A method for detecting monovalent mercury

Abstract

The application provides a monovalent mercury detection method, and relates to the field of analytical detection technology. The monovalent mercury in a to-be-detected sample is extracted by 2-mercaptoethanol aqueous solution, and the obtained to-be-detected sample liquid is subjected to high performance liquid chromatography-atomic fluorescence spectrometry detection. In the high performance liquid chromatography separation process, the monovalent mercury is completely disproportionated into zero-valent mercury and divalent mercury, and is separated by high performance liquid chromatography, and is subjected to atomic fluorescence spectrometry detection respectively. The mercury of all valence states is reduced by a reducing agent and forms mercury vapor, and then generates a fluorescence signal, and sequentially peaks with a retention time, so that the zero-valent mercury detection peak area and the divalent mercury detection peak area are obtained. According to the zero-valent mercury detection peak area and the divalent mercury detection peak area, the detection concentration of divalent mercury and the detection concentration of zero-valent mercury are obtained by using an external standard method. The concentration of monovalent mercury in the to-be-detected sample liquid is calculated, the accuracy and the sensitivity of detection are high, and efficient analysis and detection of monovalent mercury are realized.

Description

Technical Field

[0001] This invention relates to the field of analytical testing technology, and specifically to a method for detecting monovalent mercury. Background Technology

[0002] Mercury possesses extremely high genotoxicity and neurotoxicity; severe exposure can lead to impairments such as slowed movement and speech disorders. The toxicity of mercury compounds to organisms depends not only on the exposure concentration, transmission route, and individual differences among organisms, but also on their existing form. The primary form of mercury in the environment is zero-valent mercury (Hg). 0 ), divalent mercury (Hg) 2+ ) and monovalent mercury (Hg2) 2+ The complexity of mercury's speciation determines the complexity of its transformations, which include oxidation / reduction, sulfidation, methylation, and other processes. Theoretically, mercury redox processes are mostly single-electron transfer processes; zero-valent mercury typically loses its outermost 6s electron, resulting in a [Xe]4f electron configuration. 14 5d 10 6s 1 Monovalent mercury is formed and then further oxidized to divalent mercury. This thermodynamic and kinetic characteristic indicates that monovalent mercury is an important intermediate in mercury redox reactions, playing a crucial role in the environmental migration and transformation of mercury. Detection of monovalent mercury can reveal the redox pathway of mercury. Furthermore, monovalent mercury may also undergo methylation via chemical / microbial pathways, increasing its environmental risk. Therefore, developing a detection method that can effectively capture, stabilize, and accurately determine monovalent mercury is of great significance for revealing the environmental migration and transformation mechanisms of mercury and improving the targeting of pollution control. However, monovalent mercury is metastable and unstable in the environment, readily undergoing disproportionation reactions (Hg2+). 2+ →Hg 0 +Hg 2+ In addition, its concentration in the environmental medium is extremely low, and the intrinsic accuracy of spectroscopic instruments is insufficient, resulting in low accuracy and sensitivity of conventional mercury speciation analysis methods (such as gas chromatography) for the detection of monovalent mercury. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a method for detecting monovalent mercury with high accuracy and sensitivity.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for detecting monovalent mercury, comprising the following steps: The sample to be tested was extracted using an aqueous solution of 2-mercaptoethanol to obtain the sample solution; the volume percentage of 2-mercaptoethanol in the aqueous solution was 0.15~0.2%; the mercury in the sample solution included monovalent mercury. The sample solution to be tested was subjected to high performance liquid chromatography-atomic fluorescence spectrometry to obtain the detection peak areas of zero-valent mercury and divalent mercury; based on the detection peak areas of zero-valent mercury and divalent mercury, the detection concentrations of divalent mercury and zero-valent mercury were obtained using the external standard method; based on the detection concentrations of divalent mercury and zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested was obtained. The method for obtaining the concentration of monovalent mercury in the sample solution to be tested is as follows: When the detection concentration of divalent mercury is greater than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is 2 × the detection concentration of zero-valent mercury. When the detection concentration of divalent mercury equals the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested equals 2 × the detection concentration of zero-valent mercury equals 2 × the detection concentration of divalent mercury. When the detection concentration of divalent mercury is less than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is 2 × the detection concentration of divalent mercury. The conditions for high-performance liquid chromatography (HPLC) separation in the aforementioned high-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFI) detection include: The chromatographic column is C10. 18 The chromatographic column was used; the mobile phase was an aqueous solution of 2-mercaptoethanol-ammonium acetate-methanol, wherein the volume percentage of 2-mercaptoethanol in the aqueous solution was 0.05-0.5%, the concentration of ammonium acetate was 8-50 mmol / L, and the volume percentage of methanol was 8%; the elution method was isocratic elution. The conditions for atomic fluorescence spectrometry detection in the high-performance liquid chromatography-atomic fluorescence spectrometry detection include: The carrier gas is an aqueous nitric acid solution, wherein the mass percentage of nitric acid in the aqueous nitric acid solution is 7-10%; the reducing agent is KBH4; and the carrier gas flow rate is 275-300 mL / min.

[0005] Preferably, the flow rate of the mobile phase is 0.8~1.6 mL / min; the C 18 The chromatographic column is C10. 18 Reversed-phase chromatography column.

[0006] Preferably, the carrier gas and shielding gas for atomic fluorescence spectrometry detection are independently argon; the flow rate of the shielding gas is 500~600 mL / min.

[0007] Preferably, the guard column in the high-performance liquid chromatography separation is a SecurityGuard guard column system, with a guard column shell of Phenomenex KJ0-4282 and a guard column core of Phenomenex AJ0-4287.

[0008] Preferably, the excitation source for the atomic fluorescence spectrometry detection is a mercury hollow cathode lamp; the lamp current is 30mA; the lamp voltage is 270V; the pump flow rate is 80mL / min; and the photochemical vapor generation source is an ultraviolet lamp.

[0009] Preferably, the KBH4 is used in the form of a KBH4-KOH aqueous solution, wherein the mass percentage of KBH4 in the KBH4-KOH aqueous solution is 2% and the mass percentage of KOH is 0.35%.

