CN103969377A - Method for detecting trace ammonium ions in complicated sample on line through ion chromatography - Google Patents
Method for detecting trace ammonium ions in complicated sample on line through ion chromatography Download PDFInfo
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- CN103969377A CN103969377A CN201410193786.3A CN201410193786A CN103969377A CN 103969377 A CN103969377 A CN 103969377A CN 201410193786 A CN201410193786 A CN 201410193786A CN 103969377 A CN103969377 A CN 103969377A
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Abstract
The invention discloses a method for detecting trace ammonium ions in a complicated sample on line through ion chromatography. A system comprises a steel gas bottle, a liquid conveying pump, a six-way valve, a ten-way valve, a quantification ring, a protection column, an analysis column, a suppressor, a conductivity detector, a self-made degassing device, a self-made enrichment column and a waste liquid bottle, wherein a sample injector is connected with the six-way valve; the six-way valve is connected with the self-made degassing device and is connected with the steel gas bottle and the ten-way valve respectively; the ten-way valve is connected with the quantification ring and the self-control enrichment column and is also connected with the liquid conveying pump and the protection column respectively; the analysis column, the suppressor, the conductivity detector and the waste liquid bottle are connected behind the protection column in sequence. The system is high in generality and easy to implement; furthermore, the degassing device and the enrichment column which are used in the system are self-made, are low in cost and are readily available; the operation cost of the system is lower, and the system is easy to implement; furthermore, the automation degree is high, and the application range is wide.
Description
Technical field
The present invention relates to a kind of chromatography of ions valve switched system, specifically, is the method for the ammonium ion of trace in the online detection of complex sample of a kind of chromatography of ions, can realize the online detection to ammonium ion in complex sample.
Technical background
NH
4 +be the important composition composition of the circulation-nitrogen cycle of occurring in nature maximum, be extensively present in the each field of nature.As nutriment, compare NO
3 -, NH
4 +more easily be absorbed and used by plants, still, excessive NH in aqueous solution
4 +existence by promoting the eutrophication process of water body, impel phytoplankton bloom, to such an extent as to dissolved oxygen DO in water consumed in a large number, cause the mass mortality of the animals such as fishes and shrimps.At present, NH
4 +be listed in the significant ion of body eutrophication.Therefore, NH
4 +quantitative detection received increasing concern.Because NH
4 +itself does not have uv absorption, is not suitable for atomic spectrum method yet, and therefore traditional detection method is to adopt derivative reagent to NH
4 +carry out derivatization, then utilize the methods such as ultraviolet, fluorescence, chemiluminescence to detect.Although the method can meet to a certain extent to NH
4 +the demand detecting, but operation steps complexity is time-consuming, and need extra derivative reagent, in the time that sample substrate is comparatively complicated, be easily disturbed.
There is bibliographical information that sample is carried out to basification, make NH
4 +with NH
3form see through degassing film, use derivative spectrophotometric method at the opposite side of degassing film
[1,2]or NH
3selective probe
[3]detect NH in sample
4 +content.Avoid to a certain extent complex sample matrix to spectrophotometric method or NH though use degassing film material
4 +the interference of selective probe, but still there is the pollution problem to degassing film.
Chromatography of ions is present analysis ionic substance effective method the most, and the contribution of its maximum aspect cation detection is exactly to NH
4 +detection.But, as water-soluble sample substrate complexity and NH
4 +concentration when lower, the application of chromatography of ions is just limited by very large.There is bibliographical information to use the method for chromatography of ions valve switching to trace NH under high base status
4 +detect
[4], cost is low and automaticity is high, but the method needs different pretreatment columns and different valve handover schemes to different samples, and versatility is poor.The present invention utilizes self-control degasser and enriching column to set up a set of chromatography of ions valve switched system, can be to the trace NH in different complex matrices samples
4 +detect online, without sample pre-treatments.In this system valve handoff procedure, there is the participation of gas, it is simplified to the analysis that can be used for gaseous sample, expanded the range of application of chromatography of ions.
List of references
1.M.T.Oms,A.Cerda,A.Cladera,V.Cerda,R.Forteza,Gas diffusion techniques coupled sequentialinjection analysis for selective determination of ammonium.Analytica Chimica Acta318,251-260(1996).
2.M.-J.Almendral-Parra,
Alonso-Mateos,M.-S.Fuentes-Prieto,A gas diffusion technique coupled withflow injection systems.Optimization of the process in its application to the fluorimetric determination ofammonium in water samples.Journal of fluorescence20,55-65(2010).
3.S.R.Ash.(Ammonia sensor and system for use,US08409864,2013).
