CN111830182A - Method for simultaneously determining various arsenic forms in food - Google Patents
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Abstract
The invention discloses a method for simultaneously measuring various arsenic form compounds, which comprises the following steps: extracting and purifying arsenic form in food by shaking table, introducing into high performance liquid chromatograph, and separating with mobile phase of 0.5mmol/L (NH)4)2CO3(pH8.5) and 50mmol/L (NH)4)2CO3(pH8.5) after gradient elution separation, detecting the arsenic forms separated at different times by using an inductively coupled plasma mass spectrometer, taking the retention time as the qualitative property, and quantifying by adopting a peak area external standard method. The method can simultaneously determine 9 kinds of arsenic forms in food, including arsenous acid [ As (III)]Arsenic acid [ As (V)]Methyl Arsenic (MMA), dimethyl arsenic (DMA), arsenic betaine (AsB), arsenic choline (AsC), 4-aminophenylarsenic acid (p-ASA), Roxarsone (ROX) and 2-aminophenylarsenic acid (o-ASA), the method is quick, simple, accurate, sensitive and good in reproducibility, and makes up the defect that the standard and literature can only simultaneously measure 4-6 arsenic formsThe method has important practical significance for reasonably evaluating the food quality safety, and is suitable for popularization and application in detection institutions or laboratories.
Description
Technical Field
The invention relates to a method for determining morphological compounds, in particular to a method for analyzing and determining various arsenic morphologies in food, belonging to the technical field of chemical detection and analysis.
Background
Arsenic is an element widely distributed in nature, and common arsenic compounds are: arsenous acid [ As (III) ], arsenic acid [ As (V) ], monomethylarsenic acid (MMA), dimethylarsenic acid (DMA), arsenobetaine (AsB), arsine (AsC), 4-aminophenylarsenic acid (p-ASA), Roxarsine (ROX), 2-aminophenylarsenic acid (o-ASA). The biological toxicity of arsenic is not only related to its content, but is largely determined by its existing form, and the toxicity of compounds with different forms of arsenic is greatly different. Inorganic arsenic is the most toxic, organic arsenic is less toxic, the more arsenic is bound to organic groups the less toxic, and generally, arsenobetaine and arsine are considered non-toxic. It is therefore not scientific to test only the total arsenic amount without indicating the arsenic form when evaluating food safety. Arsenic morphometry has become an important research method for modern chemical analysis. Currently, domestic arsenic form detection can only detect 4-6 arsenic forms generally, and no national standard or industrial standard method is available for simultaneously determining the content of more types of arsenic form compounds in food. In the national standard, the liquid chromatography (HPLC) -Atomic Fluorescence (AFS) combined system is used for detecting food, the method can only detect four arsenic forms of arsenous acid [ As (III) ], arsenic acid [ As (V) ], monomethylarsenic acid (MMA) and dimethyl arsenic acid (DMA), and cannot detect the arsenic betaine (AsB) which is a main component in food: in addition, the second method of the national standard utilizes a method of combining liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS), only arsenous acid [ As (III) ], arsenic acid [ As (V) ], monomethylarsenic acid (MMA), dimethyl arsenic acid (DMA) and arsenic betaine (AsB) can be detected, and the arsenic compound, namely arsenic choline (AsC), which is high in content and is common in marine products can not be detected.
Disclosure of the invention
In order to overcome the above prior art, the present invention provides a rapid, simple, accurate and sensitive method for determining various forms of arsenic in food: arsenous acid [ As (III) ], arsenic acid [ As (V) ], monomethylarsenic acid (MMA), dimethyl arsenic acid (DMA), arsenic betaine (AsB), arsenic choline (AsC), 4-aminophenylarsenic acid (p-ASA), Roxarsone (ROX) and 2-aminophenylarsenic acid (o-ASA) so as to meet the requirements of various social circles on food quality safety analysis results.
The invention provides a method for analyzing and determining element morphology, which is a High Performance Liquid Chromatography (HPLC) -inductively coupled plasma mass spectrometry (ICP-MS) combined morphology analysis method and comprises the following steps: the food is crushed (solid) or pulped (fresh sample), then is subjected to shaking table oscillation extraction, is separated by a high performance liquid chromatograph after being purified, and then enters an inductively coupled plasma mass spectrometer for detection.
Homogenizing the sample, crushing or pulping, performing ultrasonic extraction, centrifuging at low temperature, and filtering with microporous membrane to obtain clear solution.