[0010] Preferably, the extraction is an oscillating extraction; the oscillating extraction speed is 200~250 rpm, the temperature is 20~25℃, and the time is 2~4h.

[0011] Preferably, the external standard method includes obtaining a standard curve for zero-valent mercury and a standard curve for divalent mercury; The linear range of the zero-valent mercury standard curve is 100~5000 μg / L; The linear range of the divalent mercury standard curve is 100~5000 μg / L.

[0012] Preferably, the mass-to-volume ratio of the sample to be tested and the 2-mercaptoethanol aqueous solution is 1 g: 40~50 mL.

[0013] Preferably, the samples to be tested include fly ash from waste incineration power plants, phosphorus powder from waste fluorescent lamps, desulfurization gypsum, flue ash from coal-fired power plants, or soil and plant samples from mercury mining areas.

[0014] This invention provides a method for detecting monovalent mercury, comprising the following steps: extracting the sample to be tested using a 2-mercaptoethanol aqueous solution to obtain a sample solution; the volume percentage of 2-mercaptoethanol in the 2-mercaptoethanol aqueous solution is 0.15~0.2%; the mercury in the sample solution includes monovalent mercury; performing high-performance liquid chromatography-atomic fluorescence spectrometry on the sample solution to obtain the detection peak area of ​​zero-valent mercury and the detection peak area of ​​divalent mercury; based on the detection peak areas of zero-valent mercury and divalent mercury, using the external standard method to obtain the detection concentrations of divalent mercury and zero-valent mercury; and obtaining the detection concentration of the sample solution based on the detection concentrations of divalent mercury and zero-valent mercury. The concentration of monovalent mercury in the sample solution is measured. The method for obtaining the concentration of monovalent mercury in the sample solution is as follows: when the detection concentration of divalent mercury is greater than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution is 2 × the detection concentration of zero-valent mercury; when the detection concentration of divalent mercury is equal to the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution is 2 × the detection concentration of zero-valent mercury = 2 × the detection concentration of divalent mercury; when the detection concentration of divalent mercury is less than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution is 2 × the detection concentration of divalent mercury. The conditions for high-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFI) separation include: a C10 column. 18The chromatographic column was used. The mobile phase was a 2-mercaptoethanol-ammonium acetate-methanol aqueous solution, wherein the volume percentage of 2-mercaptoethanol in the 2-mercaptoethanol-ammonium acetate-methanol aqueous solution was 0.05-0.5%, the concentration of ammonium acetate was 8-50 mmol / L, and the volume percentage of methanol was 8%. The elution method was isocratic elution. The conditions for atomic fluorescence spectrometry detection in the high performance liquid chromatography-atomic fluorescence spectrometry detection included: the carrier gas was an aqueous nitric acid solution, wherein the mass percentage of nitric acid in the aqueous nitric acid solution was 7-10%; the reducing agent was KBH4; and the carrier gas flow rate was 275-300 mL / min. This invention first extracts monovalent mercury from the test sample using an aqueous solution of 2-mercaptoethanol (2-ME). The monovalent mercury and 2-mercaptoethanol form a complex, which is then extracted into the test sample solution. The monovalent mercury in the resulting test sample solution exists in a weak disproportionation equilibrium (i.e., monovalent mercury hardly undergoes disproportionation and exists stably in its monovalent form). Then, the obtained test sample solution is analyzed by high-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFI). During the HPLC separation process, zero-valent mercury and divalent mercury are separated, the weak disproportionation equilibrium is disrupted, and the monovalent mercury undergoes a continuous disproportionation reaction, thereby… Mercury is completely disproportionated into zero-valent and divalent mercury, which are then separated by high-performance liquid chromatography (HPLC) and detected separately by atomic fluorescence spectrometry (AFS). Mercury in all valence states is reduced by the reducing agent KBH4 to form mercury vapor, which generates a fluorescence signal. Peaks emerge sequentially with retention time, yielding the detection peak areas for zero-valent and divalent mercury. Based on these peak areas, the detection concentrations of divalent and zero-valent mercury are determined using the external standard method. Finally, the concentration of monovalent mercury in the sample solution is calculated. This method offers high accuracy and sensitivity, achieving efficient analysis and detection of monovalent mercury. Attached Figure Description

[0015] Figure 1 High-performance liquid chromatography-atomic fluorescence spectrum of a 100 μg / L monovalent mercury standard solution; Figure 2 High-performance liquid chromatography-atomic fluorescence spectrum of a 200 μg / L monovalent mercury standard solution; Figure 3 High-performance liquid chromatography-atomic fluorescence spectrum of a 300 μg / L monovalent mercury standard solution; Figure 4 High-performance liquid chromatography-atomic fluorescence spectrum of a 400 μg / L monovalent mercury standard solution; Figure 5 High-performance liquid chromatography-atomic fluorescence spectrum of a 500 μg / L monovalent mercury standard solution; Figure 6 High-performance liquid chromatography-atomic fluorescence spectrum of a 600 μg / L monovalent mercury standard solution; Figure 7High-performance liquid chromatography-atomic fluorescence spectrum of a 700 μg / L monovalent mercury standard solution; Figure 8 High-performance liquid chromatography-atomic fluorescence spectrum of 800 μg / L monovalent mercury standard solution; Figure 9 High-performance liquid chromatography-atomic fluorescence spectrum of a 900 μg / L monovalent mercury standard solution; Figure 10 High-performance liquid chromatography-atomic fluorescence spectrum of a 1.0 mg / L monovalent mercury standard solution; Figure 11 High-performance liquid chromatography-atomic fluorescence spectrum of a 2.0 mg / L monovalent mercury standard solution; Figure 12 High-performance liquid chromatography-atomic fluorescence spectrum of a 3.0 mg / L monovalent mercury standard solution; Figure 13 High-performance liquid chromatography-atomic fluorescence spectrum of a 4.0 mg / L monovalent mercury standard solution; Figure 14 High-performance liquid chromatography-atomic fluorescence spectrum of a 5.0 mg / L monovalent mercury standard solution; Figure 15 This is the standard curve for zero-valent mercury; Figure 16 This is the standard curve for divalent mercury; Figure 17 The detection curve shows that the mobile phase is L-cysteine-ammonium acetate-methanol aqueous solution. Figure 18 The detection curve shows the mobile phase of 2-mercaptoethanol-ammonium acetate-methanol aqueous solution. Figure 19 The graph shows the detection of 2-mercaptoethanol under different volume percentage conditions in different mobile phases; Figure 20 The detection graphs are shown under different mobile phase flow rates. Figure 21 The graph shows the detection results under different concentrations of ammonium acetate in the mobile phase. Figure 22 Comparison of high performance liquid chromatography-atomic fluorescence spectra of divalent mercury standard solution and monovalent mercury standard solution; Figure 23 Comparison of high-performance liquid chromatography-atomic fluorescence spectra of zero-valent mercury standard solution and monovalent mercury standard solution; Figure 24 Detection graphs under different oscillation extraction time conditions; Figure 25 This is the high performance liquid chromatography-atomic fluorescence spectrum of the sample solution A to be tested; Figure 26 The image shows the high performance liquid chromatography-atomic fluorescence spectrum of the sample solution B to be tested. Figure 27 This is the high performance liquid chromatography-atomic fluorescence spectrum of the sample solution C to be tested. Detailed Implementation

