CN110398557A - The purification and analysis method of chlorine isotope in a kind of complex matrices sample - Google Patents
The purification and analysis method of chlorine isotope in a kind of complex matrices sample Download PDFInfo
- Publication number
- CN110398557A CN110398557A CN201910560974.8A CN201910560974A CN110398557A CN 110398557 A CN110398557 A CN 110398557A CN 201910560974 A CN201910560974 A CN 201910560974A CN 110398557 A CN110398557 A CN 110398557A
- Authority
- CN
- China
- Prior art keywords
- sample
- column
- ion
- purification
- solution
- 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.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/96—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 using ion-exchange
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/065—Preparation using different phases to separate parts of sample
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The present invention provides the purifications and analysis method of chlorine isotope in a kind of complex matrices sample, include the following steps: A, the removal of organic matter and sample cleanup in sample, the removal of inorganic chaff interferent and separating-purifying in B, sample: B-1, the collection for carrying out high pure sample；B-2, selection ion chromatographic separation column, adjustment suppressor inhibit electric current to be greater than the 10-50mA or more of corresponding eluent concentration recommendation, carry out gradient elution；B-3, solution is collected into sample by loading after filtering with microporous membrane；B-4, concentration: the sample of collection is baked to removal part moisture content on hot plate；B-5, distillate is crossed to caesium cation exchange resin column Cs column, obtains High Purity Caesium Chloride solution；C, thermal ionization mass spectrometry (tims) measurement and correction.Operation of the present invention is easy, and exploitativeness is strong；Purification efficiency is high, can reach the refining effect close to 100% by single purification；Testing background is low, accurate high, is suitable for batch sample test.
Description
Technical field
The invention belongs to Stable Isotopic Analysis field, it is specifically related to a kind of mentioning for chlorine isotope in complex matrices sample
Pure and analysis method can be applied to seawater, river water, underground water, inorganic chlorine isotopic ratio in pore water and sewage
High accuracy analysis.
Background technique
Chlorine element stable isotope containing there are two types of in nature, respectively35Cl and37Cl.The variation of chlorine isotope is for grinding
Study carefully geochemical cycle, seawater invasion, the recharge of ground water and excretion, the paleo-climate change, evaporite feature, mineral deposit shape of chlorine element
There is important indicative significance at, chlorinatedorganic degradation etc..Compared to elements such as carbon, hydrogen, oxygen, chlorine element is because of tool
There is stable physicochemical characteristic and is not likely to produce isotope fractionation.But due to35Cl and37There are relatively large matter between Cl
Amount difference causes it that isotope fractionation can occur in evaporative crystallization, ion diffusion, infiltration convection current, biodegradation process, thus right
Instruction or directive function are played in scientific research and engineering construction.According to it is current existing research shows that nature mesosphere,
The variation range of chlorine isotope is -14 ‰~+16 ‰ in hydrosphere, lithosphere, and a few studies show that chlorine isotope fractionation reaches
30 ‰ or more, the special fractionation of chlorine isotope is concentrated mainly in atmospheric thermodynamics and volcano system.
The analysis test method of chlorine isotope includes gas-chromatography-isotope ratio mass spectrometry (GC-IRMS), thermal ionization at present
Mass spectrography (TIMS) receives inductively coupled plasma mass spectrometry (MC-ICP-MS) etc. more, although various methods respectively have excellent lack
Point, but Thermal Ionization Mass Spectrometry analysis chlorine isotope forms the advantage for still having its irreplaceable.With Xiao Yingkai before nineteen ninety-five
The method that Research Team headed by teacher just establishes and improves PTIMS method method measurement chlorine isotope, and in halogen
It is widely used in the chlorine isotope test of the samples such as water, rock, pore water.Repeatedly facts have proved for this method is a small amount of
Sulfate etc. isotope test is influenced smaller, therefore be significantly higher than the water body of sulfate radical, nitrate anion, forefathers for chlorinity
The high precision measurement that thermal ionization mass spectrometry (tims) realizes chlorine isotope composition can be used.But the nitric acid largely coexisted in sample
The substances such as salt, sulfate, fluoride, organic matter will seriously affect the transmitting of thermal ionization mass spectrometry (tims) ion, to influence the same position of chlorine
The test accuracy of element, particularly with the chlorinities such as surface water, underground water, rainwater and the comparable water of sulfate radical, nitrate radical content
Body also cannot achieve the Accurate Determining of chlorine isotope at present.Therefore it purifies and is being continuously improved always with the method for purification, be based on shape
It is effective for precipitating at AgCl in the method for removing nitrate anion, but due to the complexity of operating process and may cause high sky
White chlorine and be restricted, developed Ba- type resin or and BaCO again later3The method for removing sulfate radical is reacted, but due to tree
The limitation of rouge itself performance, if the underground water or sewage sample for high-content want that it is very difficult for completely removing sulfate radical.