Adding 50 mu L of disodium ethylene diamine tetraacetate solution with the concentration of 100mmol/L into 1mL of clear liquid to obtain a solution to be detected, and adding the disodium ethylene diamine tetraacetate enables the arsenic form compound and the arsenic form compound to form an anionic complex compound, so that strong retention characteristics are generated in a chromatographic column, and the arsenic forms are separated.
The liquid to be detected enters HPCL-ICP-MS for detection, and the conditions of a detection instrument are as follows:
the sample volume is 50 mu L;
mobile phase A: 0.5mmol/L ammonium carbonate [ (NH)4)2CO3](pH＝8.5)；
Mobile phase B: 50mmol/L ammonium carbonate [ (NH)4)2CO3](pH＝8.5)；
Gradient elution;
gradient elution conditions gradient elution was performed according to the conditions in table 1.
TABLE 1
Anion chromatography column: hamilton PRP-X100 anion analysis column (250 mm. times.4 mm, 10 μm) + protective column core PRP-X100(RP1Kit 5/Pk) + protective column jacket PRP-X100.
ICP-MS conditions: mass number 75(As), m/z acquisition mode: TRA, sampling period: 1.0s, acquisition time: 1200s, carrier gas: high purity liquid argon (purity 99.99%), atomizer: concentric atomizer, carrier gas flow rate: 1.0L/min, flow rate of auxiliary gas: 0L/min.
The invention solves the problem that various arsenic forms can not be simultaneously measured in food, and can simultaneously analyze and measure arsenous acid [ As (III) ], arsenic acid [ As (V) ], monomethylarsenic acid (MMA), dimethyl arsenic acid (DMA), arsenic betaine (AsB), arsenic choline (AsC), 4-aminophenylarsenic acid (p-ASA), Rocksaarsenic (ROX) and 2-aminophenylarsenic acid (o-ASA). Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) a nontoxic extraction reagent is adopted, so that the situation that an experimenter inhales toxic substances in the operation process is avoided;
(2) complex and fussy pretreatment process is cancelled, and pretreatment time and cost are saved;
(3) the varieties of arsenic forms detected at the same time at least reach 9 types, and the defect that the standard and the method can only detect 4-6 types of arsenic forms at the same time is overcome;
(4) the method has the advantages that the peak emergence time is fast, the arsenic form peak emergence time is 20min, the peak emergence time of 6 most common arsenic forms of arsenous acid [ As (III) ], arsenic acid [ As (V) ], methyl arsenate (MMA), dimethyl arsenate (DMA), arsenic betaine (AsB) and arsenic choline (AsC) is less than 6min, and the defect that the 6 substances need 12-20 min elution time in the standard and method is overcome.
(5) The sensitivity is good, the detection limits of arsenous acid [ As (III) ], arsenic acid [ As (V) ], monomethylarsenic acid (MMA), dimethyl arsenic acid (DMA), arsenic betaine (AsB), arsenic choline (AsC) and 4-aminobenzene arsenic acid (p-ASA) are below 1 mu g/L, and the detection limits of Rocksaarsenic (ROX) and 2-aminobenzene arsenic acid (o-ASA) are below 10 mu g/L.
(6) The reproducibility was good, with RSD at one-time detection limit addition level of 15% (n-6).
Based on the advantages, the method can quickly, simply and accurately analyze and quantify 9 arsenic forms in the food simultaneously, has important practical significance for reasonably evaluating the food quality safety, and is suitable for popularization and application in detection institutions or laboratories.
Drawings
FIG. 1: method operation flow chart
FIG. 2: chromatogram of 9 arsenic forms
FIG. 3: standard curve of 9 arsenic forms
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example of implementation: determination of arsenic form in cultured shrimps:
1. instrument and apparatus
1.1 HPLC: agilent 1200, with Hamilton PRP-X100 anion analysis column (250 mm. times.4 mm, 10 μm) + protective column core PRP-X100(RP1Kit 5/Pk) + protective column jacket PRP-X100.
1.2 ICP-MS: agilent 7700, with concentric glass atomizer.
1.3 analytical balance: METTLER TOLEDO MS3002 SE/01.
1.4 shaking Table Oscillator (IKA-WERKE HS 501).
1.5 high speed centrifuge (Hettich).
1.6 pH Meter (METTLER).
1.7 ultrapure water treatment system (Millipoplus 2150).