[0016] This invention provides a method for detecting monovalent mercury, comprising the following steps: The sample to be tested was extracted using an aqueous solution of 2-mercaptoethanol to obtain the sample solution; the volume percentage of 2-mercaptoethanol in the aqueous solution was 0.15~0.2%; the mercury in the sample solution included monovalent mercury. The sample solution to be tested was subjected to high performance liquid chromatography-atomic fluorescence spectrometry to obtain the detection peak areas of zero-valent mercury and divalent mercury; based on the detection peak areas of zero-valent mercury and divalent mercury, the detection concentrations of divalent mercury and zero-valent mercury were obtained using the external standard method; based on the detection concentrations of divalent mercury and zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested was obtained. The method for obtaining the concentration of monovalent mercury in the sample solution to be tested is as follows: When the detection concentration of divalent mercury is greater than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is 2 × the detection concentration of zero-valent mercury. When the detection concentration of divalent mercury equals the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested equals 2 × the detection concentration of zero-valent mercury equals 2 × the detection concentration of divalent mercury. When the detection concentration of divalent mercury is less than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is 2 × the detection concentration of divalent mercury. The conditions for high-performance liquid chromatography (HPLC) separation in the aforementioned high-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFI) detection include: The chromatographic column is C10. 18 The chromatographic column was used; the mobile phase was an aqueous solution of 2-mercaptoethanol-ammonium acetate-methanol, wherein the volume percentage of 2-mercaptoethanol in the aqueous solution was 0.05-0.5%, the concentration of ammonium acetate was 8-50 mmol / L, and the volume percentage of methanol was 8%; the elution method was isocratic elution. The conditions for atomic fluorescence spectrometry detection in the high-performance liquid chromatography-atomic fluorescence spectrometry detection include: The carrier gas is an aqueous nitric acid solution, wherein the mass percentage of nitric acid in the aqueous nitric acid solution is 7-10%; the reducing agent is KBH4; and the carrier gas flow rate is 275-300 mL / min.

[0017] Unless otherwise specified, the materials and equipment used in this invention are all commercially available products in the field.

[0018] This invention uses 2-mercaptoethanol aqueous solution to extract the sample to be tested, thus obtaining the sample solution to be tested.

[0019] In this invention, the sample to be tested may include fly ash from waste-to-energy incineration plants, phosphorus powder from waste fluorescent lamps, desulfurization gypsum, flue ash from coal-fired power plants, or soil and plant samples from mercury mines; the particle size of the sample to be tested may be 80-100 mesh, specifically 85 mesh, 90 mesh, or 95 mesh. In this invention, the fly ash from waste-to-energy incineration plants may also undergo crushing and screening before extraction. This invention does not specifically limit the conditions for crushing and screening, as long as the particle size of the sample to be tested is within the range of 80-100 mesh. In this invention, crushing may specifically be grinding. In one embodiment of this invention, the uniformity of the sample to be tested is ensured by grinding and screening the fly ash from waste-to-energy incineration plants.

[0020] In this invention, the volume percentage of 2-mercaptoethanol in the 2-mercaptoethanol aqueous solution is 0.15-0.2%, specifically 0.16%, 0.17%, or 0.19%; the mass-to-volume ratio of the sample to be tested and the 2-mercaptoethanol aqueous solution can be 1g:40-50mL, specifically 1g:42mL, 1g:45mL, or 1g:48mL. In this invention, the extraction can be a shaking extraction; the shaking extraction speed can be 200-250 rpm, specifically 210 rpm, 220 rpm, or 240 rpm; the shaking extraction temperature can be 20-25℃, specifically 21℃, 23℃, or 24℃; the shaking extraction time can be 2-4 hours, specifically 2.5 hours, 3 hours, or 3.5 hours. In one embodiment of this invention, shaking extraction at room temperature avoids the transformation of monovalent mercury caused by high-temperature, ultrasonic, and microwave extraction.

[0021] After the extraction is completed, the present invention further includes solid-liquid separation of the extracted liquid to obtain the extract to be tested. In the present invention, the solid-liquid separation may include filtration; the filtration may specifically be performed using a 0.22μm polyethersulfone (PES) filter membrane.

[0022] After obtaining the sample solution to be tested, the present invention performs high performance liquid chromatography-atomic fluorescence spectrometry on the sample solution to obtain the detection peak area of ​​zero-valent mercury and the detection peak area of ​​divalent mercury; based on the detection peak areas of zero-valent mercury and divalent mercury, the detection concentration of divalent mercury and the detection concentration of zero-valent mercury are obtained by external standard method; based on the detection concentrations of divalent mercury and zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is obtained.

