CN112557560A - Detection method for detecting selenate and selenite in soil by HPLC-ICP-MS - Google Patents
Detection method for detecting selenate and selenite in soil by HPLC-ICP-MS Download PDFInfo
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Abstract
The invention discloses a detection method for detecting selenate and selenite in soil by HPLC-ICP-MS, which comprises the following steps: (1) sample pretreatment; (2) determination of total selenium in soil; (3) measuring the selenium form in the soil; (4) and (5) establishing a method. The method for simultaneously measuring the forms of selenium such as selenate and selenite in the soil by adopting a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) combined technology is proposed for the first time, and the method has the following advantages: (1) the extraction process and the pretreatment time are short, the precision and the accuracy are good, and the method can be used for large-batch detection. (2) Qualitative and quantitative analysis of selenate and selenite in soil is realized, the detection limit of various selenium form methods is lower than 0.02mg/kg, the precision (RSD) reaches within 10 percent, the sample standard recovery rate reaches 80 to 120 percent, and the analysis requirement of actual samples is met. (3) Provides a feasible method for simultaneously analyzing the selenium form in the soil, and fills the technical blank of the detection of the selenium form in the soil.
Description
Technical Field
The invention relates to a detection method for detecting selenate and selenite in soil by HPLC-ICP-MS.
Background
Selenium is one of essential trace elements for human body, is an important component for forming glutathione peroxidase, and has the functions of delaying senility, resisting and preventing cancers, improving immunity, antagonizing heavy metal toxicity, eliminating harmful free radicals in human body and the like. Meanwhile, selenium is one of typical bifunctional elements, the physiological demand range is narrow, and the selenium deficiency can be caused by low daily intake; too high daily intake can lead to selenium poisoning. After the selenium in the soil is absorbed by plants, the selenium is absorbed and utilized by human bodies through plant chains, which is the most main source of the selenium in the human bodies. The absorption effect of plants on selenium not only depends on the total amount of selenium, but also is closely related to the chemical form of selenium. Selenite and selenate can be dissolved in water or adsorbed on the surface of soil, the plant utilization rate is highest, while elemental selenium and selenide cannot be dissolved in water, and the plant utilization rate is low, so that the morphological analysis of the selenate and the selenite in the soil has important significance.
At present, the national standard methods for measuring the selenium content in soil comprise NY/T1104-2006 soil total selenium measurement and HJ680-2013 soil and sediment mercury, arsenic, selenium, bismuth and antimony microwave digestion/atomic fluorescence measurement, but the total amount of selenium in soil can only be measured. For extraction of selenium form in soil, at present, a continuous leaching method (seven-step extraction) is mostly adopted at home and abroad to measure water-soluble form, ion exchange form, carbonate binding form, humic acid binding form, iron-manganese binding form, strong organic binding form and residue form selenium in soil, but the continuous leaching method has complex extraction steps, easily causes selenium loss and form conversion, and can only measure the total amount of selenium element in each state of extracting solution. A detection method for simultaneously analyzing selenate and selenite in soil has not been reported in documents at present.
The method combines the current test situation of selenium form analysis at present, and establishes an analysis method for measuring selenate and selenite in soil by fully researching and comparing a sample extraction mode, a measurement method selection, instrument parameter conditions and the like, and a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) combined technology, wherein the technical indexes of test quality can meet the analysis requirements of actual samples: the detection limit of the selenium form is lower than 0.02mg/kg, the precision reaches within 10 percent, and the sample standard adding recovery rate is between 80 and 120 percent and is superior to the DD2005-03 technical requirement for analyzing the ecological geochemical evaluation sample. Provides technical support and scientific basis for the efficient and scientific utilization of the selenium-rich soil and the production of selenium-rich agricultural products.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention firstly provides an analysis method for measuring selenate and selenite in soil by adopting a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) combined technology, and realizes simultaneous analysis. Provides a feasible method for analyzing the selenium form in the soil, meets the requirement of geological work development, provides technical support for the land quality ecological geochemical investigation work, and also provides powerful technical support for the high-efficiency scientific benefit of the selenium-rich soil. .
