CN104122349A - Method for extracting, separating and analyzing Cr (III) and Cr (VI) in smoke of cigarettes - Google Patents
Method for extracting, separating and analyzing Cr (III) and Cr (VI) in smoke of cigarettes Download PDFInfo
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Abstract
The invention belongs to the technical field of smoke analysis, and particularly relates to a method for extracting, separating and analyzing Cr (III) and Cr (VI) in the smoke of cigarettes. The method is characterized by mainly comprising the following steps of (1) trapping chromium in the smoke of the cigarettes; (2) treating gas phase matter and particle phase matter in the smoke; and (3) carrying out high performance liquid chromatography (HPLC)-inductively coupled plasma (ICP)-mass spectrometry (MS) online separation and analysis. The method has the advantages that after a rotary table smoke sucking machine-electrostatic trapping method is adopted, chromium with different element forms in the main stream smoke of the cigarettes can be trapped; Cr (III) and Cr (VI) in the smoke can be directly extracted by mobile phase; Cr (III) is enable to have a complexation reaction with ethylene diamine tetraacetic acid (EDTA) at certain temperature; after that, base line separation is carried out on Cr (III) and Cr (VI) by a chromatographic separation column, and 52Cr is measured by ICP-MS, so that the quantitative analysis of Cr (III) and Cr (VI) in the smoke of the cigarettes can be realized. After the method is adopted, the sample pretreatment is simple, convenient and rapid, and the quantitative analysis of Cr (III) and Cr (VI) can be completed within 10 minutes, so that a technical support is provided for accurate evaluation of the harm of heavy metal chromium in the smoke to a human body and the environment.
Description
Technical field
The present invention relates to chromium element morphology in cigarette smoke and extract method for separating and analyzing, specifically refer to chromium element different shape in buffer solution extraction flue gas, use again chromium element morphology in high performance liquid chromatography and inductivity coupled plasma mass spectrometry (HPLC-ICP-MS) coupling technique compartment analysis cigarette smoke, can quantitative test flue gas in the burst size of different shape chromium element.
Background technology
Chromium is a kind of metal with silvery white gloss, and chemical property is very stable, conventionally with Cr
+ 3to Cr
+ 6the state of oxidation exist, wherein Cr
+ 3for Essential metal elements of human, NRC CFN adult every day definite in 1989, the estimation range of applicable cr intake was 50 ~ 200 μ g.Also not evidence show at present Cr
+ 3can in biology system, change Cr into
+ 6.High concentration Cr
+ 6expose the damage that mainly causes acute renal glomerulus and renal tubule.Chronic contact Cr
+ 6can cause respiratory tumor.Cr
+ 6be decided to be 1 class carcinogenic substance by IARC.Therefore,, for the harmfulness of accurate evaluation heavy metal in flue gas chromium to human body and environment, also must analyze it and have form.
Sexavalent chrome, adopts spectrophotometric method to analyze mensuration conventionally.Along with the industries such as food, water quality, toy and cosmetics have been formulated comparatively strict sexavalent chrome limitation requirement, the method sensitivity can not meet sexavalent chrome and detect needs.Therefore, researched and developed both at home and abroad quick and precisely, highly sensitive trace sexavalent chrome analytical approach, its maximum feature is that sexavalent chrome is first separated to rear detection with trivalent chromium.Along with analytical technology development, HPLC-ICP-MS merges the efficient separation characteristic of HPLC and ICP-MS has low detection limit, wide dynamic range liner scope and can follow the tracks of the advantages such as multielement isotope signal intensity, be widely used at present food, environment, medicine and biological sample etc., analyze the chromium morphological analysis in the samples such as natural water as the people such as Wolf utilize HPLC-ICP-MS coupling technique, the people such as Kuo carry out morphological analysis to chromium element in soil and plant body.Tobacco business is mainly paid close attention to the total volume of chromium element in cigarette mainstream flue gas at present, does not relate to the morphological analysis of chromium element in cigarette smoke; In view of chromic harmfulness, be necessary to study the form that exists of chromium element in main flume, at home and abroad there is no at present the morphological analysis research report of chromium element in flue gas.
Summary of the invention
Object of the present invention: set up Cr(III in cigarette smoke) and Cr(VI) form extraction separation method, then analyze its burst size with HPLC-ICP-MS, for heavy metal chromium in accurate evaluation of flue gas provides technical support to the harmfulness of human body and environment.
The object of the invention can be achieved through the following technical solutions:
Cr(III in a kind of cigarette smoke) and Cr(VI) extract separation and analysis method, it is characterized in that: concrete steps are as follows:
1, the trapping of chromium in cigarette smoke
Experiment cigarette balance 48 h in the environment of temperature (22 ± 1) DEG C, relative humidity (60 ± 5) %.Prop up with average resistance to suction ± 49 Pa/ and prop up sorting by cigarette average quality ± 0.02 g/, with 1～10 mmol/L EDTA solution (pH=7.0) the trapping flue gas gas gas-phase objects of rotating disk smoking machine Electrostatic method trapping Smoke Particulate and 10～40 mL, be to make trivalent chromium and EDTA complexing by the object of this solution, thereby trivalent chromium is separated on separating column with sexavalent chrome.
