CN111693512A - Method for quantitatively detecting heavy metal elements in milk based on laser-induced breakdown spectroscopy - Google Patents
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- 239000008267 milk Substances 0.000 title claims abstract description 85
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- 235000013336 milk Nutrition 0.000 title claims abstract description 85
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 title claims abstract description 26
- 238000001228 spectrum Methods 0.000 claims abstract description 49
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
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- 230000000694 effects Effects 0.000 claims abstract description 7
- 230000002860 competitive effect Effects 0.000 claims abstract description 6
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- 239000010439 graphite Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000010238 partial least squares regression Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
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- 239000010949 copper Substances 0.000 description 19
- 229910000861 Mg alloy Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
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- 108090000623 proteins and genes Proteins 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
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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
Abstract
The invention discloses a method for quantitatively detecting heavy metal elements in milk based on laser-induced breakdown spectroscopy, which comprises the following steps: preprocessing the sample milk by using a preprocessing enrichment device to obtain spectral information data of the sample milk; selecting an element analysis spectrum peak to be detected from the spectrum information data, and carrying out normalization processing by using elements contained in the alloy electrode; performing spectrum preprocessing by combining high-density wavelet transform and a competitive adaptive reweighting algorithm; establishing an optimal correction model by using a partial least square regression method, and verifying the effect of the correction model by using a prediction set; and (4) determining the content of the heavy metal elements in the milk sample to be detected. According to the invention, the heavy metal elements in the milk are replaced on the solid by using the pretreatment enrichment device, and then the detection is carried out by adopting the laser-induced breakdown spectroscopy technology, so that the method has the advantages of rapidness, simplicity and convenience in operation, low instrument requirement, high sensitivity and the like, and the efficiency of quantitative detection of the heavy metal elements in the milk can be effectively improved.
Description
Technical Field
The invention relates to the technical field of heavy metal detection, in particular to a method for quantitatively detecting heavy metal elements in milk based on laser-induced breakdown spectroscopy.
Background
The heavy metal pollution in the milk can cause serious harm to the human health. Therefore, there are strict national standards governing the limitation of heavy metals and the related detection methods.
The current standard detection methods comprise an electrochemical method, an atomic absorption spectrometry, an inductively coupled plasma atomic emission spectrometry and the like. The methods have the defects of complicated pretreatment process, complex detection process, long detection time, high requirements on laboratories and laboratory personnel and the like.
Therefore, how to provide a new detection method, which can simply and rapidly detect the content of heavy metal elements in milk, is an important issue to be solved urgently in the industry.
In recent years, Laser-Induced Breakdown Spectroscopy (LIBS) has attracted much attention due to its advantages of high sensitivity, simple operation, and little damage to a sample. The LIBS system focuses and irradiates the surface of a sample by using high-energy laser to form laser plasma, so that an atomic emission spectrum is generated, and qualitative and quantitative analysis can be performed on almost all elements in the sample by using the collected spectrum. Therefore, the content of the heavy metal in the milk can be rapidly and quantitatively detected by utilizing the laser-induced breakdown spectroscopy technology.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for quantitatively detecting heavy metal elements in milk based on laser-induced breakdown spectroscopy (LIBS), aiming at realizing rapid and simple and convenient detection.
In order to solve the technical problem, the invention provides a method for quantitatively detecting heavy metal elements in milk based on laser-induced breakdown spectroscopy, which comprises the following steps:
replacing heavy metals in sample milk onto an alloy electrode by using a pretreatment enrichment device, and detecting the alloy electrode by using laser-induced breakdown spectroscopy to obtain spectral information data of the sample milk;
step two, selecting an analysis spectrum peak of the element to be detected from the spectrum information data, and carrying out normalization processing by using the element contained in the alloy electrode; performing spectrum preprocessing by combining high-density wavelet transform and a competitive adaptive reweighting algorithm;
establishing a correction model by using a partial least square regression method, and verifying the effect of the correction model by using a prediction set;
step four, determining the heavy metal element content of the milk sample to be detected, comprising the following steps: and (3) acquiring spectral data of the milk to be detected according to the step one, performing spectral pretreatment on the milk to be detected according to the step two, and inputting the pretreated spectrum into the correction model obtained in the step three, namely, measuring the content of heavy metal elements in the milk.