[0023] In this invention, the conditions for high-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFI) separation in the HPLC-AFI detection include: the chromatographic column is C2000. 18 chromatographic column; the C 18 The chromatographic column can be C 18Reversed-phase chromatographic column, specifically ThermoAcclaim TM 120 C 18 The reversed-phase chromatographic column has a size of 4.6 × 150 mm; the mobile phase is an aqueous solution of 2-mercaptoethanol-ammonium acetate-methanol, wherein the volume percentage of 2-mercaptoethanol in the aqueous solution is 0.05~0.5%, specifically 0.1%, 0.2%, 0.35% or 0.45%; the concentration of ammonium acetate in the aqueous solution is 8~50 mmol / L, specifically 10 mmol / L, 15 mmol / L, 20 mmol / L or 40 mmol / L; the volume percentage of methanol in the aqueous solution is 8%; the elution method is isocratic elution; the guard column can be a SecurityGuard guard column system, and the guard column shell is Phenomenex. KJ0-4282, the guard column core is Phenomenex AJ0-4287, the specification is 4×3.0mm; the flow rate of the mobile phase can be 0.8~1.6mL / min, specifically 1mL / min, 1.2mL / min or 1.4mL / min.

[0024] In this invention, the conditions for atomic fluorescence spectrometry detection in the high-performance liquid chromatography-atomic fluorescence spectrometry detection include: the carrier gas is an aqueous nitric acid solution, wherein the mass percentage of nitric acid in the aqueous nitric acid solution is 7-10%; the reducing agent is KBH4; the carrier gas flow rate is 275-300 mL / min, specifically 280 mL / min, 285 mL / min, 290 mL / min, or 295 mL / min; the carrier gas and the shielding gas can be argon independently; the shielding gas flow rate can be 500-600 mL / min, specifically 520 mL / min, 540 mL / min, 560 mL / min, or 580 mL / min; the excitation source can be a mercury hollow cathode lamp; the lamp current can be 30 mA; the lamp voltage can be 270 V; the pump flow rate is 80 mL / min; and the photochemical vapor generation source can be an ultraviolet lamp.

[0025] In this invention, KBH4 can be used in the form of an aqueous solution of KBH4-KOH, wherein the mass percentage of KBH4 in the aqueous solution can be 2% and the mass percentage of KOH can be 0.35%. This invention uses an aqueous solution of KBH4-KOH as a reducing agent, which can convert mercury in different forms into gaseous mercury (zero-valent mercury) and then send it into the atomizer by a carrier gas.

[0026] In this invention, the external standard method includes obtaining a zero-valent mercury standard curve and a divalent mercury standard curve; the linear range of the zero-valent mercury standard curve can be 100~5000 μg / L; the linear range of the divalent mercury standard curve can be 100~5000 μg / L.

[0027] In this invention, the external standard method may include the following steps: mixing mercurous nitrate and an aqueous solution of nitric acid to obtain a series of monovalent mercury standard solutions; performing high-performance liquid chromatography-atomic fluorescence spectrometry on the monovalent mercury standard solutions to obtain the peak areas of zero-valent mercury and divalent mercury, respectively; performing linear fitting with the concentration of the monovalent mercury standard solutions as the abscissa and the peak area of ​​zero-valent mercury as the ordinate to establish a zero-valent mercury standard curve; performing linear fitting with the concentration of the monovalent mercury standard solutions as the abscissa and the peak area of ​​divalent mercury as the ordinate to establish a divalent mercury standard curve; obtaining the detection concentration of divalent mercury based on the divalent mercury standard curve and the detection peak area of ​​divalent mercury; and obtaining the detection concentration of zero-valent mercury based on the zero-valent mercury standard curve and the detection peak area of ​​zero-valent mercury.

[0028] In this invention, the concentration of mercurous nitrate in the monovalent mercury standard solution can be 100~5000 μg / L, specifically 500 μg / L, 1000 μg / L, 2000 μg / L or 4000 μg / L; the mass percentage of nitric acid in the nitric acid aqueous solution can be 1~5%, specifically 2%, 3% or 4%.

[0029] In this invention, the method for obtaining the concentration of monovalent mercury in the sample solution to be tested is as follows: When the detection concentration of divalent mercury is greater than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is 2 × the detection concentration of zero-valent mercury. When the detection concentration of divalent mercury equals the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested equals 2 × the detection concentration of zero-valent mercury equals 2 × the detection concentration of divalent mercury. When the detection concentration of divalent mercury is less than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is 2 × the detection concentration of divalent mercury.

[0030] This invention uses the above method to obtain the concentration of monovalent mercury in the sample solution to be tested. Because monovalent mercury completely disproportionates into zero-valent mercury and divalent mercury (Hg2) during atomic fluorescence spectrometry detection... 2+ →Hg 0 +Hg 2+Therefore, when the sample solution contains only monovalent mercury, the concentration of divalent mercury produced by disproportionation is the same as that of zero-valent mercury (at this time, the detection concentration of divalent mercury = the detection concentration of zero-valent mercury). The concentration of monovalent mercury in the sample solution = 2 × the detection concentration of zero-valent mercury = 2 × the detection concentration of divalent mercury. When the detection concentration of divalent mercury > the detection concentration of zero-valent mercury, since zero-valent mercury is highly volatile and has low solubility in solution, it is assumed that zero-valent mercury does not exist in the sample solution. Therefore, all zero-valent mercury is converted from monovalent mercury. According to the disproportionation reaction formula, the concentration of monovalent mercury in the sample solution = 2 × the detection concentration of zero-valent mercury. When the detection concentration of divalent mercury < the detection concentration of zero-valent mercury, it is assumed that divalent mercury does not exist in the sample solution, and it is assumed that zero-valent mercury and divalent mercury do not coexist in the non-disproportionation state. Therefore, all divalent mercury is converted from monovalent mercury. According to the disproportionation reaction formula, the concentration of monovalent mercury in the sample solution = 2 × the detection concentration of divalent mercury. Therefore, by detecting the concentrations of divalent and zero-valent mercury, the present invention can directly obtain the concentration of monovalent mercury in the sample solution through the above-mentioned method. Moreover, the detection steps are not based on monovalent mercury directly, and the detection of zero-valent and divalent mercury is accurate and highly sensitive.