Currently being excessively used due to chemical fertilizer, the content of underground water, surface water, river water, nitrate from waste water and sulfate
Persistently increase, due to a large amount of uses of pesticide and plastic products, so that content of organics is also on the rise in Different Waters.In order to
The problem of better solving these two types of matrix interferences in isotope test, the invention discloses one kind to be based on improved ion chromatography
The chlorine isotope method of purification of isolation technics, and the complex matrices water body sample such as be directed to underground water, surface water, river water, sewage
Product develop whole solution.A set of ultra high efficiency chloride ion purification, purification and measuring method are ultimately formed, for standard
Really chlorine isotope composition plays key effect in measurement Complex water body.
Summary of the invention
To solve problems of the prior art, the present invention is intended to provide chlorine isotope in a kind of complex matrices sample
Analysis test method, it is more that sample type covers underground water, surface water, river water, sewage, Atmospheric precipitation, brine, pore water etc.
Kind, the core innovative point of method is that solid phase extraction techniques is utilized to remove the organic matter in sample, utilize the dedicated system of isotope
Standby type ion chromatograph (Pre-Isotope) goes the interference of Natural zeolite, nitrate anion, nitrite anions, sulfate radical plasma, thus
High-purity Chloride Solution is obtained, carries out isotope analysis eventually by thermal ionization mass spectrometry (tims).
The technical solution used in the present invention is as follows: the purification of chlorine isotope and analysis side in a kind of complex matrices sample
Method includes the following steps:
A, the removal of organic matter and sample cleanup in sample:
Phase solid phase extraction column is negated, solid-phase extraction column is activated with solvent, then passes through sample solution
Reverse phase solid phase extraction pillar after activation, flow control is in 2-10mL/min；
B, the removal of inorganic chaff interferent and separating-purifying in sample:
B-1, the signal trigger device by ion chromatograph, trigger chromatograph in the period of setting and collect sample
Product export installation fraction collector in instrument detection cell, and are associated with signal trigger device, in fixed reservation period
The upper collection for carrying out high-purity sample；
B-2, selection ion chromatographic separation column, prepare eluent solution (NaOH or Na2CO3\NaHCO3Solution), adjustment inhibits
Device inhibits electric current to be greater than the 10-50mA or more of corresponding eluent concentration recommendation, carries out gradient elution；
B-3, the solution for obtaining step A are touched by loading after filtering with microporous membrane according to the appearance time section of chloride ion
It sends out fraction collector and collects sample, need repeatedly to collect and merge if sample chloride ion content is lower；
B-4, concentration: the sample of collection is baked to removal part moisture content on hot plate；
B-5, distillate is crossed to caesium cation exchange resin column Cs column, obtains High Purity Caesium Chloride solution；
C, thermal ionization mass spectrometry (tims) measurement and correction: the graphite that above-mentioned High Purity Caesium Chloride solution is coated in thermal ionization mass spectrometer is enterprising
The test of row thermal ionization mass spectrometry (tims), obtains final δ37Cl' value.
Further, the solvent is pure water or methanol and pure water, and when solvent is methanol and pure water, the volume of pure water is
5 times or more of methanol volume guarantee that the methanol on solid-phase extraction column is substituted completely.
Further, in the step B-2, ion chromatographic separation column used is greater than 350ueq/column using column capacity
Chromatographic column type.
Further, the aperture of miillpore filter is 0.22 μm in the step B-3.
Further, the connection type of the chromatographic column and suppressor and fraction collector are as follows: ion chromatography column outlet connects
Suppressor leacheate import, leacheate outlet connect ion chromatograph conductance pond, and conductance cell outlet connects fraction collector, suppressor regeneration
Liquid entrance injects pure water by peristaltic pump, and the outlet of suppressor regenerated liquid is exhausted directly at waste liquid.
It is 1. easy to operate that the present invention obtained have the beneficial effect that, exploitativeness is strong；2. purification efficiency is high, pass through single
Purification can reach the refining effect close to 100%；3. testing background is low, accurate high.
