WO2022021867A1 - Mercury content measurement method using gas-phase molecular absorption spectrometer - Google Patents

Mercury content measurement method using gas-phase molecular absorption spectrometer Download PDF

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WO2022021867A1
WO2022021867A1 PCT/CN2021/077448 CN2021077448W WO2022021867A1 WO 2022021867 A1 WO2022021867 A1 WO 2022021867A1 CN 2021077448 W CN2021077448 W CN 2021077448W WO 2022021867 A1 WO2022021867 A1 WO 2022021867A1
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gas
mercury
absorption spectrometer
solution
molecular absorption
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PCT/CN2021/077448
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French (fr)
Chinese (zh)
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刘向东
郝俊
薛荔栋
刘丰奎
刘盼西
牛军
臧平安
陆耀
余刚
王美彩
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上海安杰环保科技股份有限公司
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    • G—PHYSICS
    • 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
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/3103—Atomic absorption analysis
    • G—PHYSICS
    • 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
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G—PHYSICS
    • 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
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/3103—Atomic absorption analysis
    • G01N2021/3107—Cold vapor, e.g. determination of Hg

Definitions

  • the invention relates to a method for measuring mercury in sewage, in particular to a method for measuring mercury content by using a gas-phase molecular absorption spectrometer.
  • the mercury standard solution of cold atomic absorption mercury measurement is prepared with HNO 3 +K 2 Cr 2 O 7 , the measurement medium is to reduce excess KMnO 4 with NH 2 OH.CL, and then use SnCL 2 to reduce divalent Hg 2+ is elemental Hg 0 to measure the absorbance of mercury atomic gas.
  • the HNO 3 +K 2 Cr 2 O 7 medium can not guarantee the stability of divalent Hg 2+ , but often volatilizes elemental Hg 0 , which gradually reduces the concentration of the standard solution.
  • SnCL 2 reduces divalent Hg 2+ to elemental Hg 0 , which is only suitable for HCL medium with a low concentration of 1 mol/L.
  • the reduction efficiency of SnCL 2 in a higher concentration HCL medium is very low, but when it is lower than 1 mol/L hydrochloric acid medium, SnCL 2 will hydrolyze and precipitate to block the liquid path, and even cannot be measured.
  • the cold atomic absorption mercury spectrometer or atomic absorption spectrophotometer is usually used for the measurement of elemental Hg 0 content. These devices have low sensitivity and low detection limit, so the detection sensitivity is low.
  • Chinese patent CN 104007076 A discloses a method for measuring mercury in sewage, which belongs to the technical field of analytical chemistry.
  • the basic detection steps include: selecting a standard liquid medium, configuring a standard stock solution, configuring a standard working solution, configuring a NaBH 4 reducing agent solution, pre-processing the sample, and connecting the generated cold vapor mercury atoms to a cold atomic absorption mercury detector for detection.
  • the patent uses a cold atomic absorption mercury measuring instrument for detection, which has high detection limit, large error, and complicated experimental process.
  • the purpose of the present invention is to provide a method for measuring mercury content by gas-phase molecular absorption spectrometer in order to overcome the defects of low detection sensitivity, many reagents used in the measurement method and complicated operation in the prior art.
  • a method for measuring mercury content by gas-phase molecular absorption spectrometer comprising the following steps:
  • step (3) adopt gas-phase molecular absorption spectrometer to detect the water sample to be measured, adopt the detection data of the water sample to be measured, and check the concentration of mercury by the standard curve drawn by step (2);
  • the gas-phase molecular absorption spectrometer adopts two-way injection, one is the mercury standard liquid or the water sample to be tested and potassium dichromate-hydrochloric acid solution, and the other is injected as KBH 4 solution, the two channels are fed into the liquid at the same time and merged with each other.
  • the potassium dichromate-hydrochloric acid solution converts the mercury in the water sample into Hg 2+
  • the KBH 4 solution reduces the Hg 2+ to elemental Hg 0 .
  • Gas-phase molecular absorption spectrometer Elemental Hg 0 was detected.
  • the concentration of the hydrochloric acid solution in the mercury standard stock solution is 0.1-5 mol/L.
  • the concentration of Hg 2+ in the concentration of the mercury standard stock solution is 1-50 ⁇ g/ml, more preferably 10 ⁇ g/ml.
