CN103091414B - Ion chromatography-online pretreatment analysis system for determining heavy metal chromium (VI) in donkey-hide gelatin - Google Patents
Ion chromatography-online pretreatment analysis system for determining heavy metal chromium (VI) in donkey-hide gelatin Download PDFInfo
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Abstract
The invention relates to a use system of chemical apparatus analysis, and particularly to an ion chromatography-online pretreatment analysis system for determining heavy metal chromium (VI) in donkey-hide gelatin. A simply processed donkey-hide gelatin sample passes through a polymer reversed-phase column, interfering substances in the donkey-hide gelatin are removed online under an alkali condition, then the processed sample solution is enriched in an enriching pipe by an ion chromatography-valve switching technology and is separated through an anion exchange chromatographic column, and then post-column derivatization visible light detection is carried out. As the ion chromatography-online pretreatment analysis system adopts an ion chromatography-online pretreatment analysis technology, fussy sample pre-treatment processes can be reduced and even omitted, the sample analysis time is shortened, and the detection efficiency is enhanced. By virtue of the post-column derivatization visible light detection, no other interfering ions appear and the selectivity is good. The ion chromatography-online pretreatment analysis system can be suitable for a series of other problems of separation and detection on ions in complex matrixes, and has a high practical value.
Description
Technical field
The use system, particularly one that the present invention relates to a kind of chemical apparatuses analysis relate to chromatography of ions-online Preprocessing system that heavy metal chromium in donkey-hide gelatin (VI) is measured.
Background technology
Chromatography of ions, as modern analysis means, is widely used in the detection of various ionic compounds.In complex sample, contain various ions, but conventionally just wherein several of our object ion sometimes due to sample substrate complexity, and can impact to the mensuration of object ion, conventionally need to consume longer time for sample pretreatment.Adopt chromatography of ions-online preconditioning technique to address this problem preferably.
Chromium (VI) has strong carcinogenic and mutagenicity, because it is more easily absorbed by the body, and large 100 times than chromium (III) of its toxicity.Long Term Contact chromium (VI), exists potential harmfulness to the mankind's health.In the last few years, " false donkey-hide gelatin " event was exposed again and again, the donkey-hide gelatin of poor quality that some illegal businessmans adopt the materials inferior such as leather-solid waste to pretend to be donkey hide to make.Because leather-solid waste can add a lot of potassium dichromates and sodium bichromate in tanning, dyeing course, therefore often the content of heavy metal chromium can severe overweight for the donkey-hide gelatin that uses it to make.Therefore, set up the method for quantitatively determining of heavy metal chromium in donkey-hide gelatin (VI), to specification donkey-hide gelatin market and ensure food safety significant.
There is no report for the quantitative measurement of heavy metal chromium in donkey-hide gelatin (VI) at present.What in donkey-hide gelatin, total chromium mensuration had been reported has flame atomic absorption method, graphite oven atomic absorption and inductively coupled plasma mass spectroscopy.Because these three kinds of methods can only be measured total chrome content, can not detect chromium (VI) content, there is certain defect in its practical significance.In other matrix, the method for measuring chromium (VI) mainly contains the methods such as direct spectrophotometry, the chromatography of ions, ion exchange column separation-inductively coupled plasma mass spectrometry and chromatography of ions-inductively coupled plasma mass spectrometry.Because spectrophotometric method precision is not high, ion exchange column separation-inductively coupled plasma mass spectrometry complex operation, chromatography of ions-inductively coupled plasma mass spectrometry pre-treatment trouble, instrument costliness, according to feasibility and replicability, intend the Research Thinking with reference to the chromatography of ions, heavy metal chromium in donkey-hide gelatin (VI) is quantitatively detected.
Summary of the invention
The present invention, just for the deficiencies in the prior art part, provides the mensuration of a kind of chromatography of ions-online preconditioning technique for donkey-hide gelatin heavy metal chromium (VI), shortens time for sample pretreatment, has improved detection efficiency.
Concrete technical scheme of the present invention is as follows:
The present invention is the chromatography of ions that in a kind of donkey-hide gelatin sample, heavy metal chromium (VI) is measured-online Preprocessing system, allow the donkey-hide gelatin sample that simple process is crossed pass through a polymkeric substance reversed-phase column, under alkali condition, the online interfering material of removing in donkey-hide gelatin, then pass through ion chromatography-valve handoff technique by the sample solution of processing enrichment in enrichment pipe, separate post-column derivation reaction visible detection through anion-exchange column.