2, the processing of flue gas gas gas-phase objects and granule phase substance
Granule phase substance on Electrostatic pipe is all rinsed in 50 mL volumetric flasks with the EDTA solution that traps gas gas-phase objects, after constant volume at 40～80 DEG C water-bath 0.5～4 h, make the complete complexing of trivalent chromium and EDTA, get 5 mL extracts after Graphon pillar purified treatment, obtain cigarette smoke sample preparation liquid.
3, HPLC-ICP-MS ON-LINE SEPARATION and analysis
Between HPLC and ICP-MS, be connected by 50 cm PEEK pipes: one end of PEEK pipe connects the outflow end of chromatography column, the other end connects ICP-MS atomizer entrance; After HPLC-ICP-MS working stability, can carry out sample determination, the running parameter of HPLC and ICP-MS instrument is in table 1.
Table 1 HPLC and ICP-MS Instrument working parameter
The invention has the advantages that: adopt the trapping of rotating disk smoking machine-Electrostatic method can trap DIFFERENT Cr element morphology in cigarette mainstream flue gas, directly extract the Cr(III in flue gas with mobile phase) and Cr(VI), at a certain temperature, make Cr(III) and EDTA generation complex reaction, then with chromatography column by Cr(III) and Cr(VI) baseline separation, then measure with ICP-MS
52cr, thereby realize Cr(III in cigarette smoke) and Cr(VI) quantitative test.Sample pre-treatments is easy, quick, and can complete Cr(III in 10min) and Cr(VI) quantitative measurement, thereby technical support provided to the harmfulness of human body and environment for heavy metal chromium in accurate evaluation of flue gas.
Brief description of the drawings
Fig. 1 is the Cr(III of the inventive method) and Cr(VI) chromatogram.
Specific embodiments
The present invention is described further below in conjunction with instantiation, but does not limit the present invention.
example 1
According to step 1 balance test cigarette, and carry out sorting; With 20 certain commercially available Virginian-type cigarettes of rotating disk smoking machine suction, with Electrostatic device trapping Smoke Particulate, with EDTA solution (pH=7.0) the trapping flue gas gas gas-phase objects of 30 mL 8 mmol/L; Then use granule phase substance in gas gas-phase objects absorption liquid drip washing Electrostatic pipe in 50m L volumetric flask, through constant volume, be placed in again 60 DEG C of water-bath water-bath 2 h, get 5 mL sample solutions Graphon pillar purified treatment, obtain sample preparation liquid, this solution can carry out Cr(III with HPLC-ICP-MS) and Cr(VI) measure; Obtain Cr(III in certain commercially available Virginian-type cigarette flue gas) burst size is 15.9 ng/cig, Cr(VI) be 9.79 ng/cig.
example 2
According to step 1 balance test cigarette, and carry out sorting; With 20 certain commercially available blended type cigarettes of rotating disk smoking machine suction, with Electrostatic device trapping Smoke Particulate, with EDTA solution (pH=7.0) the trapping flue gas gas gas-phase objects of 40 mL 8 mmol/L; Then use granule phase substance in gas gas-phase objects absorption liquid drip washing Electrostatic pipe in 50 mL volumetric flasks, through constant volume, be placed in again 80 DEG C of water-bath water-bath 1 h, get 5 mL sample solutions Graphon pillar purified treatment, obtain sample preparation liquid, this solution can carry out Cr(III with HPLC-ICP-MS) and Cr(VI) measure; Obtain Cr(III in certain commercially available blended type cigarette flue gas) burst size is 4.32 ng/cig, Cr(VI) be 2.43 ng/cig.
example 3
Pipette respectively a certain amount of Cr(III) and Cr(VI) standard solution is configured to the series standard working solution of 0.5,1.0,2.0,5.0,10.0 and 20.0 μ g/L, carries out chromium Elemental Speciation Analysis with HPLC-ICP-MS.Carry out linear regression according to concentration of standard solution and each peak area, obtain standard working curve and linearly dependent coefficient, taking concentration as 1 μ g/L mixed standard solution continuous sample introduction 10 times, obtain the standard deviation of two kinds of form content, using 3 times of standard deviations as detection limit, the detection limit of method and quantitative limit are in table 2.
Table 2 Cr(III) and Cr(VI) working stamndard curve and linearly dependent coefficient
| The form of arsenic | Retention time/min | Detection limit | Quantitative limit |
| Cr（Ⅲ） | 1.75 | 0.16 | 1.34 |
| Cr（Ⅵ） | 3.45 | 0.15 | 1.03 |
example 4
According to step 1 balance test cigarette, and carry out sorting; With the suction of rotating disk smoking machine 20 certain commercially available fire-cured tobacco type and blended type cigarettes, with Electrostatic device trapping Smoke Particulate, with EDTA solution (pH=7.0) the trapping flue gas gas gas-phase objects of 30 mL 8 mmol/L; Then use granule phase substance in gas gas-phase objects absorption liquid drip washing Electrostatic pipe in 50 mL volumetric flasks, through constant volume, be placed in again 60 DEG C of water-bath water-bath 2 h, get 5 mL sample solutions Graphon pillar purified treatment, obtain sample preparation liquid, this solution can carry out Cr(III with HPLC-ICP-MS) and Cr(VI) measure, carry out 6 times measures simultaneously, calculate relative standard deviation, result method precision, between 2.6%～9.6%, shows that the method can meet detection needs.