  • the concentration of potassium dichromate in the potassium dichromate solution-hydrochloric acid solution is 0.3-0.8 ⁇ g/ml, more preferably 0.56 ⁇ g/ml, and the concentration of hydrochloric acid is 0.1-5 mol/L, more preferably 1.0 mol/L, the mass fraction of the solute in the KBH 4 solution is 0.1-0.5%, more preferably 0.2%.
  • the volume ratio of the water sample to be tested, the potassium dichromate-hydrochloric acid solution and the KBH 4 solution is 1:0.3-1:0.5-2, more preferably 1:0.5:1.
  • the mass fraction of the solute in the KBH 4 solution is 0.5% to 1%, more preferably 0.2%, and the volume ratio of the mercury standard use solution to the KBH 4 solution is 1:1 ⁇ 1.5, more preferably 1:1.
  • the model of the gas-phase molecular absorption spectrometer is AJ-3610 gas-phase molecular absorption spectrometer.
  • the detection condition of the AJ-3610 gas-phase molecular absorption spectrometer is to use an anode mercury lamp, the working current of the anode mercury lamp is 2-3 mA, and the working wavelength is 253.7 nm.
  • the gas phase molecular absorption spectrometer uses a peristaltic pump for sample introduction.
  • the water sample to be tested comes from surface water, groundwater, domestic sewage or factory discharge water.
  • the present invention has the following advantages:
  • the present invention adopts a single HCL medium to prepare and preserve the standard solution of mercury, mercury generates extremely stable HHgCl complex in a strong HCl medium, and HHgCl will not lose volatilization even if it is boiled in the HCl medium, Therefore, the concentration of the mercury standard stock solution and standard use solution of the present invention is extremely stable. 10ng/ml mercury standard solution, stored at room temperature for one year, the concentration has not changed;
  • the present invention uses 0.2% KBH 4 to reduce Hg 2+ to elemental Hg 0 , the reduction process is stable, and stable absorbance can be obtained in the range of HCL medium concentration of 0.1-5 mol/L. data.
  • the present invention adopts AJ-3610 gas-phase molecular absorption spectrometer, which has high sensitivity, low detection limit, and the minimum detection concentration is 0.002 ⁇ g/L, which is 10 times more accurate than the patent CN 104007076 A, and has a wide range of use, which is obviously better than the general Mercury meter.
  • the present invention adopts hydrochloric acid medium from the preparation of the standard solution to the determination process, and the reagent is single, economical, and easy to operate.
  • (1) adopt the concentration of 0.5mol/L hydrochloric acid solution to dilute the mercury standard stock solution step by step to make the mercury standard use solution, wherein the mercury standard stock solution contains HgCl 2 , hydrochloric acid and water, wherein the concentration of hydrochloric acid is 1mol/L, Hg The concentration of 2+ is 10 ⁇ g/ml;
  • the preparation method of mercury standard use solution is to draw 50 ⁇ l, 100 ⁇ l, 150 ⁇ l, 200 ⁇ l and 250 ⁇ l of mercury standard stock solution with a micropipette and put them into a 100ml volumetric flask, respectively, with 0.5mol/L HCl. Dilute to the mark and shake well to obtain a set of mercury standard solutions with different concentrations;
  • gas-phase molecular absorption spectrometer is used to detect the mercury standard liquid in turn.
  • the working current of the anode mercury lamp is 3mA, and the working wavelength is 253.7 nm.
  • the specific method is that the gas-phase molecular absorption spectrometer adopts a peristaltic pump two-way injection , one way of injection (water sample + potassium dichromate + hydrochloric acid), the other way into KBH 4 solution, adding 1ml of reducing agent containing 0.2% KBH 4 and 0.2% NaOH solution to reduce Hg 2+ to elemental Hg 0 , Turn on the carrier gas first, then start it with one key, and the peristaltic pump will combine the two channels of simultaneous liquid feeding to generate elemental Hg 0 vapor to obtain the analysis result, and the detection data and concentration of the mercury standard liquid are correspondingly drawn into a standard curve;
  • step (3) Take the water sample to be tested and put it in the reaction bottle, use AJ-3610 gas-phase molecular absorption spectrometer for detection, and add 0.5 ml of potassium dichromate-hydrochloric acid solution with a volume ratio of 5:0.5 to make the water sample to be tested.
