WO2020087894A1 - Outer tube injection-based atomic fluorescence analysis method and atomic fluorescence analyzer - Google Patents

Outer tube injection-based atomic fluorescence analysis method and atomic fluorescence analyzer Download PDF

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WO2020087894A1
WO2020087894A1 PCT/CN2019/084336 CN2019084336W WO2020087894A1 WO 2020087894 A1 WO2020087894 A1 WO 2020087894A1 CN 2019084336 W CN2019084336 W CN 2019084336W WO 2020087894 A1 WO2020087894 A1 WO 2020087894A1
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gas
outer tube
quartz furnace
atomic fluorescence
analysis method
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PCT/CN2019/084336
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French (fr)
Chinese (zh)
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龚治湘
杨梅
龚晖
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重庆民泰新农业科技发展集团有限公司
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Priority to MYPI2021002120A priority Critical patent/MY196504A/en
Publication of WO2020087894A1 publication Critical patent/WO2020087894A1/en
Priority to PH12021550915A priority patent/PH12021550915A1/en

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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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence
    • G01N21/6404—Atomic fluorescence
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • 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
    • G01N2021/0106—General arrangement of respective parts
    • G01N2021/0112—Apparatus in one mechanical, optical or electronic block
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence
    • G01N21/6404—Atomic fluorescence
    • G01N2021/6406—Atomic fluorescence multi-element

Definitions

  • the invention belongs to the field of analytical chemistry and relates to atomic fluorescence analysis. It changes the traditional sampling mode and corresponding technology of the atomizer in atomic fluorescence analysis, and specifically relates to the improvement of the sampling method in the original atomic fluorescence analysis method.
  • Atomic fluorescence analysis has been widely used in the determination of trace As, Sb, Bi, Hg, Se and other elements.
  • the basic principle is that the ions of the element to be tested in an acidic medium (usually hydrochloric acid) interact with a strong reducing agent (usually potassium borohydride or sodium borohydride) to be reduced to a gaseous hydride (or Hg atom), while generating a large amount hydrogen.
  • Hydride molecules dissociate into ground state atoms in a high-temperature hydrogen flame.
  • the atoms are excited to a high energy state by radiation of a specific frequency from the excitation light source. Due to the extremely unstable high energy level, the excited state atoms are emitted in the form of light radiation during the de-excitation process. Fluorescence of characteristic wavelength.
  • the fluorescence intensity is related to the concentration of the element to be measured, and the intensity of the fluorescence signal is measured by a detector (usually a photomultiplier tube) to obtain the concentration of the element to be
  • the atomic fluorometer (or atomic fluorescence photometer) designed according to the above principles mainly includes a sampling system, a gas-liquid separator (or reactor), an atomizer, an excitation light source, and a detector.
  • the test solution and reducing agent are transported through the sampling system and loaded into the reactor by the carrier fluid to undergo a chemical reaction, generating gaseous hydride molecules and hydrogen (called vapor), under the carrier of the carrier gas (usually argon) Enter the atomizer.
  • the atomizer is used to dissociate the hydride molecules into atoms.
  • the excitation light source and detector are used to excite fluorescence and collect fluorescence signals, respectively, and the detection results are obtained by calculating the fluorescence signals.
  • the atomization of the hydride depends on the high temperature of the hydrogen flame, and the atomization process is completed by the quartz furnace in the atomizer.
  • the quartz furnace is usually in the form of a sleeve, including a central tube (inner tube) and an outer tube.
  • the carrier gas (argon) carrier hydride and hydrogen have been introduced from the central tube extending into the interior of the quartz furnace.
  • the shielding gas (argon) is input from the outer tube, and the hydride from the central tube is atomized in the hydrogen flame ignited by the quartz furnace tube opening (shielding gas argon protection).
  • the steam from the reactor is usually carried into the quartz furnace with a small flow of carrier gas (Ar gas) to obtain a stable and elongated hydrogen flame.
  • the furnace wire for igniting hydrogen is located at the outer tube nozzle of the quartz furnace, because the center of the quartz furnace
  • the tube nozzle is located inside the quartz furnace, at a certain distance from the outer tube nozzle of the quartz furnace, and often cannot ignite the hydrogen flame. This problem is particularly prominent for elements that generate little hydrogen in the reaction. This becomes an obstacle for the atomic fluorometer to measure these elements.
  • the purpose of the present invention is to provide an atomic fluorescence analysis method for outer tube sampling to effectively solve the above-mentioned problems in atomic fluorescence analysis.
  • the atomic fluorescence analysis method of the outer tube sampling of the present invention includes the steps of sampling and delivery, the mixed gas generated by the carrier gas carrier gas-liquid separator entering the atomizer, atomization of the element to be measured and fluorescence detection, etc., wherein the atomization
  • the quartz furnace in the device is a set structure of an inner tube and an outer tube.
  • the mixed gas is introduced into the outer tube of the quartz furnace, and at the same time, auxiliary gas is introduced into the inner tube of the quartz furnace.
  • the flow rate of the carrier gas into the outer tube of the quartz furnace is 1000-1200 ml / min.
  • the flow rate of the auxiliary gas introduced into the inner tube of the quartz furnace is 400-600 ml / min; when the element to be measured is Cd, the flow rate of the auxiliary gas introduced into the inner tube of the quartz furnace is 0 ml / min.
  • the flow rate of the mixed gas is controlled to uniformly enter the outer tube of the quartz furnace.
  • the carrier gas into the outer tube of the quartz furnace and the auxiliary gas introduced into the inner tube of the quartz furnace are the same gas, such as argon gas.
  • the auxiliary gas is an inert gas, preferably the same gas as the carrier gas, such as argon gas.
  • the element to be measured is a single element, two or more elements.
  • the present invention provides an atomic fluorometer using the atomic fluorescence analysis method used to complete the above-mentioned outer tube sampling, which mainly includes a sampling system, a gas-liquid separator, an atomizer, an excitation light source, and a detector; the atomization
  • the quartz furnace in the device is a set structure of the inner tube and the outer tube, wherein the outer tube of the quartz furnace is connected with the mixed gas outlet branch of the atomizer, and the inner tube of the quartz furnace is connected to the auxiliary gas input tube.
  • the present invention provides an atomic fluorescence analysis method using the above-mentioned atomic fluorometer, which includes the following steps:
  • Operation 1 Connect the gas outlet branch pipe (hydride, hydrogen and carrier gas mixture) of the gas-liquid separator to the outer tube of the quartz furnace of the atomizer, and connect the inner tube of the quartz furnace to the auxiliary gas;
  • Operation 2 Turn on the power of the atomic fluorometer, set the detection conditions, light the element to be tested to excite the light source and preheat it;
  • Operation 3 Open the carrier gas and auxiliary gas cylinder valves, adjust the respective air pressure and flow according to the settings, and open the exhaust device of the atomizer, and connect the power supply of the electric furnace wire of the atomizer;
  • Operation 4 Start the sampling system to complete the sampling and delivery. After the gas-liquid separator completes the reduction reaction and generates a mixed gas, the electric furnace wire of the atomizer is ignited, the light source and the detector are excited to obtain the fluorescent signal of the element to be measured in the test solution value;
  • Operation 6 Determine the fluorescence signal value of the element to be measured in the sample solution, obtain the concentration of the element to be measured in the sample solution from the standard curve, and enter the relevant parameters to calculate the content of the element to be measured in the sample.
  • the carrier gas flow rate of the mixed gas of the carrier gas carrier tape into the outer tube of the quartz furnace is 1000-1200 ml / min.
  • the flow rate of the auxiliary gas into the inner tube of the quartz furnace is 400-600 ml / min.
  • the flow rate of the auxiliary gas into the inner tube of the quartz furnace is 0 ml / min.
  • the elements to be tested in the sample solution are two or more elements, prepare a standard mixed solution containing both elements (the concentration of each element can be different), and inject a sample and use the excitation light source corresponding to each element simultaneously to obtain different elements.
  • the fluorescence signal value of the standard series solution is measured for each element to make a fluorescence value-concentration standard curve, and the content of each element in the sample is obtained according to the standard curve of the corresponding element.
  • the carrier gas and the auxiliary gas are the same gas, preferably an inert gas, such as argon gas.
  • the present invention uses the original quartz furnace to carry out the outer tube sampling in the atomic fluorescence analysis process.
  • the inner tube is fed with auxiliary gas to overcome the defects of the inner tube sampling.
  • the hydrogen from the reactor is led to the outer tube nozzle
  • the heating of the furnace wire makes it easy to ignite the hydrogen flame.
  • the formed hydrogen flame is large and stable, which makes the detection sensitivity significantly improved.