In order to achieve the purpose, the invention provides the following technical scheme:
a detection method for measuring selenate and selenite in soil by HPLC-ICP-MS comprises the following steps:
(1) sample pretreatment
Placing the soil in an air-drying disc, spreading the soil into a thin layer of 2-3 cm, crushing and turning the soil in time, and picking out broken stones, gravels and plant residues. And after air drying, pouring the sample on an organic glass plate, crushing the sample again by using a wood bar and an organic glass bar, picking out impurities, mixing the impurities uniformly, and taking the crushed sample by a quartering method through a nylon sieve with the aperture of 0.25mm (20 meshes). And placing all the sieved samples on a colorless polyethylene film, fully and uniformly stirring, taking two parts of the sieved samples by a quartering method, storing one part of the samples in a sample warehouse, and finely grinding the other part of the samples. All samples for fine grinding are sieved by a sieve with the aperture of 0.15mm (100 meshes), and finally, the samples are sealed in a polyethylene plastic sample bottle for standby;
(2) determination of total selenium in soil
Measuring total selenium by adopting an acid dissolution digestion/atomic fluorescence method;
(3) determination of selenium form in soil
Determination of selenium morphology in soil samples by ultrasonic extraction: weighing 0.5000g of soil sample in a centrifuge tube, adding 10.00mL of 0.1mol/L sodium hydroxide solution, mixing uniformly, placing in an ultrasonic cleaner, and performing ultrasonic extraction for 30min at the temperature of 55 ℃; centrifuging at 8000r/min for 5min after ultrasonic treatment, filtering the supernatant with 0.45 μm water-based filter membrane, and performing selenium morphological analysis according to the working conditions of the instrument; reagent blank experiments were performed in the same manner.
(4) Method establishment
An analysis method for determining selenate and selenite in soil by using a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) combined technology is established, and comprises the following steps:
and (3) preparing a standard curve: preparing the selenium form standard sample into SeIV, SeVI, SeMet and SeCys2The selenium form mixed standard solution with the concentration of 100 mu g/L is respectively transferred into a 10mL volumetric flask with the selenium form mixed standard of 0, 0.10, 0.20, 0.50, 1.00, 2.00 and 5.00mL, diluted to the marked line by ultrapure water and mixed evenly. The concentrations of the mixed standard calibration series solution of the selenium form are 0.00, 1.00, 2.00, 5.00, 10.00, 20.00 and 50.00 mu g/L. And (3) carrying out selenium form analysis on the selenium form mixed standard calibration series solution according to the working conditions of the instrument, determining the peak area of the selenium form, and drawing a standard curve by taking the concentration of the selenium form as a horizontal coordinate and the peak area of the selenium form as a vertical coordinate.
Measurement of sample solution: and (3) analyzing the blank solution and the sample solution according to the working conditions of the instrument, determining the peak area of the selenium form, and obtaining the concentration of the selenium form in the sample solution according to a standard curve. If the concentration of the detected selenium form exceeds the concentration range of the calibration curve, the selenium form should be diluted and then measured again.
And (4) calculating a result: the amount of selenium in the sample is calculated according to formula (1):
in the formula:
x is the selenium form content in the sample, and the unit is mg/kg;
rho is the concentration of the selenium form in the test solution, mu g/L, found by a calibration curve;
ρ0-the measured concentration of the selenium form in the blank solution, μ g/L;
v is the volume of the determined test solution with constant volume, mL;
m-weight of sample, g;
1000-conversion factor.
The qualitative method comprises the following steps:
selenate and selenite are all prepared from77Se is a detected mass number, and the relative deviation of the retention time of the chromatographic peaks of selenate and selenite in the sample and the standard sample is notAnd if the content is more than 5%, judging that selenate and selenite exist in the sample.
The quantitative method comprises the following steps:
and (3) analyzing the selenate and selenite mixed standard working solution according to the conditions of the instrument, drawing a standard working curve by taking the concentration as an abscissa and the peak area as an ordinate, and quantifying the sample by using the standard working curve to ensure that the response values of the selenate and the selenite are within a measurement linear range.
Quality assurance and control:
blank test
Taking 1 batch of 20 samples, 1 blank experiment should be carried out, and the content of selenium form in the determination result should not exceed the detection limit of the method.
Calibration
The standard curve should contain at least 5 non-zero concentration points and the correlation coefficient r ≧ 0.995.
Parallel assay
One replicate should be analyzed every 20 samples or batch (less than 20 samples/batch), and the relative deviation of the parallel sample measurements should be < 10%.
