CN113109322A - Method for determining main heavy metal elements in marine organisms - Google Patents
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- 238000001514 detection method Methods 0.000 claims abstract description 33
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 13
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 13
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- 239000011651 chromium Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 12
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 42
- 229910017604 nitric acid Inorganic materials 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000012472 biological sample Substances 0.000 claims description 25
- 239000012086 standard solution Substances 0.000 claims description 24
- 238000000120 microwave digestion Methods 0.000 claims description 22
- 238000005259 measurement Methods 0.000 claims description 11
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- 238000011946 reduction process Methods 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
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Abstract
The invention relates to the technical field of ocean monitoring, in particular to a method for measuring main heavy metal elements in ocean organisms, which comprises the following technical steps: the digestive juice obtained after the marine organism is digested by acid enters an inductively coupled plasma emission spectrum after being lifted by a peristaltic pump, is carried into an atomization system by carrier gas for atomization (for solution sample introduction), enters a channel in a torch tube shaft in an aerosol form, and aerosol particles are fully evaporated, atomized, excited and ionized in high-temperature and inert argon atmosphere. Excited atoms and ions emit strong atomic spectral lines and strong ion spectral lines, characteristic spectral lines and intensities emitted by all elements are subjected to light splitting, photoelectric conversion, detection and data processing, and finally the content of all elements is determined. Compared with the prior art, the method has high digestion efficiency, can simultaneously determine 6 heavy metal elements of copper, lead, zinc, cadmium, chromium and arsenic, has accuracy, high sensitivity, wide linear range and low use cost, and can be widely popularized.
Description
Technical Field
The invention relates to the technical field of marine monitoring, in particular to a method for determining main heavy metal elements in marine organisms.
Background
Heavy metals, as pollutants in the environment that are present for a long time, are readily bio-enriched and not easily degraded. Research shows that marine organisms, particularly bivalve mollusks, have high accumulation capacity on heavy metals. At present, with the development of economy and the continuous improvement of living standard, the requirement of people on food safety is higher and higher, and fishes, shrimps, shellfishes, crabs and the like in the sea become table delicacies of people. Therefore, the method has great significance in carrying out the work of heavy metal content, enrichment rule, safety risk evaluation and the like in marine organisms.
The conventional heavy metal determination methods include polarography, atomic absorption, ICP-AES (inductively coupled plasma emission spectrometry) and ICP-MS (inductively coupled plasma mass spectrometry).
The standard method for measuring metal elements by using the ICP-AES method has 129 items, is mainly applied to multiple industries such as materials, chemical industry, nonferrous metals, food, environmental protection and the like, has few inductive coupling plasma emission spectrum related methods in a standard method system for soil and organism analysis in China, is generally used for measuring single elements, and has a narrow linear range.
Although the ICP-MS method can carry out multi-element simultaneous measurement, the instrument is expensive, the price reaches millions of yuan or even millions of yuan, the use and maintenance cost is high, the ICP-MS method is only available for large-scale enterprises, scientific research institutes and colleges and universities with capacity to purchase, and the ICP-MS method is suitable for measuring low-content elements due to high sensitivity. However, the content of heavy metal elements in marine organisms is relatively high, reaches dozens of even hundreds of micrograms per gram, and is somewhat large and small.
Disclosure of Invention
In order to overcome one of the defects of the prior art, the invention discloses a method for determining main heavy metal elements in marine organisms based on an ICP-AES method, which comprises the following steps:
the digestive juice obtained after the marine organism is digested by acid enters an inductively coupled plasma emission spectrum after being lifted by a peristaltic pump, is carried into an atomization system by carrier gas for atomization (for solution sample introduction), enters a channel in a torch tube shaft in an aerosol form, and aerosol particles are fully evaporated, atomized, excited and ionized in high-temperature and inert argon atmosphere. Excited atoms and ions emit strong atomic spectral lines and strong ion spectral lines, characteristic spectral lines and intensities emitted by all elements are subjected to light splitting, photoelectric conversion, detection and data processing, and finally the content of all elements is determined.
