CN108375640B - Method for extracting form of heavy metal chromium in mushroom based on tube furnace - Google Patents
Method for extracting form of heavy metal chromium in mushroom based on tube furnace Download PDFInfo
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- CN108375640B CN108375640B CN201810415887.9A CN201810415887A CN108375640B CN 108375640 B CN108375640 B CN 108375640B CN 201810415887 A CN201810415887 A CN 201810415887A CN 108375640 B CN108375640 B CN 108375640B
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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
- G01N30/02—Column chromatography
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
Abstract
The invention relates to a method for extracting the form of heavy metal chromium in mushroom. The method comprises the following steps: firstly, carbonizing a sample under the protection of inert gas, and then carrying out ultrasonic treatment; wherein the carbonization temperature is 400-550 ℃. The method has the advantages of simple operation, no need of acid-base reagent, no change of the valence state of chromium, good stability and high recovery rate. The method provides a new extraction method for the form extraction of chromium in food, and in addition, the extraction method effectively removes matrix interference and provides a good basis for subsequent detection, enrichment and computer installation.
Description
Technical Field
The invention relates to the technical field of analytical chemistry and agricultural product detection, in particular to a method for extracting the form of heavy metal chromium in mushroom based on a tube furnace.
Background
Chromium (Cr) is present in nature mainly in the form of trivalent chromium Cr (iii) and hexavalent chromium Cr (vi), chromium being present as an essential or harmful element, the valence state of which plays a decisive role. Trivalent chromium in mammal body can be used as glucose tolerance factor component to coordinate and enhance insulin effect, and participate in metabolism of sugar, lipid, protein and nucleic acid in body; hexavalent chromium is a strong carcinogen, which can rapidly enter cells through anion channels and be reduced to trivalent chromium, and some intermediates and active oxygen radicals are generated, thereby causing DNA damage. Therefore, the content and chemical morphology of trace chromium have a significant impact on human health.
The content of chromium in the black fungus is in a higher level, and the black fungus contains a large amount of polysaccharide, protein, colloid and tannin which have strong adsorption effect on heavy metal chromium, the traditional pretreatment methods such as leaching, stirring, ultrasonic extraction and the like are adopted, Cr (III) and Cr (VI) are extremely difficult to extract, and the forms of chromium are easy to mutually convert when microwave digestion, ashing, acid extraction or alkali extraction is adopted. The difficulties in chromium morphological analysis are: with the change of the pH value, the existing valence states of Cr (III) and Cr (VI) are changed. When there is a large amount of reducing components, the lowering of the pH value very easily leads to the conversion of Cr (III) into Cr (VI). Therefore, the method is simple, does not need acid-base reagents, does not change the valence state of chromium, has good stability, and has important significance for extracting the chromium form in the black fungus.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for extracting the form of heavy metal chromium in mushroom, which has the characteristics of simplicity, no need of acid-base reagents, no change of the valence state of chromium, good stability and the like.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
a method for extracting the form of heavy metal chromium in mushroom comprises the following steps: firstly, carbonizing a sample under the protection of inert gas, and then carrying out ultrasonic treatment; wherein the carbonization temperature is 400-550 ℃.
Preferably, the sample is warmed to the carbonization temperature at a rate of 10 ℃/min.
Preferably, the carbonization temperature is 450-.
Preferably, the carbonization time is 2 to 3 hours.
Preferably, the carbonization pressure is less than 0.01 Mpa.
Preferably, the inert gas is selected from nitrogen or helium.
Preferably, the carbonization treatment process is performed in a tube furnace.
Preferably, the ultrasonic power is 200-250W, and the ultrasonic time is 15-30min, preferably 15-20 min.
In the method, the mushroom is preferably black fungus, mushroom and the like; in particular to black fungus and mushroom which have higher contents of polysaccharide, protein and colloid and stronger adsorption effect on heavy metals.
In order to obtain an ideal extraction effect, the invention further defines the method, specifically as follows:
before carbonization, a sample (namely a dried mushroom sample) is crushed and sieved by a sieve of 10-20 meshes so as to ensure the extraction effect. The cutter head of the crusher is made of ceramic or titanium.
Before the carbonization treatment, inert gas is introduced into the carbonization device to ensure that air is exhausted before the temperature is raised. The inert gas may be selected from high purity nitrogen or helium.