4.Y.Huang,S.-f.Mou,J.M.Riviello,Determination of ammonium in seawater by column-switching ionchromatography.Journal of Chromatography A868,209-216(2000).
Summary of the invention
The present invention has set up the chromatography of ions valve switched system of volatile ion in a kind of Direct Analysis complex sample online, avoid loaded down with trivial details time-consuming sample pre-treatments step, in valve handoff procedure, there is the participation of nitrogen, therefore this system can be used for the mensuration of gaseous sample, the range of application that has expanded chromatography of ions, the present invention is achieved through the following technical solutions:
For detection of an ion chromatographic column switched system for volatile ion in solution, described system comprises gas bomb, infusion pump, six-way valve, ten-way valve, quantitative ring, guard column, analytical column, rejector, electric conductivity detector, self-control degasser, self-control enriching column and waste liquid bottle.Injector is connected with six-way valve; on six-way valve, connect self-control degasser; six-way valve is connected with gas bomb and ten-way valve respectively; on ten-way valve, connect quantitatively ring and self-control enriching column; ten-way valve is connected with infusion pump respectively; ten-way valve is connected with guard column, linking parsing post, rejector, electric conductivity detector and waste liquid bottle successively after described guard column.
As improving further, self-control degasser of the present invention is the obturator that comprises import and outlet, and how empty sieve plate is contained in its inside, the gas dispersion that gas bottle can be provided more even.
As improving further, in self-control enriching column post of the present invention, be filled with polymer beads, its function is to utilize the solution of adsorption to absorb the zwitterion in gas, reaches the effect of enrichment.
The present invention also provides a kind of detection method of the ion chromatographic column switched system for detection of volatile ion in solution, described method comprise baseline collection, object ion remove with enrichment, enrichment after four steps of transfer, stratographic analysis of ion, concrete steps are as follows:
(1), the drafting of baseline: leacheate is continuously delivered to above-mentioned ion chromatographic column switched system by infusion pump, makes system reach equilibrium state, and conductance signal is detected by electric conductivity detector and got off to draw out corresponding figure line by computer record;
(2), removing and enrichment of object ion: sample and auxiliary reagent are by sample introduction to self-control degasser, and the gas in gas bomb carries out enrichment by the ion band that changes gas in self-control degasser into making enriching column by oneself;
(3), the transfer of ion after enrichment: the solution that infusion pump is carried elutes the ion in self-control enriching column to be delivered in quantitative ring;
(4), the separation of chromatogram: infusion pump 14 carries leacheate that the measured ion for the treatment of in quantitatively encircling is delivered to guard column, analytical column, rejector, electric conductivity detector successively, finally enters waste liquid bottle;
Beneficial effect of the present invention is as follows:
1. versatility is good.The chromatography of ions valve switched system that the present invention sets up utilizes NH4+ volatile feature under alkali condition, in conjunction with self-control degasser and self-control enriching column, be not confined to a kind of valve handover scheme and be only applicable to the sight of simple sample matrix, the method is applicable to trace NH in different complex sample matrix
4 +detection,
2. easy to implement.The present invention does not need to use expensive degassing film material, the interference of having avoided the mensuration of the pollution of complex sample matrix to membrane material to bring, and in the present invention, degasser used and enriching column are all self-control, cheap and easy to get, make running cost of the present invention lower, easy to implement and automaticity is high.
3. applied range.The present invention is except being applicable to NH in fluid sample
4 +detection, equally also can be used for other volatilization or half volatile material in fluid sample.In addition, the chromatography of ions valve switched system that the present invention is set up is simplified, and removes self-control enriching column part, and the present invention also can be used for the detection of ammonium root in gaseous sample, has expanded the range of application of chromatography of ions.Expand the range of application of chromatography of ions.
Brief description of the drawings
Fig. 1 is the valve switched system stream schematic diagram that the present invention sets up;
In Fig. 1,1-nitrogen cylinder, 2-six-way valve, 3-injector, 4-makes degasser by oneself, 5-ten-way valve, 6-makes enriching column by oneself, and 7-quantitatively encircles, and 8,14-infusion pump, 9-waste liquid bottle, 10-electric conductivity detector, 11-rejector, 12-analytical column, 13-guard column;
Fig. 2 is the NH of 50ppb concentration under system of the present invention
4 +standard solution and the contrast collection of illustrative plates of deionized water;
Fig. 3 is the chromatographic resolution collection of illustrative plates of actual seawater sample under system of the present invention, NH
4 +concentration be 1.89ppm.
