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 PDFInfo
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- 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
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- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 238000004458 analytical method Methods 0.000 title claims abstract description 21
- 238000003672 processing method Methods 0.000 title claims abstract description 9
- 150000004678 hydrides Chemical class 0.000 claims abstract description 29
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 22
- 230000007246 mechanism Effects 0.000 claims abstract description 22
- 238000002474 experimental method Methods 0.000 claims description 16
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 230000002572 peristaltic effect Effects 0.000 claims description 7
- 238000004088 simulation Methods 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims 2
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 3
- 238000001676 hydride generation atomic fluorescence spectroscopy Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- XKNKHVGWJDPIRJ-UHFFFAOYSA-N arsanilic acid Chemical compound NC1=CC=C([As](O)(O)=O)C=C1 XKNKHVGWJDPIRJ-UHFFFAOYSA-N 0.000 description 5
- 229950002705 arsanilic acid Drugs 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000012491 analyte Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000013178 mathematical model Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 206010019133 Hangover Diseases 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- 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
- G01N21/62—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
- G01N2021/6417—Spectrofluorimetric devices
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
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- 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
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.
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Citations (3)
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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 |
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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 |
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