CN106248824B - High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method - Google Patents

High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method Download PDF

Info

Publication number
CN106248824B
CN106248824B CN201610578414.1A CN201610578414A CN106248824B CN 106248824 B CN106248824 B CN 106248824B CN 201610578414 A CN201610578414 A CN 201610578414A CN 106248824 B CN106248824 B CN 106248824B
Authority
CN
China
Prior art keywords
atomic fluorescence
liquid chromatography
hydride
high performance
performance liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610578414.1A
Other languages
Chinese (zh)
Other versions
CN106248824A (en
Inventor
崔健
崔宁
陈章侠
殷淑英
梁强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dezhou Vocational and Technical College
Original Assignee
Dezhou Vocational and Technical College
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dezhou Vocational and Technical College filed Critical Dezhou Vocational and Technical College
Priority to CN201610578414.1A priority Critical patent/CN106248824B/en
Publication of CN106248824A publication Critical patent/CN106248824A/en
Application granted granted Critical
Publication of CN106248824B publication Critical patent/CN106248824B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N2021/6417Spectrofluorimetric devices
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N2030/022Column chromatography characterised by the kind of separation mechanism
    • G01N2030/027Liquid chromatography

Landscapes

  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method, including high performance liquid chromatography mechanism, hydride generating mechanism, gas-liquid separator, Atomic Fluorescence Spectrometer and computer, the Gaussian Profile based on high performance liquid chromatography-atomic fluorescence combination analysis system HPLC mechanism establishes the functional relation between system parameters and peak shape broadening and sensitivity.The present invention effectively reduces error caused by the simple Gauss curve fitting method generallyd use using HPLC system, this carries out the later period processing of experimental data, removal interference, it effectively seeks peak area and carries out retrieving concentration, the related coefficient of standard curve is improved, it is highly advantageous for improving detection accuracy;The present invention can predict the spectral parameters such as the peak height of output signal, peak width, this adjusts Instrument working state, instrument manufacturer facility man raising instrument parameter index is helped to have higher directive significance and practical value.