The adopted technical scheme is as follows:
the method for determining the main heavy metal elements in the marine organisms is different from the prior art in that:
1) collecting samples: the collection, preparation, storage and transportation of samples is carried out according to the relevant regulations of GB17378.3 and GB 17378.6;
2) the reagent comprises:
2.1) water: primary water or water of comparable purity in accordance with GB/T6682;
2.2) nitric acid:ρ=1.42 g/mL；
2.3) nitric acid solution A: 1 mL of the nitric acid of the above 2.2) and 99 mL of the water of the above 2.1);
2.4) nitric acid solution B: the nitric acid of the above 2.2) is mixed with the water of the above 2.1) in equal volume;
2.5) standard stock solution, namely single-element or multi-element standard stock solution with the concentration of copper, lead, zinc, cadmium, chromium and arsenic elements of 100 mg/L, wherein the solvent is the nitric acid solution A of the 2.3), and the nitric acid solution is refrigerated at 4 ℃ and stored for 1 year, or purchased with a commercially available certified standard solution;
2.6) standard intermediate solution, namely, transferring 10.00 mL of the standard stock solution of the 2.5) into a 100 mL volumetric flask, fixing the volume to the marked line by using the nitric acid solution A of the 2.3), and refrigerating and storing at 4 ℃ for 1 month;
2.7) standard use solutions: transferring 10.00 mL of the standard intermediate solution of the 2.6) into a 100 mL volumetric flask, and fixing the volume to the marked line by using the nitric acid solution A of the 2.3) and preparing the solution before use;
3) the instrument device includes:
inductively coupled plasma emission spectrometer: comprises a high-frequency generator, a plasma and sample introduction system, a light splitting system and a detector;
a microwave digestion instrument: the highest digestion temperature is not lower than 200 ℃;
acid removing device: the highest temperature can reach 180 ℃;
4) the determination step comprises:
4.1) sample digestion: the biological sample digestion method adopts a microwave digestion method and comprises the following specific steps:
weighing 1.0 g of organism wet sample or 0.2 g of organism dry sample, accurately obtaining 0.0001 g of organism dry sample, placing the organism wet sample or the organism dry sample in a digestion tank of a microwave digestion instrument, adding a little water for wetting, adding 10 mL of the nitric acid of 2.2), screwing a bottle cap after the reaction is stable, placing the bottle cap in the microwave digestion instrument, and digesting according to the reference working conditions of the microwave digestion instrument; after digestion, cooling to room temperature, taking out, carefully unscrewing a cover, placing a digestion tank on an acid dispelling device, heating to dispel acid, setting the acid dispelling temperature at 160 ℃, adding 1.0 mL of the nitric acid solution B of 2.4) when the solution is nearly dry, carrying out micro-heating digestion, transferring the digestion solution into a 25 mL colorimetric tube after cooling, adding water to fix the volume to a marked line, uniformly mixing, standing, and taking supernatant, wherein the supernatant is the digestion solution; simultaneously preparing a blank solution according to the same steps of the biological sample digestion method;
the reference working conditions of the microwave digestion instrument are as follows: the power is 1600W, the temperature is increased for 6 min, the temperature is 120 ℃, and the holding time is 6 min; the power is 1600W, the temperature is increased for 6 min, the temperature is 180 ℃, and the holding time is 15 min;
4.2) standard curve drawing: taking 9 100 mL volumetric flasks, adding 0 mL, 0.05 mL, 0.10 mL, 0.50 mL, 1.00 mL, 2.00 mL, 5.00 mL, 10.00 mL of the standard use solution of the 2.7) and 5.00 mL of the standard intermediate solution of the 2.6) by using a micropipette or a pipette, diluting the solutions to a marked line by using the nitric acid solution A of the 2.3) to prepare standard series solutions with the concentrations of 0 [ mu ] g/L, 0.50 [ mu ] g/L, 1.00 [ mu ] g/L, 5.00 [ mu ] g/L, 10.00 [ mu ] g/L, 20.0 [ mu ] g/L, 50.0 [ mu ] g/L, 100 [ mu ] g/L and 500 [ mu ] g/L, measuring the standard series solutions by using an inductively coupled plasma emission spectrometer under reference working conditions, and drawing a standard curve according to the measurement results;
4.3) respectively measuring the digestion solution and the blank solution according to the reference working condition of the inductively coupled plasma emission spectrometer, wherein the measured values are X respectively0And Xi；
The reference working conditions of the inductively coupled plasma emission spectrometer are as follows: the radio frequency power is 1300W, the plasma gas flow is 15L/min, the carrier gas flow is 0.65L/min, the sample flow is 1.5L/min, and the sample introduction time is 30 s;
4.4) calculating the concentration value of each element in the digestion solution of the biological sample by using a linear regression equation of a standard curve, calculating the content of the element to be detected in the biological sample according to the formula (1), and recording the test result by using a table;
in the formula:
w i content of the element to be determined in the biological sample, Unit 10-6；
X i The concentration of the element to be detected in the digestion solution of the biological sample is unit mug/L;
X 0 -the concentration of the element to be measured in the blank solution, in μ g/L;
Vthe constant volume of the digestion solution of the biological sample is L;
m-weighing of the biological sample in g.