Traditional technology operating process is longer, easily entrains secondary interference, for high sulfate contents such as underground water, surface water
Sample easily removes not completely, another crucial difficulty is that the nitrate absolutely not method of sample is removed；With this
It compares, the present invention, which is used, efficiently separates purification schemes based on ion chromatography, ensure that by adjusting the electric current adjustment of suppressor
Distillate it is pure, pass through the trigger device and fraction of improved ion chromatograph (the dedicated preparative ion chromatograph of isotope)
Collection device realizes the rapidly and efficiently purifying of inorganic chloride ion.The implementation for cooperating solid phase extraction procedure, so that whole flow process obtains
The prepare liquid arrived is very pure, so that test data interference is minimum；Whole set process process has strong operability, dangerous system
The advantages that number is small, easy to spread.
Detailed description of the invention
Fig. 1 is whole process schematic diagram of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
The purification and analysis method of chlorine isotope, include the following steps: in a kind of complex matrices sample
A, the removal of organic matter and sample cleanup in sample:
Phase solid phase extraction column (C18, C8 or suitable person) is negated, solid-phase extraction column is activated with solvent, so
Afterwards by sample solution by the reverse phase solid phase extraction pillar after activation, flow control is in 2-10mL/min；Wherein solvent is followed successively by
Methanol and pure water, the volume of pure water are 5 times or more of methanol volume, guarantee that the methanol on solid-phase extraction column is substituted completely；
For can achieve the solid phase extraction filler of suitable adsorption effect, methanol can not had to, and directly adopt pure water activation；
B, the removal of inorganic chaff interferent and separating-purifying in sample:
B-1, ion chromatograph is installed into signal trigger device, triggers chromatograph in the period of setting and collects sample
Product export installation fraction collector in instrument detection cell, and are associated with signal trigger device, in fixed reservation period
The upper collection for carrying out high-purity sample；
The ion chromatographic separation column of the chromatographic column type of B-2, selection column capacity greater than 350ueq/column, prepares elution
Solution (NaOH or Na2CO3\NaHCO3Solution), adjustment suppressor inhibits electric current to be greater than the 10- for corresponding to eluent concentration recommendation
50mA or more carries out gradient elution；The connection type of the chromatographic column and suppressor and fraction collector are as follows: ion chromatographic column
Outlet connects suppressor leacheate import, and leacheate outlet connects ion chromatograph conductance pond, and conductance cell outlet connects fraction collector, inhibits
Device regenerated liquid entrance injects pure water by peristaltic pump, and the outlet of suppressor regenerated liquid is exhausted directly at waste liquid；
B-3, the solution for obtaining step A are loading after 0.22 μm of filtering with microporous membrane by aperture, according to chloride ion
Appearance time section triggering fraction collector collect sample, need repeatedly to collect and merge if sample chloride ion content is lower；
B-4, concentration: the sample of collection is baked to removal part moisture content on hot plate；
B-5, distillate is crossed to caesium cation exchange resin column Cs column, obtains High Purity Caesium Chloride solution；
C, thermal ionization mass spectrometry (tims) measurement and correction: the graphite that above-mentioned High Purity Caesium Chloride solution is coated in thermal ionization mass spectrometer is enterprising
The test of row thermal ionization mass spectrometry (tims), the ion peak intensity that m/e is 301,303 is received with Faraday cup simultaneously, obtains R by calculatingCl
=37Cl/35Cl, wherein 301 is corresponding133Cs2 35Cl+, 303 is corresponding133Cs2 37Cl+；According to the following formula by the R of above-mentioned calculated resultclValue
With known isotopic standard valueCorrection is compared, obtains final δ37Cl' value:
WhereinFor the isotopic ratio of standard substance SMOC.
Present invention purification is as shown in Figure 1 with the whole process figure of analysis method.
