in。
Fig. 6 is the application Cr concentration of element that obtains of internal standard method that provides of the present invention and the intensity of spectral line ratio fitting result, uses In measuring calibration factor a2inAnd b2in。
Detailed description of the invention
The present invention proposes a kind of milk powder multicomponent heavy metal lossless detection method based on LIBS, root Determine the feature analysis spectral line of heavy metal element according to the physical parameter of spectral line, the presence or absence of feature spectral peak in spectrogram infer milk Whether powder sample contains corresponding heavy metal element.
LIBS is substantially a kind of atomic emission spectrum technology, and its principle is to sample by high energy pulse laser beam focusing Product surface, produces ablation the laser plasma of association high temperature high brightness, have in plasma a large amount of free electron, ion and Atom, its Atom and ion excited after by generation transition of electronic energy and launch atom (ion) spectral line, pass through spectrum The spectral line of emission is acquired and analyzes obtaining the kind of each element and content information in sample by instrument.Variety classes atom Energy level transition launch radiation frequency be unique, therefore, it can the frequency according to spectrum and sample carried out qualitative point Analysis, carries out quantitative analysis according to intensity.According to the linear relationship of feature analysis spectral line signal intensity Yu concentration of element, derive weight The detected value of metallic element concentration, in conjunction with accompanying drawing, describes in detail as follows.Described herein a kind of based on induced with laser The implementation method of the milk powder multicomponent heavy metal lossless detection method of breakdown spectral.
Present invention can be suitably applied to all heavy metal elements detection in milk powder, existing as a example by representative heavy metal elements Pb and Cr, Illustrate to use LIBS quickly to detect the overall process of heavy metal in milk powder.Fig. 1 shows LIBS Non-Destructive Testing Flow chart, details are as follows.
(1) milk powder is carried out tabletting, milk powder print is positioned over optimum detection position.Subsequently, determining that optimal LIBS examines Using LIBS experimental provision to collect the spectroscopic data of powdered milk sample on the basis of surveying parameter, Pb and Cr can be in spectrum Figure is formed a plurality of spectral line of emission.From these spectral lines, a feature analysis spectral line, these principles are determined by certain principle Relatively strong including spectral line signal, belong to atom or primary ions spectral line, non-overlapping spectral line interference, belong to resonance line etc., according to this A little principles finally determine that the feature analysis spectral line of Pb, Cr is respectively Pb I 405.78nm, Cr I 425.43nm.
(2) the feature spectral peak of Pb, Cr it is respectively shown in Fig. 2.According to feature analysis spectral line Pb I 405.78nm, Cr I The wavelength information of 425.43nm demarcates the feature spectral peak of Pb I 405.78nm, Cr I 425.43nm in spectrogram, such as spectral peak Intensity more than the detection limit of LIBS spectrum, then containing corresponding heavy metal element in explanation powdered milk sample, otherwise does not then contain.
(3) collect Pb concentration be respectively 1.62ppm, 4.01ppm, 5.99ppm, 7.97ppm, 16.03ppm, 20.89ppm, The spectroscopic data of the milk powder standard sample of 35.20ppm, 50.66ppm, 67.05ppm, 96.85ppm.According to Fig. 3, use Standard calibration curve method is to Pb concentration of element PPbWith Pb I 405.78nm the intensity of spectral line WPbIt is fitted, Pb concentration can be obtained PPb=a1WPb+b1In calibration factor a1And b1, wherein, a1=1.653, b1=1.843, then PPb=1.653WPb+1.843。
(4) collect Cr concentration be respectively 1.51ppm, 3.95ppm, 6.08ppm, 8.16ppm, 15.03ppm, 21.72ppm, The spectroscopic data of the milk powder standard sample of 30.32ppm, 48.78ppm, 70.63ppm, 98.53ppm.According to Fig. 4, use Standard calibration curve method is to Cr concentration of element PCrWith Cr I 425.43nm the intensity of spectral line WCrIt is fitted, Cr concentration can be obtained PCr=a2WCr+b2In calibration factor a2And b2, wherein, a2=0.543, b2=-5.044, then PCr=0.543WCr-5.044。
(5) in powdered milk sample, K element content is higher, and K is as internal standard element in selection, and selected K I 769.90nm is internal standard Line.Pb concentration be respectively 1.62ppm, 4.01ppm, 5.99ppm, 7.97ppm, 16.03ppm, 20.89ppm, 35.20ppm, The spectrogram of the milk powder standard sample of 50.66ppm, 67.05ppm, 96.85ppm is demarcated the feature spectral peak of K I 769.90nm, Extract intensity W of internal standard lineiPb, calculate each group of sample P b I 405.78nm the intensity of spectral line WPbWith internal standard line intensity WiPbRatio WinPb.According to Fig. 5, use internal standard method to Pb concentration of element PPbWith WinPbIt is fitted, Pb concentration P can be obtainedPb= a1inWinPb+b1inIn calibration factor a1inAnd b1in, wherein, a1in=2962, b1in=3.584, then PPb=2962WinPb+ 3.584。
(6) Cr concentration be respectively 1.51ppm, 3.95ppm, 6.08ppm, 8.16ppm, 15.03ppm, 21.72ppm, The spectrogram of the milk powder standard sample of 30.32ppm, 48.78ppm, 70.63ppm, 98.53ppm is demarcated K I 769.90nm's Feature spectral peak, extracts intensity W of internal standard lineiCr, calculate each group of sample Cr I 425.43nm the intensity of spectral line WCrWith internal standard line intensity WiCrRatio WinCr.According to Fig. 6, use internal standard method to Cr concentration of element PCrWith WinCrIt is fitted, Cr can be obtained dense Degree PCr=a2inWinCr+b2inIn calibration factor a2inAnd b2in, wherein, a2in=1037, b2in=-1.831, then PCr= 1037WinCr-1.831。
Spectral peak Pb I 405.78nm, spectral peak Cr I 425.43nm are to enter heavy metal pollution Pb, Cr in milk powder respectively The main basis that row identifies, by that analogy, by finding the feature spectral peak of different heavy metal, it is possible to achieve all huge sum of moneys in milk powder Belong to qualitative detection while element.
According to Pb I 405.78nm, Cr I 425.43nm the intensity of spectral line WPb、WCrDerive respectively with respective alignment coefficient Pb, Cr concentration value in milk powder, it is possible to achieve the detection by quantitative of multicomponent heavy metal in milk powder.
According to the intensity of spectral line WPb、WCrCan make with ratio and the respective alignment coefficient of internal standard line K I 769.90nm intensity Obtain Pb, Cr concentration value more accurately with internal standard method, improve LIBS to the precision of multicomponent heavy metal quantitative analysis in milk powder.