The invention has the technical effects and advantages that: the method for simultaneously measuring the forms of selenium such as selenate and selenite in the soil by adopting a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) combined technology is proposed for the first time, and the method has the following advantages according to the technical characteristics and the analysis and summary of the practical application condition:
(1) the extraction process and the pretreatment time are short, the precision and the accuracy are good, and the method can be used for large-batch detection.
(2) Qualitative and quantitative analysis of selenate and selenite in soil is realized, the detection limit of various selenium form methods is lower than 0.02mg/kg, the precision (RSD) reaches within 10 percent, the sample standard recovery rate reaches 80 to 120 percent, and the analysis requirement of actual samples is met.
(3) Provides a feasible method for simultaneously analyzing the selenium form in the soil, and fills the technical blank of the detection of the selenium form in the soil.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a total ion flow diagram of selenate and selenite standard substances.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
First, instrument and main reagent
Inductively coupled plasma mass spectrometers (model 7700, Agilent, usa); high performance liquid chromatography (model 1200, Agilent, usa); PRP X-100 analytical column (250 mm. times.4.1 mm, 10 μm, Hamilton, Switzerland), PRP X-100 guard column (20 mm. times.2.1 mm, 10 μm, Hamilton, Switzerland); the chromatographic column is connected with an ICP-MS atomizer by a PEEK pipe.
MARS microwave digestion System (CEM, USA). Ultrasonic cleaning apparatus (SB-1000DYD type, Ningbo Xinzhi Biotech Co., Ltd.). A vacuum freeze dryer (model LGJ-30FD, huaxing scientific and technological development ltd, beijing pine source).
Selenate standard solution (GBW10033), selenite standard solution (GBW 10032): purchased from the national institute of metrology science. The mass spectrum tuning solution (Agilent company, USA) is a mixed standard solution with Li, Y, Ce, Tl and Co concentrations of 1 mug/L. Citric acid, ammonia water and sodium hydroxide are all analytically pure. The experimental water was ultrapure water.
Second, the working conditions of the instrument
The working conditions of HPLC and ICP-MS are shown in Table 1.
TABLE 1 working conditions List for HPLC and ICP-MS
Third, sample pretreatment
According to the requirements of technical Specification for soil environmental monitoring (HJ/T166-2004), soil is placed in an air drying disc, spread into a thin layer of 2-3 cm, crushed and turned over timely, and broken stones, gravels and plant residues are picked up. And after air drying, pouring the sample on an organic glass plate, crushing the sample again by using a wood bar and an organic glass bar, picking out impurities, mixing the impurities uniformly, and taking the crushed sample by a quartering method through a nylon sieve with the aperture of 0.25mm (20 meshes). And placing all the sieved samples on a colorless polyethylene film, fully and uniformly stirring, taking two parts of the sieved samples by a quartering method, storing one part of the samples in a sample warehouse, and finely grinding the other part of the samples. All samples for fine grinding were sieved through a 0.15mm (100 mesh) mesh sieve and finally sealed in a polyethylene plastic sample bottle for later use.
Fourthly, the selenium form in the soil sample is determined by ultrasonic extraction
Weighing 0.5000g of soil sample in a centrifuge tube, adding 10.00mL of 0.1mol/L sodium hydroxide solution, mixing uniformly, placing in an ultrasonic cleaner, and performing ultrasonic extraction for 30min at the temperature of 55 ℃. Centrifuging at 8000r/min for 5min after ultrasonic treatment, filtering the supernatant with 0.45 μm water-based filter membrane, and performing selenium morphological analysis according to the working conditions of the instrument. Reagent blank experiments were performed in the same manner.
Fifth, making standard curve
Preparing the selenium form standard sample into SeIV, SeVI, SeMet and SeCys2The selenium form mixed standard solution with the concentration of 100 mu g/L is respectively transferred into a 10mL volumetric flask with the selenium form mixed standard of 0, 0.10, 0.20, 0.50, 1.00, 2.00 and 5.00mL, diluted to the marked line by ultrapure water and mixed evenly. The concentrations of the mixed standard calibration series solution of the selenium form are 0.00, 1.00, 2.00, 5.00, 10.00, 20.00 and 50.00 mu g/L. And (3) carrying out selenium form analysis on the selenium form mixed standard calibration series solution according to the working conditions of the instrument, determining the peak area of the selenium form, and drawing a standard curve by taking the concentration of the selenium form as a horizontal coordinate and the peak area of the selenium form as a vertical coordinate.