  • the experiment proves that the invention adopts the outer tube sampling method to have high detection accuracy, and solves the problem that it is difficult to detect those elements that generate less hydrogen in the previous atomic fluorescence analysis.
  • Figure 1 is a schematic diagram of the original sampling method of quartz furnace in atomic fluorescence analysis
  • FIG. 2 is a schematic diagram of the outer tube sampling method of the present invention in atomic fluorescence analysis
  • Fig. 3 shows the peak curve of Cd (A amplitude, fluorescence value-time) and the standard curve of Cd (B amplitude, fluorescence value-concentration) of Cd measured by the atomic fluorescence analysis method of the outer tube sampling of the present invention in Example 1;
  • Fig. 4 shows the peak curve of Hg and As (A amplitude, fluorescence value-time) and the standard curve of Hg and As (B amplitude, fluorescence value) of the mixed solution measured by the atomic fluorescence analysis method of the outer tube sampling of the present invention in Example 2 -concentration).
  • Fig. 5 shows the peak curve of Pb (A amplitude, fluorescence value-time) and the standard curve of Pb (B amplitude, fluorescence value-concentration) determined by the atomic fluorescence analysis method of the outer tube sampling of the present invention in Example 3.
  • the present invention proposes a new atomic fluorescence analysis method, which includes sampling and delivery, the mixed gas generated by the carrier gas and the gas-liquid separator into the atomizer, the atomization of the element to be measured, and fluorescence detection.
  • the mixed gas enters the atom
  • the external tube sampling method is used for the carburetor. See Figure 2 and compare with Figure 1.
  • the original atomic fluorescence analysis uses 300-400ml / min carrier gas (Ar gas) to carry the reaction product Hg atoms or hydride and hydrogen into the inner tube of the quartz furnace, outside the quartz furnace
  • the tube is filled with 900-1100ml / min Ar gas as shielding gas, as shown in Figure 1.
  • the hydride and hydrogen mixed gas carried by the carrier gas (such as argon) is connected to the outer tube, and at the same time, the argon used as the shielding gas is connected to the inner tube as auxiliary gas, as shown in FIG. 2 .
  • the carrier gas carrying the mixed gas in the present invention, the outer tube Ar gas
  • increase the flow rate of the carrier gas carrying the mixed gas in the present invention, the outer tube Ar gas to 1000-1200 ml / min so that the hydrogen in the outer tube of the quartz furnace is ignited to form a larger hydrogen flame.
  • the flow rate of the auxiliary gas is reduced to 400-600ml / min, the flow rate of the auxiliary gas in the inner pipe is small, only the hydrogen flame is pushed up, even when it is detected for certain elements (such as Cd)
  • the inner tube is not even vented with auxiliary Ar gas (ie, the flow rate is 0 ml / min).
  • the flow-limiting technology is used to control the delivery speed of the mixed gas, that is, the flow rate of the mixed gas into the outer tube of the quartz furnace is controlled, so that the ground state atoms or hydrides and hydrogen of the Ar gas carrier enter the quartz at a relatively uniform flow rate The outer tube of the furnace, so that a stable hydrogen flame can be obtained.
  • the outer tube sampling method of the present invention changes the mode of the atomic fluorescence method that traditionally introduces hydride (or Hg atoms) from the inner tube.
  • the mechanism is: the gaseous atoms or molecules and hydrogen produced by the chemical reduction reaction in the reactor are introduced from the outer tube of the quartz furnace along with the carrier gas (Ar gas) carrier strip, formed by the hydride (or mercury atom) of the element to be measured and hydrogen
  • the mixed gas rises along the inner wall of the outer tube of the quartz furnace, the hydrogen gas is ignited by the heat of the quartz furnace tube mouth, and the hydride is dissociated under the high temperature of the hydrogen flame in the Ar gas atmosphere.
  • the auxiliary gas usually argon
  • the formed hydrogen flame is much larger than the inner tube sample. See Figure 2 and compare with Figure 1.
  • the hydrogen is heated by the furnace wire located at the outer tube nozzle, the hydrogen flame is easily ignited, and the formed hydrogen flame is large and stable, and the luminous solid angle is large
  • the detection sensitivity has been significantly improved, and this method has been successfully used in the determination of As, Hg, Se, Pb and Cd in various samples.
  • the outer tube sampling method makes the hydrogen closer to the furnace wire heated at the quartz furnace port, and the hydrogen flame is easily ignited. The flame cannot be ignited basically, and it is very difficult to determine these elements. It can be seen that the present invention also solves the problem of atomic fluorescence detection of elements that generate less hydrogen in the reaction.
  • the detection of the present invention can use the existing atomic fluorometer.
  • the atomic fluorometer includes a sampling system, a gas-liquid separator, an atomizer, an excitation light source and a detector.
  • the atomizer includes a quartz furnace and a quartz furnace.
  • the electric furnace wire of the nozzle and the quartz furnace are in the form of sleeves of the inner tube and the outer tube.
  • the specific operation of the detection example using this atomic fluorometer is:
  • Operation 1 Connect the gas outlet branch of the gas-liquid separator (used to guide the mixed gas formed by hydride and hydrogen of the carrier gas carrier) into the outer tube of the quartz furnace in the atomizer, and at the same time, connect the auxiliary gas (Ar Gas) connected to the inner tube of the quartz furnace;
  • Operation 2 Turn on the power of the atomic fluorometer, set the detection conditions according to the instructions of the instrument, light the excitation light source of the element to be measured and preheat for 5-10 minutes; if measuring a single element, select the single-channel mode of the instrument; simultaneously measure two elements, select Instrument dual channel mode;
  • Operation 3 Open the cylinder valve of carrier gas and auxiliary gas (can be Ar gas), adjust the respective air pressure and flow according to the settings, and open the exhaust device of the atomizer, and connect the power of the electric furnace wire;
  • auxiliary gas can be Ar gas
  • Operation 6 Determine the fluorescence signal value of the test element in the sample solution, obtain the concentration of the test element in the sample solution from the standard curve, and calculate the content of the test element in the sample after entering the relevant parameters.
  • the above method can measure a single element or two or more elements at the same time.
  • the standard curve obtains the content of the element to be measured in the sample.
  • Preparation of cadmium standard curve first prepare 10ng / ml cadmium standard solution, then take this standard solution 0, 0.5, 1.0, 1.5, 2.0, 2.5ml in a 50ml plastic quantitative bottle, and add a concentration of 50 to each solution 4ml of% HCl solution and 5ml of 5% thiourea were diluted with water to the mark to obtain a standard series solution with Cd concentration of 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng / ml. After shaking, the fluorescence signals of the blank and standard series solutions are measured according to the operation process, and a standard curve is produced (see panel B in FIG. 3). Panel A in FIG. 3 shows the peak curve of Cd.
  • both the carrier gas and the auxiliary gas use Ar gas, and the flow rate of argon gas (outer tube) as a carrier gas is controlled to 1000-1200ml / min, and the flow rate of 0ml / min is turned off as the auxiliary gas (inner tube).
  • the rice flour or soybean powder sample (about 0.1-0.2g) in a 50ml plastic quantitative bottle, add 50ml of HCl 4ml, 5% thiourea 5ml, shake for 5-10min, dilute with water to Scale, according to the volume of Table 1 to prepare the sample solution.
  • the sample solution is used as the test solution to measure the fluorescence signal of the sample solution, and the concentration of Cd is obtained from the standard curve and converted into the content in the sample. See Table 1 for the measurement results of Cd in food samples.
  • the outer tube sampling atomic fluorescence detection technology can realize the simultaneous detection of Hg and As in the same sample.
  • Preparation of standard curve prepare a mixed standard solution containing 500ng / ml As and 10ng / ml Hg in advance. Take this standard solution 0, 1, 2, 3, 4, 5ml in a 50ml plastic quantitative bottle, add 5ml of 5% Vc-5% thiourea solution, 10ml of 50% HCl concentration, and dilute with water to the mark to get 0 —No. 5 series standard solution, the order of Hg concentration in the standard solution is 0, 0.2, 0.4, 0.6, 0.8, 1.0 ng / ml, and the order of As concentration is 0, 10, 20, 30, 40, 50 ng / ml.
  • the fluorescence signals of Hg and As in the blank and standard series solutions are simultaneously measured according to the above operation process, and the Hg and As standard curves of the mixed standard solutions are prepared respectively.
  • the width A of Fig. 4 is the peak curve of Hg / As
  • the width B of Fig. 4 is the standard curve of the mixed standard solution Hg and As (the signal of the standard curve is calculated based on the area of the spectrum, and the blank area has been subtracted).
  • the carrier gas and the auxiliary gas are both Ar gas.