Description

High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing Method
Technical field
The present invention relates to chemical analysis technology fields, and in particular to a kind of high performance liquid chromatography-atomic fluorescence combination analysis System mathematic model and data processing method.
Background technique
Flow injection-hydride generation Generation-Atomic Fluorescence Spectrometry is since with high sensitivity, measurement range is wide, analysis is fast The lot of advantages such as fast are spent, are widely applied in industries such as health, environmental protection, geology, metallurgy.But influence hydride generation- There are many factor of Atomic Fluorescence Spectrometer sensitivity and spectral peak broadening, typically find best experiment item by many experiments The optimization of part, experiment condition is relatively difficult.
It is after introducing sample by flow injection mode, in acidity that (FI-HG) method, which occurs, for flow injection-hydride generation It being reacted under environment with KBH4, analyte in sample generates volatile gaseous hydride, by gas-liquid separator (GLS), Hydride is separated, and element detector (such as inductivity coupled plasma mass spectrometry (ICP-MS), inductance are sent under the purging of carrier gas Coupled Plasma Spectroscopy (ICP-AES), graphite furnace atomic absorption spectrometry (QF-AAS), atomic fluorescence spectrophotometry (AFS)).
Consider the factors such as mechanism, principle of instrument that hydrogenation occurs, influences FI-HG-AFS sensitivity and spectral peak broadening Factor mainly has sample loop volume (sample injection rate), rate of Carrier Stream, flow rate of carrier gas, GLS headspace (sky shared by gaseous state Between) etc., optimum experimental condition is found by many experiments, but since these parameters do not isolate, their joint effect sensitivity It is broadened with spectral peak, so the optimization of experiment condition is relatively difficult.So hydride is occurred, transmission and detection process take out One mathematical model simultaneously carries out sunykatuib analysis, it will help understands the effect of each factor.
Currently, the method taken aiming at the problem that this respect mainly has:
(1) influence that the influence based on pH value to HG and GLS transmit hydride establishes model, predicts the best of pH value The spectrogram peak shape of value and output signal;
(2) peak shape is improved by the error of amendment hydride generating process generation;
(3) by assuming that the pass for generating AsH3 and AAS spectrogram peak shape is reacted in Dynamics Factors, research As (III) with KBH4 System;
(4) Uniform ity Design Method is utilized, finds optimum experimental condition by many experiments.
Aforementioned four method gives the mathematical model that hydride occurs, transmits and detects, but is all based on single variable Influence for result, it is limited to the correction effect of experimental result.
Simple Gauss curve fitting method is used mostly to output spectrogram at present, but HPLC-HG-AFS system is not independent HPLC system, but associated with HPLC and HG-AFS system " combined system ", so, the HG-AFS system at rear portion will necessarily be right The signal of the Gaussian characteristics concentration distribution of HPLC output has an impact, so, the simple height generally used with HPLC system This fitting, the influence for ignoring rear portion HG-AFS system will obviously have very big deviation.
Summary of the invention
The present invention is in view of the deficienciess of the prior art, provide a kind of high performance liquid chromatography-atomic fluorescence combination analysis System mathematic model and data processing method.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of high performance liquid chromatography-atomic fluorescence combination analysis system, including high performance liquid chromatography mechanism, hydride occur Mechanism, gas-liquid separator, Atomic Fluorescence Spectrometer and computer, high performance liquid chromatography mechanism include high-pressure pump, six-way valve and sample Ring, hydride generating mechanism is by wriggling pump group, mixer and reactor group at the outlet of sample loop is communicated with pre-reactor, compacted Dynamic pump group is communicated with mixer and reactor respectively, and the outlet of mixer is connected with Reactor inlet, the outlet of reactor and gas The reaction-ure inlet pipe of liquid/gas separator is connected, and the inclination of reaction-ure inlet pipe is connected in separator body, at the top of separator body Gas outlet tube be connected with Atomic Fluorescence Spectrometer, separator body lower part side be arranged waste liquid outlet pipe, atomic fluorescence light Spectrometer is connected with computer.
The working principle of present system is:Sample is injected by six-way valve, and the revolving speed and flow rate of carrier gas of each peristaltic pump are equal Adjustable, so as to test influence of the different parameters to test result, arsanilic acid standard solution injects six-way valve sample by high-pressure pump Product ring is mixed into chromatographic column, the acid current-carrying hydrochloric acid that chromatographic effluent is sent with peristaltic pump in a mixer with mobile phase Mixing, under acidic environment, arsenic element reacts generation gaseous hydride (AsH3) with KBH4 in analyte in the reactor, Gaseous material (AsH3, H2, Ar) in GLS separates in gas-liquid separator and enters in Atomic Fluorescence Spectrometer AFS, AsH3 quilt The detection of arsenic element hollow cathode modulation.
Above-mentioned high performance liquid chromatography-atomic fluorescence combination analysis system data processing method is based on high performance liquid chromatography- The concentration distribution that atomic fluorescence combination analysis system enters hydride generating mechanism is no longer distribution of pulses, but HPLC system Gaussian Profile, so the arsenic element in hydride generating mechanism sample is converted into the efficiency of hydride by experiment condition, sample base The influence of many conditions such as matter, it is assumed that transformation efficiency is R (value between 0 to 1, independently of each experiment parameter).Then, sample hydrogen Concentration (cAH) in (mol/L) of the compound in the gas entered in GLS can be expressed as:
(cAH)in=a × exp [- (t-b)2/c2] (1)
Assuming that GLS internal gas is concentration and the concentration inside GLS that is uniformly mixed, exporting the gaseous hydride of GLS Be it is identical, then mass-conservation equation can be expressed as:
I.e.:
It enablesb1=b, c1=c,Above formula can turn to:
The solution of above formula is:
Formula In, C1 and C2 are constant, and erf () is Gauss error function;
Enable A1=C1, A5=C2, A6=d1, then above formula can turn to:
(cAH)out=A1+{A2×erf[A3(t-A4)]+A5}×exp(-A6t) (4)
Above formula (4) is high performance liquid chromatography of the present invention-atomic fluorescence combination analysis system output signal simulation function.