[0031] To further illustrate the present invention, the solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0032] In all embodiments of the present invention, the chemicals and reagents used are as follows: L-cysteine ​​(analytical grade, Shandong Keyuan Biochemical Co., Ltd.), 2-mercaptoethanol (analytical grade, Shandong Keyuan Biochemical Co., Ltd.), ammonium acetate (analytical grade, Tianjin Kemio Chemical Reagent Co., Ltd.), methanol (analytical grade, Tianjin Kemio Chemical Reagent Co., Ltd.), mercury standard solution (Shandong Keyuan Biochemical Co., Ltd.), potassium borohydride (analytical grade, Tianjin Kemio Chemical Reagent Co., Ltd.), potassium hydroxide (analytical grade, Tianjin Kemio Chemical Reagent Co., Ltd.), nitric acid (analytical grade, Tianjin Kemio Chemical Reagent Co., Ltd.), and mercurous nitrate (analytical grade, Shanghai Maclean Biochemical Technology Co., Ltd.).

[0033] Example 1 I. Establishment of the Standard Curve Mercurous nitrate was dissolved in a 1% (w / w) aqueous nitric acid solution to prepare a series of monovalent mercury standard solutions with concentrations of 100 μg / L, 200 μg / L, 300 μg / L, 400 μg / L, 500 μg / L, 600 μg / L, 700 μg / L, 800 μg / L, 900 μg / L, 1.0 mg / L, 2.0 mg / L, 3.0 mg / L, 4.0 mg / L, and 5.0 mg / L.

[0034] The monovalent mercury standard solution was detected by high performance liquid chromatography-atomic fluorescence spectrometry, wherein: The conditions for high-performance liquid chromatography (HPLC) separation were as follows: the chromatographic column was a Thermo Acclaim. TM 120 C 18 The reversed-phase column had a size of 4.6 × 150 mm; the mobile phase was 2-mercaptoethanol-ammonium acetate-methanol aqueous solution, wherein the volume percentage of 2-mercaptoethanol was 0.5%, the concentration of ammonium acetate was 8 mmol / L, and the volume percentage of methanol was 8%; the elution method was isocratic elution; the guard column was a Phenomenex KJ0-4282 with a size of 4 × 3.0 mm; the flow rate of the mobile phase was 1 mL / min. The conditions for atomic fluorescence spectrometry detection were as follows: the carrier gas was an aqueous nitric acid solution with a mass percentage of 7%; the reducing agent was an aqueous KBH4-KOH solution with a mass percentage of 2% KBH4 and a mass percentage of 0.35% KOH; both the carrier gas and the shielding gas were high-purity argon; the carrier gas flow rate was 300 mL / min; the shielding gas flow rate was 500 mL / min; the excitation source was a mercury hollow cathode lamp; the lamp current was 30 mA; the lamp voltage was 270 V; the pump flow rate was 80 mL / min; and the photochemical vapor generator was an ultraviolet lamp (i.e., the ultraviolet lamp was set to be on).

[0035] The results of high performance liquid chromatography-atomic fluorescence spectrometry detection of a series of concentration standard solutions are as follows: Figures 1-14 As shown. Among them, Figure 1 High-performance liquid chromatography-atomic fluorescence spectrum of a 100 μg / L monovalent mercury standard solution; Figure 2 High-performance liquid chromatography-atomic fluorescence spectrum of a 200 μg / L monovalent mercury standard solution; Figure 3 High-performance liquid chromatography-atomic fluorescence spectrum of a 300 μg / L monovalent mercury standard solution; Figure 4 High-performance liquid chromatography-atomic fluorescence spectrum of a 400 μg / L monovalent mercury standard solution; Figure 5 High-performance liquid chromatography-atomic fluorescence spectrum of a 500 μg / L monovalent mercury standard solution; Figure 6 High-performance liquid chromatography-atomic fluorescence spectrum of a 600 μg / L monovalent mercury standard solution; Figure 7 High-performance liquid chromatography-atomic fluorescence spectrum of a 700 μg / L monovalent mercury standard solution; Figure 8 High-performance liquid chromatography-atomic fluorescence spectrum of 800 μg / L monovalent mercury standard solution; Figure 9 High-performance liquid chromatography-atomic fluorescence spectrum of a 900 μg / L monovalent mercury standard solution; Figure 10 High-performance liquid chromatography-atomic fluorescence spectrum of a 1.0 mg / L monovalent mercury standard solution; Figure 11High-performance liquid chromatography-atomic fluorescence spectrum of a 2.0 mg / L monovalent mercury standard solution; Figure 12 High-performance liquid chromatography-atomic fluorescence spectrum of a 3.0 mg / L monovalent mercury standard solution; Figure 13 High-performance liquid chromatography-atomic fluorescence spectrum of a 4.0 mg / L monovalent mercury standard solution; Figure 14 The image shows the high-performance liquid chromatography-atomic fluorescence spectrum of a 5.0 mg / L monovalent mercury standard solution. Figures 1-14 It is known that due to the disproportionation of monovalent mercury into two mercury forms, two peaks will be generated under the above-mentioned high-performance liquid chromatography-atomic fluorescence spectrometry detection conditions (the peak with the earlier retention time corresponds to zero-valent mercury, and the peak with the later retention time corresponds to divalent mercury). In some graphs, the peak area of ​​the divalent peak is higher than that of the zero-valent peak. This may be attributed to the intrinsic accuracy of high-performance liquid chromatography-atomic fluorescence spectrometry detection. The zero-valent mercury generated by the disproportionation of low-concentration monovalent mercury is insufficient to generate an instrument response or has a poor response, while the ratio of zero-valent mercury to divalent mercury generated by the disproportionation of high-concentration monovalent mercury is close to 1:1. Standard curves for the two mercury forms were plotted by linearly fitting the concentration of monovalent mercury in the monovalent mercury standard solution as the x-axis and the corresponding signal intensity (peak area) as the y-axis.

[0036] Figure 15 The standard curve for zero-valent mercury corresponds to the linear regression equation y = 493.11x - 93731.19, with R². 2 =0.994, Figure 16 The standard curve for divalent mercury corresponds to the linear regression equation y = 617.25x + 106480.48, with R². 2 =0.992.

