CN100529739C - Method for measuring trace amount hydrargyrum in alcoholic and acetic sample by photo-induced cold steam generation - Google Patents
Method for measuring trace amount hydrargyrum in alcoholic and acetic sample by photo-induced cold steam generation Download PDFInfo
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- CN100529739C CN100529739C CNB200510021309XA CN200510021309A CN100529739C CN 100529739 C CN100529739 C CN 100529739C CN B200510021309X A CNB200510021309X A CN B200510021309XA CN 200510021309 A CN200510021309 A CN 200510021309A CN 100529739 C CN100529739 C CN 100529739C
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Abstract
This invention relates to one new method to detect Hg trace in alcohol and vinegar samples, which is characterized by the following: needing no sample pre-process and adding any chemical agents and generating Hg cooled vapor through sample base assistant violet eradiation and guiding the Hg vapor into atom fluorescent meter for testing. The advantages are the following: a, simple method without any pre-process step; b, saving agent cost and lowering environment pollution; c, without pre-process step to realize on-line analysis and saving analysis time; d, high accuracy with low limit.
Description
Technical field:
The invention belongs to the trace analysis technical field of analytical chemistry, relate to Trace Hg method for measuring in a kind of wine, the vinegar class sample.
Background technology:
Mercury has cumulative effect in vivo.Mercury is delivered to by food chain can make in the human body that the people is caused a disease, teratogenesis, carcinogenic, and has destructive destruction to child's intelligence and to people's nervous centralis.Therefore, the mercury content in the U.S. environment protection organization prescribed water sample must not surpass 5 ng mL
-1Mercury in existing analytical technology such as the water quality is measured standard GB 7468-87, GB7469-870 and is adopted cold atom absorptiometry or spectrophotometric method respectively; The national standard (GB5009.17-85, GB5009.17-1996) of measuring mercury in the food then adopts spectrophotometric method and cold atom to absorb or atomic fluorescence spectrometry respectively.The mercury of measuring in wine or the vinegar generally is first with after the testing sample pre-service, uses cold atom absorptiometry or Cold Atomic Fluorescent Mercury spectrographic determination again.Spectrophotometric method is subject to Cu
2+Interference, complex operation, sensitivity is low.Cold atom in traditional GB5009.17-1996 method absorbs spectrophotometric and the Cold Atomic Fluorescent Mercury analysis of spectral method also will carry out sample pre-treatments.In addition, these cold atom method for generation all need reductive agent (SnCl
2Or NaBH
4) and mineral acid participate in reaction to produce simple substance mercury.These pre-treatment steps and the reductive agent that is added and mineral acid cause following shortcoming: the first, and experimental procedure is loaded down with trivial details, and it is consuming time to require great effort; The second, testing sample is increased by the probability of reagent and environmental pollution; The 3rd, NaBH
4Instability needs matching while using, and is inconvenient and increased analysis cost; The 4th, use NaBH
4Acid system is easy to be subjected to the interference of transition metal ion; The 5th, environment there is certain pollution.
Goal of the invention:
The new method that the purpose of this invention is to provide Trace Hg in a kind of highly sensitive, stable, easy, green, mensuration wine of need not chemical reagent, the vinegar class sample in view of above reason.
Technical scheme:
Wine, vinegar sample is through the steam of UV light-induced generation mercury, and after making reactant liquor that carrier gas will contain the cold steam of mercury and bring gas-liquid separator separates into argon gas then, mercury vapour enters under the drive of carrier gas and carries out assay determination in the luminoscope, the steps include:
(1) parallel 5 duplicate samples of getting are in the 25ml volumetric flask, add respectively then to be equivalent to 0,1,2,3 of mercury content in the sample, and the standard solution of 4 times of mercury is diluted to the standard series that scale is made standard addition method;
(2) go up the machine determination step
The first step, rotate T-valve by carrier gas through the photo-induced cold steam generator, peristaltic pump rotates and sample was brought in the photo-induced cold steam generator in 20 seconds; In second step, the rotation T-valve, allows sample rest on and uses UV-irradiation 20 seconds in the photo-induced cold steam generator without the photo-induced cold steam generator by carrier gas; The 3rd step, rotate T-valve and peristaltic pump rotation 35 seconds reacted solution is brought into together by photo-induced cold steam generator and current-carrying (redistilled water) by carrier gas and carries out gas-liquid separation in the gas-liquid separator, mercury vapour enters the atomic fluorescence instrument and measures under the drive of carrier gas; The 4th goes on foot, and waits for the mensuration of next standard.All these steps are all carried out under instrument and sample condition optimal conditions.