  • the flow rate of the Ar gas as the carrier gas is 1000ml / min
  • the flow rate of the Ar gas as the auxiliary gas is 500ml / min.
  • test solution Preparation and determination of test solution: Weigh 0.1-0.2g of soil sample according to the sample weight (G), place it in a 50ml PTFE sample tube, add 50% aqua regia to boil and decompose on a water bath for 1 hour, Transfer to 50ml plastic quantitative bottle with water, add 5ml of 5% Vc-5% thiourea solution, 10ml of 50% concentration of HCl, dilute to the mark with water, shake and use the sample solution as the test solution to measure Hg at the same time according to the operation process For the fluorescence signals of As and As, obtain the concentration of the corresponding element according to the respective standard curve and calculate the content of each element in the sample. The results are shown in Table 2.
  • the data shows that this method solves the difficulty of simultaneous determination of Hg and As in soil.
  • Hg content in the 6 samples differs greatly, but the test results are consistent with the recommended values, indicating that the atomic fluorescence analysis method of the present invention has high accuracy.
  • the two elements coexist in the test solution, and the sampling is completed once, and the detection can be completed synchronously by using the dual detectors, and the entire detection process is fast and convenient.
  • Test samples chemical reagents calcium chloride and calcium hydroxide
  • Preparation of lead standard curve first prepare 100ng / ml lead standard solution, then take this standard solution 0, 1, 2, 3, 4, 5ml in 50ml plastic quantitative bottle respectively, add 50% concentration to each solution 10ml of HCl solution, 5ml of 5% thiourea, diluted with water to the mark, the concentration of Pb in this standard series solution is 0, 2, 4, 6, 8, 10ng / ml. After shaking, the fluorescence signals of the blank and standard series solutions are measured according to the operation process, and a standard curve is produced, as shown in panel B in Figure 5, and panel A in Figure 5 is the peak curve of Pb.
  • the carrier gas and auxiliary gas are both Ar gas during operation, and the flow rate of argon (outer tube) as carrier gas is controlled to 1000-1200ml / min, and the flow rate of argon (inner tube) as auxiliary gas is controlled to 400-600ml / min.
  • test solution Preparation and determination of test solution: Weigh 0.2-0.3g of chemical reagent sample, transfer to a 50ml plastic quantitative bottle, add 10ml of 50% HCl and 5ml of 5% thiourea, shake for 5-10min, then dilute with water To the mark, shake and prepare the sample solution according to the volume of Table 3. According to the same operation as the standard curve measurement, the sample solution is used as the test solution to measure the fluorescence signal of the sample solution, and the concentration of Pb is obtained from the standard curve and converted into the content in the sample. The determination results of Pb in chemical reagents are shown in Table 3.
  • the original atomic fluorescence analysis requires very strict control of the acidity below 2% in the determination of Pb, otherwise the fluorescence signal cannot be detected, but the test solution after pretreatment is difficult to meet this requirement, and the 2% acidity test
  • the amount of hydrogen produced by the liquid after the reduction reaction is small and it is difficult to ignite.
  • the outer tube is used for sample injection while increasing the carrier gas flow rate. The hydrogen flame is easy to ignite.
  • Atomic fluorescence analysis of Pb in the 10% acid test solution can form an obvious Pb peak curve (see Figure 5B Amplitude) to improve the detection sensitivity and achieve the measurement of Pb.
  • the atomic fluorescence analysis method of the outer tube sampling overcomes the defect of the inner tube sampling, the hydrogen flame is easy to ignite, the formed hydrogen flame is large and stable, the measurement sensitivity is obviously improved, and it is particularly suitable for generating hydrogen The determination of few elements is suitable for industrial applications.

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Abstract

An outer tube injection-based atomic fluorescence analysis method and an atomic fluorescence analyzer. An outer tube injection-based atomic fluorescence analysis method comprises steps such as sampling and transportation, mixed gas produced by a gas-liquid separator being carried by a carrier gas to enter an atomizer, and atomization and fluorescence detection of an element to be measured, wherein a quartz furnace in the atomizer has a structure in which an inner tube and an outer tube are nested, the mixed gas is introduced into the outer tube of the quartz furnace, and an auxiliary gas is introduced into the inner tube of the quartz furnace. The use of the original quartz furnace to carry out the outer tube injection can facilitate the ignition of hydrogen flame and improve the detection sensitivity.

Description

外管进样的原子荧光分析方法及原子荧光仪Atomic fluorescence analysis method and atomic fluorescence instrument for outer tube sampling 技术领域Technical field
本发明属于分析化学领域，涉及原子荧光分析。它改变了原子荧光分析中原子化器传统的进样模式及相应技术，具体涉及对原有原子荧光分析方法中进样方法的改进。The invention belongs to the field of analytical chemistry and relates to atomic fluorescence analysis. It changes the traditional sampling mode and corresponding technology of the atomizer in atomic fluorescence analysis, and specifically relates to the improvement of the sampling method in the original atomic fluorescence analysis method.
背景技术Background technique
原子荧光分析已广泛用于痕量As、Sb、Bi、Hg、Se等元素的测定。基本原理是，在酸性介质(通常为盐酸)中待测元素的离子与强还原剂(通常为硼氢化钾或硼氢化钠)作用，被还原成气态氢化物(或Hg原子)，同时产生大量氢气。氢化物分子在高温氢火焰中解离成基态原子，原子被激发光源特定频率的辐射所激发至高能状态，由于高能级极不稳定，激发态原子在去激发过程中以光辐射的形式发射出特征波长的荧光。荧光强度与待测元素的浓度相关，通过检测器(通常为光电倍增管)测定其荧光信号强度从而能得到被测元素的浓度。Atomic fluorescence analysis has been widely used in the determination of trace As, Sb, Bi, Hg, Se and other elements. The basic principle is that the ions of the element to be tested in an acidic medium (usually hydrochloric acid) interact with a strong reducing agent (usually potassium borohydride or sodium borohydride) to be reduced to a gaseous hydride (or Hg atom), while generating a large amount hydrogen. Hydride molecules dissociate into ground state atoms in a high-temperature hydrogen flame. The atoms are excited to a high energy state by radiation of a specific frequency from the excitation light source. Due to the extremely unstable high energy level, the excited state atoms are emitted in the form of light radiation during the de-excitation process. Fluorescence of characteristic wavelength. The fluorescence intensity is related to the concentration of the element to be measured, and the intensity of the fluorescence signal is measured by a detector (usually a photomultiplier tube) to obtain the concentration of the element to be measured.
根据以上原理设计的原子荧光仪(或称原子荧光光度计)主要包括进样***、气液分离器(或称反应器)、原子化器、激发光源及检测器等部分。试液和还原剂通过进样***传送并被载流液载入反应器中发生化学反应，生成气态氢化物分子及氢气(称为蒸气)，在载气(通常为氩气)的载带下进入原子化器，原子化器用于使氢化物分子解离成原子，激发光源及检测器分别用于激发荧光和采集荧光信号，并通过对荧光信号的计算得出检测结果。The atomic fluorometer (or atomic fluorescence photometer) designed according to the above principles mainly includes a sampling system, a gas-liquid separator (or reactor), an atomizer, an excitation light source, and a detector. The test solution and reducing agent are transported through the sampling system and loaded into the reactor by the carrier fluid to undergo a chemical reaction, generating gaseous hydride molecules and hydrogen (called vapor), under the carrier of the carrier gas (usually argon) Enter the atomizer. The atomizer is used to dissociate the hydride molecules into atoms. The excitation light source and detector are used to excite fluorescence and collect fluorescence signals, respectively, and the detection results are obtained by calculating the fluorescence signals.
氢化物的原子化依赖氢火焰的高温，原子化过程通过原子化器中的石英炉完成。参见图1所示，通常石英炉为套管形式，包括中心管(内管)和外管，一直以来载气(氩气)载带氢化物及氢气从伸入石英炉内部的中心管引入，屏蔽气(氩气)从外管输入，中心管引出的氢化物在石英炉管口点燃的氢火焰中原子化(屏蔽气氩气保护)。来自反应器的蒸气通常用小流量载气(Ar气)载带进入石英炉方可获得稳定而细长的氢火焰，用于点燃氢气的炉丝位于石英炉外管管口，由于石英炉中心管管口位于石英炉内部，离石英炉外管管口有一定距离，常常无法点燃氢火焰，对反应中生成氢气少的元素该问题尤其突出。这成为原子荧光仪用以测定这些元素的障碍。The atomization of the hydride depends on the high temperature of the hydrogen flame, and the atomization process is completed by the quartz furnace in the atomizer. As shown in FIG. 1, the quartz furnace is usually in the form of a sleeve, including a central tube (inner tube) and an outer tube. The carrier gas (argon) carrier hydride and hydrogen have been introduced from the central tube extending into the interior of the quartz furnace. The shielding gas (argon) is input from the outer tube, and the hydride from the central tube is atomized in the hydrogen flame ignited by the quartz furnace tube opening (shielding gas argon protection). The steam from the reactor is usually carried into the quartz furnace with a small flow of carrier gas (Ar gas) to obtain a stable and elongated hydrogen flame. The furnace wire for igniting hydrogen is located at the outer tube nozzle of the quartz furnace, because the center of the quartz furnace The tube nozzle is located inside the quartz furnace, at a certain distance from the outer tube nozzle of the quartz furnace, and often cannot ignite the hydrogen flame. This problem is particularly prominent for elements that generate little hydrogen in the reaction. This becomes an obstacle for the atomic fluorometer to measure these elements.