After the carbonization treatment is finished, the temperature is required to be reduced to 20-40 ℃; wherein the cooling speed is 20-25 ℃/min.
In the method, after the carbonization treatment is finished, trivalent chromium and hexavalent chromium in a mixture obtained by carbonization are transferred by using a nitric acid solution, and ultrasonic treatment is carried out; in the transfer process, a small amount of the transfer is carried out for multiple times, so that the chromium ions are completely transferred; the concentration of the nitric acid solution is 0.1-0.2 mol/L.
In the method, after the chromium form is completely transferred and before ultrasonic treatment, a nitric acid solution containing trivalent chromium and hexavalent chromium is washed by EDTA disodium, the pH value is adjusted to 6.9-7.1, and the volume is fixed; wherein, the purpose of washing is to ensure the sufficient transfer of ions; the concentration of EDTA disodium is 0.4-0.7 mmol/L; in the method, dilute ammonia water or dilute nitric acid can be selected to adjust the pH value.
In the method, after ultrasonic treatment, a sample needs to be subjected to water bath standing, the temperature of the water bath is 45-65 ℃, and the standing is 50-90min, so that EDTA disodium is complexed with Cr (III).
To better achieve the extraction, the sample is taken out after water bath and cooled to 20-25 ℃, and the sample is filtered through a micro 0.45um pore filter membrane to be measured.
The invention has the following beneficial effects:
the invention provides an innovative scheme for extracting Cr (III) and Cr (VI) in mushroom, and has the characteristics of simple operation, good stability, strong repeatability and the like; the obtained sample can be directly used for carrying out quantitative analysis on the chromium form by LC-ICP-MS or IC-ICP-MS. The method can ensure that the form of chromium is not transformed, does not need acid-base reagents in the extraction process, is environment-friendly and pollution-free, and has wide application prospect in the technical field of food monitoring.
Drawings
FIG. 1 is a schematic diagram of the extraction method of the present invention.
In the figure: firstly, controlling a valve; heating the layer; thirdly, a heat-insulating layer; and fourthly, quartz crucible.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The embodiment provides a method for extracting chromium form in black fungus, which comprises the following steps:
(1) taking 100-200g of representative dried black fungus, pulverizing for 3-5min by a pulverizer with a ceramic or titanium cutter head, and sieving by a nylon sieve of 10-20 meshes;
(2) weighing 0.1g by a ten-thousandth balance, putting the weighed material into a quartz crucible, and putting the quartz crucible into a tubular furnace; checking the air tightness to ensure that the air does not leak in the extraction process; introducing high-purity nitrogen or helium as a protective gas, and evacuating for 3-5min before heating to ensure that the hearth is filled with high-purity inert gas, wherein the pressure in the furnace is less than 0.01 MPa; the air outlet is led into the beaker with purified water by a rubber tube to prevent oxygen from entering.
(3) The temperature programming is carried out at 10 ℃/min, the temperature of 400 ℃ is stabilized for 2.5h, and the temperature is reduced to 20 ℃;
(4) taking out, transferring the sample into a 50mL centrifuge tube by using 10mL of 0.15mol/L nitric acid for a plurality of times, repeatedly washing by using 0.5mmol/LEDTA disodium solution, adjusting the pH value to 7 by using dilute ammonia water or dilute nitric acid, and fixing the volume to 50 mL.
(5) And (3) firstly carrying out ultrasonic treatment on the sample with the constant volume for 15-20min at the ultrasonic power of 200W, and then standing in a water bath at the temperature of 45-65 ℃ for 50-90min to complex the EDTA disodium with Cr (III).
Examples 2 to 5 and comparative examples 1 to 4
Examples 2 to 5: the extraction method was the same as in example 1 except that the carbonization temperatures were 450, 500, 600, and 650, respectively.
Comparative examples 1 to 4: the extraction method was the same as in example 1 except that the carbonization temperatures were 200, 300, 350 and 700 ℃.
Effect verification 1
The concentrations of Cr (III) and Cr (VI) in the extract were measured at different carbonization temperatures and the results are shown in Table 1.