  • Organic mercury is converted into Hg 2+ , and then 1 ml of 0.2% NaOH solution containing 0.2% KBH 4 is added to reduce Hg 2+ to elemental Hg 0 , which is detected by AJ-3610 gas phase molecular absorption spectrometer.
  • the standard curve of step (2) finds the concentration of mercury.
  • the present embodiment only detects mercury standard stock solutions with different concentrations of hydrochloric acid, and the detection step is the same as step (2) in Example 1. It is found that when the concentration of hydrochloric acid in the mercury standard stock solution is 0.1 mol/L, KBH is used to reduce Then, the absorption peak measured by gas-phase molecular absorption spectrometer is 35mm; when the concentration of hydrochloric acid in the mercury standard stock solution is 0.5mol/L, after reduction with KBH 4 , the absorption peak measured by gas-phase molecular absorption spectrometer is 34mm; When the concentration of hydrochloric acid in the stock solution is 1 mol/L, after reduction with KBH 4 , the absorption peak measured by gas-phase molecular absorption spectrometer is 36 mm; when the concentration of hydrochloric acid in the standard mercury stock solution is 5 mol/L, after reduction with KBH 4 , the gas phase The absorption peak measured by the molecular absorption spectrometer is 36mm, and the maximum error of the

Abstract

A mercury content measurement method using a gas-phase molecular absorption spectrometer. The method comprises: diluting a mercury standard stock solution step by step by using a hydrochloric acid solution to prepare a mercury standard working solution; testing the mercury standard working solution by using the gas-phase molecular absorption spectrometer, and drawing the test data and concentration correspondingly into a standard curve; and testing a water sample to be tested by using the gas-phase molecular absorption spectrometer, and using the test data of the water sample to obtain the concentration of mercury by looking through the drawn standard curve. The gas-phase molecular absorption spectrometer uses two paths of sample injection, one path of sample injection is of a mercury standard working solution or a water sample to be tested and potassium dichromate-hydrochloric acid solution, the other path of sample injection is of a KBH4 solution, and required solutions are injected into the two paths at the same time and then are converged with each other. The standard solution is stable, and can be stored for a long time; the present invention is high in test sensitivity, is accurate and stable in measurement result, and is convenient to operate.

Description

一种利用气相分子吸收光谱仪测量汞含量的方法A method for measuring mercury content by gas-phase molecular absorption spectrometer 技术领域technical field
本发明涉及污水测汞方法，尤其是涉及一种利用气相分子吸收光谱仪测量汞含量的方法。The invention relates to a method for measuring mercury in sewage, in particular to a method for measuring mercury content by using a gas-phase molecular absorption spectrometer.
背景技术Background technique
一直以来，冷原子吸收测汞法的汞标准溶液都是用HNO 3+K 2Cr 2O 7配制，测定介质是用NH 2OH.CL还原过剩的KMnO 4，再用SnCL 2还原二价Hg 2+为单质Hg 0进行测定汞原子气体的吸光度。然而HNO 3+K 2Cr 2O 7介质并不能保证二价Hg 2+的稳定，而常常会挥发出单质Hg 0，使标准液浓度逐渐降低。测定时SnCL 2还原二价Hg 2+为单质Hg 0，只适用低浓度1mol/L的HCL介质，较高浓度HCL介质SnCL 2的还原效率很低，但是低于1mol/L的盐酸介质时，SnCL 2又会水解沉淀堵塞液路，甚至无法测定。另外，单质Hg 0含量测量时通常采用冷原子吸收测汞仪或者原子吸收分光光度计，这些设备灵敏度低，检出限低，因此检测灵敏度低。 For a long time, the mercury standard solution of cold atomic absorption mercury measurement is prepared with HNO 3 +K 2 Cr 2 O 7 , the measurement medium is to reduce excess KMnO 4 with NH 2 OH.CL, and then use SnCL 2 to reduce divalent Hg 2+ is elemental Hg 0 to measure the absorbance of mercury atomic gas. However, the HNO 3 +K 2 Cr 2 O 7 medium can not guarantee the stability of divalent Hg 2+ , but often volatilizes elemental Hg 0 , which gradually reduces the concentration of the standard solution. During the determination, SnCL 2 reduces divalent Hg 2+ to elemental Hg 0 , which is only suitable for HCL medium with a low concentration of 1 mol/L. The reduction efficiency of SnCL 2 in a higher concentration HCL medium is very low, but when it is lower than 1 mol/L hydrochloric acid medium, SnCL 2 will hydrolyze and precipitate to block the liquid path, and even cannot be measured. In addition, the cold atomic absorption mercury spectrometer or atomic absorption spectrophotometer is usually used for the measurement of elemental Hg 0 content. These devices have low sensitivity and low detection limit, so the detection sensitivity is low.
