AU2021102452A4 - Detection Method of Inorganic Lead Ions in Marine Shellfish by HPLC-ICP-MS Technique - Google Patents
Detection Method of Inorganic Lead Ions in Marine Shellfish by HPLC-ICP-MS Technique Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G01N1/4055—Concentrating samples by solubility techniques
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- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/02—Food
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- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/84—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving inorganic compounds or pH
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- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention relates to a detection method of inorganic lead ions in marine shellfish by
HPLC-ICP-MS technique, comprising the following steps: 1) selection of instrument and
equipment, HPLC-ICP-MS coupling system, 2) configuration of reagents and standard
solution, 3) steps of sample processing, 4) instrument conditions used for the experiment, 5)
sample detection and result calculation: chromatography column for cation exchange can
adsorb the inorganic lead ions in the sample extract, and the inorganic lead ions are eluted by
the complexation of oxalic acid on the lead ions in the mobile phase, and the inorganic lead
ions are analyzed by inductively coupled plasma mass spectrometer to obtain the retention time
of the inorganic lead ions and the pulse intensity of their separation. According to the intensity
of the standard series solution and the pulse intensity, the linear regression equation is fitted by
the instrument computer. The present invention can accurately detect inorganic lead elements
in aquatic products, which can accurately and scientifically evaluate the quality and safety of
aquatic products and their quality, and is also important for the development of new standards
for the limits of harmful elements in aquatic products.
1/1
FIGURES
Pb
6000
5000
4000
3000
2000
1000
0.0 0.5 1.0 1.5 20 25 3.0 35 4.0 4.5 5.0
Time (min)
Figure 1
Pb
5500
5000
a4500
4000
3500
3000
0.0 05 1.0 1.5 20 25 3.0 3.5 4.0 4.5 5.0
Time (min)
Figure 2
7000 Pb
6500
6000
5500
5000
4500
3500
3000
0.0 05 1.0 1.5 20 25 30 35 40 45 5.0
Time (min)
Figure 3
Description
1/1 FIGURES
Pb
6000
5000
4000
3000
2000
1000 0.0 0.5 1.0 1.5 20 25 3.0 35 4.0 4.5 5.0 Time (min)
Figure 1
Pb 5500
5000
a4500
4000
3500
3000
0.0 05 1.0 1.5 20 25 3.0 3.5 4.0 4.5 5.0 Time (min)
Figure 2
7000 Pb
6500
6000
5500
5000
4500
3500
3000 0.0 05 1.0 1.5 20 25 30 35 40 45 5.0 Time (min)
Figure 3
Detection Method of Inorganic Lead Ions in Marine Shellfish by HPLC-ICP-MS
Technique
The present invention belongs to the field of aquatic product detection technology, and specifically relates to a method for the detection of inorganic lead ions in aquatic products by effective liquid chromatography-inductively plasma mass spectrometry (HPLC-ICP-MS) technique. BACKGROUND
Lead is one of the toxic heavy metal pollutants, and once it enters the human body, it is very difficult to eliminate. It is harmful to the nervous system, skeletal hematopoietic function, digestive system, male reproductive system, etc., and has a chronic poisoning effect. Lead can directly harm human brain cells, especially the fetal nervous system, which can cause congenital mental retardation, especially children whose brains are in the sensitive period of the nervous system and have special sensitivity to lead. Lead also has carcinogenic and mutagenic effects. The contamination of aquatic products by lead is mainly caused by the discharge of large amount of lead pollutants into water. Lead enters into the surface sediment through ion exchange, adsorption, complexation, flocculation, precipitation and so on, and finally the majority of lead enters into the surface sediment, so that the lead content in the water is reduced. And the large accumulation of lead in sediment has potential pollution and harm. Therefore, lead migrates and transforms between water, substrate and organisms as chemical factors of the water environment change. Aquatic organisms ingest lead contaminants, which cause lead to accumulate in aquatic organisms, thus causing contamination to aquatic products. Shellfish, as a class of mollusk invertebrate aquatic animals with worldwide distribution, is one of the most vulnerable aquatic products contaminated by lead and other heavy