CN111060632A - Method for detecting tetraethyl lead in water - Google Patents
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- CN111060632A CN111060632A CN201911238188.2A CN201911238188A CN111060632A CN 111060632 A CN111060632 A CN 111060632A CN 201911238188 A CN201911238188 A CN 201911238188A CN 111060632 A CN111060632 A CN 111060632A
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- 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
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Abstract
The invention discloses a method for detecting tetraethyl lead in water, which comprises the following steps: (1) preparing tetraethyl lead standard solution, and filling the tetraethyl lead standard solution in a sample bottle; (2) adding methanol into a sample bottle, and then adding a water sample to obtain a detection water sample; (3) analyzing the standard solution obtained in the step (1) by using purging and trapping-gas chromatography/mass spectrometry, and obtaining an linear regression equation y as bx + a according to the concentration of the standard solution and the peak area generated by an instrument, wherein x is the concentration of tetraethyl lead, and y is the peak area; (4) analyzing the detected water sample in the step (2) by using a purging and trapping-gas chromatography/mass spectrometry method, and calculating the concentration of the tetraethyl lead in the sample by using a regression equation in the step (3). The problems of complicated operation steps, low precision and low sensitivity of the detection method in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of water quality environment monitoring, in particular to a method for detecting tetraethyl lead in water.
Background
Tetraethyl lead is an organometallic compound that is 100 times more toxic than metallic lead. It is very volatile at normal temperature, can be poisoned by skin contact and inhalation, and tetraethyl lead is a severe nerve poison and is easy to invade the central nervous system. The national standards of environmental quality of surface water (GB3838-2002) and sanitary Standard of Drinking Water (GB5749-2006) both stipulate the limit value of tetraethyl lead, and the limit value is required to be not more than 0.0001 mg/L. Tetraethyl lead is widely used as an additive in gasoline once, and in order to protect the environment, the national technical supervision agency issues mandatory national standards of vehicle unleaded gasoline on 28 th 12 th 1999, and starts to implement on 1 st 2000. So far, tetraethyl lead can still be detected from some environmental water bodies, soil and human blood, and certain harm is caused to the environment.
The dithizone colorimetric method is recommended in 'Metal index of Standard test method for Drinking Water' GB/T5750.6-2006, the whole detection process needs extraction, concentration, bromination, addition of a color-developing agent and the like, the operation is complicated, the precision and the sensitivity are not high, the detection limit is equivalent to the evaluation standard, whether tetraethyl lead pollution exists or not can not be accurately judged, and the used potassium cyanide is a highly toxic substance and has potential threats to the environment and experimenters.
At present, the detection method of tetraethyl lead in water mainly comprises a spectrophotometry method, an atomic absorption spectrometry method, a gas chromatography-mass spectrometry method, a plasma emission mass spectrometry method, a liquid chromatography method and the like. For example, the methods for measuring tetraethyl lead in an environmental water sample by a graphite furnace atomic absorption method published in 2009 in environmental monitoring of china, the methods for measuring tetraethyl lead by a double gas circuit calibration-solid phase microextraction inductively coupled plasma mass spectrometry published in 2007 in analytical laboratories, the methods for measuring tetraethyl lead in water by an automatic headspace-gas chromatography published in 2014 in environmental science and technology, the methods for measuring tetraethyl lead in water by a solid phase extraction-gas chromatography published in 2012 in physicochemical examination-chemical division book in 2012 in 2011 in the environmental monitoring management and technology in 2011 in the methods for measuring tetraethyl lead in water by a liquid-liquid extraction-high performance liquid chromatography. Some detection methods have complicated operation steps, and some detection methods have sensitivity which cannot meet the requirement of environmental quality analysis.
Disclosure of Invention
Aiming at the problems mentioned in the background technology, the invention provides a method for detecting tetraethyl lead in water, which solves the problems of complicated operation steps and low precision and sensitivity of the detection method in the prior art.
In order to achieve the above object, the present invention provides a method for detecting tetraethyl lead in water, comprising the following steps:
(1) preparing tetraethyl lead standard solution, and filling the tetraethyl lead standard solution in a sample bottle;
(2) adding methanol into a sample bottle, and then adding a water sample to obtain a detection water sample;
(3) analyzing the standard solution obtained in the step (1) by using purging and trapping-gas chromatography/mass spectrometry, and obtaining an linear regression equation y which is bx + a according to the concentration of the standard solution and the peak area generated by an instrument, wherein x is the concentration of tetraethyl lead, and y is the peak area;
(4) analyzing the detected water sample in the step (2) by using a purging and trapping-gas chromatography/mass spectrometry method, and calculating the concentration of the tetraethyl lead in the sample by using a regression equation in the step (3).
Further, the purging and trapping conditions in the step (3) and the step (4) are as follows: the blowing temperature is 20-35 ℃; purge flow rate: 30-45 ml/min; purging time: 7-11 min; dry purge time: 1 min; pre-desorption temperature: 180 ℃; desorption temperature: 190 ℃; desorption time: 2 min; baking temperature: 200 ℃; baking time: and 6 min.