1.8 aqueous microporous membrane (0.45 μm).
1.9 Polytetrafluoroethylene centrifuge tubes (50mL and 1.5 mL).
1.10 sample vial (1.5 mL).
2. Reagent and standard solution
2.1 reagents
2.1.1 ammonium carbonate: and (5) analyzing and purifying.
2.1.2 methanol: HPLC grade.
2.1.3 formic acid: and (5) analyzing purity, and adjusting the pH value of the mobile phase.
2.1.4 Ammonia: and (5) analyzing purity, and adjusting the pH value of the mobile phase.
2.1.5 disodium edetate: HPLC grade.
2.1.6100 mmol/L disodium ethylenediaminetetraacetate solution: 3.7224g of disodium diamine tetraacetate was dissolved in 100mL of water.
2.1.7 0.5mmol/L(NH4)2CO3(pH 8.5): 7.8560g (NH) was taken4)2CO3Dissolved in 1000mL of water, and adjusted to pH8.5 with aqueous ammonia, hereinafter referred to as mobile phase A.
2.1.8 50mmol/L(NH4)2CO3(pH 8.5): 0.0786g (NH) was taken4)2CO3Dissolved in 1000mL of water, and adjusted to pH8.5 with formic acid, hereinafter referred to as mobile phase B.
2.2 Standard substance
2.2.1 arsenic standard stock solution: as (III) (GBW0866, concentration 75.7 + -1.2 mg/L), As (V) (GBW08667, concentration 17.5 + -0.4 mg/L), MMA (GBW08668, concentration 46.2 + -1.5 mg/L), DMA (GBW08669, concentration 97.4 + -3.3 mg/L), AsB (GBW08670, concentration 92.2 + -2.7 mg/L), AsC (GBW08671, concentration 91.6 + -3.7 mg/L)
2.2.2 arsenic standards (solids): ROX (16820200), p-ASA (10300250), o-ASA (F58WD-HK)
2.2.31000 μ g/mL ROX, p-ASA, o-ASA Standard stock solutions: accurately weighing 100.0mg of ROX, p-ASA and o-ASA, dissolving with water, diluting to a constant volume in a 100mL volumetric flask, and preparing into 1000 microgram/mL ROX, p-ASA and o-ASA stock solutions.
2.2.41 μ g/mL arsenic Compound Standard use solution:
as (III) Standard use solution at 1. mu.g/mL: 0.1g of As (III) standard stock solution was weighed out and made up to 12.43g with water.
As (V) Standard use solution at 1. mu.g/mL: 0.2g of As (V) standard stock solution is weighed out and made up to 6.48g with water.
MMA Standard at 1. mu.g/mL use solution: 0.2g of MMA standard stock solution was weighed out and made up to 9.24g with water.
1 μ g/mL of DMA Standard use solution: 0.1g of DMA standard stock solution was weighed out and made up to 9.74g with water.
1 μ g/mL of AsB standard use solution: 0.1g of AsB standard stock solution was weighed out and made up to 9.22g with water.
1 μ g/mL of AsC standard use solution: 0.1g of AsC standard stock solution was weighed out and made up to 9.16g with water.
ROX standard use solution at 1. mu.g/mL: 10. mu.L of ROX standard stock solution with a concentration of 1000. mu.g/mL was pipetted and quantified to 10mL to prepare 1. mu.g/mL of standard use solution.
1 μ g/mL of p-ASA standard using solution: 10. mu.L of p-ASA standard stock solution with a concentration of 1000. mu.g/mL was pipetted and quantified to 10mL to prepare a 1. mu.g/mL standard use solution.
1 μ g/mL o-ASA standard used solutions: 10. mu.L of o-ASA standard stock solution with a concentration of 1000. mu.g/mL was pipetted and quantified to 10mL to prepare a 1. mu.g/mL standard use solution.
2.2.5 Mass Spectrometry tuning fluids: y, Ce at 10. mu.g/L, available from Agilent, 1% HNO before use3Diluted to 50. mu.g/L.
2.2.6 Standard Curve series solutions: 0, 1, 5, 10, 50 and 100 mu L of each standard use solution with the concentration of AsC, As (III), DMA, MMA, As (V), p-ASA, ROX and o-ASA being 1 mu g/mL is sucked, the volume is increased to 1mL by water, so As to prepare 0, 1, 5, 10, 50 and 100 mu g/L of standard series solution, and 50 mu L of disodium ethylene diamine tetraacetate solution with the concentration of 100mmol/L is added before the solution is fed into an HPLC-ICP-MS machine.