Further, the required glassware is soaked in 20% nitric acid for 24h, washed clean by water repeatedly, and finally washed clean by the water in the step 2.1).
Further, the detection limit was 1.0X 10-6(ii) a Lead: 0.5X 10-6(ii) a Zinc: 2.0X 10-6(ii) a Cadmium: 0.3X 10-6(ii) a Chromium: 0.3X 10-6(ii) a Arsenic: 0.3X 10-6。
Furthermore, the recovery rate ranges from 80% to 120%.
Further, the relative standard deviation within a batch is less than 10% and the relative standard deviation between batches is less than 10%.
Further, in step 4.1), if the blank value is too high, checking the reagent blank and the sample analysis and test process, and selecting a reagent with higher purity or purifying the reagent to reduce the reagent interference; when the sample is digested, the amount of the acid can be properly increased or decreased according to the amount of the sample.
Further, in the step 4.2), the range of the standard curve can be adjusted according to the content of the element to be detected in the sample, or the sample digestion solution is diluted, so that the linearity of the standard curve is ensured, and the content of the element to be detected is ensured to be within the range of the drawn standard curve.
An inductively coupled plasma mass spectrometer (ICP-MS) is an analysis instrument combining an ICP technology and a mass spectrum, wherein the ICP utilizes a high-power high-frequency radio-frequency signal applied on an inductance coil to form high-temperature plasma inside the coil, the balance and continuous ionization of the plasma are guaranteed through the pushing of gas, the ICP plays a role of an ion source in the ICP-MS, the high-temperature plasma enables most elements in a sample to be ionized into an electron to form monovalent positive ions, the mass spectrum is a mass screening and analyzing instrument, the strength of a certain ion is detected through selecting ions with different mass-nuclear ratios (m/z), the strength of a certain element is analyzed and calculated, and the type and the content of the element in the sample can be known through comparing with a standard solution. An inductively coupled plasma emission spectrometer (ICP-AES) also utilizes the ICP technology, a strong high-power high-frequency radio-frequency signal applied to an inductance coil forms high-temperature plasma inside the coil, when sample aerosol enters plasma flame, most of the sample aerosol is immediately decomposed into excited atomic and ionic states, when the excited particles return to a stable ground state, certain energy (expressed as certain wavelength) needs to be emitted, the specific spectral line and the specific intensity of each element are measured, and compared with a standard solution, the type and the content of the elements contained in the sample can be known.
The inductively coupled plasma mass spectrometry (ICP-MS) can be used for simultaneously measuring multiple elements, but instruments are expensive, the price reaches millions or even millions of yuan, the use and maintenance cost is high, the instruments are only available for large-scale enterprises, scientific research institutes and colleges with strength, the instruments are suitable for measuring low-content elements, the content of heavy metal elements in marine organisms is relatively high and reaches dozens or even hundreds of micrograms per gram, the inductively coupled plasma emission spectrometry (ICP-AES) can completely meet the detection requirement, the instrument price is low, the instruments are only 1/4-1/3 of ICP-MS, the use and maintenance cost is low, the popularization range is wide, and the characteristics of high sensitivity, wide linear range and capability of simultaneously measuring multiple heavy metal elements are also achieved.
The ICP-MS method is known to measure 6 elements of lead, cadmium, chromium, copper, zinc and nickel in marine sediments at the same time, but the detection of heavy metal elements in organisms, particularly marine organisms, is not reported at present, the invention measures 6 elements of lead, cadmium, chromium, copper, zinc and arsenic in marine organisms, the 6 elements measured by the invention correspond to 6 heavy metal elements in the current national standard GB18421-2001 marine organism quality, the measurement result can provide direct basis for the classification of the marine organism quality, further provide data support for the work of content distribution, enrichment rule, safety risk evaluation and the like of the heavy metal elements in the marine organisms, provide research basis for the development of marine fishery and the protection of marine environment, and provide technical support for marine management departments.
The ICP-AES method of the prior art does not explain the acid-dispelling process in detail, but the ICP-AES method of the invention is verified by experiments aiming at the characteristic that the boiling point of the arsenic element in the measured elements is lower, the 160 ℃ is the best acid-dispelling temperature, the character characteristics of the acid-dispelling end point are described in detail, and the judgment and the operation are easier. While the standard ICP-MS method does not provide a specific setting method for the operating parameters of the instrument, the ICP-AES method of the present invention provides more detailed reference operating conditions of the instrument, including rf power, plasma gas flow, carrier gas flow, sample flow, and sample injection time.