metals because of its wide distribution, poor mobility, filter feeding and strong bioaccumulation ability to heavy metals and pollutants. The current method of lead detection is based on the method for the determination of lead in food specified in the national standard GB 5009.12-2017, in which various forms of lead in aquatic products are dissolved into lead by high temperature and strong oxidants (nitric acid and perchloric acid), so the method detects the total amount of lead in aquatic products. Since different forms of lead have different biological toxicity and biological effectiveness, the research on the morphological analysis technique of lead in shellfish is of great significance to improve the quality and safety of shellfish. At present, there is no method standard for the determination of inorganic lead ions in aquatic products in the international ISO and CAC standards. SUMMARY 1. detection method of inorganic lead ions in marine shellfish by HPLC-ICP-MS technique, characterizes in that the method includes the following steps:1) selection of instrument and equipment, HPLC-ICP-MS coupling system, 2) configuration of reagents and standard solution, 3) steps of sample processing, 4) instrument conditions used for the experiment, 5) sample detection and result calculation: The specific steps are as follows. 1) The selection of instruments and equipment include: (1) Liquid chromatograph HPLC: using a SERIES 200 high-pressure liquid pump with an automatic injection device, equipped with a guard column CG5A 4x50 mm and a CS5A 4x250 mm cation exchange column packed with the same material. (2) Inductively coupled plasma mass spectrometer ICP-MS: equipped with dynamic reaction cell, injection system, RF generator, plasma system, Chromera morphological analysis fully automated processing interface, ion lens system, quadrupole, vacuum system, detector and gas circuit control system. 2) Configuration of reagents and standard solutions includes: (1) Extraction solution: 1.0 mmol/L acetic acid (2) Mobile phase: 50 mM oxalic acid + 95 mM lithium hydroxide solution pH=4.8, filtered through a 0.22 m membrane and degassed by ultrasound before use. (3) Standard using solution for inorganic lead ions. Dilute 1000pg/mL Pb ion standard solution to 1.00pg/mL reserve solution, store at 4°C in the refrigerator, dilute 1.00pg/mL Pb ion reserve solution with water to 10.Ong/mL, 20.0 ng/mL, 50.0 ng/mL, 100.0 ng/mL, 200.0 ng/mL standard-use solution. The solution should be prepared on the spot.
3) Steps of sample processing:
After homogenize the shellfish samples,freeze-dry and grind the sample, weigh the samples in centrifuge tubes, add the extracted solution before vortex mixing, ultrasonically extract, centrifuge, take out the supernatant and filter with aqueous microporous filter membrane for the sample solution to be measured, transfer into the sample bottle, test the value of lead ions in the sample solution to be measured through machine. 4) Instrumental conditions used for the experiment. (1) High performance liquid chromatography conditions: mobile phase was 50mM oxalic acid + 95 mM lithium hydroxide mixed solution, pH of the mixed solution to 4.8
, flow rate 1.0 mL/min; injection volume 20 L,with automatic injection. (2) Inductively coupled plasma mass spectrometer conditions: RF power 1150 W, plasma gas flow rate: 15 L/min, atomization gas flow rate 0.92 L/min, lens voltage 7.00 V, auxiliary gas flow rate 1.2 L/min, detector analog stage voltage -1800 V, detector pulse stage voltage 900 V, mass passband width 0.25, sampling time 5 min. The pH of the 50 mM oxalic acid + 95 mM lithium hydroxide mixture was adjusted with aqueous lithium hydroxide solution. 5) Sample detection and result calculation:
After turning on the machine, the instrument was set up according to the above instrument conditions, and after being stabilized, the standard curve was made first, and then the prepared sample solution to be measured was measured; 20 L of the sample was injected into the fully automatic injector under the above conditions of high-performance liquid chromatography and inductively coupled plasma mass spectrometer for detection and the high performance liquid chromatograph was used for separation, and the inductively coupled plasma mass spectrometer was used for detection of lead ions; the retention time of lead ions under the above instrument conditions was 2.4 min. Quantification: the