CN2788181Y - Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system - Google Patents
Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system Download PDFInfo
- Publication number
- CN2788181Y CN2788181Y CN 200420073019 CN200420073019U CN2788181Y CN 2788181 Y CN2788181 Y CN 2788181Y CN 200420073019 CN200420073019 CN 200420073019 CN 200420073019 U CN200420073019 U CN 200420073019U CN 2788181 Y CN2788181 Y CN 2788181Y
- Authority
- CN
- China
- Prior art keywords
- gas
- arsenic
- liquid separator
- liquid
- outlet
- 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 - Lifetime
Links
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The utility model relates to shape analysis of arsenic in environmental or biological samples, particularly a high-efficiency liquid-phase chromatograph and hydride generating atomic fluorescence spectrum on-line coupled arsenic shape analyzing system which comprises a high-efficiency liquid-phase chromatographic pump, a liquid-phase chromatograph sampling valve, a liquid-phase chromatographic column, a three-way connecting device, an ultraviolet light on-line decomposing device, a peristaltic pump, a hydride generator, a gas-liquid separator and an atomic fluorescence spectrum instrument. Arsenic compounds with different shapes in samples are separated on the liquid-phase chromatographic column, the separated components pass through the ultraviolet light on-line decomposing device and then are pushed to enter the hydride generator through three-way acid loading flows and generate reaction with a reducing agent to produce gaseous hydride which passes through the gas-liquid separator to be led in the atomic fluorescence spectrum instrument by carrier gas to be detected, and signals are recorded and processed by a self-developing workstation. The arsenic shape analyzing coupled system of the utility model has the advantages of rapid, sensitive and accurate analysis, convenient operation and low cost and running expense. The coupled system of the utility model is suitable for the shape analysis of the arsenic in the environmental and the biological samples.
Description
Technical field
The utility model relates to the instrumental analysis field, specifically establishes to relate to the arsenium morphological analysis combined system.
Background technology
Arsenic is a kind of poisonous element, and once excessive absorption arsenic can cause acute poisoning; Long-term low dose exposes can cause arsenicalism, brings out various skin diseases and can cause hepatic and renal function impaired.The toxicity of arsenic and the chemical form of its existence are closely related, the arsenic of different shape, and its toxicity differs greatly.The inorganic arsenic form (comprises trivalent arsenic As
3+With pentavalent arsenic As
5+) have strong toxicity, Comparatively speaking, the toxicity of methyl arsenic morphology (comprising monomethyl arsenic MMA and dimethyl arsenic DMA) a little less than, and arsenic betaine AsB, the arsenocholine AsC, the more complicated arsenic compound forms such as arsenic sugar AsS, arsenic fat AsL that extensively are present in the aquatic organism can be excreted rapidly, and it is very low or nontoxic to be considered to toxicity usually.The toxicity difference of different shape arsenic compound, metabolic mechanism biosome is also different, make the mensuration of arsenic total amount can not satisfy the research needs in fields such as environmental science, life science, medical and health, set up a kind of quick, accurate, sensitive arsenium morphological analysis method and seemed very necessary.
