CN113341057A - Method for rapidly and accurately detecting mercury compounds with different forms in marine products based on IC-ICP-MS - Google Patents
Method for rapidly and accurately detecting mercury compounds with different forms in marine products based on IC-ICP-MS Download PDFInfo
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- CN113341057A CN113341057A CN202110604771.1A CN202110604771A CN113341057A CN 113341057 A CN113341057 A CN 113341057A CN 202110604771 A CN202110604771 A CN 202110604771A CN 113341057 A CN113341057 A CN 113341057A
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- G—PHYSICS
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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
- G01N30/96—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 using ion-exchange
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
Abstract
The invention discloses a method for rapidly and accurately detecting mercury compounds with different forms in marine products based on IC-ICP-MS, which comprises the steps of firstly extracting the mercury compounds with different forms in the marine products such as fish by adopting a microwave-assisted extraction method, wherein the extraction efficiency is high, the extraction rate of the mercury compounds with different forms in all the fish can reach more than 90 percent, the forms of the mercury compounds with different forms are kept unchanged, the cost is low, and the extracting solution can be directly used for the subsequent IC-ICP-MS mercury form analysis; the Hg in the extractive solution of marine products such as fish can be removed within 300 s by using a protective column (Zorbax SCX 4 × 12.5 mm) as a separation column2+、CH3Hg+And C2H5Hg+The price of the used separation column is only 1/25 of the existing separation column. The invention can realize fishHg in marine products2+、CH3Hg+And C2H5Hg+The method has the advantages of rapid and low-cost accurate detection, and provides technical support for more scientifically and objectively evaluating the health risk of mercury in marine products and formulating more reasonable mercury limit standards.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a method for rapidly and accurately detecting mercury compounds with different forms in marine products based on IC-ICP-MS.
Background
The large amount of waste water and waste slag generated in the industrial process is discharged into the environment and enters the ocean along with the water flow, so that the offshore area is causedThe mercury content in the water area rises rapidly. Inorganic mercury (Hg) discharged into water2+) Can be converted into organic mercury with higher toxicity by microbial action, such as methyl mercury (CH)3Hg+) And ethyl mercury (C)2H5Hg+). Methyl mercury (CH)3Hg+) And ethyl mercury (C)2H5Hg+) Not only has far more toxicity than inorganic mercury, but also is easier to be enriched in animal bodies to generate biological enrichment and biological amplification effects. Thus, seafood such as fish typically contains many different forms of mercury compounds, including inorganic mercury (Hg)2+) Methyl mercury (CH)3Hg+) And ethyl mercury (C)2H5Hg+) And the concentration is higher. Therefore, it is unscientific and inaccurate to evaluate the health risk of mercury in seafood such as fish based on total mercury content and to establish total mercury limits. In order to more scientifically and objectively evaluate the health risk of mercury in marine products such as fish and to establish a more reasonable limit standard for mercury in marine products such as fish, the form of mercury in marine products such as fish must be accurately analyzed.
The first problem of accurate analysis of mercury compounds in different forms in marine products such as fish is how to completely extract mercury compounds in different forms in marine products such as fish without changing their chemical forms. At present, the extraction method of mercury compounds with different forms mainly comprises an ultrasonic auxiliary extraction method, and the existing extraction method is used for extracting mercury compounds with different forms in soil or Chinese patent medicine, so that a satisfactory extraction effect can be obtained. However, no matter how the concentration and the amount of the solvent are changed, the method cannot achieve a satisfactory effect on marine products such as fish, and the extraction rate is lower than 60%, so that the method cannot meet the requirement of accurately analyzing mercury compounds in different forms in marine products such as fish.
At present, instrument combination technologies, in particular inductively coupled plasma mass spectrometry (ICP-MS) combination technologies, including High Performance Liquid Chromatography (HPLC) and ICP-MS combination technologies (HPLC-ICP-MS), Capillary Electrophoresis (CE) and ICP-MS combination technologies (CE-ICP-MS), Gas Chromatography (GC) and ICP-MS combination technologies (GC-ICP-MS) and the like are mainly adopted for accurate analysis of mercury compounds with different forms. In the existing methods, the CE-ICP-MS has poor stability and low sensitivity, and cannot meet the requirement of accurately analyzing mercury compounds with different forms in marine products such as fish and the like; and the GC-ICP-MS needs derivatization pretreatment, the derivatization treatment is complex in operation, time-consuming and low in efficiency, and morphological changes can be generated in the derivatization process. The reported HPLC-ICP-MS method usually adopts a C18 column or a C8 column as a separation column, and the separation column is expensive (the price of a protective column and the separation column is more than 2 ten thousand yuan), so the analysis cost is higher and the separation time is longer.