peak retention time of lead ion in the sample solution to be measured is considered to be the substance to be measured if it changes within 10% compared with the standard solution used Calculation and presentation of results: Using the external standard method in the data processing software, the retention time and separation pulse intensity of lead ions are determined, and the standard working curve is drawn with the concentration as the horizontal coordinate and the pulse intensity integral as the vertical coordinate, and then the peaks of the sample solution to be measured are analyzed and processed to obtain the concentration of inorganic lead ions in the sample solution to be measured, according to the following equation (1). (1) X=CxV/mx1000 X-content of inorganic lead ions in the sample, mg/kg. C- concentration of inorganic lead ions in the sample solution to be measured, ng/mL. M-weighing volume of the sample, g. V-Total volume of the measured liquid, mL. The beneficial effects of the present invention compared with the prior art are. 1. The present invention uses high performance liquid chromatography-inductively coupled plasma mass spectrometry to analyze inorganic lead ions in seafood shellfish. The extract is firstly separated from inorganic lead ions in the extract by high performance liquid chromatography, using cation exchange chromatography technique, and then analyzed by inductively coupled plasma mass spectrometer as a detector. The cation exchange chromatographic column can adsorb the inorganic lead ions in the extraction solution, and the inorganic lead ions are eluted by the complexation of oxalic acid on the lead ions in the mobile phase, and the inorganic lead ions are analyzed by inductively coupled plasma mass spectrometer to obtain the retention time of the inorganic lead ions and the pulse intensity of their separation. The linear regression equation was obtained by fitting the instrument computer according to the intensity and pulse intensity integral of the standard series solution. The experimental conditions were chosen reasonably, and the detection data were accurate and reliable. 2. The present invention uses 1.0 mmol/L acetic acid for ultrasonic extraction of lead in shellfish, which can extract the water-soluble and exchangeable forms of lead in the sample. The cation exchange column can adsorb the inorganic lead ions in the extraction solution, and the mobile phase used has strong complexation of oxalic acid to lead ions and forms soluble complexes, so it can adsorb and elute the inorganic forms of lead ions in the extraction solution. A good separation of lead ions in the sample was achieved. 3, The invention fills the blank of only total lead detection method but no lead element form the method in the current national standard, which can accurately and scientifically evaluate the quality and safety of aquatic products and their products, and at the same time, it is of great significance to the development of new standards for the limit of harmful elements in aquatic products.
Fig. 1 Chromatogram of 20ng/mL Pb(II) standard solution. Figure 2 Analytical chromatogram of Pb(II) in scallop. Figure 3 Analytical chromatogram of Pb(II) in Mactra veneriformis DESCRIPTION OF THE INVENTION
The technical solutions of the present invention are described in detail below by means of embodiments, but the scope of protection of the present invention is not limited in any form by the embodiments.The present invention is a method for the analysis of inorganic lead ions in shellfish using high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS technique) comprising the following steps: 1) selection of instrument and equipment, 2) configuration of reagents and standard solution, 3) steps of sample processing, 4) instrument conditions used for the experiment, 5) sample detection and result calculation. Shellfish, including Pectinidae, Ostrea gigas tnunb, Ruditapes philippinarum, Mactra veneriformis, Mytilus edulis, etc., have a much higher enrichment capacity for heavy metals than fish, shrimp, crabs and other aquatic products because of their poor mobility and filter feeding characteristics during their growth. During our risk monitoring of heavy metals in major seafood shellfish in China, we found that the lead content in different shellfish varied greatly, so we selected Pectinidae and Mactra veneriformis, which have higher lead content, as the implementation examples for validation. Example 1: Detection of inorganic lead ions, i.e. Pb(II), in Mactra veneriformis. 