In the prior art, the standard solution needs to be removed during measurement by an ICP-MS method, and the internal standard solution containing elements such as scandium, indium, germanium and the like needs to be prepared besides the sample solution and the blank solution.
In a word, compared with the prior art, the analysis method for rapid pretreatment of the microwave digestion instrument and simultaneous determination of multiple elements of the inductively coupled plasma emission spectrometer has the characteristics of rapid organism digestion, high digestion efficiency, capability of simultaneously determining 6 heavy metal elements of copper, lead, zinc, cadmium, chromium and arsenic, accuracy, high sensitivity, wide linear range, low use cost and wide popularization. The device can improve the working efficiency of scientific research institutions and detection institutions, reduce the input cost, provide technical support for researching content distribution of heavy metals in marine organisms, potential ecological risk evaluation and the like, and provide research basis for marine environment protection.
Drawings
FIG. 1 is a graph of 6 heavy metal elements of Cu, Pb, Zn, Cd, Cr and As in the specific embodiment.
Detailed Description
1) Collecting samples: the collection, preparation, storage and transportation of samples is carried out according to the relevant regulations of GB17378.3 and GB 17378.6;
2) the reagent comprises:
2.1) water: primary water or water of comparable purity in accordance with GB/T6682;
2.2) nitric acid:ρ=1.42 g/mL；
2.3) nitric acid solution A: 1 mL of the nitric acid of the above 2.2) and 99 mL of the water of the above 2.1);
2.4) nitric acid solution B: the nitric acid of the above 2.2) is mixed with the water of the above 2.1) in equal volume;
2.5) standard stock solution, namely single-element or multi-element standard stock solution with the concentration of copper, lead, zinc, cadmium, chromium and arsenic elements of 100 mg/L, wherein the solvent is the nitric acid solution A of the 2.3), and the nitric acid solution is refrigerated at 4 ℃ and stored for 1 year, or purchased with a commercially available certified standard solution;
2.6) standard intermediate solution, namely, transferring 10.00 mL of the standard stock solution of the 2.5) into a 100 mL volumetric flask, fixing the volume to the marked line by using the nitric acid solution A of the 2.3), and refrigerating and storing at 4 ℃ for 1 month;
2.7) standard use solutions: transferring 10.00 mL of the standard intermediate solution of the 2.6) into a 100 mL volumetric flask, and fixing the volume to the marked line by using the nitric acid solution A of the 2.3) and preparing the solution before use;
3) the instrument device includes:
inductively coupled plasma emission spectrometer: comprises a high-frequency generator, a plasma and sample introduction system, a light splitting system and a detector;
a microwave digestion instrument: the highest digestion temperature is not lower than 200 ℃;
acid removing device: the highest temperature can reach 180 ℃;
4) the determination step comprises:
4.1) sample digestion: the biological sample digestion method adopts a microwave digestion method and comprises the following specific steps:
weighing 1.0 g of organism wet sample or 0.2 g of organism dry sample, accurately obtaining 0.0001 g of organism dry sample, placing the organism wet sample or the organism dry sample in a digestion tank of a microwave digestion instrument, adding a little water for wetting, adding 10 mL of the nitric acid of 2.2), screwing a bottle cap after the reaction is stable, placing the bottle cap in the microwave digestion instrument, and digesting according to the reference working conditions of the microwave digestion instrument; after digestion, cooling to room temperature, taking out, carefully unscrewing a cover, placing a digestion tank on an acid dispelling device, heating to dispel acid, setting the acid dispelling temperature at 160 ℃, adding 1.0 mL of the nitric acid solution B of 2.4) when the solution is nearly dry, carrying out micro-heating digestion, transferring the digestion solution into a 25 mL colorimetric tube after cooling, adding water to fix the volume to a marked line, uniformly mixing, standing, and taking supernatant, wherein the supernatant is the digestion solution; simultaneously preparing a blank solution according to the same steps of the biological sample digestion method;
the reference working conditions of the microwave digestion instrument are as follows: the power is 1600W, the temperature is increased for 6 min, the temperature is 120 ℃, and the holding time is 6 min; the power is 1600W, the temperature is increased for 6 min, the temperature is 180 ℃, and the holding time is 15 min;
the inventor researches the digestion effects of a nitric acid digestion system and a nitric acid and hydrogen peroxide system, and the result shows that the digestion effects of the two digestion systems have no significant difference statistically. However, hydrogen peroxide is relatively unstable, and a nitric acid digestion system is selected for the reduction process. Acidity is within 30% and the effect is within 10%.
