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CN111366649A - Method for measuring 5 anions in eggs and marinated egg products by ion chromatography - Google Patents

Method for measuring 5 anions in eggs and marinated egg products by ion chromatography Download PDF

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CN111366649A
CN111366649A CN202010216842.6A CN202010216842A CN111366649A CN 111366649 A CN111366649 A CN 111366649A CN 202010216842 A CN202010216842 A CN 202010216842A CN 111366649 A CN111366649 A CN 111366649A
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anions
standard
ultrapure water
eggs
solution
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魏益华
张金艳
严寒
昌晓宇
陈庆隆
邱素艳
聂根新
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Institute Of Agricultural Products Quality Safety And Standard Jiangxi Academy Of Agricultural Sciences
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/86Signal analysis
    • G01N30/8624Detection of slopes or peaks; baseline correction
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    • GPHYSICS
    • G01MEASURING; TESTING
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    • G01N30/8675Evaluation, i.e. decoding of the signal into analytical information
    • G01N30/8679Target compound analysis, i.e. whereby a limited number of peaks is analysed
    • GPHYSICS
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N2030/062Preparation extracting sample from raw material

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Abstract

The invention discloses a method for measuring 5 anions in eggs and marinated egg products by ion chromatography, wherein five anions are F、Cl、NO2 、SO4 2‑And NO3 And performing ultrasonic extraction and centrifugal filtration on the sample, and purifying by using a C18 solid phase extraction column. IonPac AS19 is selected AS an analytical column by optimizing ion chromatography conditions, the concentration of KOH eluent is 30.00 mmoL/L, the flow rate is 1.00 mL/mim, the injection volume is 500 muL, and the peak height is quantified by an external standard method. The method can simultaneously determine F in egg and egg product at one time、Cl、NO2 、SO4 2‑And NO3 Anion, simple operation, rapidness, sensitivity and accuracy.