Further, the method for quantitatively detecting the heavy metal elements in the milk based on the laser-induced breakdown spectroscopy comprises the specific steps of taking a proper amount of sample milk, adding a proper amount of 1mol/L hydrochloric acid, and adjusting the pH of the milk to 4.6 +/-0.1 (protein isoelectric point); centrifuging at 12000rpm for 5min, taking supernatant, placing into a beaker, placing a fixing plate fixed with the graphite electrode and the alloy electrode which are connected by using conductive adhesive into the beaker, and waiting for 1 min; taking out the fixed plate and unloading the alloy electrode; collecting spectral data of the alloy electrode by using a laser-induced breakdown spectroscopy system, wherein the laser wavelength of a laser is 1064nm, and the laser energy is 100-150 mJ; the wavelength response range of the spectrometer is 200-880 nm, and the optical resolution is 0.1nm full width at half maximum; and selecting 20 points of the alloy electrode reaction area to acquire data, wherein each point acquires 1 time of spectrum, and calculating the average value of the 20 data to be used as the spectral information data of the sample milk.
The specific process of the second step is that aiming at measuring different elements, according to an atomic spectrum database of NIST, the corresponding wave bands of the different elements are intercepted from the spectral information data of the sample milk obtained in the first step; if the element wave bands are discontinuous, splicing the element wave bands; then, selecting variables related to the measured elements by using a high-density wavelet transform algorithm and a competitive adaptive re-weighting algorithm, and deleting irrelevant variables; randomly distributing the spectrum data of all samples subjected to the spectrum pretreatment to obtain calibration set spectrum data and predicted collection spectrum data; and (3) measuring the heavy metal elements in the sample milk by adopting an inductively coupled plasma atomic emission spectrometry in the GB5009-2017 standard to obtain the content of the heavy metal elements in the sample milk.
Combining the spectral data of the correction set obtained in the step two with the content of heavy metal elements in the sample milk obtained in the step two, and establishing a correction model by using a partial least squares regression method; inputting the predicted spectrum data obtained in the second step into a correction model, determining, comparing the content of heavy metal in the obtained milk with the content of heavy metal in sample milk determined by referring to an inductively coupled plasma atomic emission spectrometry (ICP-AES) method in GB5009-2017 standard, and verifying the effect of the correction model.
Compared with the prior art, the invention has the beneficial effects that:
(1) the detection speed is high. The milk reacts with the alloy in only one minute, and the LIBS spectrum is acquired in only one minute. Therefore, the total time for detecting a milk sample is not more than 15 minutes, and the result can be obtained.
(2) The requirement on the instrument is low. Only a solid sample stage is needed, and complex equipment such as a liquid sample cell is not needed.
(3) The sensitivity is improved, and the detection limit is reduced. By the pretreatment enrichment device, the elements to be detected with very low concentration in the milk are enriched on the surface of the alloy. Under the condition of not changing the spectrum hardware, the detection sensitivity of the instrument is improved, and the detection limit of the detection liquid is reduced.
Drawings
FIG. 1 is a flow chart of the method of the present invention;
FIG. 2 is a schematic view of the structure of the pretreatment enrichment apparatus used in the present invention, wherein: 1-graphite electrode, 2-alloy electrode, 3-conductive adhesive, 4-glass beaker, 5-cover plate;
FIG. 3 is a graph of a spectrum of an AZ31B magnesium alloy obtained using laser induced breakdown spectroscopy in accordance with an embodiment of the present invention;
FIG. 4 is a chart of a copper-containing magnesium alloy in an embodiment of the present invention;
FIG. 5 is a schematic diagram illustrating a comparison between predicted values and actual values of copper elements in milk of a calibration model established by a PLSR modeling method according to an embodiment of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
The invention provides a method for quantitatively detecting heavy metal elements in milk based on laser-induced breakdown spectroscopy, which comprises the following steps of:
(1) preprocessing a sample by using a preprocessing enrichment device as shown in fig. 2, wherein the preprocessing enrichment device mainly comprises a glass beaker 4 for placing milk to be detected; the graphite electrode plate 1 is used as an electrode of a primary battery reaction; the alloy electrode slice 2 is used for replacing heavy metal elements in the milk; the conductive adhesive 3 is used for connecting the graphite electrode plate 1 and the alloy electrode plate 2, so that the whole device forms a loop; and the cover plate 5 is used for fixing the graphite electrode 1 and the alloy electrode 2. And (3) replacing heavy metal in the sample milk onto the alloy electrode 2, taking out the cover plate 5, dismounting the alloy electrode 2, and waiting for subsequent spectrum collection.