[0037] II. Verification of the Standard Curve Mercurous nitrate was dissolved in a 1% (w / w) nitric acid aqueous solution to prepare monovalent mercury sample solutions with concentrations of 400 μg / L, 600 μg / L, 700 μg / L, 800 μg / L, 900 μg / L, 2000 μg / L, and 4000 μg / L for verification. The above-mentioned high-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AQIS) method was used for detection, and the peak areas were obtained. Simultaneously, the theoretical standard peak areas were calculated using the obtained zero-valent mercury standard curve and divalent mercury standard curve. The standard peak areas and the detected peak areas were compared, and the relative error was calculated. The results are shown in Table 1.

[0038] Table 1. Verification results of the zero-valent mercury standard curve and the divalent mercury standard curve.

[0039] As shown in Table 1, the standard curves for zero-valent mercury and divalent mercury have good accuracy for both high and low concentrations, with relative errors of ≤15%.

[0040] III. Determination of Limit of Detection, Limit of Quantitation, and Precision The limits of detection, limits of quantitation, and precision were calculated based on the obtained zero-valent mercury standard curves and divalent mercury standard curves. The calculation formulas are shown in Equations 1 to 4, and the results are shown in Table 2. Residual standard deviation (SE) = Formula 1; Limit of Detection (LOD) = Formula 2; Limit of Quantification (LOQ) = Formula 3; Precision is expressed as relative standard deviation (RSD), RSD = ×100% Equation 4.

[0041] Table 2. Limits of detection, limits of quantitation, and precision for zero-valent and divalent mercury.

[0042] As shown in Table 2, the detection method provided by this invention can stably determine both zero-valent and divalent mercury with good precision (RSDs of 6.5% and 6.4%, respectively), meeting the requirements of routine analysis. Although the detection limit for zero-valent mercury is relatively high, this sensitivity is sufficient for quantitative detection in non-trace analysis scenarios. The detection performance for divalent mercury is even better, with a detection limit as low as 432 μg / L, and a wider range of applications.

[0043] Example 2 I. Determination of Mobile Phase Type The mobile phase type was optimized based on a 100 μg / L monovalent mercury standard solution. Based on the high-performance liquid chromatography-atomic fluorescence spectrometry detection method provided in Example 1, the following different types of mobile phases were used: (1) an acetonitrile aqueous solution with a volume percentage of 20%; (2) an acetonitrile-ammonium acetate-2-mercaptoethanol aqueous solution, wherein the volume percentage of acetonitrile is 3%, the mass percentage of ammonium acetate is 0.5%, and the volume percentage of 2-mercaptoethanol is 0.03%; (3) (3) Acetonitrile-ammonium acetate aqueous solution, wherein the volume percentage of acetonitrile is 3% and the concentration of ammonium acetate is 60 mmol / L; (4) L-cysteine-ammonium acetate-methanol aqueous solution, wherein the volume percentage of L-cysteine ​​is 0.1%, the concentration of ammonium acetate is 8 mmol / L and the volume percentage of methanol is 8%; (5) 2-mercaptoethanol-ammonium acetate-methanol aqueous solution, wherein the volume percentage of 2-mercaptoethanol is 0.5%, the concentration of ammonium acetate is 8 mmol / L and the volume percentage of methanol is 8%. Among them, when using mobile phases (1), (2) and (3), no monovalent mercury-related peaks were observed; when using mobile phases (4) and (5), two mercury separation peaks were observed. This phenomenon can be attributed to the disproportionation reaction of monovalent mercury during high performance liquid chromatography (HPLC) separation, where monovalent mercury is converted into zero-valent mercury and divalent mercury.

[0044] Figure 17 The detection diagram is for L-cysteine-ammonium acetate-methanol aqueous solution as the mobile phase (mobile phase (4)); Figure 18 The detection chromatogram shows that the mobile phase was 2-mercaptoethanol-ammonium acetate-methanol aqueous solution (mobile phase (5)). Figure 17 and Figure 18 It can be seen that using mobile phase (4) as the mobile phase for detecting monovalent mercury has high sensitivity, with mercury speciation retention time <120s and chromatographic peaks without obvious tailing or impurity interference. However, there is an overlapping peak at 110s, and zero-valent mercury and divalent mercury cannot be completely separated. When using mobile phase (5) as the mobile phase for detecting monovalent mercury, the disproportionated zero-valent mercury peak (660s) and divalent mercury peak (720s) can be effectively separated, and the repeatability is good. Therefore, 0.5% (v / v) 2-mercaptoethanol-8mmol / L ammonium acetate-8% (v / v) methanol aqueous solution is used as the mobile phase for subsequent high performance liquid chromatography-atomic fluorescence spectrometry detection.

[0045] II. Determination of the volume percentage of 2-mercaptoethanol in the mobile phase Keeping other conditions constant, the mobile phase was 2-mercaptoethanol-8 mmol / L ammonium acetate-8% (v / v) methanol aqueous solution, wherein the volume percentage of 2-mercaptoethanol was 0.05%, 0.1%, 0.2%, 0.35% and 0.5%, respectively. Figure 19This is a chromatogram showing the detection of 2-mercaptoethanol at different volume percentages in different mobile phases (the main observation is the change in the peak shape of divalent mercury, therefore only the divalent peak is shown in the figure). Figure 19 It can be seen that as the volume percentage of 2-mercaptoethanol in the mobile phase increases from 0.05% to 0.5%, the monovalent mercury signal peak gradually increases, and the highest peak height / peak area response is observed at a volume percentage of 0.35%. At this concentration, Hg... 2+ The detection sensitivity of the complex with 2-ME was the highest, but the peak value decreased with further increases in concentration. This may be because when the concentration of 2-ME is low, a stable mercury complex cannot be formed; when the concentration of 2-ME is high, excess 2-ME may introduce interference, and the formed mercury complex may be partially dissolved in the excess hydrophilic 2-ME. Therefore, 0.35% (v / v) was selected as the optimal volume percentage of 2-mercaptoethanol in the mobile phase.