中国专利CN 104007076 A公布了一种污水测汞方法，属于分析化学技术领域。其基本的检测步骤包括：选取标准液介质、配置标准贮备液、配备标准使用液、配备NaBH 4还原剂溶液、样品预处理以及将产生的冷蒸汽汞原子接入冷原子吸收测汞仪进行检测的步骤，该专利采用冷原子吸收测汞仪进行检测，检测限高、误差较大，并且实验过程复杂。 Chinese patent CN 104007076 A discloses a method for measuring mercury in sewage, which belongs to the technical field of analytical chemistry. The basic detection steps include: selecting a standard liquid medium, configuring a standard stock solution, configuring a standard working solution, configuring a NaBH 4 reducing agent solution, pre-processing the sample, and connecting the generated cold vapor mercury atoms to a cold atomic absorption mercury detector for detection. The patent uses a cold atomic absorption mercury measuring instrument for detection, which has high detection limit, large error, and complicated experimental process.
发明内容SUMMARY OF THE INVENTION
本发明的目的就是为了克服上述现有技术存在的检测灵敏度低、测量方法使用的试剂多、操作复杂的缺陷而提供一种利用气相分子吸收光谱仪测量汞含量的方法。The purpose of the present invention is to provide a method for measuring mercury content by gas-phase molecular absorption spectrometer in order to overcome the defects of low detection sensitivity, many reagents used in the measurement method and complicated operation in the prior art.
本发明的目的可以通过以下技术方案来实现：The object of the present invention can be realized through the following technical solutions:
一种利用气相分子吸收光谱仪测量汞含量的方法，包括以下步骤：A method for measuring mercury content by gas-phase molecular absorption spectrometer, comprising the following steps:
(1)采用盐酸溶液将汞标准贮备液逐级稀释制成汞标准使用液；(1) adopting the hydrochloric acid solution to dilute the mercury standard stock solution step by step to prepare the mercury standard use solution;
(2)采用气相分子吸收光谱仪检测汞标准使用液，将检测数据和浓度对应绘制成标准曲线；(2) adopt the gas-phase molecular absorption spectrometer to detect the mercury standard liquid, and draw the detection data and the corresponding concentration into a standard curve;
(3)采用气相分子吸收光谱仪检测待测水样，采用待测水样的检测数据，由步骤(2)所绘制的标准曲线查得汞的浓度；(3) adopt gas-phase molecular absorption spectrometer to detect the water sample to be measured, adopt the detection data of the water sample to be measured, and check the concentration of mercury by the standard curve drawn by step (2);
其中，步骤(2)、(3)测试时，气相分子吸收光谱仪采用两路进样，一路进样为汞标准使用液或待测水样与重铬酸钾-盐酸溶液，另一路进样为KBH 4溶液，将两路同时进液，相互汇合，重铬酸钾-盐酸溶液使水样中的汞转化为Hg 2+，KBH 4溶液将Hg 2+还原为单质Hg 0，气相分子吸收光谱仪对单质Hg 0进行检测。 Wherein, when testing in steps (2) and (3), the gas-phase molecular absorption spectrometer adopts two-way injection, one is the mercury standard liquid or the water sample to be tested and potassium dichromate-hydrochloric acid solution, and the other is injected as KBH 4 solution, the two channels are fed into the liquid at the same time and merged with each other. The potassium dichromate-hydrochloric acid solution converts the mercury in the water sample into Hg 2+ , and the KBH 4 solution reduces the Hg 2+ to elemental Hg 0 . Gas-phase molecular absorption spectrometer Elemental Hg 0 was detected.
优选地，步骤(1)中，所述的汞标准贮备液中盐酸溶液浓度为0.1～5mol/L。Preferably, in step (1), the concentration of the hydrochloric acid solution in the mercury standard stock solution is 0.1-5 mol/L.