发明内容Summary of the invention
本发明目的在于提供一种外管进样的原子荧光分析方法，以有效解决原子荧光分析中的上述问题。The purpose of the present invention is to provide an atomic fluorescence analysis method for outer tube sampling to effectively solve the above-mentioned problems in atomic fluorescence analysis.
本发明外管进样的原子荧光分析方法，包括取样输送、载气载带气液分离器产生 的混合气体进入原子化器、待测元素原子化和荧光检测等步骤，其中，所述原子化器中的石英炉为内管与外管的套装结构，将所述混合气体引入石英炉的外管，同时在石英炉的内管引入辅助气。The atomic fluorescence analysis method of the outer tube sampling of the present invention includes the steps of sampling and delivery, the mixed gas generated by the carrier gas carrier gas-liquid separator entering the atomizer, atomization of the element to be measured and fluorescence detection, etc., wherein the atomization The quartz furnace in the device is a set structure of an inner tube and an outer tube. The mixed gas is introduced into the outer tube of the quartz furnace, and at the same time, auxiliary gas is introduced into the inner tube of the quartz furnace.
所述载带混合气体进入石英炉外管的载气流量为1000-1200ml/min。The flow rate of the carrier gas into the outer tube of the quartz furnace is 1000-1200 ml / min.
所述引入石英炉内管的辅助气流量为400-600ml/min；待测元素为Cd时，所述引入石英炉内管的辅助气流量为0ml/min。The flow rate of the auxiliary gas introduced into the inner tube of the quartz furnace is 400-600 ml / min; when the element to be measured is Cd, the flow rate of the auxiliary gas introduced into the inner tube of the quartz furnace is 0 ml / min.
控制所述混合气体的流速使其均匀进入石英炉的外管。The flow rate of the mixed gas is controlled to uniformly enter the outer tube of the quartz furnace.
所述载带混合气体进入石英炉外管的载气以及石英炉内管引入的辅助气为同一气体，例如同为氩气。The carrier gas into the outer tube of the quartz furnace and the auxiliary gas introduced into the inner tube of the quartz furnace are the same gas, such as argon gas.
所述辅助气为惰性气体，优选与载气相同的气体，如氩气。The auxiliary gas is an inert gas, preferably the same gas as the carrier gas, such as argon gas.
所述待测元素为单一元素、两个或两个以上元素。The element to be measured is a single element, two or more elements.
用于样品中As、Hg、Se、Pb和Cd的测定。Used for the determination of As, Hg, Se, Pb and Cd in samples.
用于样品中痕量Pb的测定。Used for the determination of trace Pb in samples.
本发明提供一种原子荧光仪，使用其用于完成上述外管进样的原子荧光分析方法，主要包括进样***、气液分离器、原子化器、激发光源和检测器；所述原子化器中的石英炉为内管与外管的套装结构，其中，石英炉的外管与原子化器的混合气体出口支管连接，同时石英炉的内管连接辅助气输入管。The present invention provides an atomic fluorometer using the atomic fluorescence analysis method used to complete the above-mentioned outer tube sampling, which mainly includes a sampling system, a gas-liquid separator, an atomizer, an excitation light source, and a detector; the atomization The quartz furnace in the device is a set structure of the inner tube and the outer tube, wherein the outer tube of the quartz furnace is connected with the mixed gas outlet branch of the atomizer, and the inner tube of the quartz furnace is connected to the auxiliary gas input tube.
本发明提供一种利用上述原子荧光仪进行原子荧光分析的方法，包括以下操作步骤：The present invention provides an atomic fluorescence analysis method using the above-mentioned atomic fluorometer, which includes the following steps:
操作1.将气液分离器的气体出口支管(氢化物、氢气及载气混合气)接入原子化器石英炉外管，同时将石英炉内管接通辅助气； Operation 1. Connect the gas outlet branch pipe (hydride, hydrogen and carrier gas mixture) of the gas-liquid separator to the outer tube of the quartz furnace of the atomizer, and connect the inner tube of the quartz furnace to the auxiliary gas;
操作2.接通原子荧光仪电源，设置检测条件，点亮待测元素激发光源并预热； Operation 2. Turn on the power of the atomic fluorometer, set the detection conditions, light the element to be tested to excite the light source and preheat it;
操作3.打开载气和辅助气钢瓶阀门，按设定调节各自气压和流量，并打开原子化器的排风装置，接通原子化器的电炉丝电源； Operation 3. Open the carrier gas and auxiliary gas cylinder valves, adjust the respective air pressure and flow according to the settings, and open the exhaust device of the atomizer, and connect the power supply of the electric furnace wire of the atomizer;
操作4.启动进样***完成取样输送，待气液分离器完成还原反应产生混合气体后，使原子化器的电炉丝点火、激发光源和检测器工作，获得试液中待测元素的荧光信号值； Operation 4. Start the sampling system to complete the sampling and delivery. After the gas-liquid separator completes the reduction reaction and generates a mixed gas, the electric furnace wire of the atomizer is ignited, the light source and the detector are excited to obtain the fluorescent signal of the element to be measured in the test solution value;
操作5.分别测得各标准系列溶液中待测元素的荧光信号值，并制作荧光值—浓度标准曲线； Operation 5. Measure the fluorescence signal value of the element to be measured in each standard series solution separately, and make a fluorescence value-concentration standard curve;
操作6.测定样品溶液中待测元素的荧光信号值，从标准曲线得到样品溶液中待测元素的浓度，输入相关参数后计算出样品中被测元素的含量。Operation 6. Determine the fluorescence signal value of the element to be measured in the sample solution, obtain the concentration of the element to be measured in the sample solution from the standard curve, and enter the relevant parameters to calculate the content of the element to be measured in the sample.
所述载气载带的混合气体进入石英炉外管的载气流量为1000-1200ml/min。The carrier gas flow rate of the mixed gas of the carrier gas carrier tape into the outer tube of the quartz furnace is 1000-1200 ml / min.
所述辅助气进入石英炉内管的流量为400-600ml/min。The flow rate of the auxiliary gas into the inner tube of the quartz furnace is 400-600 ml / min.
待测元素为Cd时，所述辅助气进入石英炉内管的流量为0ml/min。When the element to be measured is Cd, the flow rate of the auxiliary gas into the inner tube of the quartz furnace is 0 ml / min.
样品溶液中待测元素为两种或以上元素时，配制同时含有各元素的(各元素浓度可以不相同)的标准混合溶液，一次进样并同步使用各元素对应的激发光源，分别获得不同元素的荧光信号值，对标准系列溶液测定后分别针对每种元素制作荧光值—浓度标准曲线，根据对应元素的标准曲线得到该试样中各待测元素的含量。When the elements to be tested in the sample solution are two or more elements, prepare a standard mixed solution containing both elements (the concentration of each element can be different), and inject a sample and use the excitation light source corresponding to each element simultaneously to obtain different elements. The fluorescence signal value of the standard series solution is measured for each element to make a fluorescence value-concentration standard curve, and the content of each element in the sample is obtained according to the standard curve of the corresponding element.
所述载气及辅助气体为同一种气体，优选为惰性气体，例如氩气。The carrier gas and the auxiliary gas are the same gas, preferably an inert gas, such as argon gas.
采用以上方案，本发明在原子荧光分析过程利用原石英炉实施外管进样，内管通入辅助气，克服了内管进样的缺陷，来自反应器的氢气被引至外管管口的炉丝加热，极易点燃氢火焰，形成的氢火焰形体大且稳定，使得检测灵敏度得到明显提高。实验证明，本发明采用外管进样的方式检测准确性高，解决了之前原子荧光分析中对于那些产生氢气少的元素难以检测的难题。Using the above scheme, the present invention uses the original quartz furnace to carry out the outer tube sampling in the atomic fluorescence analysis process. The inner tube is fed with auxiliary gas to overcome the defects of the inner tube sampling. The hydrogen from the reactor is led to the outer tube nozzle The heating of the furnace wire makes it easy to ignite the hydrogen flame. The formed hydrogen flame is large and stable, which makes the detection sensitivity significantly improved. The experiment proves that the invention adopts the outer tube sampling method to have high detection accuracy, and solves the problem that it is difficult to detect those elements that generate less hydrogen in the previous atomic fluorescence analysis.