(2) Collecting spectral data of the alloy electrode by using a laser-induced breakdown spectroscopy system, wherein the laser wavelength of a laser is 1064nm, and the laser energy is 100-150 mJ; the wavelength response range of the spectrometer is 200-880 nm, and the optical resolution is about 0.1nm (FWHM). And selecting 20 points of the alloy electrode reaction area to acquire data, wherein each point acquires 1 time of spectrum, and calculating the average value of the 20 data to be used as the spectral information data of the sample milk.
(3) Spectrum preprocessing to obtain correction set spectrum data and prediction collection spectrum data: and (3) selecting an analysis spectral peak of an element to be measured from the spectral information data, and carrying out normalization processing by using the element contained in the alloy electrode 2, namely, intercepting corresponding wave bands of different elements from the obtained spectral information data of the sample milk according to an atomic spectral data base (ASD) of National Institute of Standards and Technology (NIST) aiming at measuring different elements. And if the element wave bands are discontinuous, splicing the element wave bands. Then, selecting variables related to the measured elements by using a high-density wavelet transform algorithm and a competitive adaptive re-weighting algorithm, and deleting irrelevant variables; randomly distributing all sample data subjected to the spectrum pretreatment to obtain calibration set spectrum data and predicted collection spectrum data; thereby establishing a correction set and a prediction set to prepare for the subsequent establishment of a correction model.
(4) And (3) determining heavy metal elements in the sample milk by adopting an inductively coupled plasma atomic emission spectrometry (ICP-AES) method in the GB5009-2017 standard to obtain a true value of the content of the heavy metal elements in the sample milk.
(5) Establishing a correction model by combining the processed spectrum data of the correction set with the content of heavy metal elements in the sample milk obtained in the step (4) and applying a Partial Least Squares (PLSR) regression method;
(6) inputting the processed predicted spectrum data into a correction model, determining, comparing the content of heavy metal in the obtained predicted milk with the content of heavy metal elements in sample milk determined by referring to an inductively coupled plasma atomic emission spectrometry (ICP-AES) method in GB5009-2017 standard, verifying the effect of the correction model, and if the decision coefficient R2 is more than 0.9 and the predicted root mean square error RMSEP is less than 0.2, indicating that the established correction model is stable and reliable.
(7) And (3) determining the content of heavy metal elements in a milk sample to be determined, acquiring spectral data of the milk to be determined by utilizing the processes of the steps (1) and (2), performing spectral pretreatment on the milk to be determined according to the process of the step (3), inputting the spectrum after pretreatment into the correction model which is established in the step (5) and verified in the step (6), and performing rapid determination, so as to rapidly determine the content of heavy metal elements in the milk to be determined.
Example (b): pretreatment and quantitative detection method for detecting copper element in milk
(1) Sample pretreatment, namely replacing copper element on the surface of the magnesium alloy
And obtaining a milk sample to be detected, wherein the sample to be detected is derived from commercially available milk of different famous brands at home and abroad, and copper elements with different concentrations are added for 40 parts in total. Taking 20ml of milk to be detected, adding 600 mu L of 1mol/L hydrochloric acid, adjusting the pH of the milk to 4.6 +/-0.1 (protein isoelectric point), centrifuging at 12000rpm for 5min, and removing precipitates to obtain a milk supernatant. In this example, the alloy electrode 2 in the pretreatment enrichment apparatus (fig. 2) was AZ31B magnesium alloy, the size of the alloy electrode 2 was 50mm × 10mm, and the size of the graphite electrode 1 was 60mm × 15 mm. The sample milk supernatant is respectively put into a glass beaker 4 in a pretreatment enrichment device, the alloy electrodes 2 (one for each sample) are replaced by brand new ones and are fixed on a cover plate 5 by conductive adhesive 3. The cover plate 5 to which the alloy electrode 2 and the graphite electrode 1 are fixed is covered on a glass beaker 4, and is connected thereto using a conductive paste 3. Taking out after timing for one minute. The alloy electrode 2 is removed for subsequent spectral collection.