优选地，所述汞标准贮备液的浓度中Hg 2+的浓度为1-50μg/ml，进一步优选为10μg/ml。 Preferably, the concentration of Hg 2+ in the concentration of the mercury standard stock solution is 1-50 μg/ml, more preferably 10 μg/ml.
优选地，所述重铬酸钾溶液-盐酸溶液中重铬酸钾的浓度为0.3～0.8μg/ml，进一步优选为0.56μg/ml，盐酸的浓度为0.1-5mol/L，进一步优选为1.0mol/L，所述KBH 4溶液中溶质的质量分数为0.1-0.5％，进一步优选为0.2％。 Preferably, the concentration of potassium dichromate in the potassium dichromate solution-hydrochloric acid solution is 0.3-0.8 μg/ml, more preferably 0.56 μg/ml, and the concentration of hydrochloric acid is 0.1-5 mol/L, more preferably 1.0 mol/L, the mass fraction of the solute in the KBH 4 solution is 0.1-0.5%, more preferably 0.2%.
优选地，所述待测水样、重铬酸钾-盐酸溶液和KBH 4溶液的体积比为1：0.3～1：0.5～2，进一步优选为1：0.5：1。 Preferably, the volume ratio of the water sample to be tested, the potassium dichromate-hydrochloric acid solution and the KBH 4 solution is 1:0.3-1:0.5-2, more preferably 1:0.5:1.
优选地，步骤(3)中，所述KBH 4溶液中溶质的质量分数为0.5％～1％，进一步优选为0.2％，所述汞标准使用液与KBH 4溶液的体积比为1：1～1.5，进一步优选为1：1。 Preferably, in step (3), the mass fraction of the solute in the KBH 4 solution is 0.5% to 1%, more preferably 0.2%, and the volume ratio of the mercury standard use solution to the KBH 4 solution is 1:1～ 1.5, more preferably 1:1.
优选地，所述的气相分子吸收光谱仪的型号为AJ-3610气相分子吸收光谱仪。Preferably, the model of the gas-phase molecular absorption spectrometer is AJ-3610 gas-phase molecular absorption spectrometer.
优选地，所述AJ-3610气相分子吸收光谱仪的检测条件为采用阳极汞灯，该阳极汞灯的工作电流为2～3mA，工作波长为253.7nm。Preferably, the detection condition of the AJ-3610 gas-phase molecular absorption spectrometer is to use an anode mercury lamp, the working current of the anode mercury lamp is 2-3 mA, and the working wavelength is 253.7 nm.
优选地，气相分子吸收光谱仪采用蠕动泵进样。Preferably, the gas phase molecular absorption spectrometer uses a peristaltic pump for sample introduction.
优选地，所述待测水样来源于地表水、地下水、生活污水或工厂排放水。Preferably, the water sample to be tested comes from surface water, groundwater, domestic sewage or factory discharge water.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明采用单一的HCL介质配制和保存汞的标准溶液，汞在较强的HCl介质中生成了极其稳定的HHgCl 3配合物，HHgCl 3在HCl介质中即使煮沸也不会挥发损失，因此本发明的汞标准贮备液以及标准使用液浓度极其稳定。10ng/ml汞标准液，常温下保存一年，浓度未变； (1) the present invention adopts a single HCL medium to prepare and preserve the standard solution of mercury, mercury generates extremely stable HHgCl complex in a strong HCl medium, and HHgCl will not lose volatilization even if it is boiled in the HCl medium, Therefore, the concentration of the mercury standard stock solution and standard use solution of the present invention is extremely stable. 10ng/ml mercury standard solution, stored at room temperature for one year, the concentration has not changed;
(2)本发明采用0.2％的KBH 4将Hg 2+还原为单质Hg 0，还原过程稳定，在HCL介质浓度在0.1-5mol/L范围内均可以得到稳定的吸光度，由此计算出稳定的数据。 (2) The present invention uses 0.2% KBH 4 to reduce Hg 2+ to elemental Hg 0 , the reduction process is stable, and stable absorbance can be obtained in the range of HCL medium concentration of 0.1-5 mol/L. data.
(3)本发明采用AJ-3610气相分子吸收光谱仪，灵敏度高，检出限低，最低检测浓度为0.002μg/L，比专利CN 104007076 A精确10倍，且使用范围广，明显优于一般的测汞仪。(3) The present invention adopts AJ-3610 gas-phase molecular absorption spectrometer, which has high sensitivity, low detection limit, and the minimum detection concentration is 0.002 μg/L, which is 10 times more accurate than the patent CN 104007076 A, and has a wide range of use, which is obviously better than the general Mercury meter.