4.2) standard curve drawing: taking 9 100 mL volumetric flasks, adding 0 mL, 0.05 mL, 0.10 mL, 0.50 mL, 1.00 mL, 2.00 mL, 5.00 mL, 10.00 mL of the standard use solution of the 2.7) and 5.00 mL of the standard intermediate solution of the 2.6) by using a micropipette or a pipette, diluting the solutions to a marked line by using the nitric acid solution A of the 2.3) to prepare standard series solutions with the concentrations of 0 [ mu ] g/L, 0.50 [ mu ] g/L, 1.00 [ mu ] g/L, 5.00 [ mu ] g/L, 10.00 [ mu ] g/L, 20.0 [ mu ] g/L, 50.0 [ mu ] g/L, 100 [ mu ] g/L and 500 [ mu ] g/L, measuring the standard series solutions by using an inductively coupled plasma emission spectrometer under reference working conditions, and drawing a standard curve according to the measurement results;
4.3) respectively measuring the digestion solution and the blank solution according to the reference working condition of the inductively coupled plasma emission spectrometer, wherein the measured values are X respectively0And Xi；
The reference working conditions of the inductively coupled plasma emission spectrometer are as follows: the radio frequency power is 1300W, the plasma gas flow is 15L/min, the carrier gas flow is 0.65L/min, the sample flow is 1.5L/min, and the sample introduction time is 30 s;
4.4) calculating the concentration value of each element in the digestion solution of the biological sample by using a linear regression equation of a standard curve, calculating the content of the element to be detected in the biological sample according to the formula (1), and recording the test result by using a table;
in the formula:
w i content of the element to be determined in the biological sample, Unit 10-6；
X i The concentration of the element to be detected in the digestion solution of the biological sample is unit mug/L;
X 0 -the concentration of the element to be measured in the blank solution, in μ g/L;
Vthe constant volume of the digestion solution of the biological sample is L;
m-weighing of the biological sample in g.
In the embodiment, the required glassware is soaked in 20% nitric acid for 24h, washed clean with water repeatedly, and finally washed clean with the water of 2.1).
According to A.1.1 in the technical guide of revision of environmental monitoring and analysis method Standard (HJ 168-. The detection limit was calculated by the method of calculating the target deviation S for 7 measurements, and the detection limit was set to 4 times as the quantitative limit (lower measurement limit). The detection limit is calculated according to equation (2):
in the formula: MDL-method detection limits;
n is the number of parallel determinations of the sample;
t-distribution of t with degree of freedom n-1 and confidence of 99% (one-sided);
s-standard deviation of n replicates.
Table 1 detection limit and quantitation limit units for each element: x 10-6
For 12 parts of each of 3 marine biological samples of national standard substances GBW10050(GSB-28) prawn, GBW10024(GSB-15) scallop and GBW10023(GSB-14) laver which represent different sample matrixes, 6 samples are prepared in parallel by a microwave digestion method, the rest 6 samples are added with standard solutions with the same concentration, the standard solutions are digested by the microwave digestion method, the content of each element in the samples is measured, the precision, the accuracy and the recovery rate are calculated, and the measurement results are shown in a table 2. The measurement results are all within the certificate reference value range of the standard reference substance, which indicates that the method has good accuracy, the parallel test is carried out for 6 times, the Relative Standard Deviation (RSD) is calculated for 6 times, the result is less than or equal to 10.0 percent, and the standard recovery rate range of the 6 elements is 80 to 120 percent.
Table 2 units of assay results for microwave digestion of marine organism standards: x 10-6
5 method verification
The cooperative verification experiment is completed by 3 laboratories in province, namely a Shandong province geological engineering exploration institute, a fourth geological team and a Shandong province geological mineral exploration and development institute, wherein the eighth geological team is the Shandong province geological exploration and development institute. And linear experiments, method detection limits, and verification of method accuracy and precision are carried out. And (3) performing a synergistic experiment on the national standard reference substance, wherein the measurement result of the target element is within the standard reference value range, and the precision meets the requirement.