(2) Collecting LIBS spectral information data of the alloy electrode plate to be detected
Commercial LIBS systems were used, including CFR Nd: YAG laser (LIBS-LAS200MJ, Big SkyLaser technologies), ocean optics LIBS2500-7 multi-channel fiber optic spectrometer, optical fiber, detector and computer. The system adopts Nd: YAG laser with laser wavelength of 1064nm, laser energy of 130mJ, pulse width of 9.5ns and pulse repetition frequency of 10 Hz. The wavelength response range of a spectrometer in the system is 200-880 nm, the optical resolution is about 0.1nm (FWHM), a linear silicon CCD array with 7 2048 pixels is adopted, and the minimum integration time is 2.1 ms. The CCD detection trigger time delay is controlled by a computer, the delay time is adjustable within the range of-121 to +135 mu s, and the adjustment step length is 0.42 mu s. The delay time is set to 0.83 μ s. And selecting 20 points of the alloy electrode as data acquisition points, acquiring the spectrum of each point for 1 time, and taking the average value of the 20 data obtained by calculation as the spectrum information data of the sample. FIG. 3 shows a spectrum of an AZ31B magnesium alloy electrode in this example, including spectral information from 200nm to 880 nm.
(3) Spectrum preprocessing to obtain correction set spectrum data and prediction set spectrum data
For measuring elemental copper, according to an Atomic Spectral Database (ASD) of the National Institute of Standards and Technology (NIST), peaks of copper at the wavelengths of 325.1nm and 327.8nm are selected as analysis peaks, a band including the two peaks is cut, and 85 variables in total are shown in FIG. 4, which shows a spectrum of an AZ31B magnesium alloy containing copper element in the present example and a peak position of the copper element analysis peak cut according to the ASD database. The signal noise was removed using high density wavelet transform and the peak intensity of the peak band of the analysis spectrum was divided by the peak intensity of aluminum at 394.4nm for normalization of the data due to the aluminum element contained in the alloy. And establishing a subsequent correction model by using the normalized data. Calculating the probability of 85 variables to appear by using a competition adaptive re-weighting algorithm, selecting the 40 variables with high probability of appearing and the variables related to the measured element, and deleting the irrelevant variables. And randomly classifying the data of the 40 processed samples to obtain the spectral data of the correction set and the spectral data of the prediction set, wherein 30 samples are set as the correction set, and 10 samples are set as the prediction set.
(4) And (3) determining copper metal elements in the sample milk by adopting an inductively coupled plasma atomic emission spectrometry (ICP-AES) method in the GB5009-2017 standard to obtain a true value of the content of the copper elements in the sample milk.
(5) And combining the correction set with the copper content measured by an inductively coupled plasma atomic emission spectrometry (ICP-AES) method measured by referring to the GB5009.13-2017 method, and establishing a correction model by applying a partial least squares regression method (PLSR).
(6) Predictive set validation model effects
Inputting the processed predicted spectrum data into a correction model, measuring to obtain the predicted heavy metal content in the milk, and comparing the predicted heavy metal content with the copper element content measured by referring to an inductively coupled plasma atomic emission spectroscopy (ICP-AES) method in GB5009.13-2017 standard, wherein FIG. 5 is a schematic diagram showing the comparison between the predicted value and the actual value of the copper element in the milk of the optimal correction model established by the PLSR modeling method in the embodiment, wherein the linear correlation coefficient R2 of the optimal correction model reaches 0.9481, and the predicted root mean square error RMSEP is 0.1260, which shows that the model can well predict the copper element content in the milk.
(7) Determination of copper content of unknown sample
And (4) collecting the spectral data of the milk to be detected, performing spectral processing by using the step (3), inputting the processed spectrum into the established correction model, and performing rapid determination to obtain the content of the copper element in the milk.