Description

Method for measuring 5 anions in eggs and marinated egg products by ion chromatography
Technical Field
The invention relates to the technical field of ion detection, in particular to a method for determining F in eggs and marinated egg products by using ion chromatography-、Cl-、NO2 -、SO4 2-And NO3 -5 kinds of anion method.
Background
The lack or excessive accumulation of fluorine in human body can cause the occurrence of related diseases, the lack of fluorine is easy to cause dental caries, and the excessive intake of fluorine can cause fluorosis, dental fluorosis, fluorobonosis and the like. Prolonged intake of excessive chlorine can cause hyperchloremia, renal failure, etc. Nitrite enters the body to make hemoglobin in the body lose oxygen carrying capacity, so that suffocation and even death can be caused seriously, and the nitrite can also react with secondary amines in food or stomach to generate ammonium nitrite (carcinogen). The toxicity of nitrate to the human body is mainly caused by reduction to nitrite. The conventional analysis method for determining anions in food has the disadvantages of long operation steps, various related reagents and medicines, large workload and low detection efficiency. Ion chromatography is widely applied to daily monitoring and scientific research of food due to its advantages of rapidness, accuracy, sensitivity and the like. At present, the ion chromatography in food mainly focuses on anions (cations), bromates, organic acids, sugar alcohols, nitrogen and phosphorus, organic phosphorus pesticides, environmental pollutants (such as perchlorate) and the like.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a method for measuring 5 anions in eggs and marinated egg products by using ion chromatography, wherein the 5 anions are F-、Cl-、NO2 -、SO4 2-And NO3 -An ion chromatograph is used for establishing a method for simultaneously measuring F in eggs and egg products-、Cl-、NO2 -、SO4 2-And NO3 -5 kinds of yinThe ion method uses RFC-30 to automatically generate KOH on line AS eluent, uses IonPac AS19 AS an analytical column, and uses an ion chromatograph to quickly and accurately measure F in eggs and marinated eggs by optimizing the flow rate and the intensity of the eluent-、Cl-、NO2 -、SO4 2-And NO3 -5 kinds of anions, and the method is simple, convenient, rapid, sensitive and accurate.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
Method for measuring 5 anions in eggs and marinated egg products by ion chromatography, wherein five anions are F-、Cl-、NO2 -、SO4 2-And NO3 -The method is characterized by comprising the following steps:
(1) sample pretreatment:
weighing 2-5 g (accurate to 0.0001 g) of the homogenized sample, placing the sample in a 250 mL conical flask, adding 30 mL of ultrapure water, and carrying out ultrasonic extraction for 20 min. Standing in 75 deg.C water bath for 30 min, transferring into centrifuge tube, and centrifuging at 10000 r.min-1Centrifuging for 15min, and filtering to fix the volume to a 50 mL volumetric flask. Taking 10 mL of filtrate for 2-3 mL/min-1Flowing through a C18 solid phase extraction column at a certain flow rate, discarding the first 3 mL of effluent, and collecting the effluent to be tested;
(2) preparation of standard solution:
2.2100 g NaF, 1.6480 g NaCl and 1.500 g NaNO are accurately weighed2、1.4890 g Na2SO4、1.3710 gNaNO3,All the drugs were analytically pure, dried at 65 ℃ for 2 h, dissolved in ultrapure water, transferred into different 1000 mL volumetric flasks, respectively, to prepare F-、Cl-、NO2 -、SO4 2-And NO3 -In this case, the concentration of each of the anionic stock solutions was 1000 mg/L. A certain volume was drawn from the above 5 kinds of anion stock solutions, diluted with ultrapure water, and prepared to contain 10mg/L F-、NO2 -And 100mg/L Cl-、SO4 2-、NO3 -And (4) standard mixed liquor. Reused ultrapure waterDiluting the standard mixture to obtain a mixture containing F at concentrations of 0, 0.1, 0.8,. 2 and 4mg/L-、NO2 -A standard working solution; 0.1, 8, 20 and 40 mg/L Cl-、SO4 2-、NO3 -A standard working solution.
(3) Chromatographic conditions are as follows:
DIONEX ICS-1500 ion chromatograph, IonPac AS19 analytical column, Degan company, USA, 30.00 mmoL/L KOH eluent, 1.00 mL/min flow rate, 30 ℃ column temperature, 500 uL sample volume, qualitative retention time, and quantitative external standard peak height. The standard solution is directly processed on a machine to determine the contents of F-, Cl-, NO2-, SO 42-and NO 3-.
Has the advantages that: the conventional analysis method for determining anions in food has the disadvantages of long operation steps, various related reagents and medicines, large workload and low detection efficiency. The ion chromatograph for the experiment establishes a method for simultaneously measuring F in eggs and egg products at one time-、Cl-、NO2 -、SO4 2-And NO3 -5 kinds of anion method, which is simple, fast, sensitive and accurate.
Drawings
FIG. 1 is a spectrum of an egg, a marinated egg, and a standard solution;