3. Measurement procedure
3.1 weighing 1.0g of the cultured shrimps which are homogenized and pulped in the stirrer, placing the weighed cultured shrimps in a 50mL centrifuge tube, adding 20mL deionized water, covering the centrifuge tube with a cover, shaking the mixture evenly, and performing shaking extraction for 2 hours in a shaking table at 300 r/min. Add 1mL acetic acid and shake. And (3) placing the sample liquid in a refrigerator at the temperature of-18 ℃ for 1-2 hours or overnight in a refrigerator at the temperature of 0-6 ℃ to solidify the grease in the sample liquid and stratify the grease with the clear liquid in the sample liquid.
3.2 taking 1.5mL of the clear extraction liquid to a centrifuge tube, setting the temperature of the centrifuge to be-2 ℃, and centrifuging for 10min at 14000 r/min.
3.5 draw 1mL of supernatant through a 0.45 μm filter into a sample vial, and add 50 μ L of 100mmol/L disodium EDTA solution before loading on the HPLC-ICP-MS machine.
3.6 HPLC conditions: hamilton PRP-X100 anion analysis column (250mm X4 mm, 10 μm) + protective column core PRP-X100(RP1Kit 5/Pk) + protective column sleeve PRP-X100; sample introduction amount: 50 mu L of the solution; gradient elution, mobile phase a: 0.5mmol/L (NH)4)2CO3(pH8.5), mobile phase B: 50mmol/L (NH)4)2CO3(pH＝8.5)。
3.7 gradient elution conditions, gradient elution was performed according to the conditions of Table 1.
3.8 ICP-MS conditions: mass number 75(As), m/z acquisition mode: TRA, sampling period: 1.0s, acquisition time: 1200s, carrier gas: high purity liquid argon (purity 99.99%), atomizer: concentric atomizer, carrier gas flow rate: 1.0L/min, flow rate of auxiliary gas: 0L/min.
3.9 tuning: the ICP-MS instrument tuning, He mode selection and mass number selection are required before the sample testing89Y，156CeO，140Ce，70Ce++，78ArAr is used for adjustment, and the tuning result needs to be as follows:89the Y count is greater than 6000CPS,78ArAr count < 10CPS, percent count156CeO/140Ce is less than 3 percent, and the counting percentage is70Ce++/140Ce＜1.5％。
3.10 detection: and after tuning is finished, connecting a remote port of the HLPC automatic sample injector module and a remote port of the ICP-MS by using a connecting wire, and connecting a peak pipe at the outlet end of the chromatographic column to a sample inlet of the atomizer. The ICP-MS window of operation adds the batch to the queue and the HPLC window of operation clicks "start" to elute the arsenic form.
4. Result settlement
4.1 qualitative: and after starting up, setting according to the conditions, and connecting the ports of the HPLC and the ICP-MS when the tuning parameters meet the requirements. And detecting the standard solution to obtain the retention time and the standard peak area of each compound, and quantifying by adopting a peak area external standard method. Under the above conditions of the chromatographic mass spectrometry, the retention times of arsenous acid [ As (III) ], arsenic acid [ As (V) ], monomethylarsenic acid (MMA), dimethylarsenic acid (DMA), arsenobetaine (AsB), arsine (AsC), 4-aminophenylarsenic acid (p-ASA), Roxarsine (ROX) and 2-aminophenylarsenic acid (o-ASA) were 1.99, 2.39, 3.19, 4.28, 4.95, 5.72, 6.47, 14.91 and 17.68min, respectively.
4.2 quantification: the substance to be measured is determined as arsenous acid (As (III)), arsenic acid [ As (V) ], monomethyl arsenic acid (MMA), dimethyl arsenic acid (DMA), arsenic betaine (AsB), arsenopyrine (AsC), 4-aminophenylarsenic acid (p-ASA), Roxarsone (ROX) and 2-aminophenylarsenic acid (o-ASA) in the sample to be measured, wherein the change range of the retention time of the chromatographic peak is +/-5% compared with that of the standard solution.