TABLE 1 concentrations (. mu.g/L) of Cr (III) and Cr (VI) extracted at different temperatures
As can be seen from Table 1, the concentrations of the extract solutions of examples 1 to 5 were significantly higher than those of comparative examples 1 to 4. The reason is that under the condition of being lower than 400 ℃, the sample has poor carbonization effect, and some macromolecular organic substances are not carbonized completely, so that some bound chromium can not be released, and the detection value is low; when the temperature is higher than 650 ℃, the chromium is volatile, and the chromium reacts with the carbon at high temperature to generate refractory chromium carbide compounds. In order to shorten the cooling time, the carbonization temperature is 400-550 ℃ to ensure the optimal comprehensive effect.
Examples 6 to 8 and comparative examples 5 to 8
Examples 6 to 8: the carbonization temperature was 400 ℃ in the same manner as in example 1, except that the carbonization time was 2 hours, 2.5 hours and 3 hours, respectively.
Comparative examples 5 to 8: the carbonization temperature was 400 ℃ in the same manner as in example 1, except that the carbonization time was 1 hour, 1.5 hours, 3.5 hours and 4 hours, respectively.
Effect verification 2
The concentrations of Cr (III) and Cr (VI) in the extract were determined at different carbonization times, as shown in Table 2.
TABLE 2 Cr (III) and Cr (VI) concentrations (. mu.g/L) extracted at different stabilization times
As is clear from Table 2, the chromium concentrations in the extracts of examples 6 to 8 were higher than those in the extracts of comparative examples 5 to 8. The reason is that the organic matters in the sample are not completely carbonized within less than 2 hours, and the combined chromium is not completely released, so that the detection result is low; it can be seen that the carbonization time is preferably selected from 2 to 3 hours.
Examples 9 to 11 and comparative examples 9 to 11
Examples 9 to 12: the carbonization temperature was 400 ℃ in the same manner as in example 1, except that the ultrasonic treatment time was 15min, 20min and 30 min.
Comparative examples 9 to 11: the carbonization temperature was 400 ℃ in the same manner as in example 1, except that the ultrasonic treatment time was 0min, 5min and 10 min.
Effect verification 3
The extraction efficiency was measured for different sonication times and is shown in table 3.
TABLE 3 extraction efficiency of Cr (III) and Cr (VI) at different sonication times
As can be seen from Table 3, the extraction efficiency tends to be stable when the ultrasound is carried out for more than 15min, so the ultrasound time is selected to be 15-30 min.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. A method for extracting the form of heavy metal chromium in mushroom is characterized by comprising the following steps: firstly, carbonizing a sample under the protection of inert gas, and then carrying out ultrasonic treatment;
wherein the carbonization temperature is 400-550 ℃;
the sample is heated to the carbonization temperature at the speed of 10 ℃/min;
the carbonization time is 2-3 h;
the carbonization pressure is less than 0.01 MPa;
the power of the ultrasonic treatment is 200-250W; the ultrasonic treatment time is 15-30 min;
the pH value of the system is 6.9-7.1.
2. The method as claimed in claim 1, wherein the carbonization temperature is 450-550 ℃.
3. The method according to claim 1 or 2, wherein the inert gas is selected from nitrogen or helium.
4. The method according to claim 1 or 2, wherein the time of the sonication is 15-20 min.
5. The method according to claim 1 or 2, wherein the mushrooms are black fungus, shiitake mushroom.
6. The method according to claim 1 or 2, characterized in that after the carbonization treatment is finished, trivalent chromium and hexavalent chromium in the mixture obtained by the carbonization are transferred by a nitric acid solution and subjected to ultrasonic treatment.
7. The method of claim 6, wherein after the chromium form is completely transferred and before the ultrasonic treatment, the nitric acid solution containing trivalent chromium and hexavalent chromium is washed by disodium EDTA, the pH value is adjusted to 6.9-7.1, and the volume is fixed.
8. The method of claim 6, wherein the sample is subjected to a water bath standing step after the ultrasonic treatment, wherein the temperature of the water bath is 45-65 ℃.
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Effective date of registration: 20220718 Address after: 100097 No. 9 middle garden, Shuguang garden, Beijing, Haidian District Patentee after: BEIJING ACADEMY OF AGRICULTURE AND FORESTRY SCIENCES Address before: 1210, seed building, Beijing Academy of agriculture and Forestry Sciences, 9 Shuguang Huayuan Middle Road, Haidian District, Beijing 100097 Patentee before: BEIJING RESEARCH CENTER FOR AGRICULTURAL STANDARDS AND TESTING |