Disclosure of Invention
The invention aims to provide a method for rapidly and accurately detecting mercury compounds with different forms in marine products based on IC-ICP-MS, which not only has high extraction rate of the mercury compounds with different forms in the marine products and can keep the forms unchanged, but also can realize the mercury compounds (Hg) with different forms in the marine products2+、CH3Hg+And C2H5Hg+) The method has the advantages of high speed, low cost and accurate detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for rapidly and accurately detecting mercury compounds with different forms in marine products such as fish and the like based on IC-ICP-MS comprises the following steps: (1) extracting mercury compounds with different forms in marine products with 50 mM dilute nitric acid as extraction solvent under the assistance of microwave; (2) by adopting an IC-ICP-MS coupling technology, two cation exchange protective columns are connected in series to form a separation column, a mixed solution of 0.2 mM L-cysteine and 1.0 mM nitric acid is used as an eluent, and Hg is rapidly separated and detected2+、CH3Hg+And C2H5Hg+。
The step (1) is specifically as follows: adding 7 mL of 50 mM dilute nitric acid into 0.1 g of marine product sample, soaking overnight, performing microwave-assisted extraction, and performing centrifugal separation; extracting the residue with 4mL of 50 mM dilute nitric acid under microwave assistance, and centrifuging; the two extracts were combined and used directly for the analytical determination of IC-ICP-MS. Temperature control during microwave-assisted extraction: heating to 120 deg.C within 10 min, maintaining the temperature for 30 min, and cooling to 80 deg.C within 10 min.
The step (2) is specifically as follows: connecting two cation exchange protective columns in series, connecting the two cation exchange protective columns to an ion chromatograph as a separation column, activating by using a mobile phase for 1 hour, starting an ICP-MS (inductively coupled plasma-mass spectrometry), tuning to an optimal state, and connecting the ion chromatography and the ICP-MS; sampling marine product extract into ion chromatography, eluting Hg at 30 deg.C and flow phase flow rate of 1 mL/min by isocratic elution method2+、CH3Hg+And C2H5Hg+Carrying out rapid separation; utilization of Hg2+、CH3Hg+And C2H5Hg+Peak area of signal peak, standard curve method for Hg2+、CH3Hg+And C2H5Hg+The concentration of (b) is accurately measured. Preferably, the cation exchange protective column is of the type Zorbax SCX 4X 12.5mM, and the mobile phase is a mixed solution of 0.2 mM L-cysteine and 1.0 mM nitric acid.
The invention has the beneficial effects that:
1. the extraction method of mercury compounds with different forms in marine products such as fish and the like, which is established by the invention, can extract mercury compounds with different forms on the premise of not changing the forms of the mercury compounds in the marine products, the extraction efficiency reaches more than 90 percent, and the extracting solution can be directly used for IC-ICP-MS analysis of the forms of mercury.
2. The cheaper Zorbax SCX 4X 12.5mm guard column is used in series as the separation column, and the cost of the separation column is only 1/25 of the traditional separation column.
3. The analysis speed is high, and Hg in the extraction solution of marine products such as fish can be completed within 300 s2+、CH3Hg+And C2H5Hg+And (4) accurate detection.
Drawings
FIG. 1 is IC-ICP-MS analysis spectrum of mercury compounds with different forms in Miichthys miiuy samples. A: reagent blank; b: a brown croaker sample; c Miichthys miiuy + Hg2+、CH3Hg+And C2H5Hg+And (4) standard.
FIG. 2 shows different shapes of golden pomfret sampleAnd (4) an IC-ICP-MS analysis spectrum of the mercury compound in the state. A: reagent blank; b: golden pomfret samples; c, golden pomfret + Hg2+、CH3Hg+And C2H5Hg+And (4) standard.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
A method for rapidly and accurately detecting mercury compounds with different forms in marine products based on IC-ICP-MS comprises the following specific steps:
(1) adding 7 mL of extraction solvent (50 mM dilute nitric acid) into 0.1 g of marine product sample such as fish, soaking overnight, and performing microwave-assisted extraction (microwave extraction temperature is controlled: 10 min heating to 120 deg.C, maintaining at 120 deg.C for 30 min, and then cooling to 80 deg.C within 10 min). And when the temperature of the solution is reduced to room temperature, centrifugally separating the extracting solution. The residue was extracted once more with 4mL of extraction solvent (50 mM dilute nitric acid) directly (without soaking) following the above extraction procedure. The two extraction solutions were combined and used directly for the following analytical determination of IC-ICP-MS.