Chromium of the present invention (VI), by post-column derivation visible detection, is not subject to the interference of other ion, and selectivity is strong.
System of the present invention can be reduced or remitted loaded down with trivial details sample pretreatment process, shortens sample analysis time, improves detection efficiency, goes for the problem that series of complex matrix intermediate ion ON-LINE SEPARATION detects, and has very high practical value.
The present invention is a kind of chromatography of ions-online Preprocessing system, for the mensuration of donkey-hide gelatin heavy metal chromium (VI).Chromium (VI) is strong oxidizing property under sour environment, and being easily reduced property material is reduced to chromium (III), and therefore the extraction of sample should be carried out under alkali condition.The principal ingredient of donkey-hide gelatin is protein and catabolite and some other reducing substances, and these compositions can bring certain influence to the separation determination of chromium (VI), and the not treated ion chromatograph that directly enters can cause damage to pillar.So before chromatographic resolution, conventionally will spend a large amount of time carries out sample pre-treatments.First the present invention allows donkey-hide gelatin sample by a polymkeric substance reversed-phase column, under alkali condition, remove online the interfering material in donkey-hide gelatin, and by chromium (VI) enrichment in enrichment pipe, separate again post-column derivation reaction visible detection through anion-exchange column.The present invention has adopted a kind of online pretreated method, has greatly shortened analysis time, has improved analysis efficiency.
Chromium of the present invention (VI), by post-column derivation visible detection, is not subject to the interference of other interfering material, and selectivity is strong, and analytical instrument is cheap compared with Other Instruments, has very high practical value.
Ion chromatography-valve handoff technique provided by the invention, can be used for the mensuration of heavy metal chromium in donkey-hide gelatin (VI).When all substances in sample are in the time that six-way valve enters pre-treatment chromatographic column, in sample, interfering material is retained and other ion flows in the enrichment pipe of ten-way valve subsequently and carries out enrichment, enrichment a period of time is until all after measured ion all flows out in sample, switched the ion in enriching column is poured and in analytical column below, separates detection by ten-way valve.Pre-treatment post above changes leacheate into acetonitrile by quaternary gradient pump, pre-treatment post is rinsed, for next sample preparation ready.
Tool of the present invention has the following advantages:
1. the present invention adopts chromatography of ions-online Preprocessing technology, can reduce or remit loaded down with trivial details sample pretreatment process, shortens sample analysis time, improves detection efficiency.
2. adopt post-column derivation visible detection, go out peak without other interfering ions, selectivity is good.
3. the present invention can also be applicable to other series of complex matrix intermediate ion and separate the problem detecting, and has very high practical value.
Brief description of the drawings
Fig. 1 is that sample loads schematic diagram;
Fig. 2 is the online pre-service of sample and enrichment schematic diagram;
Fig. 3 is that sample separation and pretreatment column clean schematic diagram;
Fig. 4 is sample analysis and system balancing schematic diagram;
Fig. 5 is the standard model chromatogram of chromatography of ions-online Preprocessing system;
Fig. 6 is the donkey-hide gelatin sample mark-on chromatogram of chromatography of ions-online Preprocessing system;
In Fig. 1,2,3,4, mark is:
1-injection port; 2-quantitatively encircles; The online pre-eluent of 3-is processed post; 4-quaternary gradient pump; The online pretreatment column of 5-; 6-enrichment pipe; 7-ion chromatograph carries pump; 8-guard column 1; 9-guard column 2; 10-analytical column; 11-reaction woollen yarn knitting pipe; 12-infusion pump; 13-variable wavelength UV-vis detector; 14-six-way valve; 15-ten-way valve; 16-waste liquid.
Embodiment
The present invention utilizes Dionex ICS-2100 ion chromatograph to join EG leacheate generator, Dionex Ultimate 3000 variable wavelength UV-vis detectors, Dionex Ultimate 3000 quaternary gradient pumps, Shimadzu LC-9A infusion pump to realize the mensuration of heavy metal chromium in donkey-hide gelatin (VI).Pre-treatment post, guard column 1, guard column 2, analytical column etc. are linked in sequence on Dionex ICS-2100 ion chromatograph.