Early stage arsenium morphological analysis adopts spectrophotometric method, atomic absorption spectrography (AAS) directly to measure by the sample pre-treatments utilization more, as select suitable complexing agent and the complexing of a certain form arsenic compound, by liquid-liquid extraction or Solid-Phase Extraction the arsenic of different shape is separated, utilize spectrophotometric method or atomic absorption light popularize law to measure separately respectively then; Also can utilize electrochemical method directly to measure the trivalent inorganic arsenic, but the electrochemical behavior of arsenic is subjected to the influence of factors such as electrolytical composition, concentration, the sensitivity of method and stability are all undesirable; Along with the appearance of hydride generation system, people make the trivalent inorganic arsenic produce hydride respectively under different experiment conditions with the pentavalent inorganic arsenic by selecting different acidity, realize the purpose that the arsenic to different valence state separates.More than the method for early stage arsenium morphological analysis be confined to analysis to the inorganic arsenic form more, and the arsenic content of different shape adopts minusing to calculate gained, the easy like this analysis result deviation that causes is bigger; Simultaneously, because of experiment condition needs strict control, practical operation difficulty, the stability of method and reappearance are not easy to hold.In recent years, some combined apparatus had been used to the analysis of arsenic morphology.These combined apparatus combine by special interface arrangement the high efficiency separation system with high selectivity, high-sensitive spectral detection instrument, improved the accuracy and the sensitivity of arsenium morphological analysis greatly.The separation means that adopts mainly comprises high-efficient liquid phase chromatogram HPLC, gas chromatography GC and Capillary Electrophoresis CE isochromatic spectrum isolation technics.In these separation means high-efficient liquid phase chromatogram HPLC with its good separating effect to arsenic compound, be easy to be widely used with other detecting device couplings; Aspect detection means, be often used as the detecting device of arsenium morphological analysis system as the spectral instrument of the sensitivity of measuring arsenic, special efficacy such as Atomic Absorption Spectrometer AAS, atomic fluorescence spectrometer AFS, icp ms ICP-MS.Inductivity coupled plasma mass spectrometry is highly sensitive, selectivity good, but the expense costliness of its price and instrument operation; The price and the operating cost of atomic absorption spectrum are lower, but the sensitivity of mensuration arsenic is not high.By contrast, the instrument price and the operating cost of atomic fluorescence spectrophotometry are all cheaper, and the sensitivity of analyzing is than highly sensitive 1-2 the order of magnitude of atomic absorption detecting arsenic, and hydride generating system can make tested element separate with matrix, reduce interference to a great extent, improved sensitivity.Hydride atomic fluorescence spectrometetry has been widely used in every field such as environmental protection, chemical industry, medical and health as the special efficacy of arsenic, sensitive detection means.
The utility model content
In liquid chromatography and atomic fluorescence spectrophotometry combined system, the connecting interface technology is the key that whole combined system is successfully realized compound separation and every analysis indexes.Problem to be solved in the utility model provides maturation, the stable interface technology of a whole set of high performance liquid chromatography that is used for arsenium morphological analysis and atomic fluorescence spectrophotometry coupling, sets up quick, accurate, sensitive arsenium morphological analysis on-line coupled system.
The technical solution of the utility model is: the arsenic compound of different shape is the dissociation constant difference under certain condition, and then the retention behavior difference on ion-exchange chromatography.Select suitable anion-exchange column can realize being separated from each other between the different arsenic compounds for the liquid chromatography separating column.Analyzed component in the sample arsenic compound of form (neither with) (comprises efficient liquid-phase chromatographic pump through the high efficiency separation system, the liquid chromatography sampling valve, liquid-phase chromatographic column) after the separation, after the online degraded of ultraviolet light, promoted enter hydride generator by the hydrochloric acid current-carrying with certain flow rate by the T-valve that is provided with behind the post, and mix with reductive agent (solution of potassium borohydride) at this, produce the gaseous hydride of arsenic, subsequently through the separation of the gas-liquid separator of design voluntarily, again after carrier gas imports the further separation of secondary gas-liquid device, enter atomizer and detect, fluorescence signal is by independently developed workstation record, handle.
Description of drawings
Accompanying drawing 1 is the utility model arsenium morphological analysis on-line coupled system device synoptic diagram.
Accompanying drawing 2 is the utility model arsenium morphological analysis on-line coupled system gas-liquid separator synoptic diagram.
Embodiment
As shown in Figure 1, the utility model device consists of the following components: efficient liquid-phase chromatographic pump 1, liquid chromatography sampling valve (having quantitative ring) 2, liquid-phase chromatographic column 3, ultraviolet degradation system 7, T-valve 4 and 8, atomic fluorescence spectrometer 11, computing machine and workstation1 2, hydride generation system 9, gas-liquid separator 10, peristaltic pump 13.Polytetrafluoroethylene (PTFE) conduit by suitable aperture between the each several part connects.