in the figure, 1 is an egg, 2 is a marinated egg, and 3 is a standard solution.
Detailed Description
The invention is further illustrated by the following examples and figures.
1. Experimental part
1.1 Instrument and reagent selection:
DIONEX ICS-1500 type ion chromatograph (Daidan, USA), IonPac AG19 (4 × 50 mm) anion protection column, IonPac AS19 type analytical column (4 × 250 0 mm), ASRS 300 (4 mm) anion suppressor, RFC-30 leacheate automatic generator, Bond Elut C18 solid phase extraction small column (Warran, USA), 0.22 um microporous membrane (Tianjin enrichment science and technology Co., Ltd.), SK5200LHC ultrasonic cleaner (Shanghai science and ultrasound apparatus Co., Ltd.), HHS type constant temperature water bath (Shanghai Bo reality medical equipment Co., Ltd.), CR-G III centrifuge (Hitachi, Japan), DZG-303A ultrapure water apparatus (Doudo's Kongning science and technology development Co., Ltd.).
NaF、NaCl、Na2SO4(analytical reagent, national pharmaceutical group chemical Co., Ltd.), NaNO2(analytical purity, Shanghai Fine and Fine institute of technology and technology), NaNO3(analytical purity, Shanghai science Fine Chemicals Co.). The test water is ultrapure water with the resistivity of more than 18.2M omega/cm.
1.2 the detection method comprises the following steps:
(1) sample pretreatment
Weighing 2-5 g (accurate to 0.0001 g) of the homogenized sample, placing the sample in a 250 mL conical flask, adding 30 mL of ultrapure water, and carrying out ultrasonic extraction for 20 min. Standing in 75 deg.C water bath for 30 min, transferring into centrifuge tube, and centrifuging at 10000 r.min-1Centrifuging for 15min, and filtering to fix the volume to a 50 mL volumetric flask. Taking 10 mL of filtrate for 2-3 mL/min-1Flowing through a C18 solid phase extraction column, discarding the first 3 mL of effluent, and collecting the subsequent effluent to be tested.
(2) Preparation of Standard solutions
2.2100 g NaF, 1.6480 g NaCl and 1.500 g NaNO are accurately weighed2、1.4890g Na2SO4、1.3710 gNaNO3(all the drugs were dried at 65 ℃ for 2 hours), dissolved in ultrapure water, transferred into different 1000 mL volumetric flasks, respectively, to prepare F-、Cl-、NO2 -、SO4 2-And NO3 -In this case, the concentration of each of the anionic stock solutions was 1000 mg/L. A certain volume was drawn from the above 5 kinds of anion stock solutions, diluted with ultrapure water, and prepared to contain 10mg/L F-、NO2 -And 100 mg/LCl-、SO4 2-、NO3 -And (4) standard mixed liquor. Diluting the standard mixed solution with ultrapure water to obtain F solutions containing 0, 0.1, 0.8, 2 and 4mg/L-、NO2 -A standard working solution; 0.1, 8, 20 and 40 mg/L Cl-、SO4 2-、NO3 -Standard working solutionAnd (4) liquid.
(3) Chromatographic conditions
IonPac AS19 analytical column, 30.00 m moL/L KOH eluent, 1.00 mL/min flow rate, 30 ℃ column temperature, 500 μ L sample injection amount, qualitative retention time, and quantitative external standard method peak height. The standard solution is directly measured on a machine. The spectrogram of the egg, the marinated egg and the standard solution is shown in figure 1, wherein the spectrogram 1 is the egg, 2 is the marinated egg and 3 is the standard solution.
2 results and discussion
2.1 detection limits, regression equations and correlation coefficients for the method
Detection limit of ion chromatography: DL =2 baseline noise detected ion concentration/detected ion peak height. As can be seen from Table 1, the method is used for F in water samples-、Cl-、NO2 -、SO4 2-And NO3 -The detection limits are 0.003, 0.004, 0.008 and 0.011 mg/L respectively. Therefore, the method is low in detection limit and good in linear relation.
Table 1 method detection limits, regression equations, linear ranges and correlation coefficients
Figure 342643DEST_PATH_IMAGE001
2.2 determination and recovery of samples
The results of the spiking recovery test were shown in Table 2, while the samples were measured. As can be seen from Table 2, F in egg-、Cl-、NO2 -、SO4 2-And NO3 -The concentration is 12.703, 1220.578, 2.090, 137.308 and 7.369 mg/kg respectively, and the standard recovery rate is 90.0-101.5%. The RSD of the 5 anions is 1.53-3.93% when the same egg sample is subjected to parallel measurement for 7 times. In marinated eggs F-、Cl-、NO2 -、SO4 2-And NO3 -The concentrations are 15.424, 1526.569, 0.511, 174.544 and 8.831 mg/kg respectively, and the anion content is except NO2 -The content of anions in the egg is obviously higher than that in the egg.
Figure 122381DEST_PATH_IMAGE002
"*": when Cl is measured, the sample needs to be diluted by 10 times
3 conclusion
The conventional analysis method for determining anions in food has the disadvantages of long operation steps, various related reagents and medicines, large workload and low detection efficiency. The ion chromatograph for the experiment establishes a method for simultaneously measuring F in eggs and egg products at one time-、Cl-、NO2 -、SO4 2-And NO3 -5 kinds of anion method, which is simple, fast, sensitive and accurate.