Sixthly, measurement of sample solution
And (3) analyzing the blank solution and the sample solution according to the working conditions of the instrument, determining the peak area of the selenium form, and obtaining the concentration of the selenium form in the sample solution according to a standard curve. If the concentration of the detected selenium form exceeds the concentration range of the calibration curve, the selenium form should be diluted and then measured again.
Seventhly, calculating the result
The amount of selenium in the sample is calculated according to formula (1):
in the formula:
x is the selenium form content in the sample, and the unit is mg/kg;
rho is the concentration of the selenium form in the test solution, mu g/L, found by a calibration curve;
ρ0-the measured concentration of the selenium form in the blank solution, μ g/L;
v is the volume of the determined test solution with constant volume, mL;
m-weight of sample, g;
1000-conversion factor.
Eighth, qualitative method
Selenate and selenite are all prepared from77Se is a detection mass number, the relative deviation of the retention time of the chromatographic peaks of selenate and selenite in the sample and the standard substance is not more than 5 percent, and the existence of selenate and selenite in the sample can be judged.
Ninth, quantitative method
And (3) analyzing the selenate and selenite mixed standard working solution according to the conditions of the instrument, drawing a standard working curve by taking the concentration as an abscissa and the peak area as an ordinate, and quantifying the sample by using the standard working curve to ensure that the response values of the selenate and the selenite are within a measurement linear range. Under the above instrument conditions, the total ion flow diagram of selenate and selenite standard substance liquid is shown in figure 2.
Ninth, quality assurance and control
9.1 blank test
Taking 1 batch of 20 samples, 1 blank experiment should be carried out, and the content of selenium form in the determination result should not exceed the detection limit of the method.
9.2 calibration
The standard curve should contain at least 5 non-zero concentration points and the correlation coefficient r ≧ 0.995.
9.3 parallel assay
One replicate should be analyzed every 20 samples or batch (less than 20 samples/batch), and the relative deviation of the parallel sample measurements should be < 10%.
The points to be finally explained are: first, in the description of the present application, it should be noted that, unless otherwise specified and limited, the terms "mounted," "connected," and "connected" should be understood broadly, and may be a mechanical connection or an electrical connection, or a communication between two elements, and may be a direct connection, and "upper," "lower," "left," and "right" are only used to indicate a relative positional relationship, and when the absolute position of the object to be described is changed, the relative positional relationship may be changed;
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (7)
1. A detection method for measuring selenate and selenite in soil by HPLC-ICP-MS is characterized by comprising the following steps: the method comprises the following steps:
(1) sample pretreatment
Placing the soil in an air-drying disc, spreading the soil into a thin layer of 2-3 cm, crushing and turning the soil in time, and picking out broken stones, gravels and plant residues; after air drying, pouring the sample on an organic glass plate, crushing the sample again by using a wood bar and an organic glass bar, picking up impurities, mixing the impurities uniformly, taking the crushed sample by using a quartering method, sieving the crushed sample by using a sieve with the aperture of 0.25mm/20 meshes, putting all the sieved samples on a colorless polyethylene film, fully and uniformly stirring the samples, taking two parts of the crushed samples by using the quartering method, storing one part of the samples in a sample storage, and finely grinding the other part of the samples; all samples for fine grinding are sieved by a sieve with the aperture of 0.15mm/100 meshes, and finally, the samples are sealed in a polyethylene plastic sample bottle for standby;
(2) determination of total selenium in soil
Measuring total selenium by adopting an acid dissolution digestion/atomic fluorescence method;
(3) determination of selenium form in soil
Determining the selenium form in the soil sample by ultrasonic extraction;
(4) method establishment
An analytical method for determining selenate and selenite in soil by establishing a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) combined technology comprises the following steps: making a standard curve; measuring a sample solution; calculating a result; performing qualitative analysis; carrying out quantitative analysis; quality assurance and control.
2. The detection method for detecting selenate and selenite in soil by HPLC-ICP-MS as claimed in claim 1, wherein the method for detecting the selenium form in the soil sample by ultrasonic extraction is as follows: weighing 0.5000g of soil sample in a centrifuge tube, adding 10.00mL of 0.1mol/L sodium hydroxide solution, mixing uniformly, placing in an ultrasonic cleaner, and performing ultrasonic extraction for 30min at the temperature of 55 ℃; centrifuging at 8000r/min for 5min after ultrasonic treatment, filtering the supernatant with 0.45 μm water-based filter membrane, and performing selenium morphological analysis according to the working conditions of the instrument; reagent blank experiments were performed in the same manner.