Although the method for quantitatively detecting the heavy metal elements in the milk based on the laser-induced breakdown spectroscopy is applied to the implementation process of detecting the copper elements in the milk by using the method of the invention is described in detail in the figures and the examples. However, the present invention is not limited to the above embodiments, which are only illustrative and not restrictive, and the method can be applied not only to copper, but also to other heavy metal elements in milk, such as cadmium, lead, etc. Those skilled in the art, having the benefit of this disclosure, will appreciate that many modifications are possible in the exemplary embodiments without departing from the scope and spirit of the present invention, as described herein.
Claims (4)
1. A method for quantitatively detecting heavy metal elements in milk based on laser-induced breakdown spectroscopy is characterized by comprising the following steps:
replacing heavy metals in sample milk onto an alloy electrode by using a pretreatment enrichment device, and detecting the alloy electrode by using laser-induced breakdown spectroscopy to obtain spectral information data of the sample milk;
step two, selecting an analysis spectrum peak of the element to be detected from the spectrum information data, and carrying out normalization processing by using the element contained in the alloy electrode; performing spectrum preprocessing by combining high-density wavelet transform and a competitive adaptive reweighting algorithm;
establishing a correction model by using a partial least square regression method, and verifying the effect of the correction model by using a prediction set;
step four, determining the heavy metal element content of the milk sample to be detected, comprising the following steps: and (3) acquiring spectral data of the milk to be detected according to the step one, performing spectral pretreatment on the milk to be detected according to the step two, and inputting the pretreated spectrum into the correction model obtained in the step three, namely, measuring the content of heavy metal elements in the milk.
2. The method for quantitatively detecting the heavy metal elements in the milk based on the laser-induced breakdown spectroscopy as claimed in claim 1, wherein the specific process of the first step is,
taking a proper amount of sample milk, adding a proper amount of 1mol/L hydrochloric acid, and adjusting the pH value of the milk to 4.6 +/-0.1; centrifuging at 12000rpm for 5min, taking supernatant, placing into a beaker, placing a fixing plate fixed with the graphite electrode and the alloy electrode which are connected by using conductive adhesive into the beaker, and waiting for 1 min; taking out the fixed plate and unloading the alloy electrode;
collecting spectral data of the alloy electrode by using a laser-induced breakdown spectroscopy system, wherein the laser wavelength of a laser is 1064nm, and the laser energy is 100-150 mJ; the wavelength response range of the spectrometer is 200-880 nm, and the optical resolution is 0.1nm full width at half maximum; and selecting 20 points of the alloy electrode reaction area to acquire data, wherein each point acquires 1 time of spectrum, and calculating the average value of the 20 data to be used as the spectral information data of the sample milk.
3. The method for quantitatively detecting the heavy metal elements in the milk based on the laser-induced breakdown spectroscopy as claimed in claim 1, wherein the specific process of the second step is,
aiming at different elements to be measured, according to an atomic spectrum database of NIST, intercepting wave bands corresponding to the different elements from the spectral information data of the sample milk obtained in the step one; if the element wave bands are discontinuous, splicing the element wave bands; then, selecting variables related to the measured elements by using a high-density wavelet transform algorithm and a competitive adaptive re-weighting algorithm, and deleting irrelevant variables;
randomly distributing the spectrum data of all samples subjected to the spectrum pretreatment to obtain calibration set spectrum data and predicted collection spectrum data;
and (3) measuring the heavy metal elements in the sample milk by adopting an inductively coupled plasma atomic emission spectrometry in the GB5009-2017 standard to obtain the content of the heavy metal elements in the sample milk.
4. The method for quantitatively detecting the heavy metal elements in the milk based on the laser-induced breakdown spectroscopy of claim 3, wherein the specific process of the third step is to combine the spectrum data of the calibration set obtained in the second step with the content of the heavy metal elements in the sample milk obtained in the second step and establish a calibration model by applying a partial least squares regression method; inputting the predicted spectrum data obtained in the second step into a correction model, measuring, comparing the content of heavy metal in the obtained milk with the content of heavy metal elements in sample milk measured by referring to an inductively coupled plasma atomic emission spectrometry in GB5009-2017 standard, and verifying the effect of the correction model.
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