(4)使用单一的重铬酸钾快速氧化有机汞，操作手续简便，并且可以适用于地表水、地下水、生活污水、工厂排放水，适用范围广泛。(4) Using a single potassium dichromate to quickly oxidize organic mercury, the operation procedure is simple, and it can be applied to surface water, groundwater, domestic sewage, and factory discharge water, and has a wide range of applications.
(5)本发明从标准液的配制到测定过程，均采用盐酸介质，试剂单一，节约，操作方便。(5) The present invention adopts hydrochloric acid medium from the preparation of the standard solution to the determination process, and the reagent is single, economical, and easy to operate.
具体实施方式detailed description
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例1Example 1
一种冷原子吸收测量汞含量的方法，测量的水样为地下水，包括以下步骤：A method for measuring mercury content by cold atomic absorption, the measured water sample is groundwater, comprising the following steps:
(1)采用浓度为0.5mol/L盐酸溶液将汞标准贮备液逐级稀释制成汞标准使用液，其中汞标准贮备液含有HgCl 2、盐酸和水，其中盐酸的浓度为1mol/L，Hg 2+的浓度为10μg/ml；汞标准使用液的配制方法为用微量移液器吸取汞标准贮备液50μl、100μl、150μl、200μl、250μl分别放入100ml容量瓶中，用0.5mol/L HCl稀释至刻度，摇匀，得到一组浓度不同的汞标准使用液； (1) adopt the concentration of 0.5mol/L hydrochloric acid solution to dilute the mercury standard stock solution step by step to make the mercury standard use solution, wherein the mercury standard stock solution contains HgCl 2 , hydrochloric acid and water, wherein the concentration of hydrochloric acid is 1mol/L, Hg The concentration of 2+ is 10μg/ml; the preparation method of mercury standard use solution is to draw 50μl, 100μl, 150μl, 200μl and 250μl of mercury standard stock solution with a micropipette and put them into a 100ml volumetric flask, respectively, with 0.5mol/L HCl. Dilute to the mark and shake well to obtain a set of mercury standard solutions with different concentrations;
(2)将汞标准使用液依次采用AJ-3610气相分子吸收光谱仪进行检测，该阳极汞灯的工作电流3mA，工作波长为253.7nm，具体方法为，气相分子吸收光谱仪采用蠕动泵两路进样，一路进样(水样+重铬酸钾+盐酸)，另一路进KBH 4溶液，加入1ml含有0.2％的KBH 4的0.2％的NaOH溶液的还原剂将Hg 2+还原为单质Hg 0，先开载气，再【一键】启动，蠕动泵将两路同时进液相互汇合，产生单质Hg 0蒸汽得到分析结果，将汞标准使用液的检测数据和浓度对应绘制成标准曲线； (2) AJ-3610 gas-phase molecular absorption spectrometer is used to detect the mercury standard liquid in turn. The working current of the anode mercury lamp is 3mA, and the working wavelength is 253.7 nm. The specific method is that the gas-phase molecular absorption spectrometer adopts a peristaltic pump two-way injection , one way of injection (water sample + potassium dichromate + hydrochloric acid), the other way into KBH 4 solution, adding 1ml of reducing agent containing 0.2% KBH 4 and 0.2% NaOH solution to reduce Hg 2+ to elemental Hg 0 , Turn on the carrier gas first, then start it with one key, and the peristaltic pump will combine the two channels of simultaneous liquid feeding to generate elemental Hg 0 vapor to obtain the analysis result, and the detection data and concentration of the mercury standard liquid are correspondingly drawn into a standard curve;
(3)取待测水样置于反应瓶中，采用AJ-3610气相分子吸收光谱仪进行检测，加入体积比为5：0.5的重铬酸钾-盐酸溶液0.5ml，使待测水样中的有机汞转化为Hg 2+，然后加入含有0.2％的KBH 4的0.2％的NaOH溶液1ml将Hg 2+还原为单质Hg 0，利用AJ-3610气相分子吸收光谱仪进行检测，检测出数据后，通过步骤(2)的标准曲线查得汞的浓度。 (3) Take the water sample to be tested and put it in the reaction bottle, use AJ-3610 gas-phase molecular absorption spectrometer for detection, and add 0.5 ml of potassium dichromate-hydrochloric acid solution with a volume ratio of 5:0.5 to make the water sample to be tested. Organic mercury is converted into Hg 2+ , and then 1 ml of 0.2% NaOH solution containing 0.2% KBH 4 is added to reduce Hg 2+ to elemental Hg 0 , which is detected by AJ-3610 gas phase molecular absorption spectrometer. The standard curve of step (2) finds the concentration of mercury.