It is theoretical and establish data processing method that the present invention analyzes HPLC-HG-AFS combined system, by with experiment number According to fitting, it was confirmed that the correctness of model effectively reduces the simple Gauss curve fitting method generallyd use using HPLC system Generated error, this carries out the later period processing of experimental data, and it is anti-effectively to seek peak area progress concentration for removal interference It drills, improves the related coefficient of standard curve, it is highly advantageous for improving detection accuracy;The HPLC-HG-AFS system proposed simultaneously Mathematical model establishes the functional relation between system parameters and peak shape broadening and sensitivity, can be predicted according to this model defeated The spectral parameters such as the peak height of signal, peak width out, this adjusts Instrument working state, instrument manufacturer facility man is helped to improve instrument ginseng Number index has higher directive significance and practical value.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the structural schematic diagram of analysis system of the present invention;
Fig. 2 is the structural schematic diagram of gas-liquid separator of the present invention;
Fig. 3 is the pattern function figure of present system;
Fig. 4 is the Gaussian function figure of high performance liquid chromatography;
Fig. 5 is that the detection spectrogram (dotted line) of concentration 1.0ppm arsanilic acid standard solution and matched curve functional digraph Gauss intend Close result figure;
Fig. 6 is the detection spectrogram (dotted line) and matched curve function of present system concentration 1.0ppm arsanilic acid standard solution Pattern fits result figure;
Fig. 7 is that the experiment spectrogram that present system model detects As (III), As (V), the mixed mark of MMA, DMA carries out The result of multimodal fitting.
1 high-pressure pump, 2 six-way valves, 3 sample loops, 4 peristaltic pumps, 5 mixers, 6 reactors, 7 gas-liquid separators, 8 atoms in figure Fluorescence Spectrometer, 9 computers, 71 separator bodies, 72 reaction-ure inlet pipes, 73 gas outlet tubes, 74 waste liquid outlet pipes.
Specific embodiment
As depicted in figs. 1 and 2:A kind of high performance liquid chromatography-atomic fluorescence combination analysis system, including high performance liquid chromatography Mechanism, hydride generating mechanism, gas-liquid separator, Atomic Fluorescence Spectrometer and computer, high performance liquid chromatography mechanism include high pressure Pump, six-way valve and sample loop, hydride generating mechanism by wriggling pump group, mixer and reactor group at, the outlet of sample loop with Pre-reactor communicates, and peristaltic pump group is communicated with mixer and reactor respectively, and the outlet of mixer is connected with Reactor inlet, instead The outlet of device is answered to be connected with the reaction-ure inlet pipe of gas-liquid separator, the inclination of reaction-ure inlet pipe is connected in separator body, Gas outlet tube at the top of separator body is connected with Atomic Fluorescence Spectrometer, and waste liquid outlet is arranged in separator body lower part side Pipe, Atomic Fluorescence Spectrometer are connected with computer.
The working principle of present system is:Sample is injected by six-way valve, and the revolving speed and flow rate of carrier gas of each peristaltic pump are equal Adjustable, so as to test influence of the different parameters to test result, arsanilic acid standard solution injects six-way valve sample by high-pressure pump Product ring is mixed into chromatographic column, the acid current-carrying hydrochloric acid that chromatographic effluent is sent with peristaltic pump in a mixer with mobile phase Mixing, under acidic environment, arsenic element reacts generation gaseous hydride (AsH3) with KBH4 in analyte in the reactor, Gaseous material (AsH3, H2, Ar) in GLS separates in gas-liquid separator and enters in Atomic Fluorescence Spectrometer AFS, AsH3 quilt The detection of arsenic element hollow cathode modulation.
Above-mentioned high performance liquid chromatography-atomic fluorescence combination analysis system data processing method is based on high performance liquid chromatography- The concentration distribution that atomic fluorescence combination analysis system enters hydride generating mechanism is no longer distribution of pulses, but HPLC system Gaussian Profile, so the arsenic element in hydride generating mechanism sample is converted into the efficiency of hydride by experiment condition, sample base The influence of many conditions such as matter, it is assumed that transformation efficiency is R (value between 0 to 1, independently of each experiment parameter).Then, sample hydrogen Concentration (cAH) in (mol/L) of the compound in the gas entered in GLS can be expressed as:
(cAH)in=a × exp [- (t-b)2/c2] (1)
Assuming that GLS internal gas is concentration and the concentration inside GLS that is uniformly mixed, exporting the gaseous hydride of GLS Be it is identical, then mass-conservation equation can be expressed as:
I.e.:
It enablesb1=b, c1=c,Above formula can turn to:
The solution of above formula is:
Formula In, C1 and C2 are constant, and erf () is Gauss error function;
Enable A1=C1, A5=C2, A6=d1, then above formula can turn to:
(cAH)out=A1+{A2×erf[A3(t-A4)]+A5}×exp(-A6t) (4)
Above formula (4) is high performance liquid chromatography of the present invention-atomic fluorescence combination analysis system output signal simulation function, Its functional digraph is as shown in figure 3, Fig. 4 is the functional digraph of Gaussian function, it can be seen that the HPLC-HG-AFS system obtained There is difference, Gaussian function is symmetric figure for simulated function figure and traditional HPLC system Gaussian function simulation figure, and Obtained HPLC-HG-AFS system model functional digraph be not it is symmetrical, output there is bigger trailing phenomenon.So And observe the primary output signal of FI-HPLC-HG-AFS combined system shown in fig. 5, it can be seen that actual signal is also to deposit In larger hangover, moreover, obtained system model functional digraph and true spectrogram are closely similar.
Fig. 5 and Fig. 6 is the detection spectrogram (dotted line) and matched curve function of concentration 1.0ug mL-1 arsanilic acid standard solution Figure (solid line), Fig. 5 are Gaussian fitting result, and Fig. 6 is present system pattern function fitting result, it can be seen from the figure that Fig. 5 Gaussian curve is symmetrical curve, and experimental data be not it is symmetrical, it is bent to obtain making most data points to fall on fitting Fitting effect on line, there is biggish deviations between Gauss curve fitting curve and some experimental data, especially tail part. It is however clear from fig. 6 that utilizing the obtained fitting function figure of present system models fitting experimental data for comparing Similarity is very high between shape and experiment spectrogram, especially particularly evident at tail of the peak.
Fig. 7 is that the experiment spectrogram that present system model detects As (III), As (V), the mixed mark of MMA, DMA carries out Multimodal fitting result, it can be seen that for multimodal be fitted, the model established be also it is adequate, this for the later period into The processing of row experimental data, removal interference effectively seek peak area and carry out retrieving concentration, improve the related coefficient of standard curve, It is highly advantageous for improving detection accuracy.