附图说明BRIEF DESCRIPTION
图1为原子荧光分析中石英炉原有进样方式的示意图；Figure 1 is a schematic diagram of the original sampling method of quartz furnace in atomic fluorescence analysis;
图2为原子荧光分析中本发明外管进样方式的示意图；2 is a schematic diagram of the outer tube sampling method of the present invention in atomic fluorescence analysis;
图3为实施例1用本发明外管进样的原子荧光分析方法测定Cd的峰值曲线(A幅，荧光值-时间)和Cd的标准曲线(B幅，荧光值-浓度)；Fig. 3 shows the peak curve of Cd (A amplitude, fluorescence value-time) and the standard curve of Cd (B amplitude, fluorescence value-concentration) of Cd measured by the atomic fluorescence analysis method of the outer tube sampling of the present invention in Example 1;
图4为实施例2用本发明外管进样的原子荧光分析方法同时测定Hg和As的峰值曲线(A幅，荧光值-时间)以及混合液的Hg和As标准曲线(B幅，荧光值-浓度)。Fig. 4 shows the peak curve of Hg and As (A amplitude, fluorescence value-time) and the standard curve of Hg and As (B amplitude, fluorescence value) of the mixed solution measured by the atomic fluorescence analysis method of the outer tube sampling of the present invention in Example 2 -concentration).
图5为实施例3用本发明外管进样的原子荧光分析方法测定Pb的峰值曲线(A幅，荧光值-时间)和Pb的标准曲线(B幅，荧光值-浓度)。Fig. 5 shows the peak curve of Pb (A amplitude, fluorescence value-time) and the standard curve of Pb (B amplitude, fluorescence value-concentration) determined by the atomic fluorescence analysis method of the outer tube sampling of the present invention in Example 3.
具体实施方式detailed description
以下结合附图和实施例对本发明做详细说明。The present invention will be described in detail below with reference to the drawings and embodiments.
本发明提出一种新的原子荧光分析方法，包括取样输送、载气载带气液分离器产生的混合气体进入原子化器、待测元素原子化和荧光检测等步骤，其中，混合气体进入原子化器时采用外管进样的方式。参见图2所示并与图1比较，原有原子荧光分析采用300-400ml/min载气(Ar气)载带反应产物Hg原子或氢化物及氢气从石英炉的内管进入，石英炉外管则通入900-1100ml/min Ar气作为屏蔽气，如图1所示。本发明则将载气(如氩气)载带的氢化物及氢气混合气改接在外管上，同时将原作为屏蔽气的氩气改接在内管上作为辅助气，如图2所示。另一方面，将载带混合气的载气(本发明为外管Ar气)流量增加至1000-1200ml/min从而使在石英炉外管中的氢气被点燃形成体型较大的氢火焰，将辅助气(本发明为内管Ar气)流量降低至400-600ml/min， 内管的辅助气流量较小，仅将氢火焰起向上推升作用，甚至在针对某些元素(如Cd)检测时，内管甚至不通入辅助Ar气(即流量0ml/min)。同时，采用限流技术，将混合气体的输送速度进行控制，即控制通入石英炉外管中混合气的流速，使Ar气载带的基态原子或氢化物、氢气以较均匀的流速进入石英炉外管，这样便能得到稳定的的氢火焰。The present invention proposes a new atomic fluorescence analysis method, which includes sampling and delivery, the mixed gas generated by the carrier gas and the gas-liquid separator into the atomizer, the atomization of the element to be measured, and fluorescence detection. The mixed gas enters the atom The external tube sampling method is used for the carburetor. See Figure 2 and compare with Figure 1. The original atomic fluorescence analysis uses 300-400ml / min carrier gas (Ar gas) to carry the reaction product Hg atoms or hydride and hydrogen into the inner tube of the quartz furnace, outside the quartz furnace The tube is filled with 900-1100ml / min Ar gas as shielding gas, as shown in Figure 1. In the present invention, the hydride and hydrogen mixed gas carried by the carrier gas (such as argon) is connected to the outer tube, and at the same time, the argon used as the shielding gas is connected to the inner tube as auxiliary gas, as shown in FIG. 2 . On the other hand, increase the flow rate of the carrier gas carrying the mixed gas (in the present invention, the outer tube Ar gas) to 1000-1200 ml / min so that the hydrogen in the outer tube of the quartz furnace is ignited to form a larger hydrogen flame. The flow rate of the auxiliary gas (Ar gas in the present invention) is reduced to 400-600ml / min, the flow rate of the auxiliary gas in the inner pipe is small, only the hydrogen flame is pushed up, even when it is detected for certain elements (such as Cd) At this time, the inner tube is not even vented with auxiliary Ar gas (ie, the flow rate is 0 ml / min). At the same time, the flow-limiting technology is used to control the delivery speed of the mixed gas, that is, the flow rate of the mixed gas into the outer tube of the quartz furnace is controlled, so that the ground state atoms or hydrides and hydrogen of the Ar gas carrier enter the quartz at a relatively uniform flow rate The outer tube of the furnace, so that a stable hydrogen flame can be obtained.
本发明外管进样方式，改变了原子荧光法历来由内管引入氢化物(或Hg原子)的模式。其机理是：反应器中化学还原反应产生的气态原子或分子及氢气，随载气(Ar气)载带从石英炉的外管引入，待测元素氢化物(或汞原子)和氢气形成的混合气体沿石英炉外管内壁上升，氢气在石英炉管口遇热被点燃，氢化物在Ar气氛围中氢火焰高温作用下被解离。而进入内管的辅助气(通常为氩气)将该氢火焰向上推升，所形成的氢焰形体比内管进样大许多，参见图2所示，并与图1比较。The outer tube sampling method of the present invention changes the mode of the atomic fluorescence method that traditionally introduces hydride (or Hg atoms) from the inner tube. The mechanism is: the gaseous atoms or molecules and hydrogen produced by the chemical reduction reaction in the reactor are introduced from the outer tube of the quartz furnace along with the carrier gas (Ar gas) carrier strip, formed by the hydride (or mercury atom) of the element to be measured and hydrogen The mixed gas rises along the inner wall of the outer tube of the quartz furnace, the hydrogen gas is ignited by the heat of the quartz furnace tube mouth, and the hydride is dissociated under the high temperature of the hydrogen flame in the Ar gas atmosphere. The auxiliary gas (usually argon) that enters the inner tube pushes up the hydrogen flame. The formed hydrogen flame is much larger than the inner tube sample. See Figure 2 and compare with Figure 1.
利用这种外管进样方式结合原有的原子荧光分析过程，使氢气被位于外管管口的炉丝加热，氢火焰极易点燃，且形成的氢火焰形体大且稳定，发光立体角大，测定灵敏度得到明显提高，该方法已成功用于多种样品中As、Hg、Se、Pb和Cd的测定。对反应中产生氢气较少的元素，如Pb和Sn，外管进样方式使氢气离位于石英炉口加热的炉丝较近，氢火焰容易点燃，而之前技术中从内管进样，氢火焰基本上不能点燃，测定这些元素十分困难，可见本发明还解决了对反应中产生氢气少的元素的原子荧光检测难题。Using this outer tube sampling method combined with the original atomic fluorescence analysis process, the hydrogen is heated by the furnace wire located at the outer tube nozzle, the hydrogen flame is easily ignited, and the formed hydrogen flame is large and stable, and the luminous solid angle is large The detection sensitivity has been significantly improved, and this method has been successfully used in the determination of As, Hg, Se, Pb and Cd in various samples. For elements that produce less hydrogen in the reaction, such as Pb and Sn, the outer tube sampling method makes the hydrogen closer to the furnace wire heated at the quartz furnace port, and the hydrogen flame is easily ignited. The flame cannot be ignited basically, and it is very difficult to determine these elements. It can be seen that the present invention also solves the problem of atomic fluorescence detection of elements that generate less hydrogen in the reaction.