实施例2Example 2
本实施例仅对盐酸浓度不同的汞标准贮备液进行检测，检测步骤与实施例1中的步骤(2)相同，发现当汞标准贮备液中盐酸浓度为0.1mol/L时，采用KBH 4还原后，气相分子吸收光谱仪测得的吸收峰为35mm；当汞标准贮备液中盐酸浓度为0.5mol/L时，采用KBH 4还原后，气相分子吸收光谱仪测得的吸收峰为34mm；当汞标准贮备液 中盐酸浓度为1mol/L时，采用KBH 4还原后，气相分子吸收光谱仪测得的吸收峰为36mm；当汞标准贮备液中盐酸浓度为5mol/L时，采用KBH 4还原后，气相分子吸收光谱仪测得的吸收峰为36mm，吸收峰最大误差2mm；表明本发明的方法可以承受较大的盐酸浓度范围，还原效果稳定，不受盐酸浓度的影响。 The present embodiment only detects mercury standard stock solutions with different concentrations of hydrochloric acid, and the detection step is the same as step (2) in Example 1. It is found that when the concentration of hydrochloric acid in the mercury standard stock solution is 0.1 mol/L, KBH is used to reduce Then, the absorption peak measured by gas-phase molecular absorption spectrometer is 35mm; when the concentration of hydrochloric acid in the mercury standard stock solution is 0.5mol/L, after reduction with KBH 4 , the absorption peak measured by gas-phase molecular absorption spectrometer is 34mm; When the concentration of hydrochloric acid in the stock solution is 1 mol/L, after reduction with KBH 4 , the absorption peak measured by gas-phase molecular absorption spectrometer is 36 mm; when the concentration of hydrochloric acid in the standard mercury stock solution is 5 mol/L, after reduction with KBH 4 , the gas phase The absorption peak measured by the molecular absorption spectrometer is 36mm, and the maximum error of the absorption peak is 2mm; it shows that the method of the invention can withstand a large concentration range of hydrochloric acid, and the reduction effect is stable and not affected by the concentration of hydrochloric acid.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above-mentioned specific embodiments, and those skilled in the art can make various variations or modifications within the scope of the claims, which do not affect the essential content of the present invention.

Claims (10)

  1. 一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，包括以下步骤：A method of utilizing gas-phase molecular absorption spectrometer to measure mercury content, it is characterized in that, comprises the following steps:
    (1)采用盐酸溶液将汞标准贮备液逐级稀释制成汞标准使用液；(1) adopting the hydrochloric acid solution to dilute the mercury standard stock solution step by step to prepare the mercury standard use solution;
    (2)采用气相分子吸收光谱仪检测汞标准使用液，将检测数据和浓度对应绘制成标准曲线；(2) adopt the gas-phase molecular absorption spectrometer to detect the mercury standard liquid, and draw the detection data and the corresponding concentration into a standard curve;
    (3)采用气相分子吸收光谱仪检测待测水样，采用待测水样的检测数据，由步骤(2)所绘制的标准曲线查得汞的浓度；(3) adopt gas-phase molecular absorption spectrometer to detect the water sample to be measured, adopt the detection data of the water sample to be measured, and check the concentration of mercury by the standard curve drawn by step (2);
    其中，步骤(2)、(3)测试时，气相分子吸收光谱仪采用两路进样，一路进样为汞标准使用液或待测水样与重铬酸钾-盐酸溶液，另一路进样为KBH 4溶液，将两路同时进液，相互汇合，重铬酸钾-盐酸溶液使水样中的汞转化为Hg 2+，KBH 4溶液将Hg 2+还原为单质Hg 0，气相分子吸收光谱仪对单质Hg 0进行检测。 Wherein, when testing in steps (2) and (3), the gas-phase molecular absorption spectrometer adopts two-way injection, one is the mercury standard liquid or the water sample to be tested and potassium dichromate-hydrochloric acid solution, and the other is injected as KBH 4 solution, the two channels are fed into the liquid at the same time and merged with each other. The potassium dichromate-hydrochloric acid solution converts the mercury in the water sample into Hg 2+ , and the KBH 4 solution reduces the Hg 2+ to elemental Hg 0 . Gas-phase molecular absorption spectrometer Elemental Hg 0 was detected.