1. selection of instrument and equipment: HPLC- ICP-MS combined system. (1) HPLC (Perkin-Elmer, USA, model Series 200) section: using a SERIES 200 high pressure liquid pump with autosampler, equipped with a guard column CG5A 4x50mm and a CS5A 4x250mm cation exchange column packed with the same material. (2) ICP-MS (Perkin-Elmer, USA, model ELAN DRC II) section: equipped with dynamic reaction cell, automatic injection system, RF generator, plasma system, Chromera morphological analysis fully automated processing interface, ion lens system, quadrupole, vacuum system, detector, gas circuit control system. (3) Cooling circulating water (POLYSCIENCE, USA, model SHA-C). (4) vortex mixer (IKA MS 3 basic). (5) pure water system (U.S. Millipore, Milli-Q Gradient A10). (6) circulating vacuum sand core filter pump (vacuum pump, Shanghai Yarong Biochemical Instrument Factory, model SHZ-III; sand core filter device, model SH/T0093). (7) high-speed frozen centrifuge (Thermo, model D-37520). (8) CNC ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd., model KQ 600DE). (9) aqueous microporous filter membrane (0.22 m). (10) argon gas (purity > 99.99%). 2. Configuration of reagents and standard solutions. (1) extraction solution: 1.0 mmol/L acetic acid. (2) mobile phase: 50 mM oxalic acid + 95 mM lithium hydroxide solution (pH=4.8), filtered through 0.22 m membrane and degassed by ultrasound before use. All reagents were of superior-level purity, and ultrapure water was used throughout the experiment; the glass instruments were soaked in 15% nitric acid for 24 h before use. (2)Standard use solution for inorganic lead ion Pb(II). The standard solution of 1000 pg/mL Pb(II) was purchased from the National Center for Reference Materials and diluted to 1.00 pg/mL as Pb(II) stock solution (stored at 4°C in the refrigerator); the 1.00 pg/mL Pb(II) stock solution was diluted with water into 10.0 ng/mL, 20.0 ng/mL, 50.0 ng/mL, 100.0 ng/mL, and 200.0 ng/mL. ng/mL, 200.0 ng/mL of Pb(II) standard use solution.The solution should be prepared on the spot. 3.Step of sample processing:. The homogenized Pectinidae sample was frozen at -20°C and then freeze-dried under vacuum, crushed, weighed about 0.2000g of powder in a 50mL stoppered centrifuge tube, mixed with 15mL of 1.Ommol/L acetic acid, sonicated for 40min, centrifuged at 8000r/min 4°C for 10min, the supernatant was removed and filtered with 0.22 micron aqueous microporous filter membrane, transferred into the sample injection. The value of inorganic lead ions in the sample solution to be measured was determined by the machine. 4. Instrumental conditions used for the experiment. (1) High performance liquid chromatography conditions (HPLC): mobile phase: 50 mM oxalic acid + 95 mM lithium hydroxide solution (pH=4.8), flow rate 1 mL/min; injection volume 20 L, automatic injection. (2) Inductively coupled plasma mass spectrometer conditions (ICP-MS): RF power 1150 W, plasma gas flow rate 15 L/min, atomization gas flow rate 0.92 L/min, lens voltage 7.00 V, auxiliary gas flow rate 1.2 L/min, detector analog stage voltage -1800 V, detector pulse stage voltage 900 V, mass passband bandwidth 0.25. Sampling time 5 min. 5, Sample detection and result calculation:
(1) Qualitative: After turning on the machine, set up according to the above conditions, wait for stabilization, take 1mL of the standard use solution and transfer it into the injection bottle, inject the sample into the high performance liquid chromatograph (HPLC) automatically, elute and separate the components, then apply the inductively coupled plasma mass spectrometer (ICP/MS) as the detector to analyze Pb(II), determine the retention time of Pb(II) and its separation of the pulse intensity, with the concentration as the horizontal coordinate and the integration of the pulse intensity as the vertical coordinate, and a linear fit was made by the computer of the instrument to obtain the equation of the standard curve. Under the above conditions of high performance liquid chromatography and inductively coupled plasma mass spectrometer, 20 L of sample extract was injected into a full auto injector for detection, and the separation was performed by high performance liquid chromatography, and Pb(II) was detected by inductively coupled plasma mass spectrometer; the retention time of