The gas-liquid separator that the utility model on-line coupled system interface arrangement adopts as shown in Figure 2, the gas-liquid mixture that hydride generator 9 produces enters gas-liquid separator by inlet 20, carrier gas enters gas-liquid separator by carrier gas inlet 19 by fritted glass ball 23, the fritted glass ball had not just been had by waste liquid liquid level 25, and hydrops 26 volumes are about 2mL.Carrier gas can make not the fully liquid 26 of reaction further fully reaction under the mild agitation of carrier gas air-flow by not entering gas-liquid separator in subsurface fritted glass ball, improves the hydride luminous efficiency.After the gas of gas-liquid separator separates is imported the further separation of secondary gas-liquid separators by carrier gas by the ground piston 24 of taking mouth 21 out of, enter atomizer and detect.Waste liquid in time enters waste liquid bottle 17 by waste liquid outlet 22.
Ultraviolet degradation system 7 is by ultraviolet lamp tube 5 with through crooked and parallelly form attached to the quartz ampoule on the ultraviolet lamp tube 56, and the nearly outlet of quartz ampoule 6 is connected with conduit by adapter.The ultraviolet degradation device is packed shielding, exposes to prevent ultraviolet light.Whether ultraviolet degradation system 7 can use according to the needs decision of arsenium morphological analysis in the actual sample.If only carry out inorganic arsenic (As
3+And As
5+), the compartment analysis of monomethyl arsenic (MMA) and dimethyl arsenic (DMA), can not use ultraviolet degradation system 7, the analysis component of separating through liquid-phase chromatographic column 3 is directly imported T-valve 8 and produces hydride and detect; Can the more complicated arsenic compound form of separation determination by ultraviolet degradation, as arsenic betaine (AsB) and arsenocholine (AsC).
When using the utility model to carry out arsenium morphological analysis, sample is by sampling valve 2 sample introductions, is written into liquid-phase chromatographic column 3 by liquid chromatography pump 1 with certain flow rate (1mL/min) moving phase and separates, and separated component enters ultraviolet degradation system 7, through quartz capillary 6, at potassium persulfate (K
2S
2O
8) being degraded or directly imported T-valve 8 by ultraviolet light 5 under 16 situations about existing is written into hydride generator 9 and potassium borohydride (KBH by hydrochloric acid current-carrying 14 with certain flow rate
4) solution 15 dynamically mixes the generation gaseous hydride with proper ratio, after the gaseous hydride that produces carries out gas-liquid separation through gas-liquid separator 10, imported atomic fluorescence spectrometer 11 by carrier gas (argon gas) 18, after secondary gas-liquid separator (Beijing Rayleigh AF-610A carries) separates, enter atomizer and detect, fluorescence signal is by computing machine and workstation1 2 records and processing.
In analytic process, peristaltic pump 13 is used for realizing hydrochloric acid (HCl) current-carrying 14, potassium borohydride (KBH
4) solution 15 and potassium persulfate (K
2S
2O
8) solution 16 keeps permanent current stabilization speed.By selecting suitable hydrochloric acid (HCl) current-carrying 14 and potassium borohydride (KBH
4) flow of the flow velocity of solution 15 and concentration proportioning and suitable carrier gas 18 guarantees that the atomizer in the atomic fluorescence spectrometer 11 produces stable flame.The waste liquid that gas-liquid separator 10 separates is imported into waste liquid bottle 17.