The verification conclusion shows that: the method has the advantages of reasonable sample pretreatment method, strong operability, and satisfying the requirements of analysis and detection in the aspects of detection limit, accuracy and precision (see the verification report for detailed results). The results of the validation experiments for the three units are summarized below:
5.1 Shandong province Lunan geological engineering investigation institute experimental test center
5.1.1 method Linear Range
TABLE 36 Linear Range, Linear equation and correlation coefficient of the major heavy Metal elements
5.1.2 detection Limit
The method determines the detection limit of the method by adding a standard solution into a blank sample for digestion:
when the copper element standard solution in the blank sample is added to reach the concentration level of 1.0 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 1.0 multiplied by 10-6(ii) a When the addition level is 3.0 × 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 3.0 multiplied by 10-6。
When the lead element standard solution in the blank sample reaches the addition concentration level of 0.5 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 0.5 multiplied by 10-6(ii) a When the addition level is 1.5X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 1.5 multiplied by 10-6。
When the zinc element standard solution in the blank sample is added to reach the concentration level of 2.0 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 2.0 multiplied by 10-6(ii) a When the addition level is 6.0X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 6.0 multiplied by 10-6。
When the standard solution of cadmium, chromium and arsenic element in the blank sample is added to the sample to reach the concentration level of 0.3 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 0.3 multiplied by 10-6(ii) a When the addition level is 0.9X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 0.9 multiplied by 10-6。
5.1.3 method accuracy and precision
TABLE 4 GBW10050(GSB-28) prawn assay results units: x 10-6
5.2 Experimental testing center for the fourth geological team of geological mineral exploration and development bureau of Shandong province
5.2.1 method Linear Range
Table 56 linear ranges, linear equations and correlation coefficients of the main heavy metal elements
5.2.2 detection Limit
The method determines the detection limit of the method by adding a standard solution into a blank sample for digestion:
when the copper element standard solution in the blank sample is added to reach the concentration level of 1.0 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 1.0 multiplied by 10-6(ii) a When the addition level is 3.0 × 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 3.0 multiplied by 10-6。
When the lead element standard solution in the blank sample reaches the addition concentration level of 0.5 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 0.5 multiplied by 10-6(ii) a When the addition level is 1.5X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 1.5 multiplied by 10-6。
When the zinc element standard solution in the blank sample is added to reach the concentration level of 2.0 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 2.0 multiplied by 10-6(ii) a When the addition level is 6.0X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 6.0 multiplied by 10-6。
When the standard solution of cadmium, chromium and arsenic element in the blank sample is added to the sample to reach the concentration level of 0.3 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 0.3 multiplied by 10-6(ii) a When the addition level is 0.9X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 0.9 multiplied by 10-6。
5.2.3 method accuracy and precision
TABLE 6 GBW10050(GSB-28) prawn assay results units: x 10-6
5.3 Experimental testing center for the eighth geological team of geological mineral exploration and development bureau of Shandong province
5.3.1 method Linear Range
Table 76 main heavy metal element linear range, linear equation and correlation coefficient
5.3.2 detection Limit
The method determines the detection limit of the method by adding a standard solution into a blank sample for digestion:
when the copper element standard solution in the blank sample is added to reach the concentration level of 1.0 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 1.0 multiplied by 10-6(ii) a When the addition level is 3.0 × 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 3.0 multiplied by 10-6。
When the lead element standard solution in the blank sample reaches the addition concentration level of 0.5 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 0.5 multiplied by 10-6(ii) a When the addition level is 1.5X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 1.5 multiplied by 10-6。
When the zinc element standard solution in the blank sample is added to reach the concentration level of 2.0 multiplied by 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 2.0 multiplied by 10-6(ii) a When the addition level is 6.0X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 6.0 multiplied by 10-6。
When the standard solution of cadmium, chromium and arsenic element in the blank sample is added to reach the concentration levelTo 0.3X 10-6When the signal-to-noise ratio (S/N) is more than 3, the detection limit of the method can reach 0.3 multiplied by 10-6(ii) a When the addition level is 0.9X 10-6When the signal-to-noise ratio (S/N) is more than 10, the method has the quantitative limit of 0.9 multiplied by 10-6。
5.3.3 method accuracy and precision
TABLE 8 GBW10050(GSB-28) prawn assay results units: x 10-6
Claims (7)