Further, the gas chromatography conditions in step (3) and step (4) are as follows: sample inlet temperature: 220-280 ℃; carrier gas: helium gas; sample introduction mode: shunting and sampling; column flow rate: 0.8-1.2 ml/min; temperature rising procedure: the initial temperature is 30-50 ℃, and the temperature is increased to 180-220 ℃.
Furthermore, the split ratio of split sampling is 3: 1-7: 1.
Furthermore, the initial temperature is kept at 30-50 ℃ for 1min, and the temperature is kept for 1min after being increased to 180-220 ℃.
Furthermore, the heating rate is 10-20 ℃/min.
Further, the mass spectrum conditions in the step (3) and the step (4) are as follows: an ion source: an EI source; ion source temperature: 230 ℃; ionization energy: 70 eV; interface temperature: 280 ℃; quadrupole temperature: 150 ℃; the scanning mode is as follows: selecting ion scanning; target scanning ion: 208, 237, 295; and (3) quantifying ions: 237.
further, a purging and trapping-gas chromatography/mass spectrometry method is characterized in that a sample is placed in a purging sample bottle, the tetra-ethyl lead in the sample is adsorbed in a trapping pipe after being purged by high-purity nitrogen, the trapping pipe is heated and back-purged by the high-purity nitrogen, components desorbed by heat are separated by gas chromatography, a mass spectrometer is used for detection, and the components are qualitative through retention time of a target object to be detected and a standard mass spectrogram, and are quantitative through peak areas.
Compared with the traditional detection method:
the detection method has the advantages of simple operation flow, high detection precision and sensitivity, more accurate detection data and capability of accurately judging whether the environment is polluted by the tetraethyl lead contained in the water; meanwhile, the detection reagent used by the invention does not contain highly toxic substances, does not cause harm to the environment, does not cause damage to the health of experimenters, and realizes the protection of the environment and the health of the experimenters.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the detection method provided by the invention is simple in operation flow, high in detection precision and sensitivity, more accurate in detection data, and capable of accurately judging whether the environment is polluted by the tetraethyl lead contained in the water.
(2) The detection reagent used in the invention has no highly toxic substances, does not cause harm to the environment, does not cause damage to the health of experimenters, and realizes the protection of the environment and the health of the experimenters.
Detailed Description
All features disclosed in this specification may be combined in any combination, except features and/or steps that are mutually exclusive.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to specific examples.
1. Selection of purge time
The test was carried out at room temperature with the same concentration of 1.00. mu.g/L of the standard solution at purge times of 7, 8, 9, 10 and 11min, respectively. And drawing a curve by taking the purging time as an abscissa and the chromatographic peak area of the target as an ordinate. When the purge time was 9min, the chromatographic peak area was the largest, and therefore, the tetraethyl lead purge time was determined to be 9 min.
2. Selection of purge flow rate
Under the condition of determined purging time, the purging flow rates of 30 ml/min, 33 ml/min, 35 ml/min, 40ml/min and 45ml/min are respectively set for the same standard solution with the concentration of 1.00 mu g/L, and curves are drawn by taking the purging flow rate as an abscissa and the chromatographic peak area of the target as an ordinate. When the purge flow rate was 40ml/min, the chromatographic peak area was the largest, and therefore, the tetraethyl lead flow rate was determined to be 40 ml/min.
3. Selection of purge temperature
Under the condition of determined purging time, the temperatures of the purging tubes of the standard solution with the same concentration of 1.00 mu g/L are respectively set to be 20 ℃, 25 ℃, 30 ℃ and 35 ℃ for testing, and a curve is drawn by taking the purging temperature as an abscissa and the chromatographic peak area of the target object as an ordinate. When the purge temperature was 25 ℃, the chromatographic peak area was the largest, and therefore, the tetraethyl lead purge temperature was determined to be 25 ℃.
4. Selection of gas chromatography conditions
On the premise of ensuring the gasification efficiency of tetraethyl lead, selecting the temperature of a sample inlet to be 250 ℃, selecting the flow rate of a column to be 1.0ml/min, and selecting a split ratio of 5: 1, the initial temperature is 40 ℃, the temperature is kept for 1min, the temperature is raised to 200 ℃ at the speed of 15 ℃/min, and the temperature is kept for 1 min.
5. Selection of purge trap conditions
Purging temperature: 25 ℃; purge flow rate: 40 ml/min; purging time: 9 min; dry purge time: 1 min; pre-desorption temperature: 180 ℃; desorption temperature: 190 ℃; desorption time: 2 min; baking temperature: 200 ℃; baking time: and 6 min.
6. Selection of Mass Spectrometry conditions
An ion source: an EI source; ion source temperature: 230 ℃; ionization energy: 70 eV; interface temperature: 280 ℃; fourth-stage rod temperature: 150 ℃; the scanning mode is as follows: a selective ion Scan (SIM); target scanning ion: 208, 237, 295; and (3) quantifying ions: 237.