Claims (1)

1. be suitable to a milk powder multicomponent heavy metal lossless detection method, the method for every kind of heavy metal element to be analyzed, The steps is used to detect:
(1) the best features analysis spectral line of this Heavy Metallic Elements is determined.
(2) it is pressed into standard milk powder print by organizing the different milk powder standard sample of this Heavy Metallic Elements content more；
(3) gather the LIBS of often group standard milk powder print, comprise wavelength and signal strength information, utilize feature The principle that the signal intensity of analysis spectral line is linear with corresponding heavy metal element concentration, the concentration to this Heavy Metallic Elements P carries out curve fitting with the relation of feature analysis the intensity of spectral line W；
(4) for powdered milk sample to be measured, it is compressed into milk powder print, gathers the LIBS of milk powder print, bag Containing wavelength and signal strength information；
(5) for heavy metal element to be analyzed, according to its best features analysis spectral line wavelength, the induced with laser at milk powder print hits Wear the feature spectral peak demarcating this heavy metal element corresponding in spectrum, by the presence or absence of feature spectral peak i.e. deducibility powdered milk sample Whether contain corresponding heavy metal element；
(6) if existing, extracting the intensity level of feature spectral peak extreme higher position, according to the relation of (3) matching, obtaining this heavy metal species unit Concentration P of element.
CN201610257937.6A 2016-04-21 2016-04-21 One is suitable to milk powder multicomponent heavy metal lossless detection method Pending CN106124481A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108333171A (en) * 2018-04-23 2018-07-27 天津大学 The method for detecting micronutrient levels in milk powder based on laser induced breakdown spectroscopy
CN111665233A (en) * 2020-06-15 2020-09-15 天津大学 Method for quantitatively detecting lactoferrin in dairy products based on laser-induced breakdown spectroscopy
CN111965170A (en) * 2020-08-27 2020-11-20 天津大学 Method for detecting heavy metal in cream cosmetics
WO2022126695A1 (en) * 2020-12-15 2022-06-23 华中科技大学 Online powder detection apparatus based on laser‑induced breakdown spectroscopy

Citations (3)

* Cited by examiner, † Cited by third party
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.
CN102519918A (en) * 2011-12-08 2012-06-27 大连理工大学 Method for rapid detection of waste oil based on laser-induced breakdown spectroscopy
CN103983618A (en) * 2014-05-14 2014-08-13 四川大学 Pretreatment method of powder sample for laser induced breakdown spectrographic detection

Patent Citations (3)

* Cited by examiner, † Cited by third party
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.
CN102519918A (en) * 2011-12-08 2012-06-27 大连理工大学 Method for rapid detection of waste oil based on laser-induced breakdown spectroscopy
CN103983618A (en) * 2014-05-14 2014-08-13 四川大学 Pretreatment method of powder sample for laser induced breakdown spectrographic detection

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
杨平等: "集成ICCD光谱仪LIBS检测奶粉中Cr元素的定量分析研究", 《江西农业大学学报》 *
龚刚猛等: "激光诱导击穿光谱快速检测奶粉中重金属Cr的定量分析研究", 《安徽农业科学》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108333171A (en) * 2018-04-23 2018-07-27 天津大学 The method for detecting micronutrient levels in milk powder based on laser induced breakdown spectroscopy
CN108333171B (en) * 2018-04-23 2021-07-27 天津大学 Method for detecting content of trace elements in milk powder based on laser-induced breakdown spectroscopy
CN111665233A (en) * 2020-06-15 2020-09-15 天津大学 Method for quantitatively detecting lactoferrin in dairy products based on laser-induced breakdown spectroscopy
CN111965170A (en) * 2020-08-27 2020-11-20 天津大学 Method for detecting heavy metal in cream cosmetics
WO2022126695A1 (en) * 2020-12-15 2022-06-23 华中科技大学 Online powder detection apparatus based on laser‑induced breakdown spectroscopy

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Inventor after: Lin Jiahai

Inventor after: Chen Da

Inventor before: Zhao Chao

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Effective date of registration: 20170925

Address after: 318000, room 11, No. 139, Zhongshan branch, Jiaojiang District, Zhejiang, Taizhou

Applicant after: Zhejiang Da Da Technology Co., Ltd.

Address before: 300070, Binhai New District, Tianjin, Xin Huan Xi Road, 19 TEDA Service Outsourcing Industrial Park, building 8, 2, 2215

Applicant before: TIANJIN ZHIQIAO DATA TECHNOLOGY CO., LTD.

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Application publication date: 20161116