Embodiment:
Below by specific embodiment, technical scheme of the present invention is described in further detail:
The following stated is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
The detection of ammonium root in seawater
Fig. 1 is the schematic diagram of the chromatography of ions valve switched system set up of the present invention, and this system comprises gas bomb 1, infusion pump 8,14, six-way valve 2, ten-way valve 5, quantitatively encircles 7, guard column 13, analytical column 12, rejector 11, electric conductivity detector 10, self-control degasser 4, self-control enriching column 6 and waste liquid bottle 9.Wherein injector 3 is connected with six-way valve 2; on six-way valve 2, connect self-control degasser 4; six-way valve 2 is connected with gas bomb 1 and ten-way valve 5 respectively; on ten-way valve 5, connect quantitatively ring 7 and self-control enriching column 6; ten-way valve 5 is connected with infusion pump 8,14 respectively; ten-way valve 5 is connected with guard column 13, linking parsing post 12, rejector 11, electric conductivity detector 10 and waste liquid bottle 9 successively after described guard column 13.Alkaline solution and sample feeding are arrived after self-control degasser 4, open the valve of nitrogen cylinder 1 and switch six-way valve 2, under the effect of nitrogen, sample and alkaline solution fully mix, NH
4 +just enter into self-control enriching column 6 and got off by enrichment with nitrogen with the form of NH3, switching ten-way valve 5, infusion pump 8 carry acid solution by self-control enriching column 6 NH
4 +bring to quantitative ring 7, again switch ten-way valve 5, infusion pump 14 carries leacheate by the NH quantitatively encircling in 7
4 +be delivered to successively guard column 13, separating column 12, rejector 11, electric conductivity detector 10, be finally drained into waste liquid bottle 9.
Concrete steps are as follows:
The configuration of standard solution: take a certain amount of ammonium chloride analytical reagent, the standard reserving solution of configuration 1000mg/L is preserved at 4 DEG C, and standard reserving solution is diluted to desired concn by the used time.
Removing and enrichment of ammonium root: respectively by the sodium hydroxide solution of 100 μ L50% and 2mL standard solution (0.05-10ppm) sample introduction in degasser 4, switch six-way valve 2, gas bomb 1 provides nitrogen that ammonia is brought into the interior enrichment of self-control enriching column 6.
The transfer of ammonium root: after 10 minutes, switch ten-way valve 5, infusion pump 8 carries the pyrovinic acid solution of 45mM that the ammonium root of self-control enriching column 6 interior enrichments is transferred to quantitative ring 7.
The compartment analysis of ammonium root: again switch ten-way valve 5, ammonium root in 7 is brought guard column 13 into the pyrovinic acid leacheate that infusion pump 14 is carried 45mM successively, separating column 12 carries out Analyze & separate, draws NH by quantitatively encircling
4 +typical curve.Fig. 2 is the standard solution of 50ppbNH4+ and the chromatogram of deionized water, shows that the method has higher detection sensitivity and lower detectability.
The sodium hydroxide solution of 100 μ L50% and 2mL seawater sample sample introduction, in degasser 4, are repeated to above step.
Fig. 3 is seawater sample chromatogram, has substantially eliminated high concentration Na completely
+interference.
Finally, it is also to be noted that, what more than enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. for detection of an ion chromatographic column switched system for volatile ion in solution, it is characterized in that, described system comprises gas bomb (1), infusion pump (8, 14), six-way valve (2), ten-way valve (5), quantitatively ring (7), guard column (13), analytical column (12), rejector (11), electric conductivity detector (10), self-control degasser (4), self-control enriching column (6) and waste liquid bottle (9), injector (3) is connected with six-way valve (2), the upper self-control degasser (4) that connects of six-way valve (2), six-way valve (2) is connected with gas bomb (1) and ten-way valve (5) respectively, ten-way valve (5) is upper to be connected quantitatively ring (7) and makes enriching column (6) by oneself, ten-way valve (5) respectively with infusion pump (8, 14) connect, ten-way valve (5) is connected with guard column (13), linking parsing post (12) successively after described guard column (13), rejector (11), electric conductivity detector (10) and waste liquid bottle (9).
2. the ion chromatographic column switched system for detection of volatile ion in solution according to claim 1, is characterized in that, the obturator of described self-control degasser (4) for comprising import and outlet, and how empty sieve plate is contained in its inside.
3. the ion chromatographic column switched system for detection of volatile ion in solution according to claim 1, is characterized in that, in described self-control enriching column (6) post, is filled with polymer beads.