1. The method for determining the main heavy metal elements in the marine organisms is characterized by comprising the following steps:
1) collecting samples: the collection, preparation, storage and transportation of samples is carried out according to the relevant regulations of GB17378.3 and GB 17378.6;
2) the reagent comprises:
2.1) water: primary water or water of comparable purity in accordance with GB/T6682;
2.2) nitric acid:ρ=1.42 g/mL；
2.3) nitric acid solution A: 1 mL of the nitric acid of the above 2.2) and 99 mL of the water of the above 2.1);
2.4) nitric acid solution B: the nitric acid of the above 2.2) is mixed with the water of the above 2.1) in equal volume;
2.5) standard stock solution, namely single-element or multi-element standard stock solution with the concentration of copper, lead, zinc, cadmium, chromium and arsenic elements of 100 mg/L, wherein the solvent is the nitric acid solution A of the 2.3), and the nitric acid solution is refrigerated at 4 ℃ and stored for 1 year, or purchased with a commercially available certified standard solution;
2.6) standard intermediate solution, namely, transferring 10.00 mL of the standard stock solution of the 2.5) into a 100 mL volumetric flask, fixing the volume to the marked line by using the nitric acid solution A of the 2.3), and refrigerating and storing at 4 ℃ for 1 month;
2.7) standard use solutions: transferring 10.00 mL of the standard intermediate solution of the 2.6) into a 100 mL volumetric flask, and fixing the volume to the marked line by using the nitric acid solution A of the 2.3) and preparing the solution before use;
3) the instrument device includes:
inductively coupled plasma emission spectrometer: comprises a high-frequency generator, a plasma and sample introduction system, a light splitting system and a detector;
a microwave digestion instrument: the highest digestion temperature is not lower than 200 ℃;
acid removing device: the highest temperature can reach 180 ℃;
4) the determination step comprises:
4.1) sample digestion: the biological sample digestion method adopts a microwave digestion method and comprises the following specific steps:
weighing 1.0 g of organism wet sample or 0.2 g of organism dry sample, accurately obtaining 0.0001 g of organism dry sample, placing the organism wet sample or the organism dry sample in a digestion tank of a microwave digestion instrument, adding a little water for wetting, adding 10 mL of the nitric acid of 2.2), screwing a bottle cap after the reaction is stable, placing the bottle cap in the microwave digestion instrument, and digesting according to the reference working conditions of the microwave digestion instrument; after digestion, cooling to room temperature, taking out, carefully unscrewing a cover, placing a digestion tank on an acid dispelling device, heating to dispel acid, setting the acid dispelling temperature at 160 ℃, adding 1.0 mL of the nitric acid solution B of 2.4) when the solution is nearly dry, carrying out micro-heating digestion, transferring the digestion solution into a 25 mL colorimetric tube after cooling, adding water to fix the volume to a marked line, uniformly mixing, standing, and taking supernatant, wherein the supernatant is the digestion solution;
simultaneously preparing a blank solution according to the same steps of the biological sample digestion method;
the reference working conditions of the microwave digestion instrument are as follows: the power is 1600W, the temperature is increased for 6 min, the temperature is 120 ℃, and the holding time is 6 min; the power is 1600W, the temperature is increased for 6 min, the temperature is 180 ℃, and the holding time is 15 min;
4.2) standard curve drawing: taking 9 100 mL volumetric flasks, adding 0 mL, 0.05 mL, 0.10 mL, 0.50 mL, 1.00 mL, 2.00 mL, 5.00 mL, 10.00 mL of the standard use solution of the 2.7) and 5.00 mL of the standard intermediate solution of the 2.6) by using a micropipette or a pipette, diluting the solutions to a marked line by using the nitric acid solution A of the 2.3) to prepare standard series solutions with the concentrations of 0 [ mu ] g/L, 0.50 [ mu ] g/L, 1.00 [ mu ] g/L, 5.00 [ mu ] g/L, 10.00 [ mu ] g/L, 20.0 [ mu ] g/L, 50.0 [ mu ] g/L, 100 [ mu ] g/L and 500 [ mu ] g/L, measuring the standard series solutions by using an inductively coupled plasma emission spectrometer under reference working conditions, and drawing a standard curve according to the measurement results;
4.3) respectively measuring the digestion solution and the blank solution according to the reference working condition of the inductively coupled plasma emission spectrometer, wherein the measured values are X respectively0And Xi；
The reference working conditions of the inductively coupled plasma emission spectrometer are as follows: the radio frequency power is 1300W, the plasma gas flow is 15L/min, the carrier gas flow is 0.65L/min, the sample flow is 1.5L/min, and the sample introduction time is 30 s;
4.4) calculating the concentration value of each element in the digestion solution of the biological sample by using a linear regression equation of a standard curve, calculating the content of the element to be detected in the biological sample according to the formula (1), and recording the test result by using a table;
in the formula:
w i content of the element to be determined in the biological sample, Unit 10-6；
X i The concentration of the element to be detected in the digestion solution of the biological sample is unit mug/L;
X 0 -the concentration of the element to be measured in the blank solution, in μ g/L;
Vthe constant volume of the digestion solution of the biological sample is L;
m-weighing of the biological sample in g.