  2. 根据权利要求1所述的一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，步骤(1)中，所述的汞标准贮备液中盐酸溶液浓度为0.1～5mol/L。A method for measuring mercury content by gas-phase molecular absorption spectrometer according to claim 1, characterized in that, in step (1), the concentration of the hydrochloric acid solution in the mercury standard stock solution is 0.1-5 mol/L.
  3. 根据权利要求1所述的一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，所述汞标准贮备液的浓度中Hg 2+的浓度为1-50μg/ml。 The method for measuring mercury content by gas-phase molecular absorption spectrometer according to claim 1, wherein the concentration of Hg 2+ in the concentration of the mercury standard stock solution is 1-50 μg/ml.
  4. 根据权利要求1所述的一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，所述重铬酸钾溶液-盐酸溶液中重铬酸钾的浓度为0.3～0.8μg/ml，盐酸的浓度为0.1-5mol/L，所述KBH 4溶液中溶质的质量分数为0.1-0.5％。 A kind of method that utilizes gas-phase molecular absorption spectrometer to measure mercury content according to claim 1, it is characterized in that, the concentration of potassium dichromate in described potassium dichromate solution-hydrochloric acid solution is 0.3～0.8 μ g/ml, hydrochloric acid The concentration of the KBH 4 solution is 0.1-5 mol/L, and the mass fraction of the solute in the KBH 4 solution is 0.1-0.5%.
  5. 根据权利要求4所述的一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，所述待测水样、重铬酸钾-盐酸溶液和KBH 4溶液的体积比为1：0.3～1：0.5～2。 A method for measuring mercury content by gas-phase molecular absorption spectrometer according to claim 4, wherein the volume ratio of the water sample to be measured, potassium dichromate-hydrochloric acid solution and KBH solution is 1 :0.3～ 1: 0.5 to 2.
  6. 根据权利要求1所述的一种利用气相分子吸收光谱仪测量汞 含量的方法，其特征在于，步骤(3)中，所述KBH 4溶液中溶质的质量分数为0.5％～1％，所述汞标准使用液与KBH 4溶液的体积比为1：1～1.5。 A method for measuring mercury content by gas-phase molecular absorption spectrometer according to claim 1, characterized in that, in step (3), the mass fraction of the solute in the KBH solution is 0.5% to 1 %, and the mercury The volume ratio of standard use solution and KBH 4 solution is 1:1～1.5.
  7. 根据权利要求1所述的一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，所述的气相分子吸收光谱仪的型号为AJ-3610气相分子吸收光谱仪。A method for measuring mercury content using a gas-phase molecular absorption spectrometer according to claim 1, wherein the model of the gas-phase molecular absorption spectrometer is AJ-3610 gas-phase molecular absorption spectrometer.
  8. 根据权利要求7所述的一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，所述AJ-3610气相分子吸收光谱仪的检测条件为采用阳极汞灯，该阳极汞灯的工作电流为2～3mA，工作波长为253.7nm。A method for measuring mercury content using a gas-phase molecular absorption spectrometer according to claim 7, wherein the detection condition of the AJ-3610 gas-phase molecular absorption spectrometer is to use an anode mercury lamp, and the working current of the anode mercury lamp is 2～3mA, the working wavelength is 253.7nm.
  9. 根据权利要求1所述的一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，气相分子吸收光谱仪采用蠕动泵进样。A method for measuring mercury content using a gas-phase molecular absorption spectrometer according to claim 1, wherein the gas-phase molecular absorption spectrometer adopts a peristaltic pump for sample introduction.
  10. 根据权利要求1所述的一种利用气相分子吸收光谱仪测量汞含量的方法，其特征在于，所述待测水样来源于地表水、地下水、生活污水或工厂排放水。The method for measuring mercury content by gas-phase molecular absorption spectrometer according to claim 1, wherein the water sample to be measured comes from surface water, groundwater, domestic sewage or factory discharge water.
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