Claims (1)

1. a kind of data processing method of high performance liquid chromatography atomic fluorescence combination analysis system, it is characterized in that including high pressure liquid phase Chromatography mechanism, hydride generating mechanism, gas-liquid separator, Atomic Fluorescence Spectrometer and computer, high pressure liquid chromatography mechanism include High-pressure pump, six-way valve and sample loop, hydride generating mechanism is by wriggling pump group, mixer and reactor group at sample loop goes out Mouth is communicated with pre-reactor, and peristaltic pump group is communicated with mixer and reactor respectively, outlet and the Reactor inlet phase of mixer Even, the outlet of reactor is connected with the reaction-ure inlet pipe of gas-liquid separator, and the inclination of reaction-ure inlet pipe is connected to separator sheet On body, the gas outlet tube at the top of separator body is connected with Atomic Fluorescence Spectrometer, and the setting of separator body lower part side is useless Liquid outlet, Atomic Fluorescence Spectrometer are connected with computer, based on high pressure liquid chromatography-hydride generation-atomic fluorescence spectrometric connection It is no longer distribution of pulses with the concentration distribution that analysis system enters hydride generating mechanism, but the Gaussian Profile of HPLC system, So the arsenic element in hydride generating mechanism sample is converted into the efficiency of hydride by many items such as experiment condition, sample substrate The influence of part, it is assumed that transformation efficiency R, R value is between 0 to 1, and independently of each experiment parameter, then sample hydride is entering Concentration (cAH) in (mol/L) in gas in GLS can be expressed as:
(cAH)in=a × exp [- (t-b)2/c2] (1)
Assuming that GLS internal gas be it is uniformly mixed, the concentration and the concentration inside GLS for exporting the gaseous hydride of GLS are phases With, then mass-conservation equation can be expressed as:
I.e.:
It enablesb1=b, c1=c,Above formula can turn to:
The solution of above formula is:
In formula,
C1 and C2 is constant, and erf () is Gauss error function;
Enable A1=C1, A5=C2, A6=d1, then above formula can turn to:
(cAH)out=A1+{A2×erf[A3(t-A4)]+A5}×exp(-A6t) (4)
Above formula (4) is the output signal simulation function of high performance liquid chromatography atomic fluorescence combination analysis system of the present invention.
CN201610578414.1A 2016-07-08 2016-07-08 High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method Expired - Fee Related CN106248824B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610578414.1A CN106248824B (en) 2016-07-08 2016-07-08 High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610578414.1A CN106248824B (en) 2016-07-08 2016-07-08 High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method