Embodiment 1:
The ratio of chlorine isotope in underground water, river water, rainwater three classes sample is measured, steps are as follows:
A, the removal of organic matter and sample cleanup in sample:
Phase solid phase extraction column (production of C18,1000mg/6.0mlENVI-18, SUPELCO company) is negated, 2mL is successively used
Methanol and 10mL pure water are activated solid-phase extraction column, and sample solution is then passed through the reverse phase solid phase extraction after activation
Pillar, flow control is in 5mL/min；
B, the removal of inorganic chaff interferent and separating-purifying in sample:
B-1: the setting of ion chromatography condition
By the dedicated preparative ion chromatograph of isotope, (Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geology is ground
System, model: Pre-Isotope) signal trigger device debugged with fraction collector, it is ensured that instrument can work normally；
The IonPacAS23 high efficiency chromatography column that B-2, selection U.S. Dai An company produce, prepares sodium carbonate and sodium bicarbonate is mixed
Solution is closed as eluent solution, wherein concentration of sodium carbonate is 7mM/L, and the concentration of sodium bicarbonate is 2mM/L, according to suppressor electric current
The principle more bigger than recommendation and guarantee the pH of distillate as neutral or subacidity, determining suppressor, (Dai An company, the U.S. is raw
Producing ASRS300) electric current is set as 70mA；
B-3: the confirmation of distillate acquisition time: according to the appearance time of chloride ion, in conjunction with due to length of pipe bring
Time delay gropes the acquisition time for confirming distillate；It is dense that collection liquid in different time periods is refilled into ion chromatography progress
Degree test, calculates the rate of recovery, using the rate of recovery maximum period as acquisition time；Due to the delay of pipeline, chloride ion is main
Fraction distillated in 7-8min, accounted for the 65.57% of total amount；It is that 6-7min collects chloride ion in retention time, is only capable of receiving
Collect 11.53%；It remains to be collected into a small amount of chloride ion in 8-9min and 9-10min；In view of if the time, extend again might
Other interfering ions are brought, therefore final choice 6-10min, as best acquisition time, collection efficiency is up to 98.65%.
B-4: the impurity such as nitrate and sulfate remove effect confirmation
The water sample of different content is selected to carry out as retention time of the analog sample to nitrate ion and sulfate ion
Confirmation, the simulated water sample number that this example uses is respectively M354, TWS015 and S133, is found through experiments that, nitrate anion goes out
Peak time is between 12min-14min, and the appearance time of sulfate radical is between 15-17.5min.According to true in B-2 step
The chloride ion acquisition time recognized collects sample, and collection liquid is then injected ion chromatography again, finds to evaporate between 12-17.7min
Nitrate anion and sulfate interference out has completely removed clean.
The Fraction collection of the actual samples such as B-5 underground water, river water, rainwater
The sample solution that step A is obtained is loading after 0.22 μm of filtering with microporous membrane by aperture, will be filtered
Ion chromatography carries out separating-purifying on solution, collects the distillate of chloride ion appearance time section (6.0-10.0min).
Sample is baked removal part moisture content by B-6 on hot plate, and concentrate is then passed through caesium cation exchange resin
Column (Cs column), obtains High Purity Caesium Chloride solution, uses for next step isotope analysis；
C, thermal ionization mass spectrometry (tims) measurement and correction:
High Purity Caesium Chloride solution obtained by previous step is coated in progress thermal ionization mass spectrometry (tims) test on the graphite of thermal ionization mass spectrometer,
Thermal ionization mass spectrometer preferably uses the TritonTI type of Finnigan company, uses Faraday cup while quality of reception number for 301
With 303 ionic strength and calculate chlorine isotope ratio Rcl；Finally according to following formula by the R of above-mentioned calculated resultclValue with
Know that isotopic standard value (SMOC) is corrected, obtains final δ37Cl value:WhereinFor the isotopic ratio of standard substance SMOC.
The measurement result of the present embodiment is as shown in the table:
| Sample number into spectrum | Pendulous frequency | δ37Cl'[‰] | Precision [‰] |
| M354 | 7 | -0.02 | ±0.11 |
| TWS015 | 7 | -0.68 | ±0.44 |
| S133 | 6 | 2.43 | ±0.36 |
Claims (5)
1. the purification and analysis method of chlorine isotope in a kind of complex matrices sample, characterized by the following steps:
A, the removal of organic matter and sample cleanup in sample:
Phase solid phase extraction column is negated, solid-phase extraction column is activated with solvent, sample solution is then passed through into activation
Reverse phase solid phase extraction pillar afterwards, flow control is in 2-10mL/min；
B, the removal of inorganic chaff interferent and separating-purifying in sample:
B-1, the signal trigger device that ion chromatograph is arranged, trigger chromatograph in the period of setting and collect sample,
Installation fraction collector is exported in instrument detection cell, and is associated with signal trigger device, in fixed reservation period
Carry out the collection of high pure sample；
B-2, selection ion chromatographic separation column, prepare eluent solution (NaOH or Na2CO3\NaHCO3Solution), adjustment suppressor suppression
Electric current processed is greater than the 10-50mA or more of corresponding eluent concentration recommendation, carries out gradient elution；
B-3, the solution for obtaining step A are evaporated by loading after filtering with microporous membrane according to the triggering of the appearance time section of chloride ion
Divide collector to collect sample, needs repeatedly to collect and merge if sample chloride ion content is lower；
B-4, concentration: the sample of collection is baked to removal part moisture content on hot plate；
B-5, distillate is crossed to caesium cation exchange resin column Cs column, obtains High Purity Caesium Chloride solution；
C, thermal ionization mass spectrometry (tims) measurement and correction: above-mentioned High Purity Caesium Chloride solution is coated on the graphite of thermal ionization mass spectrometer and carries out heat
Ionization mass spectrometry test, obtains final δ37Cl' value.