4. the detection method of the ion chromatographic column switched system for detection of volatile ion in solution according to claim 1, it is characterized in that, described method comprise baseline collection, object ion remove with enrichment, enrichment after four steps of transfer, stratographic analysis of ion, concrete steps are as follows:
(1), the drafting of baseline: leacheate is continuously delivered to above-mentioned ion chromatographic column switched system by infusion pump (14), make system reach equilibrium state, conductance signal is detected and is got off to draw out corresponding figure line by computer record by electric conductivity detector (10);
(2), the removing and enrichment of object ion: sample and auxiliary reagent are by sample introduction to self-control degasser (4), and the gas in gas bomb (1) carries out enrichment by making the ion band that changes gas in degasser (4) into by oneself to making enriching column (6) by oneself;
(3), the transfer of ion after enrichment: the solution that infusion pump (8) is carried elutes and is delivered in quantitative ring (7) make the interior ion of enriching column (6);
(4), the separation of chromatogram: infusion pump (14) carries leacheate will treat that measured ion is delivered to guard column (13), analytical column (12), rejector (11) and electric conductivity detector (10) successively; finally be discharged in waste liquid bottle (9), conductance signal is collected and is processed by computer.
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| CN201410193786.3A CN103969377B (en) | 2014-05-08 | 2014-05-08 | The method of the ammonium ion of trace in chromatography of ions on-line checking complex sample |
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| CN201410193786.3A CN103969377B (en) | 2014-05-08 | 2014-05-08 | The method of the ammonium ion of trace in chromatography of ions on-line checking complex sample |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110178026A (en) * | 2016-09-28 | 2019-08-27 | 埃沃赛普私人有限责任公司 | System for carrying out chromatography to sample |
| CN110178027A (en) * | 2016-09-28 | 2019-08-27 | 埃沃赛普私人有限责任公司 | The chromatography concentrated again using low pressure double gradient |
| CN112946120A (en) * | 2021-02-01 | 2021-06-11 | 西安奕斯伟硅片技术有限公司 | Ion concentration detection equipment and method |
Citations (4)
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|---|---|---|---|---|
| US4348359A (en) * | 1980-07-16 | 1982-09-07 | Mitsubishi Chemical Industries, Limited | Device for determining various types of trace nitrogen |
| JPH10104218A (en) * | 1996-09-27 | 1998-04-24 | Shimadzu Corp | Ammonia and anion analyzing chromatograph |
| CN101059465A (en) * | 2007-06-12 | 2007-10-24 | 北京大学 | Ammonia test method and device |
| CN103760277A (en) * | 2013-12-31 | 2014-04-30 | 江苏有能电力自动化有限公司 | Degassing device |
-
2014
- 2014-05-08 CN CN201410193786.3A patent/CN103969377B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4348359A (en) * | 1980-07-16 | 1982-09-07 | Mitsubishi Chemical Industries, Limited | Device for determining various types of trace nitrogen |
| JPH10104218A (en) * | 1996-09-27 | 1998-04-24 | Shimadzu Corp | Ammonia and anion analyzing chromatograph |
| CN101059465A (en) * | 2007-06-12 | 2007-10-24 | 北京大学 | Ammonia test method and device |
| CN103760277A (en) * | 2013-12-31 | 2014-04-30 | 江苏有能电力自动化有限公司 | Degassing device |
Non-Patent Citations (3)
| Title |
|---|
| A.M.Y. JABER等: "Determination of ammonium and organic bound nitrogen by inductively coupled plasma emission spectroscopy", 《TALANTA》, vol. 78, 31 December 2009 (2009-12-31), pages 1298 - 1302, XP026035215, DOI: 10.1016/j.talanta.2009.01.060 * |
| STUART W. GIBB等: "Analysis of ammonia and methylamines in natural waters by flow injection gas diffusion coupled to ion chromatography", 《ANALYTICA CHIMICA ACTA》, vol. 316, 31 December 1995 (1995-12-31), pages 291 - 304 * |
| YUAN HUANG等: "Determination of ammonium in seawater by column-switching ion chromatography", 《JOURNAL OF CHROMATOGRAPHY A》, vol. 868, 31 December 2000 (2000-12-31), pages 209 - 216, XP004186600, DOI: 10.1016/S0021-9673(99)01195-4 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110178026A (en) * | 2016-09-28 | 2019-08-27 | 埃沃赛普私人有限责任公司 | System for carrying out chromatography to sample |
| CN110178027A (en) * | 2016-09-28 | 2019-08-27 | 埃沃赛普私人有限责任公司 | The chromatography concentrated again using low pressure double gradient |
| CN112946120A (en) * | 2021-02-01 | 2021-06-11 | 西安奕斯伟硅片技术有限公司 | Ion concentration detection equipment and method |
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