7. drawing a tetraethyl lead standard curve
100mg/L of tetraethyl lead certified standard solution was diluted with methanol to 1mg/L of standard use solution. Taking 6 50ml volumetric flasks, respectively adding 1ml methanol, preparing the tetraethyl lead standard use solution into standard curve series with the concentrations of 0.00, 0.10, 0.50, 1.00, 2.00 and 5.00 mu g/L, and measuring the tetraethyl lead by adopting a purging trapping-gas chromatography/mass spectrometry method to obtain a linear relation regression equation of the concentration of the tetraethyl lead standard series and the chromatographic peak area: 27592.965 x-2242.777.
8. Sample assay
Adding 0.80ml of methanol into 40ml of sample, directly carrying out computer analysis, and calculating according to a standard curve to obtain the concentration of tetraethyl lead in the water sample of 0.04 mu g/L;
taking 40ml of domestic drinking water, putting the drinking water into a sample bottle added with 0.80ml of methanol, and directly carrying out on-machine analysis, wherein the result shows that the concentration of the tetra-ethyl lead in the sample is less than 0.03 mu g/L, and the standard addition recovery rate is 92.5-98.8%;
taking 40ml of surface water, putting the surface water into a sample bottle added with 0.80ml of methanol, and directly carrying out computer analysis, wherein the result shows that the concentration of tetraethyl lead in the sample is 0.06 mu g/L, and the standard addition recovery rate is 82.9-95.7%;
taking 40ml of sewage into a sample bottle added with 0.80ml of methanol, and directly carrying out on-machine analysis, wherein the result shows that the concentration of tetraethyl lead in the sample is 0.17 mu g/L, and the standard addition recovery rate is 85.9-93.7%.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (8)
1. A method for detecting tetraethyl lead in water is characterized by comprising the following steps:
(1) preparing tetraethyl lead standard solution, and filling the tetraethyl lead standard solution in a sample bottle;
(2) adding methanol into a sample bottle, and then adding a water sample to obtain a detection water sample;
(3) analyzing the standard solution obtained in the step (1) by using purging and trapping-gas chromatography/mass spectrometry, and obtaining an linear regression equation y as bx + a according to the concentration of the standard solution and the peak area generated by an instrument, wherein x is the concentration of tetraethyl lead, and y is the peak area;
(4) analyzing the detected water sample in the step (2) by using a purging and trapping-gas chromatography/mass spectrometry method, and calculating the concentration of the tetraethyl lead in the sample by using a regression equation in the step (3).
2. The method for detecting tetraethyl lead in water according to claim 1, wherein the purging and trapping conditions in step (3) and step (4) are as follows: the blowing temperature is 20-35 ℃; purge flow rate: 30-45 ml/min; purging time: 7-11 min; dry purge time: 1 min; pre-desorption temperature: 180 ℃; desorption temperature: 190 ℃; desorption time: 2 min; baking temperature: 200 ℃; baking time: and 6 min.
3. The method for detecting tetraethyl lead in water according to claim 1, wherein the gas chromatography conditions in step (3) and step (4) are as follows: sample inlet temperature: 220-280 ℃; carrier gas: helium gas; sample introduction mode: shunting and sampling; column flow rate: 0.8-1.2 ml/min; temperature rising procedure: the initial temperature is 30-50 ℃, and the temperature is increased to 180-220 ℃.
4. The method for detecting tetraethyl lead in water according to claim 3, wherein the split ratio in split sample injection is 3: 1-7: 1.
5. The method for detecting tetraethyl lead in water according to claim 3, wherein the initial temperature is 30-50 ℃ and is kept for 1min, and the temperature is kept for 1min after being increased to 180-220 ℃.
6. The method for detecting tetraethyl lead in water according to claim 3, wherein the temperature rise rate is 10-20 ℃/min.
7. The method for detecting tetraethyl lead in water according to claim 1, wherein the mass spectrometry conditions in step (3) and step (4) are as follows: an ion source: an EI source; ion source temperature: 230 ℃; ionization energy: 70 eV; interface temperature: 280 ℃; quadrupole temperature: 150 ℃; the scanning mode is as follows: selecting ion scanning; target scanning ion: 208, 237, 295; and (3) quantifying ions: 237.
8. a purging trap-gas chromatography/mass spectrometry as claimed in claim 1, characterized in that the sample is filled in a purging sample bottle, tetraethyl lead in the sample is purged with high purity nitrogen and then adsorbed in a trap tube, the trap tube is heated and back-blown with high purity nitrogen, the thermally desorbed components are separated by gas chromatography, detected by a mass spectrometer, and quantified by the retention time with the target to be measured and a standard mass spectrum.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112630329A (en) * | 2020-12-08 | 2021-04-09 | 浙江中一检测研究院股份有限公司 | Method for detecting tetraethyl lead in water by negative pressure headspace gas chromatography-mass spectrometry |
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| CN104360003A (en) * | 2014-12-05 | 2015-02-18 | 山东省城市供排水水质监测中心 | Method for detecting tetraethyl lead in water |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112630329A (en) * | 2020-12-08 | 2021-04-09 | 浙江中一检测研究院股份有限公司 | Method for detecting tetraethyl lead in water by negative pressure headspace gas chromatography-mass spectrometry |
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