2. according to claim 1 in a kind of complex matrices sample chlorine isotope purification and analysis method, it is characterised in that:
The solvent is pure water or methanol and pure water, and when solvent is methanol and pure water, the volume of pure water be 5 times of methanol volume and with
On, guarantee that the methanol on solid-phase extraction column is substituted completely.
3. according to claim 1 in a kind of complex matrices sample chlorine isotope purification and analysis method, it is characterised in that:
In the step B-2, ion chromatographic separation column used is greater than the chromatographic column type of 350ueq/column using column capacity.
4. according to claim 1 in a kind of complex matrices sample chlorine isotope purification and analysis method, it is characterised in that:
The aperture of miillpore filter is 0.22 μm in the step B-3.
5. according to claim 1 in a kind of complex matrices sample chlorine isotope purification and analysis method, it is characterised in that:
The connection type of the chromatographic column and suppressor and fraction collector are as follows: ion chromatography column outlet connects suppressor leacheate import,
Leacheate outlet connects ion chromatograph conductance pond, and conductance cell outlet connects fraction collector, and suppressor regenerated liquid entrance is infused by peristaltic pump
Enter pure water, the outlet of suppressor regenerated liquid is exhausted directly at waste liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910560974.8A CN110398557A (en) | 2019-06-26 | 2019-06-26 | The purification and analysis method of chlorine isotope in a kind of complex matrices sample |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910560974.8A CN110398557A (en) | 2019-06-26 | 2019-06-26 | The purification and analysis method of chlorine isotope in a kind of complex matrices sample |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110398557A true CN110398557A (en) | 2019-11-01 |
Family
ID=68323481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910560974.8A Pending CN110398557A (en) | 2019-06-26 | 2019-06-26 | The purification and analysis method of chlorine isotope in a kind of complex matrices sample |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110398557A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101718753A (en) * | 2009-11-10 | 2010-06-02 | 浙江大学 | Ion chromatography single-pump column switching system |
| CN103983685A (en) * | 2014-05-30 | 2014-08-13 | 中国地质科学院水文地质环境地质研究所 | Low-temperature conversion and determination method of chlorine isotopes in chloro herbicide |
| CN103983686A (en) * | 2014-05-30 | 2014-08-13 | 中国地质大学（北京） | Low-temperature conversion and measurement method of chlorine isotope in chlorohydrocarbon |
-
2019
- 2019-06-26 CN CN201910560974.8A patent/CN110398557A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101718753A (en) * | 2009-11-10 | 2010-06-02 | 浙江大学 | Ion chromatography single-pump column switching system |
| CN103983685A (en) * | 2014-05-30 | 2014-08-13 | 中国地质科学院水文地质环境地质研究所 | Low-temperature conversion and determination method of chlorine isotopes in chloro herbicide |
| CN103983686A (en) * | 2014-05-30 | 2014-08-13 | 中国地质大学（北京） | Low-temperature conversion and measurement method of chlorine isotope in chlorohydrocarbon |
Non-Patent Citations (9)
| Title |
|---|
| YEVGENI ZAKON 等: "37Cl/35Cl isotope ratio analysis in perchlorate by ion chromatography/multi collector -ICPMS: Analytical performance and implication for biodegradation studies", 《CHEMOSPHERE》 * |
| 侯晓虹 等: "《环境污染物分析》", 31 January 2017, 中国建材工业出版社 * |
| 刘肖 等: "利用AutoPrep离子色谱技术实现复杂基体样品中重稀土元素的分离和制备", 《岩矿测试》 * |
| 刘肖 等: "利用谱睿(Pre)在线样品前处理技术检测高碳酸盐基体中阴离子", 《岩矿测试》 * |
| 史碧波 等: "《现代食品检测技术实训教程》", 30 June 2016, 武汉大学出版社 * |
| 李崇瑛 等: "新型固相萃取-离子色谱在线联用技术测定水中F-,Cl-,NO3-,SO42-", 《成都理工大学学报(自然科学版)》 * |
| 李艳平 等: "海洋沉积物中孔隙水的氯同位素测量方法研究", 《高校地质学报》 * |
| 杨广峤 等: "离子色谱法同时测定饮用水中F-、Cl-、NO3-和SO42-", 《供水技术》 * |