Table 3 method precision
Note :/represent not detect.
Claims (3)
1. Cr(III in cigarette smoke) and Cr(VI) extract a separation and analysis method, it is characterized in that: concrete steps are as follows:
1) trapping of chromium in cigarette smoke
Choose experiment cigarette, with 1～10 mmol/L EDTA solution (pH=7.0) the trapping flue gas gas gas-phase objects of rotating disk smoking machine Electrostatic method trapping Smoke Particulate and 10～40 mL;
2) processing of flue gas gas gas-phase objects and granule phase substance
Granule phase substance on Electrostatic pipe is all rinsed in 50 mL volumetric flasks with the EDTA solution that traps gas gas-phase objects, after constant volume at 40～80 DEG C water-bath 0.5～4 h, get 5 mL extracts through Graphon pillar purified treatment, remove most of organism in extraction solution, obtain cigarette smoke sample preparation liquid;
3) HPLC-ICP-MS ON-LINE SEPARATION and analysis
Between HPLC and ICP-MS, be connected by 50 cm PEEK pipes: one end of PEEK pipe connects the outflow end of chromatography column, the other end connects ICP-MS atomizer entrance; After HPLC-ICP-MS working stability, can carry out sample determination.
2. Cr(III in cigarette smoke according to claim 1) and Cr(VI) extract separation and analysis method, it is characterized in that: the running parameter of described HPLC and ICP-MS instrument is as follows:
HPLC condition: chromatographic column Agilent anion-exchange column specification 4.6mm × 30mm, mobile phase: 5 mmol/L EDTA solution, pH=7.0; Type of elution: isocratic elution; Flow velocity: 0.95 mL/min, sampling volume: 100 μ l,, acquisition time: 10 min;
ICP-MS: radio-frequency power: 1360 w, flow rate of carrier gas: 1.05 L/min, sampling depth: 6.8 mm, atomizer: Babington, spray chamber temperature: 2 DEG C, integral time: 0.3 s.
3. Cr(III in cigarette smoke according to claim 1) and Cr(VI) extraction separation and analysis method, it is characterized in that: experiment cigarette balance 48 h in the environment of temperature (22 ± 1) DEG C, relative humidity (60 ± 5) %, by cigarette average quality ± 0.02 g/ prop up and on average resistance to suction ± 49 Pa/ prop up sorting.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104597108A (en) * | 2015-01-21 | 2015-05-06 | 上海烟草集团有限责任公司 | Method for detecting content of mercury in cigarette mainstream smoke |
| CN104833750A (en) * | 2015-04-22 | 2015-08-12 | 上海烟草集团有限责任公司 | Method for separating and determining chromium elements with different valences in tobacco and tobacco products |
| CN106324140A (en) * | 2016-08-28 | 2017-01-11 | 中华人民共和国慈溪出入境检验检疫局 | Method for determining migratable Cr(III) and migratable Cr(VI) in toy material simultaneously |
| CN106984065A (en) * | 2017-03-14 | 2017-07-28 | 中国地质大学（武汉） | A kind of method of scene separation chromium form |
| CN107576742A (en) * | 2017-09-22 | 2018-01-12 | 广东中测食品化妆品安全评价中心有限公司 | The detection method of trivalent chromium in a kind of health food |
-
2014
- 2014-08-14 CN CN201410399347.8A patent/CN104122349B/en active Active
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104597108A (en) * | 2015-01-21 | 2015-05-06 | 上海烟草集团有限责任公司 | Method for detecting content of mercury in cigarette mainstream smoke |
| CN104597108B (en) * | 2015-01-21 | 2018-07-20 | 上海烟草集团有限责任公司 | A kind of detection method of Hg element in cigarette mainstream smoke content |
| CN104833750A (en) * | 2015-04-22 | 2015-08-12 | 上海烟草集团有限责任公司 | Method for separating and determining chromium elements with different valences in tobacco and tobacco products |
| CN106324140A (en) * | 2016-08-28 | 2017-01-11 | 中华人民共和国慈溪出入境检验检疫局 | Method for determining migratable Cr(III) and migratable Cr(VI) in toy material simultaneously |
| CN106984065A (en) * | 2017-03-14 | 2017-07-28 | 中国地质大学（武汉） | A kind of method of scene separation chromium form |
| CN107576742A (en) * | 2017-09-22 | 2018-01-12 | 广东中测食品化妆品安全评价中心有限公司 | The detection method of trivalent chromium in a kind of health food |
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