[0046] III. Determination of Mobile Phase Velocity Based on the above results, using 0.35% (v / v) 2-mercaptoethanol-8 mmol / L ammonium acetate-8% (v / v) methanol aqueous solution as the mobile phase, and keeping other conditions unchanged, the flow rates of the mobile phase were 0.8 mL / min, 1.0 mL / min, 1.2 mL / min, 1.4 mL / min and 1.6 mL / min respectively. Figure 20 The graphs show the detection results under different mobile phase flow rates (focusing on the changes in the peak shape of divalent mercury, therefore only divalent peaks are shown in the graphs). Figure 20 It was found that as the mobile phase flow rate increased from 0.8 mL / min to 1.6 mL / min, the detector response (peak value) also increased accordingly, and the instrument sensitivity significantly improved. The highest peak response value was observed at a flow rate of 1.2 mL / min. This is attributed to the fact that as the flow rate increases, the reaction time between the sample and the reducing agent decreases, and the reduction reaction may be insufficient, resulting in a decrease in the amount of mercury vapor generated and a lower response value. Moreover, the increased flow rate shortens the retention time, and different forms of mercury may exhibit overlapping peaks, making it difficult to separate zero-valent and divalent mercury, thus compromising good separation. Therefore, 1.2 mL / min is considered the optimal mobile phase flow rate.

[0047] IV. Determination of the concentration of ammonium acetate in the mobile phase The mobile phase flow rate was kept at 1.2 mL / min, and other conditions remained unchanged. The mobile phase was 0.35% (v / v) 2-mercaptoethanol-ammonium acetate-8% (v / v) methanol aqueous solution, with the concentrations of ammonium acetate being 10 mmol / L, 20 mmol / L, 30 mmol / L, 40 mmol / L, and 50 mmol / L, respectively. Figure 21This is a graph showing the detection of ammonium acetate at different concentrations in the mobile phase (focusing on the changes in the peak shape of divalent mercury, therefore only divalent peaks are shown in the graph). Figure 21 It is known that a mobile phase ammonium acetate concentration of 10 mmol / L provides the strongest response signal and the highest sensitivity (425 mV), which is beneficial for monovalent mercury analysis. Furthermore, 10 mmol / L ammonium acetate stabilizes the pH and is less likely to cause ion source contamination or signal suppression. Moreover, 10 mmol / L is a commonly used and safe concentration range. Further increasing the ammonium acetate concentration will suppress the detection signal, which is attributed to the high salt concentration inhibiting ionization efficiency and reducing the signal. Excessively high buffer salt concentrations may also accelerate column aging, clog the system flow path, or cause precipitation. Therefore, 10 mmol / L is considered the optimal concentration of ammonium acetate in the mobile phase.

[0048] Example 3 Using 0.5% (v / v) 2-mercaptoethanol-8 mmol / L ammonium acetate-8% (v / v) methanol aqueous solution as the mobile phase, and keeping other conditions unchanged from Example 1, it was verified that monovalent mercury disproportionates to generate divalent mercury and zero-valent mercury.

[0049] Verification of monovalent and divalent mercury A 1000 ppm mercury standard solution was mixed with a 1 wt% nitric acid solution to prepare a 300 ppb divalent mercury standard solution. The 300 ppb divalent mercury standard solution was then analyzed by high-performance liquid chromatography-atomic fluorescence spectrometry. Figure 22 This is a comparison of the high-performance liquid chromatography-atomic fluorescence spectra of divalent mercury standard solutions and monovalent mercury standard solutions. Figure 22 It can be seen that the peak position of the divalent mercury standard sample is similar to that of the divalent mercury peak generated by the disproportionation of monovalent mercury, indicating that the monovalent mercury standard solution underwent a disproportionation reaction and generated divalent mercury during high performance liquid chromatography-atomic fluorescence spectrometry detection.

[0050] II. Verification of Zero-Valence Mercury Zero-valent mercury standard solution was prepared by reducing divalent mercury standard solution with acidic SnCl2 solution. 25 mL of a 2 mg / L divalent mercury standard solution was mixed with 20 mL of a 20% (m / V) SnCl2 solution (dissolved in 10% hydrochloric acid), and the mixture was placed in a headspace reactor at a constant temperature (25°C) and sealed. High-purity N2 was then introduced. 2， The solution was purged at a flow rate of less than 10 mL / min for 2 hours. Connecting the bottle to a volumetric flask containing 0.2% (v / v) 2-mercaptoethanol, extremely slow bubble formation was observed. Zero-valent mercury, due to its high volatility, was effectively purged and transferred to the absorbent with the carrier gas. The absorbent was detected using high-performance liquid chromatography-atomic fluorescence spectrometry. Figure 23This is a comparison of the high-performance liquid chromatography-atomic fluorescence spectra of zero-valent mercury standard solutions and monovalent mercury standard solutions. Figure 23 It can be seen that the peak position of the zero-valent mercury standard sample is similar to that of the zero-valent mercury peak generated by the disproportionation of monovalent mercury, indicating that the monovalent mercury standard solution underwent a disproportionation reaction and generated zero-valent mercury during high performance liquid chromatography-atomic fluorescence spectrometry detection.

[0051] Example 4 Using 0.35% (v / v) 2-mercaptoethanol-10 mmol / L ammonium acetate-8% (v / v) methanol aqueous solution as the mobile phase, with a flow rate of 1.2 mL / min, and other conditions being the same as in Example 1, different test samples were tested.

[0052] I. Determination of Sample Extraction Time A fly ash sample from a waste-to-energy incineration plant was ground and sieved to 80-100 mesh to ensure uniformity. 0.5 g of the treated sample was weighed and extracted with 20 mL of a 0.15% (v / v) 2-mercaptoethanol aqueous solution (prepared with ultrapure water). All extraction experiments were conducted in a constant-temperature shaker at 200 rpm and 25°C for 0 h, 2 h, 4 h, 6 h, and 8 h. After extraction, the sample was filtered through a 0.22 μm polyethersulfone membrane to obtain the test sample solution. High-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFI) was performed under the above conditions to detect the mercury concentration in the test sample solution, and the concentration of monovalent mercury was calculated. Figure 24 The images show the detection results under different oscillation extraction time conditions. Figure 24 It can be seen that as the shaking extraction time is gradually extended to 4 hours, the concentration of monovalent mercury reaches its peak (448 μg / L), and further shaking extraction does not significantly improve it. Therefore, 4 hours is the optimal shaking extraction time.