Pb(II) under the above instrument conditions was about 2.4 min; see Figure 1 for details. (2) Quantification: the peak retention time of Pb(II) in the sample to be measured is considered to be the substance to be measured if it changes within 10% compared with the standard solution. Calculation and presentation of results. Using the external standard method in the data processing software (chromera), the retention time and separation pulse intensity of Pb (II) were determined, and the standard working curve was plotted with the concentration as the horizontal coordinate and the pulse intensity integral as the vertical coordinate, and the standard working curve was saved, and then the sample peaks were analyzed and processed to obtain the concentration of Pb (II) in the sample solution to be measured, which was calculated according to the following formula (1), and the Pb (II) in the sample could be obtained The content of Pb(II) in the sample can be calculated according to the following formula (1). (1)X=CxV/mx1000 X-content of inorganic lead ions in the sample, mg/kg. C- concentration of inorganic lead ions in the sample solution to be measured, ng/mL. M-weighing volume of the sample, g. V-Total volume of the measured liquid, mL. 6. Results. The detection limit of Pb (II) in this method is 0.30 mg/kg. By the spiked recovery test on scallop samples, the recovery was >83% with the relative standard deviation <5%, which proved the feasibility of the above detection method. The detection method for inorganic lead ions in Mactra veneriformis was the same as that for Pectinidae, and the results of the spiked recoveries for Pectinidae and Mactra veneriformis are shown in Table 1.
Table 1 Pectinidae and Mactra veneriformis spiked recovery detection results Elements variety Backgr Spiked Measurement Reco Concentr ound concentration ng/mL very ation measur ng/mL % mg/Kg ement ng/mL Pb (II) Pectinida 10.80 10 19.47 86.7 0.81 e Mactra 13.07 10 21.45 83.8 0.98 venerifor mis
In order to ensure the accuracy and reliability of the experimental data, we took the following measures: ( the shellfish tissues were first homogenized uniformly, frozen at °C and then crushed uniformly by vacuum freeze-drying, which can improve the uniformity of the samples and make the samples representative and completely extracted; the extraction with 1.0 mmol/L acetic acid extract can ensure the extraction of the water-soluble and exchangeable Pb in the samples; @ the selected protective column CG5A 4x 50mm, analytical column CS5A 4x250mm cation exchange column can adsorb the ionic state Pb(II), and then form soluble complexes by complexation of oxalic acid, which is eluted to make the ionic state Pb well separated, see Figure 2 and Figure 3. Therefore, high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) technique is the preferred method for the analysis of inorganic lead ions in seafood shellfish. This method has high recovery, good stability, high sensitivity and easy pre-treatment, which solves the problem of analyzing inorganic lead ions with high toxicity in aquatic products, especially for seafood shellfish such as Pectinidae,Ostreagigas tnunb and Mactra with high enrichment characteristics, this method can more clearly and accurately reflect the content of inorganic lead ions in them, which provides important technical support for scientific and accurate quality and safety evaluation.
Claims (5)
1. A method for the detection of inorganic lead ions in marine shellfish by HPLC ICP-MS technique, characterized in that the method comprises the steps of 1) selection of instrument and equipment, HPLC-ICP-MS coupling system, 2) configuration of reagents and standard solution, 3) steps of sample processing, 4) instrument conditions used for the experiment, 5) sample detection and result calculation: The specific steps are as follows. 1) The selection of instruments and equipment include: (1) Liquid chromatograph HPLC: using a SERIES 200 high-pressure liquid pump with an automatic injection device, equipped with a guard column CG5A 4x50 mm and a CS5A 4x250 mm cation exchange column packed with the same material. (2) Inductively coupled plasma mass spectrometer ICP-MS: equipped with dynamic reaction cell, injection system, RE generator, plasma system, Chromera morphological analysis fully automated processing interface, ion lens system, quadrupole, vacuum system, detector and gas circuit control system.