本发明的检测可利用已有的原子荧光仪，原子荧光仪包括进样***、气液分离器、原子化器、激发光源和检测器等几部分，其中原子化器包括石英炉和位于石英炉管口的电炉丝，石英炉为内管和外管的套管形式。利用该原子荧光仪检测实例的具体操作为：The detection of the present invention can use the existing atomic fluorometer. The atomic fluorometer includes a sampling system, a gas-liquid separator, an atomizer, an excitation light source and a detector. The atomizer includes a quartz furnace and a quartz furnace. The electric furnace wire of the nozzle and the quartz furnace are in the form of sleeves of the inner tube and the outer tube. The specific operation of the detection example using this atomic fluorometer is:
操作1.将气液分离器的气体出口支管(用以引导载气载带的由氢化物和氢气形成的混合气体)接入原子化器中的石英炉的外管，同时将辅助气(Ar气)与石英炉的内管连接； Operation 1. Connect the gas outlet branch of the gas-liquid separator (used to guide the mixed gas formed by hydride and hydrogen of the carrier gas carrier) into the outer tube of the quartz furnace in the atomizer, and at the same time, connect the auxiliary gas (Ar Gas) connected to the inner tube of the quartz furnace;
操作2.接通原子荧光仪电源，按仪器说明设置检测条件，点亮待测元素激发光源并预热5-10分钟；若测定单一元素，选择仪器单道模式；同时测定两个元素，选择仪器双道模式； Operation 2. Turn on the power of the atomic fluorometer, set the detection conditions according to the instructions of the instrument, light the excitation light source of the element to be measured and preheat for 5-10 minutes; if measuring a single element, select the single-channel mode of the instrument; simultaneously measure two elements, select Instrument dual channel mode;
操作3.打开载气和辅助气(可均为Ar气)钢瓶阀门，按设定调节各自气压和流量，并打开原子化器的排风装置，接通电炉丝电源； Operation 3. Open the cylinder valve of carrier gas and auxiliary gas (can be Ar gas), adjust the respective air pressure and flow according to the settings, and open the exhaust device of the atomizer, and connect the power of the electric furnace wire;
操作4.启动进样***进样，气液分离器完成还原反应后，使石英炉口的电炉丝点燃、激发光源和检测器工作，获得试液中待测元素的荧光信号值；荧光信号的峰值曲线(荧光值-时间)可同步生成； Operation 4. Start the sample injection system, after the gas-liquid separator completes the reduction reaction, the electric furnace wire of the quartz furnace port is ignited, the light source and the detector are excited, and the fluorescent signal value of the element to be measured in the test solution is obtained; Peak curve (fluorescence value-time) can be generated synchronously;
操作5.分别获得各标准溶液中待测元素的荧光信号值，并制作荧光值—浓度标准曲线； Operation 5. Obtain the fluorescence signal value of the element to be measured in each standard solution, and make a fluorescence value-concentration standard curve;
操作6.测定样品溶液中待测元素的荧光信号值，从标准曲线得到样品溶液中待测元素的浓度，输入相关参数后计算出样品中被测元素的含量。Operation 6. Determine the fluorescence signal value of the test element in the sample solution, obtain the concentration of the test element in the sample solution from the standard curve, and calculate the content of the test element in the sample after entering the relevant parameters.
以上方法可测定单一元素，也可同时测定两个或以上元素。测定多元素时，配制同时含有各元素的(各元素浓度可以不相同)的标准混合溶液，一次进样并同步使用各元素对应的激发光源，分别获得不同元素的荧光信号值，根据对应元素的标准曲线得到该试样中该待测元素的含量。The above method can measure a single element or two or more elements at the same time. When measuring multiple elements, prepare a standard mixed solution that also contains each element (the concentration of each element can be different), one injection and use the excitation light source corresponding to each element simultaneously to obtain the fluorescence signal values of different elements, according to the corresponding element's The standard curve obtains the content of the element to be measured in the sample.
以下结合具体实施例进一步说明本发明，实施例中所列内容为示例而非对本发明的限制。实施例中试剂浓度“％”表示为质量百分浓度。The present invention will be further described below with reference to specific embodiments. The contents listed in the embodiments are examples rather than limitations to the present invention. The reagent concentration "%" in the examples is expressed as a mass percentage concentration.
实施例1：Cd的分析Example 1: Analysis of Cd
检测样本：大米、黄豆Test samples: rice, soybean
镉标准曲线的制作：先配制10ng/ml镉标准溶液，然后分别取此标准溶液0、0.5、1.0、1.5、2.0、2.5ml于50ml塑料定量瓶中，于每个溶液中各加入浓度为50％的HCl溶液4ml，5％硫脲5ml，用水稀释至刻度，得到Cd的浓度为0、0.1、0.2、0.3、0.4、0.5ng/ml标准系列溶液。摇匀后按操作过程测定空白和标准系列溶液的荧光信号，制作标准曲线(见图3的B幅)，图3的A幅显示了Cd的峰值曲线。操作中载气和辅助气均用Ar气，控制作为载气的氩气(外管)流量1000-1200ml/min，关闭作为辅助气的氩气(内管)，即流量为0ml/min。Preparation of cadmium standard curve: first prepare 10ng / ml cadmium standard solution, then take this standard solution 0, 0.5, 1.0, 1.5, 2.0, 2.5ml in a 50ml plastic quantitative bottle, and add a concentration of 50 to each solution 4ml of% HCl solution and 5ml of 5% thiourea were diluted with water to the mark to obtain a standard series solution with Cd concentration of 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng / ml. After shaking, the fluorescence signals of the blank and standard series solutions are measured according to the operation process, and a standard curve is produced (see panel B in FIG. 3). Panel A in FIG. 3 shows the peak curve of Cd. In operation, both the carrier gas and the auxiliary gas use Ar gas, and the flow rate of argon gas (outer tube) as a carrier gas is controlled to 1000-1200ml / min, and the flow rate of 0ml / min is turned off as the auxiliary gas (inner tube).
试液的制备和测定：Preparation and determination of test solution:
称取大米粉或黄豆粉样本(在0.1-0.2g左右)置于50ml塑料定量瓶中，各加入浓度为50％的HCl 4ml，5％硫脲5ml，振摇5-10min后，用水稀释至刻度，按表1体积制备样本溶液。按操作过程将样本溶液作为试液分别测定样本溶液的荧光信号，从标准曲线中获得Cd的浓度并换算为在样本中的含量。食品样品中Cd的测定结果见表1。Weigh the rice flour or soybean powder sample (about 0.1-0.2g) in a 50ml plastic quantitative bottle, add 50ml of HCl 4ml, 5% thiourea 5ml, shake for 5-10min, dilute with water to Scale, according to the volume of Table 1 to prepare the sample solution. According to the operation process, the sample solution is used as the test solution to measure the fluorescence signal of the sample solution, and the concentration of Cd is obtained from the standard curve and converted into the content in the sample. See Table 1 for the measurement results of Cd in food samples.
表1.大米及黄豆粉中Cd的测试结果(ng/g)Table 1. Test results of Cd in rice and soybean powder (ng / g)
Figure PCTCN2019084336-appb-000001
Figure PCTCN2019084336-appb-000001
从表1中的数据可以看出，称样量(G)虽相差很大，使用外管进样的原子荧光分析能快速测定大米等食品中镉的含量，且称样量相差较大的平行测定值几乎一致，测 得样本中Cd的含量和推荐值吻合，说明本发明的外管进样的原子荧光分析方法的准确性高。From the data in Table 1, it can be seen that although the sample size (G) is very different, atomic fluorescence analysis using outer tube sampling can quickly determine the cadmium content in rice and other foods, and the sample size is very parallel. The measured values are almost the same, and the measured Cd content in the sample is consistent with the recommended value, indicating that the atomic fluorescence analysis method of the outer tube sampling of the present invention has high accuracy.
实施例2：Hg/As同时测定Example 2: Simultaneous determination of Hg / As
检测样本：土壤Test sample: soil
由于土壤中As的含量远高于Hg，之前一直不能用原子荧光技术同时测定这种样品中的Hg和As。本实施例以外管进样原子荧光检测技术可实现同一样品中Hg和As两种元素的同时检测。Because the content of As in the soil is much higher than Hg, it has not been possible to measure Hg and As in this sample at the same time using atomic fluorescence technology. In this embodiment, the outer tube sampling atomic fluorescence detection technology can realize the simultaneous detection of Hg and As in the same sample.
标准曲线的制作：预先配制含500ng/ml As、10ng/ml Hg的混合标准溶液。分别取此标准溶液0、1、2、3、4、5ml于50ml塑料定量瓶中，各加入5％Vc—5％硫脲溶液5ml，浓度为50％的HCl 10ml，用水稀释至刻度得到0—5号系列标准溶液，标准溶液中的Hg浓度顺序为0、0.2、0.4、0.6、0.8、1.0ng/ml，As浓度顺序为0、10、20、30、40、50ng/ml。Preparation of standard curve: prepare a mixed standard solution containing 500ng / ml As and 10ng / ml Hg in advance. Take this standard solution 0, 1, 2, 3, 4, 5ml in a 50ml plastic quantitative bottle, add 5ml of 5% Vc-5% thiourea solution, 10ml of 50% HCl concentration, and dilute with water to the mark to get 0 —No. 5 series standard solution, the order of Hg concentration in the standard solution is 0, 0.2, 0.4, 0.6, 0.8, 1.0 ng / ml, and the order of As concentration is 0, 10, 20, 30, 40, 50 ng / ml.