Claims (1)

1. Method for measuring 5 anions in eggs and marinated egg products by ion chromatography, wherein the 5 anions are F-、Cl-、NO2 -、SO4 2-And NO3 -The method is characterized by comprising the following steps:
(1) sample pretreatment:
weighing 2-5 g of homogenized sample, accurately weighing to 0.0001 g, placing into a 250 mL conical flask, adding 30 mL of ultrapure water, and performing ultrasonic extraction for 20 min; standing in 75 deg.C water bath for 30 min, transferring into centrifuge tube, and centrifuging at 10000 r.min-1Centrifuging for 15min, filtering and fixing the volume to a 50 mL volumetric flask; taking 10 mL of filtrate for 2-3 mL/min-1Flowing through a C18 solid phase extraction column at a certain flow rate, discarding the first 3 mL of effluent, and collecting the effluent to be tested;
(2) preparation of standard solution:
2.2100 g NaF, 1.6480 g NaCl and 1.500 g analytically pure NaNO are accurately weighed21.4890 g of analytically pure Na2SO41.3710 g analytically pure NaNO3,All the drugs were dried at 65 ℃ for 2 h, dissolved in ultrapure water, transferred into different 1000 mL volumetric flasks, respectively, to prepare F-、Cl-、NO2 -、SO4 2-And NO3 -The concentration of each anion stock solution is 1000 mg/L;a certain volume was drawn from the above 5 kinds of anion stock solutions, diluted with ultrapure water, and prepared to contain 10mg/L F-、NO2 -And 100mg/L Cl-、SO4 2-、NO3 -Standard mixed liquor; diluting the standard mixed solution with ultrapure water to obtain F solutions containing 0, 0.1, 0.8, 2 and 4mg/L-、NO2 -A standard working solution; 0.1, 8, 20 and 40 mg/L Cl-、SO4 2-、NO3 -A standard working solution;
(3) chromatographic conditions are as follows:
DIONEX ICS-1500 ion chromatograph, IonPac AS19 analytical column, 30.00 m moL/L KOH eluent, 1.00 mL/min flow rate, 30 deg.C column temperature, 500 μ L sample volume, qualitative retention time, quantitative external standard method peak height, and direct on-machine measurement of F in standard solution-、Cl-、NO2 -、SO4 2-And NO3 -The content of (a).
CN202010216842.6A 2020-03-25 2020-03-25 Method for measuring 5 anions in eggs and marinated egg products by ion chromatography Pending CN111366649A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN113358809A (en) * 2021-06-09 2021-09-07 北京科技大学 Method for determining soluble anions of pollutants on surface of material and application of method
CN115436555A (en) * 2022-10-21 2022-12-06 广州谱临晟科技有限公司 System and method for separating perchlorate or nitrite in food by using multidimensional liquid chromatography
CN115598269A (en) * 2022-10-09 2023-01-13 上海市园林科学规划研究院(Cn) Method for determining fluorine ions and chloride ions in biomass degradation liquid

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113358809A (en) * 2021-06-09 2021-09-07 北京科技大学 Method for determining soluble anions of pollutants on surface of material and application of method
CN115598269A (en) * 2022-10-09 2023-01-13 上海市园林科学规划研究院(Cn) Method for determining fluorine ions and chloride ions in biomass degradation liquid
CN115436555A (en) * 2022-10-21 2022-12-06 广州谱临晟科技有限公司 System and method for separating perchlorate or nitrite in food by using multidimensional liquid chromatography

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Application publication date: 20200703