Description of drawings:
Fig. 1 is installation drawing of the present invention. It comprises a photo-induced cold steam generator (1), peristaltic pump (2), Gas-liquid separator (3), and triple valve (4).
Fig. 2 is the structural representation of photo-induced cold steam generator. By a uviol lamp 1, the stone of protection uviol lamp English sleeve pipe 2 and quartzy spiral reaction tube 3 form. In the cold steam generator that the photo-induced cold steam takes place, stone The English spiral reaction tube is to be wrapped on the quartz socket tube of protecting uviol lamp. The uviol lamp of other specification, uviol lamp Sleeve pipe, quartzy spiral reaction tube all are feasible, and the present invention finally adopts the photo-induced cold steam that cold steam generation takes place Device is the uviol lamp by 125w, and 250mm is long, diameter is the uviol lamp quartz socket tube of 15mm, 250mm Long, diameter is formed by the quartzy spiral reaction tube of 3mm.
The invention effect:
1. the present invention compares with the existing method of measuring mercury in wine, the vinegar class sample, mainly contains following characteristics/advantage: One, because strong ultraviolet light has the effect of clearing up with oxidation, the method goes on foot without any need for sample pre-treatments Suddenly, thus reduced the pollution that brings in the loss of mercury in the sample and the processing procedure; Two, saved chemical examination The agent cost, reduced pollution that environment is brought, reduced the potential sample contamination that is brought by chemical reagent; Three, Be easy to be implemented in line analysis and save the analytical test time; Four, antijamming capability is strong, and (common hydride takes place Atomic fluorescence spectrometry is vulnerable to very serious transition metal and disturbs). Antijamming capability of the present invention: 5ng/ml Standard liquid in contain 100 μ g/ml Co2+、Ni
2+Or 50 μ g/ml Cu2+The time to the mensuration of mercury not significantly The property impact; Five, overcome some other shortcoming of boron hydrohalogenic acid salt acid system, to now join such as boron hydrohalogenic acid salt instability Now use etc.; Six, the primary product behind the sample is CO2And H2O, environmentally friendly; Seven, highly sensitive, inspection Rising limit is low. Table 1 has been listed with ethanol, acetic acid and has been made matrix fill-in light refrigeration steam generation-atomic fluorometry The data such as the sensitivity when measuring mercury, detection limit.
The sensitivity of table 1. this method, detection limit
| Sample (that is reducing agent) | Coefficient correlation | Sensitivity ml ng-1 | Detection limit ng ml-1 |
| Ethanol | 0.997 | 181 | 0.07 |
| Acetic acid | 0.998 | 328 | 0.02 |
With the trace in matrix fill-in light refrigeration steam generation-atomic fluorescence spectrophotometric mensuration wine, the vinegar class sample Amount mercury, detection limit is better than minimum the limiting the quantity of of foodstuffs sanitary standard regulation, be a kind of novelty, fast, sensitive, The new method of mercury in green test wine, the vinegar class sample. The method also can with other atomic spectrometry determination (as ICP-AES, normal ICP-MS, AAS etc.) coupling.
Embodiment:
Several Chinese medicines are steep in wine from buying on the market, liquor and mature vinegar, directly measure mercury in these samples with photo-induced cold steam Generation-Atomic Fluorescence Spectrometry without any sample pre-treatments, take standard addition method to measure, and do not detect mercury.Then, adding the mercury standard solution respectively in these wine and vinegar sample makes its content reach 2 ng ml respectively
-1With 5 ng ml
-1The parallel homemade wine sample of getting 5 parts of 20ml is in the volumetric flask of 25ml, and the mercury standard solution that adds certain volume is then prepared to such an extent that concentration reaches 0,2,4,6,8 ng ml
-1The mercury standard series, operate the computer the step replicate determination 3 times according to described, the result is as shown in table 2.As can be seen, the recovery of this method can satisfy the requirement of trace analysis.