The operation steps of chromatography of ions-online Preprocessing system that heavy metal chromium in donkey-hide gelatin (VI) is measured is as follows:
(1) sample loads: as Fig. 1, sample injects quantitatively ring, and now six-way valve is in Load state, and ten-way valve is in A condition.Quaternary gradient pump provides the online pre-online pretreatment column of eluent balance, and ion chromatograph carries pump leacheate balanced protection post 1, guard column 2 and analytical column are provided;
(2) the online pre-service of sample and enrichment: as Fig. 2, switching six-way valve makes it in Inject state, online pre-eluent pours online pretreatment column by the sample in quantitatively encircling and processes, meanwhile, ten-way valve switches to B state, and the sample solution after treatment flowing out from online pretreatment column can be collected in the enrichment pipe ten-way valve;
(3) sample separation and pretreatment column clean: as Fig. 3, all collect and enter in enrichment pipe until the solution after sample pre-treatments, switch ten-way valve and enter A condition, the solution in enrichment pipe is poured in guard column and analytical column and carries out compartment analysis, now computer starts acquisition testing signal; Meanwhile, six-way valve switches back Load state, and quaternary gradient pump provides online pre-column cleaning fluid to clean online pretreatment column;
(4) sample analysis and system balancing: as Fig. 4, the determinand flowing out from analytical column reacts with derivative liquid, is that 545nm place produces absorption at wavelength, thereby detects.After a period of time, quaternary gradient pump is changed to the online pre-online pretreatment column of eluent balance again, for next sample introduction ready.
The detection of standard sample and actual sample:
Instrument: Dionex ICS-2100 ion chromatograph is joined EG leacheate generator, Dionex Ultimate 3000 variable wavelength UV-vis detectors, Dionex Ultimate 3000 quaternary gradient pumps, Shimadzu LC-9A infusion pump;
Sample: potassium dichromate, NaOH, acetonitrile, methyl alcohol, sulfuric acid, 1,5-diphenylcarbazide;
Online pretreatment column: Dionex IonPac NG1 (4*50mm) post;
Online pre-eluent: 30mM/L KOH;
Online pre-eluent is processed post: Dionex IonPac ATC-HC (9*75mm) post;
Online pre-column cleaning fluid: pure acetonitrile;
Online pretreatment fluid flow velocity: 0.55 mL/min;
Guard column 1:Dionex IonPac NG1 (4*50mm) post;
Guard column 2:Dionex IonPac AG19 (4*50mm) post;
Analytical column: Dionex IonPac As19 (4*250mm) anion separation column;
Leacheate: 30mM/L KOH etc. spend drip washing;
Leacheate flow velocity: 1.0 mL/min;
Derivative flow velocity: 0.5 mL/min;
Detect wavelength: 545nm;
Column temperature: 35 DEG C;
Sample size: 25mL;
Referring to Fig. 5 and Fig. 6, it is the chromatogram of object ion.
Fig. 3 is 0.08 mg/L Cr
6+standard solution chromatogram, by the chromatography of ions-online Preprocessing system proposing, Cr
6+can obtain well separating and detecting, not be subject to the interference of other ion.
Fig. 4 is donkey-hide gelatin sample mark-on 0.01 mg/L Cr
6+solution chromatogram, by the chromatography of ions-online Preprocessing system proposing, the Cr after actual sample mark-on
6+can obtain well separating and detecting, not be subject to the interference of other ion, this technology meets the requirement that actual sample detects.
Claims (3)
1. chromatography of ions-online Preprocessing system that in a donkey-hide gelatin sample, heavy metal chromium VI is measured, it is characterized in that: allow the donkey-hide gelatin sample that simple process is crossed pass through the Dionex IonPac NG1 polymkeric substance reversed-phase column of a 4*50mm, under alkali condition, the online interfering material of removing in donkey-hide gelatin, then six-way valve is switched to Inject state from Load state, ten-way valve switching state, make sample solution enrichment in enrichment pipe of processing, finally ten-way valve is switched back to original state, sample after enrichment is separated through the Dionex of 4*250mm IonPac As19 anion-exchange column, with 1, 5-diphenylcarbazide is the post-column derivation reaction visible detection of derivating agent.
2. chromatography of ions according to claim 1-online Preprocessing system, is characterized in that: chromium VI, by post-column derivation visible detection, is not subject to the interference of other ion, and selectivity is strong.
3. chromatography of ions according to claim 1-online Preprocessing system, it is characterized in that: described system can be reduced or remitted loaded down with trivial details sample pretreatment process, shorten sample analysis time, improve detection efficiency, go for the problem that series of complex matrix intermediate ion ON-LINE SEPARATION detects, there is very high practical value.
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| CN105699530A (en) * | 2016-02-26 | 2016-06-22 | 杭州飞山浩科技有限公司 | Valve switching device and method for online pretreatment of sample for determining hexavalent chromium |
| CN108169393A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | Portable high-efficiency liquid-chromatography apparatus and its application in gutter oil differentiates detection |
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