Select the efficient liquid-phase chromatographic pump P680HPLC Pump of U.S. Dai An company (Dionex) for use, anion-exchange column IonPac AS 11 and AG 11, sample introduction 20 μ L are moving phase with the sodium hydroxide solution, the flow velocity of moving phase is 1mL min
-1, gradient elution, trivalent inorganic arsenic (As
3+), pentavalent arsenic (As
5+), monomethyl arsenic (MMA), four kinds of different arsenic morphology compounds of dimethyl arsenic (MMA) wash-out and baseline separation fully within 10min.Arsenic betaine (AsB) can effectively be degraded through the online degeneration system of ultraviolet light.The retention time of arsenic betaine (AsB) on IonPac AS 11 is consistent with the retention time of dimethyl arsenic (DMA), can be by adopting degeneration system and not adopting the degeneration system dual mode to realize the mensuration respectively of dimethyl arsenic (DMA) and arsenic betaine (AsB).Hydrochloric acid with 10% (v/v) is current-carrying, and flow velocity is 2mL min
-12% (m/v) potassium borohydride (being dissolved in 0.2% (m/v) potassium hydroxide solution) is a reductive agent, and flow velocity is 4mL min
-12% (m/v) potassium persulfate (being dissolved in 1% (m/v) sodium hydroxide solution) is an oxygenant, and flow velocity is 1mL min
-1Atomic fluorescence spectrometer AF-610A (Beijing Rayleigh Analytical Instrument Co.,Ltd).This utility model arsenium morphological analysis on-line coupled system is to trivalent inorganic arsenic (As
3+), pentavalent arsenic (As
5+), monomethyl arsenic (MMA) is respectively 1.31ng mL with the detection limit of dimethyl arsenic (MMA), five kinds of different arsenic morphology compounds of arsenic betaine (AsB)
-1, 2.11ngmL
-1, 1.89ng mL
-1, 2.56ng mL
-1, 3.82ng mL
-1
The interfacing of the utility model on-line coupled system realizes separating arsenic compound applicable to different liquid chromatography separating columns with corresponding moving phase.
Claims (3)
1. arsenium morphological analysis on-line coupled system, high performance liquid chromatography and atomic spectrograph are linked in sequence; It is characterized in that: high performance liquid chromatography is connected with online degeneration system one end of ultraviolet light, the online decomposition apparatus other end of this ultraviolet light is connected with hydride generation system, hydride generation system is connected with gas-liquid separator, and gas-liquid separator is connected with atomic fluorescence spectrometer; Wherein the high pressure liquid chromatography pump is provided with sampling valve, and links to each other with the chromatographic column injection port; The chromatographic column outlet links to each other with import in the T-valve, and the bottle that potassium persulfate is housed simultaneously connects another import in this T-valve through pump; The outlet of this T-valve links to each other with teflon digestion tube inlet, and the teflon digestion tube is wrapped on the uviol lamp, forms the ultraviolet degradation system; The outlet of teflon digestion tube connects an import of this T-valve, and the bottle that hydrochloric acid is housed simultaneously connects another import of this T-valve through pump; The outlet of this T-valve connects an import of hydride generation system, and potassium borohydride is connected hydride generation system with the bottle process pump of potassium hydroxide mixed solution another import is housed simultaneously; The outlet of hydride generation system connects the upper end import of gas-liquid separator side, and argon bottle connects the lower end import of gas-liquid separator side; The outlet of gas-liquid separator lower end connects the waste liquid cylinder, and the outlet of gas-liquid separator upper end connects the atomic fluorescence detecting device, and the atomic fluorescence detecting device links to each other with computing machine by signal connecting line.
2. arsenium morphological analysis on-line coupled system according to claim 1, it is characterized in that: the gas-liquid separator of hydride generating system is made of grournd glass piston that has gas vent and glass gas-liquid separator main body, and the ground piston directly inserts gas-liquid separator main body upper end open; Gas-liquid separator side inlet and lower part outlet and gas-liquid separator main body integrate.