按上述操作过程同时测定空白和标准系列溶液中Hg和As的荧光信号，分别制作混合标准液的Hg和As标准曲线。图4的A幅为Hg/As的峰值曲线，图4的B幅为混合标准溶液Hg和As的标准曲线(标准曲线的信号根据谱图面积计算，且已减去空白面积)。操作中载气和辅助气均为Ar气，控制作为载气的Ar气(通入石英炉外管)流量为1000ml/min，控制作为辅助气的Ar气(通入石英炉内管)流量为500ml/min。The fluorescence signals of Hg and As in the blank and standard series solutions are simultaneously measured according to the above operation process, and the Hg and As standard curves of the mixed standard solutions are prepared respectively. The width A of Fig. 4 is the peak curve of Hg / As, and the width B of Fig. 4 is the standard curve of the mixed standard solution Hg and As (the signal of the standard curve is calculated based on the area of the spectrum, and the blank area has been subtracted). In the operation, the carrier gas and the auxiliary gas are both Ar gas. The flow rate of the Ar gas as the carrier gas (passing into the outer tube of the quartz furnace) is 1000ml / min, and the flow rate of the Ar gas as the auxiliary gas (passing into the inner tube of the quartz furnace) is 500ml / min.
试液的制备和测定：按称样量(G)称取土壤样本0.1-0.2g，置于50ml四氟溶样管中，各加入浓度为50％的王水于水浴上煮沸分解1小时，用水转移至50ml塑料定量瓶中，各加入5％Vc—5％硫脲溶液5ml，浓度为50％的HCl 10ml，用水稀释至刻度，摇匀后将样本溶液作为试液按操作过程同时测定Hg和As的荧光信号，依据各自的标准曲线获得对应元素的浓度并计算出各自在样品中的含量，结果见表2。Preparation and determination of test solution: Weigh 0.1-0.2g of soil sample according to the sample weight (G), place it in a 50ml PTFE sample tube, add 50% aqua regia to boil and decompose on a water bath for 1 hour, Transfer to 50ml plastic quantitative bottle with water, add 5ml of 5% Vc-5% thiourea solution, 10ml of 50% concentration of HCl, dilute to the mark with water, shake and use the sample solution as the test solution to measure Hg at the same time according to the operation process For the fluorescence signals of As and As, obtain the concentration of the corresponding element according to the respective standard curve and calculate the content of each element in the sample. The results are shown in Table 2.
表2 土壤Hg和As同时测定结果Table 2 Simultaneous determination results of soil Hg and As
Figure PCTCN2019084336-appb-000002
Figure PCTCN2019084336-appb-000002
数据表明，采用本方法解决了同时测定土壤中的Hg和As的困难。同时也看出，6个样本(标准样品)中的Hg含量相差较大，但测试结果均与推荐值相符，说明本发明原子荧光分析方法准确性高。且本实施例两种元素共存在试液中，取样一次完成， 使用双检测器能同步完成检测，整个检测过程快速便捷。The data shows that this method solves the difficulty of simultaneous determination of Hg and As in soil. At the same time, it can be seen that the Hg content in the 6 samples (standard samples) differs greatly, but the test results are consistent with the recommended values, indicating that the atomic fluorescence analysis method of the present invention has high accuracy. In addition, in this embodiment, the two elements coexist in the test solution, and the sampling is completed once, and the detection can be completed synchronously by using the dual detectors, and the entire detection process is fast and convenient.
实施例3：Pb的分析Example 3: Analysis of Pb
检测样本：化学试剂氯化钙和氢氧化钙Test samples: chemical reagents calcium chloride and calcium hydroxide
铅标准曲线的制作：先配制100ng/ml铅标准溶液，然后分别取此标准溶液0、1、2、3、4、5ml于50ml塑料定量瓶中，于每个溶液中各加入浓度为50％的HCl溶液10ml，5％硫脲5ml，用水稀释至刻度，此标准系列溶液中Pb的浓度为0、2、4、6、8、10ng/ml。摇匀后按操作过程测定空白和标准系列溶液的荧光信号，制作标准曲线，见图5的B幅，图5的A幅为Pb的峰值曲线。操作中载气和辅助气均为Ar气，控制作为载气的氩气(外管)流量1000-1200ml/min，控制作为辅助气的氩气(内管)流量400-600ml/min。Preparation of lead standard curve: first prepare 100ng / ml lead standard solution, then take this standard solution 0, 1, 2, 3, 4, 5ml in 50ml plastic quantitative bottle respectively, add 50% concentration to each solution 10ml of HCl solution, 5ml of 5% thiourea, diluted with water to the mark, the concentration of Pb in this standard series solution is 0, 2, 4, 6, 8, 10ng / ml. After shaking, the fluorescence signals of the blank and standard series solutions are measured according to the operation process, and a standard curve is produced, as shown in panel B in Figure 5, and panel A in Figure 5 is the peak curve of Pb. The carrier gas and auxiliary gas are both Ar gas during operation, and the flow rate of argon (outer tube) as carrier gas is controlled to 1000-1200ml / min, and the flow rate of argon (inner tube) as auxiliary gas is controlled to 400-600ml / min.
试液的制备和测定：称取化学试剂样本0.2-0.3g，转入50ml塑料定量瓶中，各加入浓度为50％的HCl 10ml，5％硫脲5ml，振摇5-10min后，用水稀释至刻度，摇匀后按表3体积制备样本溶液。按与标准曲线测定中相同的操作将样本溶液作为试液分别测定样本溶液的荧光信号，从标准曲线中获得Pb的浓度并换算为在样本中的含量。化学试剂中Pb的测定结果见表3。Preparation and determination of test solution: Weigh 0.2-0.3g of chemical reagent sample, transfer to a 50ml plastic quantitative bottle, add 10ml of 50% HCl and 5ml of 5% thiourea, shake for 5-10min, then dilute with water To the mark, shake and prepare the sample solution according to the volume of Table 3. According to the same operation as the standard curve measurement, the sample solution is used as the test solution to measure the fluorescence signal of the sample solution, and the concentration of Pb is obtained from the standard curve and converted into the content in the sample. The determination results of Pb in chemical reagents are shown in Table 3.
表3 氯化钙、氢氧化钙中Pb的测定结果(ng/g)Table 3 Determination results of Pb in calcium chloride and calcium hydroxide (ng / g)
Figure PCTCN2019084336-appb-000003
Figure PCTCN2019084336-appb-000003
原有的原子荧光分析在Pb的测定中需要非常严格地将酸度控制在2％以下，否则测不出荧光信号，然而经过前处理后的试液很难达到这个要求，况且2％酸度的试液在还原反应后产生的氢气量较少而难以点火。本实施例使用外管进样同时加大载气流量的方式，氢火焰易于点燃，对10％酸度的试液中的Pb进行原子荧光分析，能形成明显的Pb峰值曲线(参见图5之B幅)，提高检测灵敏度，实现对Pb的测定。The original atomic fluorescence analysis requires very strict control of the acidity below 2% in the determination of Pb, otherwise the fluorescence signal cannot be detected, but the test solution after pretreatment is difficult to meet this requirement, and the 2% acidity test The amount of hydrogen produced by the liquid after the reduction reaction is small and it is difficult to ignite. In this embodiment, the outer tube is used for sample injection while increasing the carrier gas flow rate. The hydrogen flame is easy to ignite. Atomic fluorescence analysis of Pb in the 10% acid test solution can form an obvious Pb peak curve (see Figure 5B Amplitude) to improve the detection sensitivity and achieve the measurement of Pb.
工业应用性Industrial applicability
本发明提供的外管进样的原子荧光分析方法，克服了内管进样的缺陷，氢火焰极易点燃，形成的氢火焰形体大且稳定，测定灵敏度得到明显提高，还特别适用于产生氢气少的元素的测定，适于工业应用。The atomic fluorescence analysis method of the outer tube sampling provided by the invention overcomes the defect of the inner tube sampling, the hydrogen flame is easy to ignite, the formed hydrogen flame is large and stable, the measurement sensitivity is obviously improved, and it is particularly suitable for generating hydrogen The determination of few elements is suitable for industrial applications.