4.3 calculation of results
The content of the substance to be measured in the sample is calculated according to the formula (1)
In the formula:
the content of a substance to be detected in the X-shaped sample is mg/kg;
c0-the content of the substance to be measured in the blank solution in μ g/L;
c, measuring the content of the substance to be measured in the solution, wherein the unit is mu g/L;
v represents the total volume of the sample solution, and the unit is mL;
m-sample weighing, wherein the unit is g;
1000-conversion factor.
5. Results and discussion
The linear regression equation for the 9 arsenic morphs is shown in Table 2 below
TABLE 2
The recovery rate of the cultured shrimps with the added standard (50 mug/L) is shown in Table 3
TABLE 3
ND＝not detected
As can be seen from Table 3, the recovery rate and the coefficient of variation of the experiment are both ideal and meet the requirements of the national standard GB/T27404-.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, therefore, any simple modifications and equivalent changes made to the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (6)
1. A method for simultaneously determining the forms of various arsenic in food, comprising arsenous acid [ As (III) ], arsenic acid [ As (V) ], monomethylarsenic (MMA), Dimethylarsine (DMA), arsenobetaine (AsB), arsine-choline (AsC), 4-aminophenylarsenic acid (p-ASA), Roxarsine (ROX), 2-aminophenylarsenic acid (o-ASA), characterized by comprising the following steps:
(1) a suitable sample extraction solvent, extraction method and purification technology;
(2) a suitable ion chelating agent enhances the separation effect of each arsenic form;
(3) separating 9 arsenic forms by adopting proper high performance liquid chromatography separation conditions to achieve baseline separation;
(4) and adopting a proper inductively coupled plasma mass spectrometry condition to simultaneously detect 9 arsenic forms.
2. The method of claim 1, further characterized by: in the step (1), the extraction solvent is deionized water; the extraction method comprises shaking extraction with a shaking table at 300 r/min; the purification technology comprises the steps of placing the extracted sample liquid in a refrigerator at the temperature of 18 ℃ below zero for 1-2 hours or a refrigerator at the temperature of 0-6 ℃ overnight to solidify grease in the sample liquid, layering the grease with clear liquid in the sample liquid, taking 1.5mL of the clear liquid into a centrifugal tube, setting the temperature of the centrifugal machine at 2 ℃ below zero, centrifuging for 10min at 14000r/min, and further filtering impurities through a filter membrane of 0.45 mu m.
3. The method of claim 1, further characterized by: in the step (2), 50 mu L of ethylene diamine tetraacetic acid solution with the concentration of 100mmol/L is adopted, and the addition of the ethylene diamine tetraacetic acid makes arsenic form compounds and the arsenic form compounds form anionic complexes, so that strong retention characteristics are generated in a chromatographic column, and the arsenic forms are separated.
4. The method of claim 1, further characterized by: in step (3), the amount of sample was set to 50. mu.L, and the mobile phase A was 0.5mM (NH)4)2CO3(pH8.5) and mobile phase B50 mM (NH)4)2CO3(pH8.5) and eluted with gradient.
5. The method of claims 1 and 4, further comprising: in step (3), the elution conditions for the liquid chromatography are as shown in the following table:
6. the method of claim 1, further characterized by: in the step (4), the inductively coupled plasma mass spectrometry conditions are mass number 75(As), m/z acquisition mode: TRA, sampling period: 1.0s, acquisition time: 1200s, carrier gas: high purity liquid argon (purity 99.99%), atomizer: concentric atomizer, carrier gas flow rate: 1.0L/min, flow rate of auxiliary gas: 0L/min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103234946A (en) * | 2013-03-19 | 2013-08-07 | 天津出入境检验检疫局动植物与食品检测中心 | Determination method for arsanilic acid, nitarsone and roxarsone in animal foodstuff |
| CN108982691A (en) * | 2018-07-25 | 2018-12-11 | 舟山市食品药品检验检测研究院 | Arsenic mercury shape simultaneous quantitative determination in aquatic products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103234946A (en) * | 2013-03-19 | 2013-08-07 | 天津出入境检验检疫局动植物与食品检测中心 | Determination method for arsanilic acid, nitarsone and roxarsone in animal foodstuff |
| CN108982691A (en) * | 2018-07-25 | 2018-12-11 | 舟山市食品药品检验检测研究院 | Arsenic mercury shape simultaneous quantitative determination in aquatic products |
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| 中华人民共和国国家质量监督检验检疫总局 中国国家标准化管理委员会: "《中华人民共和国国家标准 GB/T 23372-2009》", 16 March 2009 * |
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