Publications (2)

Publication Number Publication Date
CN106248824A CN106248824A (en) 2016-12-21
CN106248824B true CN106248824B (en) 2018-11-23

Family

ID=57603700

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610578414.1A Expired - Fee Related CN106248824B (en) 2016-07-08 2016-07-08 High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method

Country Status (1)

Country Link
CN (1) CN106248824B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2788181Y (en) * 2004-07-02 2006-06-14 中国科学院生态环境研究中心 Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system
CN101236183A (en) * 2008-02-04 2008-08-06 浙江大学 Ion chromatograph -double anode electrochemical hydride generation atomic fluorescent on-line combined system
CN101995439A (en) * 2009-08-12 2011-03-30 中国科学院生态环境研究中心 Efficient liquid chromatogram-atomic fluorescence spectrum method for measuring mercury forms

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2788181Y (en) * 2004-07-02 2006-06-14 中国科学院生态环境研究中心 Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system
CN101236183A (en) * 2008-02-04 2008-08-06 浙江大学 Ion chromatograph -double anode electrochemical hydride generation atomic fluorescent on-line combined system
CN101995439A (en) * 2009-08-12 2011-03-30 中国科学院生态环境研究中心 Efficient liquid chromatogram-atomic fluorescence spectrum method for measuring mercury forms

Also Published As

Publication number Publication date
CN106248824A (en) 2016-12-21

Similar Documents

Publication Publication Date Title
CN106596704B (en) The method that icp ms measure Se content in vegetables
CN105758927A (en) Method for simultaneously measuring iodine, boron, tin and germanium elements in soil
CN104237078A (en) Method and device for measuring molecular diffusion coefficient of voluminous powder
CN205826608U (en) High performance liquid chromatography atomic fluorescence combination analysis system
CN110082465A (en) A method of measurement people's Pb in Blood, cadmium content
CN108982691A (en) Arsenic mercury shape simultaneous quantitative determination in aquatic products
CN103293248A (en) Method for separating and enriching sulfanilamide antibiotics in water
CN107525799A (en) The method of chromium content in inductively coupled plasma mass spectrometry measure indium
CN103076384A (en) Method for testing Boron element in tobacco
CN107807117B (en) It is a kind of to measure Hg with aptamers regulation silica nanometer enzymatic activity Surface enhanced Raman spectroscopy2+Method
CN106248824B (en) High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method
Proch et al. Recent applications of continuous flow chemical vapor and hydride generation (CVG, HG) coupled to plasma–based optical emission spectrometry (ICP OES, MIP OES)
Liu et al. Fast and highly sensitive Cd isotopic analyses in low-Cd complex samples with MC-ICPMS based on plasma electrochemical vapor generation
CN103149196A (en) Method for determining content of silicon, phosphor and aluminium in ferrocolumbium through inductive coupling plasma emission spectroscopy
CN108181300A (en) The assay method of available phosphorus content in a kind of pedotheque
CN110007036A (en) The detection of different arsenic morphologies in environment water based on HPLC-ICP-MS joint technology
CN104897621A (en) Sampling device for multi-element analysis of environmental water and method for measuring concentration of metallic element
CN213239936U (en) Rapid measurement system for uranium in field ground gas
CN106872636B (en) The method that low pressure ion chromatography-inductivity coupled plasma mass spectrometry combination measures inorganic tin and organo-tin compound simultaneously
CN102331416B (en) Micro pulse sample introduction device and method for determining content of trace iron in nickel matrix solution
CN103134790A (en) Method for measuring ferrum in ethanol gasoline
CN103267797B (en) Detecting method for simultaneously analyzing a plurality of heavy metals in seed coating
CN107860728B (en) Flow injection non-connection eight-way valve adsorption pre-enrichment elution method
CN102393366B (en) Method for indirectly measuring silicon content in defoaming agent through flame atomic absorption
CN105092499A (en) Detection method of iron content in 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20181123