2) Configuration of reagents and standard solutions includes: (1) Extraction solution: 1.0 mmol/L acetic acid (2) Mobile phase: 50 mM oxalic acid + 95 mM lithium hydroxide solution pH=4.8, filtered through a 0.22 m membrane and degassed by ultrasound before use. (3) Standard using solution for inorganic lead ions. Dilute 1000pg/mL Pb ion standard solution to 1.00pg/mL reserve solution, store at 4°C in the refrigerator, dilute 1.00pg/mL Pb ion reserve solution with water to 10.ng/mL, 20.0 ng/mL, 50.0 ng/mL, 100.0 ng/mL, 200.0 ng/mL standard-use solution. The solution should be prepared on the spot.
3) Steps of sample processing:
After homogenize the shellfish samples,freeze-dry and grind the sample, weigh the samples in centrifuge tubes, add the extracted solution before vortex mixing, ultrasonically extract, centrifuge, take out the supernatant and filter with aqueous microporous filter membrane for the sample solution to be measured, transfer into the sample bottle, test the value of lead ions in the sample solution to be measured through machine.
4) Instrumental conditions used for the experiment. (1) High performance liquid chromatography conditions: mobile phase was 50 mM oxalic acid + 95 mM lithium hydroxide mixed solution, pH of the mixed solution to 4.8
, flow rate 1.0 mL/min; injection volume 20 L,with automatic injection. (2) Inductively coupled plasma mass spectrometer conditions: RF power 1150 W, plasma gas flow rate: 15 L/min, atomization gas flow rate 0.92 L/min, lens voltage 7.00 V, auxiliary gas flow rate 1.2 L/min, detector analog stage voltage -1800 V, detector pulse stage voltage 900 V, mass passband width 0.25, sampling time 5 min. The pH of the 50 mM oxalic acid + 95 mM lithium hydroxide mixture was adjusted with aqueous lithium hydroxide solution.
5) Sample detection and result calculation: After turning on the machine, the instrument was set up according to the above instrument conditions, and after being stabilized, the standard curve was made first, and then the prepared sample solution to be measured was measured; 20 L of the sample was injected into the fully automatic injector under the above conditions of high-performance liquid chromatography and inductively coupled plasma mass spectrometer for detection and the high performance liquid chromatograph was used for separation, and the inductively coupled plasma mass spectrometer was used for detection of lead ions; the retention time of lead ions under the above instrument conditions was 2.4 min. Quantification: the peak retention time of lead ion in the sample solution to be measured is considered to be the substance to be measured if it changes within 10% compared with the standard solution used Calculation and presentation of results: Using the external standard method in the data processing software, the retention time and separation pulse intensity of lead ions are determined, and the standard working curve is drawn with the concentration as the horizontal coordinate and the pulse intensity integral as the vertical coordinate, and then the peaks of the sample solution to be measured are analyzed and processed to obtain the concentration of inorganic lead ions in the sample solution to be measured, according to the following equation (1).
(1)X=CxV/mx1000 X-content of inorganic lead ions in the sample, mg/kg. C- concentration of inorganic lead ions in the sample solution to be measured, ng/mL. M-weighing volume of the sample, g. 2. The method according to claim 1, characterized in that all the reagents in step 2) configuration of reagents and standard solutions are of superior purity, and the water used throughout the experiment is ultra-pure water; the glass apparatus is soaked in 15% nitric acid for 24h before use. 3. The method according to claim 1, characterized in that the pH concentration of the 50 mM oxalic acid + 95 mM lithium hydroxide mixed solution in step 2) configuration reagents and standard solution is adjusted with lithium hydroxide aqueous solution.
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