| 章骅 等: "双系统离子色谱同时测定饮用水中氨氮、亚硝酸盐和硝酸盐的含量", 《中国食品卫生杂志》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rouxel et al. | Natural variations of Se isotopic composition determined by hydride generation multiple collector inductively coupled plasma mass spectrometry | |
| Rao et al. | Determination of antibiotics in aquatic environment by solid-phase extraction followed by liquid chromatography–electrospray ionization mass spectrometry | |
| Erdoğan et al. | Determination of inorganic arsenic species by hydride generation atomic absorption spectrometry in water samples after preconcentration/separation on nano ZrO2/B2O3 by solid phase extraction | |
| CN102520084B (en) | Method for determining trace nitrogen-containing disinfection by-product dimethyl nitrosamine in water | |
| Lintschinger et al. | The analysis of antimony species by using ESI-MS and HPLC-ICP-MS | |
| Zheng et al. | Antimony speciation in environmental samples by using high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry | |
| Li et al. | A sequential solid phase microextraction system coupled with inductively coupled plasma mass spectrometry for speciation of inorganic arsenic | |
| Şahan et al. | An on-line preconcentration/separation system for the determination of bismuth in environmental samples by FAAS | |
| Liu et al. | Determination of ultra-trace Pt, Pd and Rh in seawater using an off-line pre-concentration method and inductively coupled plasma mass spectrometry | |
| Li et al. | Separation and preconcentration of Se (IV)/Se (VI) species by selective adsorption onto nanometer-sized titanium dioxide and determination by graphite furnace atomic absorption spectrometry | |
| Serrano et al. | Fullerenes as sorbent materials for benzene, toluene, ethylbenzene, and xylene isomers preconcentration | |
| Zhu et al. | Solid phase extraction of trace copper in water samples via modified corn silk as a novel biosorbent with detection by flame atomic absorption spectrometry | |
| Smith Jr et al. | Ion chromatography | |
| Zheng et al. | Dual silica monolithic capillary microextraction (CME) on-line coupled with ICP-MS for sequential determination of inorganic arsenic and selenium species in natural waters | |
| Zheng et al. | Novel bimodal porous N-(2-aminoethyl)-3-aminopropyltrimethoxysilane-silica monolithic capillary microextraction and its application to the fractionation of aluminum in rainwater and fruit juice by electrothermal vaporization inductively coupled plasma mass spectrometry | |
| Cui et al. | The speciation analysis of iodate and iodide in high salt brine by high performance liquid chromatography and inductively coupled plasma mass spectrometry | |
| CN101711975B (en) | Method for preparing iron ion imprinted silica gel | |
| Ketterer | Determination of rhenium in groundwater by inductively coupled plasma mass spectrometry with on-line cation exchange membrane sample cleanup | |
| de Carvalho et al. | Determination of europium isotope ratios in natural waters by MC-ICP-MS | |
| CN107490647B (en) | Method for quantitatively detecting organophosphorus pesticide chlorpyrifos in ambient air | |
| CN110398557A (en) | The purification and analysis method of chlorine isotope in a kind of complex matrices sample | |
| CN102944635B (en) | Method for determining tris (2,3-dibromopropyl) phosphate content of water | |
| An et al. | Uptake and speciation of inorganic arsenic with cellulose fibre coated with yttrium hydroxide layer as a novel green sorbent | |
| Chandrasekaran et al. | On-line speciation of inorganic arsenic in natural waters using polyaniline (PANI) with determination by flow injection-hydride generation-inductively coupled plasma mass spectrometry at ultra-trace levels | |
| Ikedo et al. | Selective and simultaneous determination of phosphate and silicate ions in leaching process waters for ceramics glaze raw materials of narutal origin by ion-exclusion chromatography coupled with UV-detection after postcolumn derivatization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191101 |
|
| RJ01 | Rejection of invention patent application after publication |