[0053] II. Detection of the sample to be tested Fly ash samples were collected from three different waste-to-energy incineration plants, ground, and sieved to 80-100 mesh. 0.5 g of each processed sample was weighed and extracted with 20 mL of 0.15% (v / v) 2-mercaptoethanol aqueous solution, yielding sample solutions labeled A, B, and C. Sample solution B was found to be too concentrated and was diluted 1000-fold with 1 wt% nitric acid. High-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFI) was then performed on sample solutions A through C under the same conditions, and the concentration of monovalent mercury in each sample solution was calculated. Figure 25 This is the high-performance liquid chromatography-atomic fluorescence spectrum of sample solution A. Figure 26 This is the high-performance liquid chromatography-atomic fluorescence spectrum of sample solution B. Figure 27This is the high-performance liquid chromatography-atomic fluorescence spectrum of the sample solution C to be tested. Figures 25-27 The illustration in the figure is a bar chart of mercury concentrations, from left to right representing the concentrations of monovalent, divalent, and zero-valent mercury. Figures 25-27 It was found that monovalent mercury was present in fly ash samples from three different waste-to-energy incineration plants. The concentration of monovalent mercury in sample A was 445.8 μg / L, in sample B it was 471.0 mg / L, and in sample C it was 742.4 μg / L. It is inferred that the monovalent mercury in the fly ash samples from the three waste-to-energy incineration plants existed in the form of mercurous chloride (Hg₂Cl₂). This demonstrates that the detection method provided by this invention can be used for the analysis and detection of monovalent mercury in actual samples.

[0054] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for detecting monovalent mercury, characterized in that, Includes the following steps: The sample to be tested was extracted using an aqueous solution of 2-mercaptoethanol to obtain the sample solution; the volume percentage of 2-mercaptoethanol in the aqueous solution was 0.15~0.2%; the mercury in the sample solution included monovalent mercury. The sample solution to be tested was subjected to high performance liquid chromatography-atomic fluorescence spectrometry to obtain the detection peak areas of zero-valent mercury and divalent mercury; based on the detection peak areas of zero-valent mercury and divalent mercury, the detection concentrations of divalent mercury and zero-valent mercury were obtained using the external standard method; based on the detection concentrations of divalent mercury and zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested was obtained. The method for obtaining the concentration of monovalent mercury in the sample solution to be tested is as follows: When the detection concentration of divalent mercury is greater than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is 2 × the detection concentration of zero-valent mercury. When the detection concentration of divalent mercury equals the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested equals 2 × the detection concentration of zero-valent mercury equals 2 × the detection concentration of divalent mercury. When the detection concentration of divalent mercury is less than the detection concentration of zero-valent mercury, the concentration of monovalent mercury in the sample solution to be tested is 2 × the detection concentration of divalent mercury. The conditions for high-performance liquid chromatography (HPLC) separation in the aforementioned high-performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFI) detection include: The chromatographic column is C10. 18 The chromatographic column was used; the mobile phase was an aqueous solution of 2-mercaptoethanol-ammonium acetate-methanol, wherein the volume percentage of 2-mercaptoethanol in the aqueous solution was 0.05-0.5%, the concentration of ammonium acetate was 8-50 mmol / L, and the volume percentage of methanol was 8%; the elution method was isocratic elution. The conditions for atomic fluorescence spectrometry detection in the high-performance liquid chromatography-atomic fluorescence spectrometry detection include: The carrier gas is an aqueous nitric acid solution, wherein the mass percentage of nitric acid in the aqueous nitric acid solution is 7-10%; the reducing agent is KBH4; and the carrier gas flow rate is 275-300 mL / min.

2. The detection method according to claim 1, characterized in that, The flow rate of the mobile phase is 0.8~1.6 mL / min; The C 18 The chromatographic column is C10. 18 Reversed-phase chromatography column.

3. The detection method according to claim 1, characterized in that, The carrier gas and shielding gas for atomic fluorescence spectrometry detection are independently argon; the shielding gas flow rate is 500~600 mL / min.

4. The detection method according to claim 1, characterized in that, The guard column used in the high-performance liquid chromatography separation is the SecurityGuard guard column system, with the guard column shell being Phenomenex KJ0-4282 and the guard column core being Phenomenex AJ0-4287.

5. The detection method according to claim 1 or 3, characterized in that, The excitation source for the atomic fluorescence spectrometry detection was a mercury hollow cathode lamp; the lamp current was 30 mA; the lamp voltage was 270 V; the pump flow rate was 80 mL / min; and the photochemical vapor generation source was an ultraviolet lamp.

6. The detection method according to claim 1, characterized in that, The KBH4 is used in the form of a KBH4-KOH aqueous solution, wherein the mass percentage of KBH4 in the KBH4-KOH aqueous solution is 2% and the mass percentage of KOH is 0.35%.

7. The detection method according to claim 1, characterized in that, The extraction is an oscillating extraction; the oscillating extraction speed is 200~250 rpm, the temperature is 20~25℃, and the time is 2~4h.

8. The detection method according to claim 1, characterized in that, The external standard method includes obtaining the standard curves for zero-valent mercury and divalent mercury; The linear range of the zero-valent mercury standard curve is 100~5000 μg / L; The linear range of the divalent mercury standard curve is 100~5000 μg / L.

9. The detection method according to claim 1, characterized in that, The mass-to-volume ratio of the sample to be tested and the 2-mercaptoethanol aqueous solution is 1 g: 40~50 mL.

10. The detection method according to claim 1, characterized in that, The samples to be tested include fly ash from waste incineration power plants, phosphorus powder from waste fluorescent lamps, desulfurization gypsum, flue ash from coal-fired power plants, or soil and plant samples from mercury mining areas.

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