3. The detection method for detecting selenate and selenite in soil by HPLC-ICP-MS as claimed in claim 1, wherein the standard curve is prepared by the following steps: preparing the selenium form standard sample into SeIV, SeVI, SeMet and SeCys2The selenium form mixed standard solution with the concentration of 100 mu g/L is respectively transferred and taken out of selenium form mixed standard 0, 0.10, 0.20, 0.50, 1.00, 2.00 and 5.00mL in a 10mL volumetric flask, diluted to the marked line by ultrapure water and mixed evenly; the concentration of the selenium form mixed standard calibration series solution is 0.00, 1.00, 2.00, 5.00, 10.00, 20.00 and 50.00 mu g/L; and (3) carrying out selenium form analysis on the selenium form mixed standard calibration series solution according to the working conditions of the instrument, determining the peak area of the selenium form, and drawing a standard curve by taking the concentration of the selenium form as a horizontal coordinate and the peak area of the selenium form as a vertical coordinate.
4. The detection method for detecting selenate and selenite in soil by HPLC-ICP-MS as claimed in claim 1, wherein the detection method of the sample solution is as follows: performing selenium form analysis on the blank solution and the sample solution according to the working conditions of the instrument, determining the peak area of the selenium form, and obtaining the concentration of the selenium form in the sample solution according to a standard curve; if the concentration of the detected selenium form exceeds the concentration range of the calibration curve, the selenium form should be diluted and then the detection is carried out again;
and (4) calculating a result: the amount of selenium in the sample is calculated according to formula (1):
in the formula:
x is the selenium form content in the sample, and the unit is mg/kg;
rho is the concentration of the selenium form in the test solution, mu g/L, found by a calibration curve;
ρ0-the measured concentration of the selenium form in the blank solution, μ g/L;
v is the volume of the determined test solution with constant volume, mL;
m-weight of sample, g;
1000-conversion factor.
5. The detection method for detecting selenate and selenite in soil by HPLC-ICP-MS as claimed in claim 1, wherein the qualitative analysis method is as follows:
selenate and selenite are all prepared from77Se is a detection mass number, the relative deviation of the retention time of the chromatographic peaks of selenate and selenite in the sample and the standard substance is not more than 5 percent, and the existence of selenate and selenite in the sample can be judged.
6. The detection method for detecting selenate and selenite in soil by HPLC-ICP-MS as claimed in claim 1, wherein the quantitative analysis method is as follows:
and (3) analyzing the selenate and selenite mixed standard working solution according to the conditions of the instrument, drawing a standard working curve by taking the concentration as an abscissa and the peak area as an ordinate, and quantifying the sample by using the standard working curve to ensure that the response values of the selenate and the selenite are within a measurement linear range.
7. The detection method for detecting selenate and selenite in soil by HPLC-ICP-MS as claimed in claim 1, wherein the quality assurance and control method comprises:
blank test: taking 20 samples as 1 batch, and performing 1 blank experiment, wherein the content of the selenium form in the determination result should not exceed the detection limit of the method;
calibration: the standard curve should at least contain 5 non-zero concentration points, and the correlation coefficient r is more than or equal to 0.995;
and (3) parallel determination: one replicate should be analyzed every 20 samples or batch (less than 20 samples/batch), and the relative deviation of the parallel sample measurements should be < 10%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114705767A (en) * | 2022-03-01 | 2022-07-05 | 海南省食品检验检测中心(海南省实验动物中心) | Analysis and detection method for selenium form in rice |
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| CN103399117A (en) * | 2013-08-26 | 2013-11-20 | 中国水产科学研究院黄海水产研究所 | Detection method of selenium form in aquatic product |
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| CN103399117A (en) * | 2013-08-26 | 2013-11-20 | 中国水产科学研究院黄海水产研究所 | Detection method of selenium form in aquatic product |
| CN108693241A (en) * | 2018-03-30 | 2018-10-23 | 江西省农业科学院农产品质量安全与标准研究所 | Method that is a kind of while measuring selenium and cadmium in soil |
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| CN114705767A (en) * | 2022-03-01 | 2022-07-05 | 海南省食品检验检测中心(海南省实验动物中心) | Analysis and detection method for selenium form in rice |
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