3. arsenium morphological analysis on-line coupled system according to claim 1 is characterized in that: the gas-liquid separator lower body part is provided with a fritted glass ball.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200420073019 CN2788181Y (en) | 2004-07-02 | 2004-07-02 | Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200420073019 CN2788181Y (en) | 2004-07-02 | 2004-07-02 | Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN2788181Y true CN2788181Y (en) | 2006-06-14 |
Family
ID=36786476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200420073019 Expired - Lifetime CN2788181Y (en) | 2004-07-02 | 2004-07-02 | Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN2788181Y (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101236183B (en) * | 2008-02-04 | 2011-01-19 | 浙江大学 | Ion chromatograph -double anode electrochemical hydride generation atomic fluorescent on-line combined system |
| CN101158667B (en) * | 2007-11-19 | 2011-02-09 | 中国科学院生态环境研究中心 | Method for separating and detecting organo-mercuric compound content |
| CN101261258B (en) * | 2008-01-04 | 2011-05-18 | 中国水产科学研究院黄海水产研究所 | Aquatic product inorganic arsenic determination method |
| CN101329311B (en) * | 2008-08-04 | 2011-06-29 | 华北电力大学（保定） | Gas chromatograph pillar for volatile gaseous state arsenic compounds separation and preparation method thereof |
| CN101446577B (en) * | 2008-05-26 | 2012-02-29 | 北京瑞利分析仪器公司 | Coupling interface for realizing morphological analysis function of atomic fluorescence element |
| CN104678027A (en) * | 2015-02-04 | 2015-06-03 | 天津科技大学 | Rapid multi-mode element speciation analysis pretreatment system |
| CN105259156A (en) * | 2015-11-27 | 2016-01-20 | 天津师范大学 | Sulfur testing device and method |
| CN106248824A (en) * | 2016-07-08 | 2016-12-21 | 德州职业技术学院 | High performance liquid chromatography atomic fluorescence combination analysis system mathematic model and data processing method |
| CN106979985A (en) * | 2017-05-02 | 2017-07-25 | 维科托（北京）科技有限公司 | Liquid chromatogram atom spectrum combined system |
| CN107179359A (en) * | 2017-05-02 | 2017-09-19 | 维科托（北京）科技有限公司 | Flow path system for liquid chromatogram atomic fluorescence combined instrument |
| CN107894511A (en) * | 2017-10-27 | 2018-04-10 | 河北莱博瑞特电子科技有限公司 | A kind of Elemental Speciation Analysis instrument |
| CN107917909A (en) * | 2017-12-19 | 2018-04-17 | 农业部环境保护科研监测所 | On-line preconcentration micro low-temperature plasma atomic-emission surveys arsenic analytical equipment |
| CN108426873A (en) * | 2018-03-09 | 2018-08-21 | 中国科学院海洋研究所 | A kind of detection method and dedicated unit of hydride |
| CN111624272A (en) * | 2020-06-16 | 2020-09-04 | 中国农业科学院农业质量标准与检测技术研究所 | Device and method for improving analysis sensitivity of liquid chromatography atomic spectrometry |
-
2004
- 2004-07-02 CN CN 200420073019 patent/CN2788181Y/en not_active Expired - Lifetime
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101158667B (en) * | 2007-11-19 | 2011-02-09 | 中国科学院生态环境研究中心 | Method for separating and detecting organo-mercuric compound content |
| CN101261258B (en) * | 2008-01-04 | 2011-05-18 | 中国水产科学研究院黄海水产研究所 | Aquatic product inorganic arsenic determination method |
| CN101236183B (en) * | 2008-02-04 | 2011-01-19 | 浙江大学 | Ion chromatograph -double anode electrochemical hydride generation atomic fluorescent on-line combined system |
| CN101446577B (en) * | 2008-05-26 | 2012-02-29 | 北京瑞利分析仪器公司 | Coupling interface for realizing morphological analysis function of atomic fluorescence element |
| CN101329311B (en) * | 2008-08-04 | 2011-06-29 | 华北电力大学（保定） | Gas chromatograph pillar for volatile gaseous state arsenic compounds separation and preparation method thereof |
| CN104678027A (en) * | 2015-02-04 | 2015-06-03 | 天津科技大学 | Rapid multi-mode element speciation analysis pretreatment system |
| CN105259156A (en) * | 2015-11-27 | 2016-01-20 | 天津师范大学 | Sulfur testing device and method |
| CN106248824B (en) * | 2016-07-08 | 2018-11-23 | 德州职业技术学院 | High performance liquid chromatography-atomic fluorescence combination analysis system mathematic model and data processing method |
| CN106248824A (en) * | 2016-07-08 | 2016-12-21 | 德州职业技术学院 | High performance liquid chromatography atomic fluorescence combination analysis system mathematic model and data processing method |
| CN106979985A (en) * | 2017-05-02 | 2017-07-25 | 维科托（北京）科技有限公司 | Liquid chromatogram atom spectrum combined system |