Claims (16)

  1. 外管进样的原子荧光分析方法，包括取样输送、载气载带气液分离器产生的混合气体进入原子化器、待测元素原子化和荧光检测等步骤，其中，所述原子化器中的石英炉为内管与外管的套装结构，将所述混合气体引入石英炉的外管，同时在石英炉的内管引入辅助气。Atomic fluorescence analysis method for outer tube sampling, including sampling and delivery, mixed gas generated by carrier gas and gas-liquid separator into atomizer, atomization of elements to be measured and fluorescence detection, etc., in which the atomizer The quartz furnace has a set structure of an inner tube and an outer tube. The mixed gas is introduced into the outer tube of the quartz furnace, and at the same time, auxiliary gas is introduced into the inner tube of the quartz furnace.
  2. 根据权利要求1所述外管进样的原子荧光分析方法，其中，所述载带混合气体进入石英炉外管的载气流量为1000-1200ml/min。The atomic fluorescence analysis method of outer tube sampling according to claim 1, wherein the flow rate of the carrier gas into the outer tube of the quartz furnace is 1000-1200 ml / min.
  3. 根据权利要求1或2所述外管进样的原子荧光分析方法，其中，所述引入石英炉内管的辅助气流量为400-600ml/min；待测元素为Cd时，所述引入石英炉内管的辅助气流量为0ml/min。The atomic fluorescence analysis method of outer tube sampling according to claim 1 or 2, wherein the flow rate of the auxiliary gas introduced into the inner tube of the quartz furnace is 400-600 ml / min; when the element to be measured is Cd, the introduced quartz furnace The auxiliary gas flow rate of the inner tube is 0ml / min.
  4. 根据权利要求1或2或3所述外管进样的原子荧光分析方法，其中，控制所述混合气体的流速使其均匀进入石英炉的外管。The atomic fluorescence analysis method of outer tube sampling according to claim 1 or 2 or 3, wherein the flow rate of the mixed gas is controlled so as to evenly enter the outer tube of the quartz furnace.
  5. 根据权利要求1至4任一项所述外管进样的原子荧光分析方法，其中，所述载带混合气体进入石英炉外管的载气以及石英炉内管引入的辅助气为同一气体，例如同为氩气。The atomic fluorescence analysis method for outer tube sampling according to any one of claims 1 to 4, wherein the carrier gas into the outer tube of the quartz furnace and the auxiliary gas introduced into the inner tube of the quartz furnace are the same gas, For example, it is also argon.
  6. 根据权利要求1至5任一项所述外管进样的原子荧光分析方法，其中，所述辅助气为惰性气体，优选与载气相同的气体，如氩气。The atomic fluorescence analysis method for outer tube sampling according to any one of claims 1 to 5, wherein the auxiliary gas is an inert gas, preferably the same gas as the carrier gas, such as argon gas.
  7. 根据权利要求1至6任一项所述外管进样的原子荧光分析方法，其中，所述待测元素为单一元素、两个或两个以上元素。The atomic fluorescence analysis method for outer tube sampling according to any one of claims 1 to 6, wherein the element to be measured is a single element, two or more elements.
  8. 根据权利要求1至7任一所述外管进样的原子荧光分析方法，其中，用于样品中As、Hg、Se、Pb和Cd的测定。The atomic fluorescence analysis method for outer tube sampling according to any one of claims 1 to 7, which is used for the determination of As, Hg, Se, Pb, and Cd in a sample.
  9. 根据权利要求8所述外管进样的原子荧光分析方法，其中，用于样品中痕量Pb的测定。The atomic fluorescence analysis method of outer tube sampling according to claim 8, which is used for the determination of trace Pb in a sample.
  10. 一种原子荧光仪，主要包括进样***、气液分离器、原子化器、激发光源和检测器；所述原子化器中的石英炉为内管与外管的套装结构，其中，石英炉的外管与原子化器的混合气体出口支管连接，同时石英炉的内管连接辅助气输入管。An atomic fluorescence instrument mainly includes a sampling system, a gas-liquid separator, an atomizer, an excitation light source and a detector; the quartz furnace in the atomizer is a set structure of an inner tube and an outer tube, wherein the quartz furnace The outer tube of the tube is connected to the mixed gas outlet branch tube of the atomizer, and the inner tube of the quartz furnace is connected to the auxiliary gas input tube.
  11. 利用权利要求10所述原子荧光仪进行原子荧光分析的方法，包括以下操作步骤：The method for atomic fluorescence analysis using the atomic fluorometer of claim 10 includes the following steps:
    操作1.将气液分离器的气体出口支管(氢化物、氢气及载气混合气)接入原子化器石英炉外管，同时将石英炉内管接通辅助气；Operation 1. Connect the gas outlet branch pipe (hydride, hydrogen and carrier gas mixture) of the gas-liquid separator to the outer tube of the quartz furnace of the atomizer, and connect the inner tube of the quartz furnace to the auxiliary gas;
    操作2.接通原子荧光仪电源，设置检测条件，点亮待测元素激发光源并预热；Operation 2. Turn on the power of the atomic fluorometer, set the detection conditions, light the element to be tested to excite the light source and preheat it;
    操作3.打开载气和辅助气钢瓶阀门，按设定调节各自气压和流量，并打开原子化 器的排风装置，接通原子化器的电炉丝电源；Operation 3. Open the carrier gas and auxiliary gas cylinder valves, adjust the respective air pressure and flow according to the settings, and open the exhaust device of the atomizer, and connect the power supply of the electric furnace wire of the atomizer;
    操作4.启动进样***完成取样输送，待气液分离器完成还原反应产生混合气体后，使原子化器的电炉丝点火、激发光源和检测器工作，获得试液中待测元素的荧光信号值；Operation 4. Start the sampling system to complete the sampling and delivery. After the gas-liquid separator completes the reduction reaction and generates a mixed gas, the electric furnace wire of the atomizer is ignited, the light source and the detector are excited to obtain the fluorescent signal of the element to be measured in the test solution value;
    操作5.分别测得各标准系列溶液中待测元素的荧光信号值，并制作荧光值—浓度标准曲线；Operation 5. Measure the fluorescence signal value of the element to be measured in each standard series solution separately, and make a fluorescence value-concentration standard curve;
    操作6.测定样品溶液中待测元素的荧光信号值，从标准曲线得到样品溶液中待测元素的浓度，输入相关参数后计算出样品中被测元素的含量。Operation 6. Determine the fluorescence signal value of the element to be measured in the sample solution, obtain the concentration of the element to be measured in the sample solution from the standard curve, and enter the relevant parameters to calculate the content of the element to be measured in the sample.
  12. 根据权利要求11所述原子荧光分析方法，所述载气载带的混合气体进入石英炉外管的载气流量为1000-1200ml/min。According to the atomic fluorescence analysis method of claim 11, the flow rate of the mixed gas of the carrier gas carrier tape into the outer tube of the quartz furnace is 1000-1200 ml / min.
  13. 根据权利要求11所述原子荧光分析方法，所述辅助气进入石英炉内管的流量为400-600ml/min。According to the atomic fluorescence analysis method of claim 11, the flow rate of the auxiliary gas into the inner tube of the quartz furnace is 400-600 ml / min.
  14. 根据权利要求11所述原子荧光分析方法，待测元素为Cd时，所述辅助气进入石英炉内管的流量为0ml/min。According to the atomic fluorescence analysis method of claim 11, when the element to be measured is Cd, the flow rate of the auxiliary gas into the inner tube of the quartz furnace is 0 ml / min.
  15. 根据权利要求11至14任一项所述外管进样的原子荧光分析方法，样品溶液中待测元素为两种或以上元素时，配制同时含有各元素的(各元素浓度可以不相同)的标准混合溶液，一次进样并同步使用各元素对应的激发光源，分别获得不同元素的荧光信号值，对标准系列溶液测定后分别针对每种元素制作荧光值—浓度标准曲线，根据对应元素的标准曲线得到该试样中各待测元素的含量。According to the atomic fluorescence analysis method of outer tube sampling according to any one of claims 11 to 14, when the element to be measured in the sample solution is two or more elements, the preparation containing both elements (the concentration of each element may be different) Standard mixed solution, one injection and simultaneous use of the excitation light source corresponding to each element to obtain the fluorescence signal values of different elements respectively, and the fluorescence value-concentration standard curve is prepared for each element after the standard series solution is measured, according to the standard of the corresponding element The curve obtains the content of each element to be measured in the sample.
  16. 根据权利要求11至15任一项所述原子荧光分析方法，所述载气及辅助气体为同一种气体，优选为惰性气体，例如氩气。According to the atomic fluorescence analysis method according to any one of claims 11 to 15, the carrier gas and the auxiliary gas are the same gas, preferably an inert gas, such as argon gas.
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