2. The method for determining the main heavy metal elements in marine organisms according to claim 1, wherein: soaking the required glassware in 20% nitric acid for 24h, repeatedly washing with water, and finally washing with the water of 2.1).
3. The method for determining the main heavy metal elements in marine organisms according to claim 1, wherein: detection limit of 1.0 × 10-6(ii) a Lead: 0.5X 10-6(ii) a Zinc: 2.0X 10-6(ii) a Cadmium: 0.3X 10-6(ii) a Chromium: 0.3X 10-6(ii) a Arsenic: 0.3X 10-6。
4. The method for determining the main heavy metal elements in marine organisms according to claim 1, wherein: the recovery rate is 80-120%.
5. The method for determining the main heavy metal elements in marine organisms according to claim 1, wherein: the relative standard deviation within a batch is less than 10% and the relative standard deviation between batches is less than 10%.
6. The method for determining the main heavy metal elements in marine organisms according to claim 1, wherein: in the step 4.1), if the blank value is too high, the analysis and test process of the reagent blank and the sample is checked, and the reagent with higher purity is selected or purified to reduce the interference of the reagent; when the sample is digested, the amount of the acid can be properly increased or decreased according to the amount of the sample.
7. The method for determining the main heavy metal elements in marine organisms according to claim 1, wherein: in the step 4.2), the range of the standard curve can be adjusted according to the content of the element to be detected in the sample, or the sample digestion solution is diluted, so that the linearity of the standard curve is ensured, and the content of the element to be detected is ensured to be in the range of the drawn standard curve.
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|---|---|---|---|---|
| CN114210727A (en) * | 2021-12-17 | 2022-03-22 | 生态环境部南京环境科学研究所 | Preparation method of heavy metal contaminated soil phytoremediation enhancer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5986757A (en) * | 1997-09-17 | 1999-11-16 | The United States Of America As Represented By The Secretary Of The Navy | Correction of spectral interferences arising from CN emission in continuous air monitoring using inductively coupled plasma atomic emission spectroscopy |
| CN101349646A (en) * | 2007-07-19 | 2009-01-21 | 北京有色金属与稀土应用研究所 | Method for measuring impurity in high pure gold by plasma atomic emission spectrometer |
| CN104215627A (en) * | 2014-05-09 | 2014-12-17 | 武汉红金龙印务股份有限公司 | Method for microwave digestion-inductively coupled plasma mass spectrometer (ICP-MS) determination of metal ions such as lead, arsenic, cadmium and chromium in cigarette case |
| CN110320264A (en) * | 2019-08-09 | 2019-10-11 | 福建省农业科学院农业质量标准与检测技术研究所 | Inductively coupled plasma mass spectrometry measure marine sediment in lead, cadmium, chromium, copper, zinc, nickel content detection method |
-
2021
- 2021-04-15 CN CN202110403135.2A patent/CN113109322A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5986757A (en) * | 1997-09-17 | 1999-11-16 | The United States Of America As Represented By The Secretary Of The Navy | Correction of spectral interferences arising from CN emission in continuous air monitoring using inductively coupled plasma atomic emission spectroscopy |
| CN101349646A (en) * | 2007-07-19 | 2009-01-21 | 北京有色金属与稀土应用研究所 | Method for measuring impurity in high pure gold by plasma atomic emission spectrometer |
| CN104215627A (en) * | 2014-05-09 | 2014-12-17 | 武汉红金龙印务股份有限公司 | Method for microwave digestion-inductively coupled plasma mass spectrometer (ICP-MS) determination of metal ions such as lead, arsenic, cadmium and chromium in cigarette case |
| CN110320264A (en) * | 2019-08-09 | 2019-10-11 | 福建省农业科学院农业质量标准与检测技术研究所 | Inductively coupled plasma mass spectrometry measure marine sediment in lead, cadmium, chromium, copper, zinc, nickel content detection method |
Non-Patent Citations (1)
| Title |
|---|
| 陈伟珍 等: "微波消解ICP-AES法测定食品中重金属的研究", 《食品研究与开发》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114210727A (en) * | 2021-12-17 | 2022-03-22 | 生态环境部南京环境科学研究所 | Preparation method of heavy metal contaminated soil phytoremediation enhancer |
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