| CN107179359A (en) * | 2017-05-02 | 2017-09-19 | 维科托（北京）科技有限公司 | Flow path system for liquid chromatogram atomic fluorescence combined instrument |
| CN106979985B (en) * | 2017-05-02 | 2020-07-28 | 维科托（北京）科技有限公司 | Liquid chromatogram atomic spectrum combined system |
| CN107894511A (en) * | 2017-10-27 | 2018-04-10 | 河北莱博瑞特电子科技有限公司 | A kind of Elemental Speciation Analysis instrument |
| CN107894511B (en) * | 2017-10-27 | 2023-09-15 | 河北莱博瑞特电子科技有限公司 | Elemental morphology analyzer |
| CN107917909A (en) * | 2017-12-19 | 2018-04-17 | 农业部环境保护科研监测所 | On-line preconcentration micro low-temperature plasma atomic-emission surveys arsenic analytical equipment |
| CN108426873A (en) * | 2018-03-09 | 2018-08-21 | 中国科学院海洋研究所 | A kind of detection method and dedicated unit of hydride |
| CN111624272A (en) * | 2020-06-16 | 2020-09-04 | 中国农业科学院农业质量标准与检测技术研究所 | Device and method for improving analysis sensitivity of liquid chromatography atomic spectrometry |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN2788181Y (en) | Highly-efficient liquid phase chromatogram-atomic fluorescence spectrum arsenic shape analysis on-line coupled system | |
| Chen et al. | Determination of Cr (VI) in rice using ion chromatography inductively coupled plasma mass spectrometry | |
| Brinckman et al. | Application of a liquid chromatograph coupled with a flameless atomic absorption detector for speciation of trace organometallic compounds | |
| Krull et al. | Determination of inorganic and organomercury compounds by high-performance liquid chromatography-inductively coupled plasma emission spectrometry with cold vapour generation | |
| Anthemidis et al. | Determination of arsenic (III) by flow injection solid phase extraction coupled with on-line hydride generation atomic absorption spectrometry using a PTFE turnings-packed micro-column | |
| Chana et al. | Urinary arsenic speciation by high-performance liquid chromatography/atomic absorption spectrometry for monitoring occupational exposure to inorganic arsenic | |
| Dong et al. | On-line coupling of flow injection displacement sorption preconcentration to high-performance liquid chromatography for speciation analysis of mercury in seafood | |
| Harrington et al. | Atomic spectrometry update. Elemental speciation | |
| CN102707005B (en) | Method for synchronously analyzing ferric iron and ferrous iron in water sample online | |
| CN101893612A (en) | Method for determining content of astaxanthin in antarctic krill oil by chromatography | |
| CN108982691A (en) | Arsenic mercury shape simultaneous quantitative determination in aquatic products | |
| CN113267588B (en) | Method for simultaneously detecting 7 acrylic acid and acrylic ester monomers in plastic product | |
| Hemida et al. | Small footprint liquid chromatography-mass spectrometry for pharmaceutical reaction monitoring and automated process analysis | |
| Pyrzynska et al. | On-line sorption-based systems for determination of cadmium with atomic spectrometry detectors | |
| Simon et al. | Speciation analysis of organoarsenical compounds in biological matrices by coupling ion chromatography to atomic fluorescence spectrometry with on-line photooxidation and hydride generation | |
| CN1749750A (en) | High efficiency liquid phase chromatograph | |
| Jones et al. | Aqueous phase high speed liquid chromatographic separation and atomic absorption detection of amino carboxylic acid-copper chelates | |
| CN105158189A (en) | Method for analyzing content of antioxidants in vegetable oil on basis of criterion of space angle | |
| Petry-Podgorska et al. | Speciation analysis of mercury employing volatile species generation: Approaches to reliable determination in blood and hair | |
| CN105092561A (en) | Method for determining content of methyl mercury in fish meat | |
| Semenova et al. | Sequential injection analysis system for total inorganic arsenic determination by hydride generation-atomic fluorescence spectrometry | |
| Gerwinski et al. | Automated solid-phase extraction for trace-metal analysis of seawater: sample preparation for total-reflection X-ray fluorescence measurements | |
| CN101419205B (en) | Method for measuring residual organic solvent in pectins | |
| CN2620871Y (en) | Automatic analyser for metallic element | |
| Zhang et al. | Hybrid flow system for automatic dynamic fractionation and speciation of inorganic arsenic in environmental solids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20140702 Granted publication date: 20060614 |