Table 2, the sample analysis result
The present invention advances a description:
For a long time, the researcher finds that ultraviolet lighting is mapped to nano-TiO
2The time can produce photohole and light induced electron, nano-TiO can be moved in light induced electron and hole under the effect of field force
2The surface.Photohole can the mineralising organism be CO
2And H
2O, the principle of Here it is photocatalysis to degrade organic matter; Light induced electron also can reduce and be adsorbed on TiO
2The heavy metal ion on surface; Light induced electron and hole also are easy to the compound heat of emitting simultaneously, so, the photocatalytic oxidation degradation organism still is that the photo catalytic reduction heavy metal ion all must add some oxygenants or reductive agent delays light induced electron and hole-recombination, thereby improve the efficient of photochemical catalytic oxidation and reduction, why Here it is will add some low molecular weight organic acids or pure reason when reduction mercury waste water.The present invention is not having TiO
2Existence under, low-molecular-weight acetate or ethanol also can reduce mercury ion.Key reaction mechanism is: acetate or ethanol can produce carbonyl free radical, hydroperoxyl radical under ultraviolet irradiation, and these free radicals can be with Hg
2+Be reduced into Hg
0And wine, vinegar class sample principal ingredient are ethanol or acetate, therefore do not need to add any chemical reagent when measuring the mercury content of these samples, only need use UV-irradiation.Key point of the present invention that Here it is.
Claims (1)
1. the method for Trace Hg in wine, the vinegar class sample takes place to measure in the photo-induced cold steam, it is characterized in that wine, vinegar class sample are through UV light-induced generation mercury vapour, after doing carrier gas and separate in gas-liquid separator with argon gas then, mercury vapour enters the atomic fluorescence instrument and carries out assay determination, the steps include:
(1) adding the mercury standard solution respectively in wine and vinegar sample makes its content reach 2ngml respectively
-1And 5ngml
-1, parallel 5 duplicate samples of getting add respectively then and are equivalent to 0,1,2,3 of mercury content in the sample in the 25ml volumetric flask, and the standard solution of 4 times of mercury is diluted to the standard series that scale is made standard addition method;
(2) go up the machine determination step
The first step, rotate T-valve by carrier gas by the photo-induced cold steam generator, peristaltic pump rotates and sample was brought in the photo-induced cold steam generator in 20 seconds; In second step, the rotation T-valve, allows sample rest on and uses UV-irradiation 20 seconds in the photo-induced cold steam generator without the photo-induced cold steam generator by carrier gas; The 3rd step, rotate T-valve and pass through the photo-induced cold steam generator by carrier gas, peristaltic pump rotated 35 seconds simultaneously, with current-carrying reacted solution was pushed into and carried out gas-liquid separation in the gas-liquid separator, and mercury vapour enters in the atomic fluorescence instrument under the drive of carrier gas and measures; The 4th goes on foot, and waits for the mensuration of next standard.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510021309XA CN100529739C (en) | 2005-07-22 | 2005-07-22 | Method for measuring trace amount hydrargyrum in alcoholic and acetic sample by photo-induced cold steam generation |
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|---|---|---|---|
| CNB200510021309XA CN100529739C (en) | 2005-07-22 | 2005-07-22 | Method for measuring trace amount hydrargyrum in alcoholic and acetic sample by photo-induced cold steam generation |
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| CN1737537A CN1737537A (en) | 2006-02-22 |
| CN100529739C true CN100529739C (en) | 2009-08-19 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100543461C (en) * | 2007-05-31 | 2009-09-23 | 中国铝业股份有限公司 | The assay method of Trace Mercury in a kind of aluminium ingot |
| CN101358924B (en) * | 2007-08-03 | 2011-05-04 | 北京路捷仪器有限公司 | Morphological analysis apparatus for mercury element and analysis method thereof |
| CN101482506B (en) * | 2008-01-10 | 2012-03-28 | 江苏江分电分析仪器有限公司 | Mercury content measuring method and device |
| CN101776585B (en) * | 2010-03-09 | 2011-07-20 | 四川大学 | Photochemical steam generating-atomic spectrometry for determining trace iron |
| CN102253168B (en) * | 2011-04-21 | 2014-01-22 | 上海理工大学 | Method and apparatus for producing mercury vapor with standard concentration |
| CN103776805B (en) * | 2012-10-17 | 2016-06-15 | 北京瑞利分析仪器有限公司 | Constant temperature steam generation sampling system |
| WO2020087891A1 (en) * | 2018-10-29 | 2020-05-07 | 重庆民泰新农业科技发展集团有限公司 | Water-carrying atomic fluorescence analysis device and atomic fluorescence analysis method |
| CN113019266A (en) * | 2019-12-09 | 2021-06-25 | 上海合全药业股份有限公司 | Continuous photocatalytic pipeline reactor and method for carrying out trifluoromethylation reaction |
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