(2) Two cation exchange protective columns (Zorbax SCX 4X 12.5 mM) were connected in series and connected to an ion chromatograph as separation columns, and after activation with a mobile phase (a mixed solution of 0.2 mM L-cysteine (cys) and 1.0 mM nitric acid) for 1 hour before use, ICP-MS was started up and tuned to the optimum conditions of the apparatus, and ion chromatography and ICP-MS were connected. Introducing the above marine product extract such as fish into ion chromatography, eluting Hg with IC-ICP-MS at a flow rate of 1 mL/min and a column temperature of 30 deg.C in isocratic manner2+、CH3Hg+And C2H5Hg+And (5) carrying out separation detection. Utilization of Hg2+、CH3Hg+And C2H5Hg+Peak area of signal peak, standard curve method for Hg2+、CH3Hg+And C2H5Hg+The concentration of (b) is accurately measured.
As can be seen from tables 1 and 2, the mercury in the marine products of different types of fishes can be completely extracted by using the microwave-assisted extraction method, the extraction rate reaches more than 93 percent, and the reproducibility is good. As can be seen from fig. 1 and 2, the mercury compounds with different forms in the marine products of different species of fish are not changed in the microwave-assisted extraction process, and the mercury compounds with different forms are detected from the marine products of different species of fish; hg is added into different fish species2+、CH3Hg+And C2H5Hg+Examination of the standard samples also indicated the added Hg2+、CH3Hg+And C2H5Hg+The standard has no morphological change, Hg, in the microwave-assisted extraction process2+、CH3Hg+And C2H5Hg+The recovery rate of the added standard is above 95%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A method for rapidly and accurately detecting mercury compounds with different forms in marine products based on IC-ICP-MS is characterized by comprising the following steps: the method comprises the following steps: (1) extracting mercury compounds with different forms in marine products with 50 mM dilute nitric acid as extraction solvent under the assistance of microwave; (2) by adopting an IC-ICP-MS coupling technology, two cation exchange protective columns are connected in series to form a separation column, a mixed solution of 0.2 mM L-cysteine and 1.0 mM nitric acid is used as an eluent, and Hg is rapidly separated and detected2+、CH3Hg+And C2H5Hg+。
2. The method of claim 1, wherein: the marine product comprises fish.
3. The method of claim 1, wherein: the step (1) is specifically as follows: adding 7 mL of 50 mM dilute nitric acid into 0.1 g of marine product sample, soaking overnight, performing microwave-assisted extraction, and performing centrifugal separation; extracting the residue with 4mL of 50 mM dilute nitric acid under microwave assistance, and centrifuging; the two extracts were combined and used directly for the analytical determination of IC-ICP-MS.
4. The method of claim 3, wherein: temperature control during microwave-assisted extraction: heating to 120 deg.C within 10 min, maintaining the temperature for 30 min, and cooling to 80 deg.C within 10 min.
5. The method of claim 1, wherein: the step (2) is specifically as follows: connecting two cation exchange protective columns in series, connecting the two cation exchange protective columns to an ion chromatograph as a separation column, activating by using a mobile phase for 1 hour, starting an ICP-MS (inductively coupled plasma-mass spectrometry), tuning to an optimal state, and connecting the ion chromatography and the ICP-MS; sampling marine product extract into ion chromatography, eluting Hg at 30 deg.C and flow phase flow rate of 1 mL/min by isocratic elution method2+、CH3Hg+And C2H5Hg+Carrying out rapid separation; utilization of Hg2+、CH3Hg+And C2H5Hg+Peak area of signal peak, standard curve method for Hg2+、CH3Hg+And C2H5Hg+The concentration of (b) is accurately measured.
6. The method of claim 5, wherein: the cation exchange protective column is in the model of Zorbax SCX 4X 12.5mM, and the mobile phase is a mixed solution of 0.2 mM L-cysteine and 1.0 mM nitric acid.
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| JP2006266822A (en) * | 2005-03-23 | 2006-10-05 | Toshiba Corp | Pretreatment method of sample and method of measuring amount of mercury in sample |
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