CN104122349B - Cr (III) and Cr (VI) extraction and isolation and analytical approach in a kind of cigarette smoke - Google Patents
Cr (III) and Cr (VI) extraction and isolation and analytical approach in a kind of cigarette smoke Download PDFInfo
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Abstract
The invention belongs to stack-gas analysis technology field, specifically Cr(III in a kind of cigarette smoke) and Cr(VI) extraction and isolation and analytical approach, it is characterized in that: mainly comprise the following steps: the 1) trapping of chromium in cigarette smoke; 2) process of flue gas gas gas-phase objects and granule phase substance; 3) HPLC-ICP-MS ON-LINE SEPARATION and analysis.The invention has the advantages that: adopt rotating disk smoking machine-Electrostatic method trapping can trap DIFFERENT Cr element morphology in cigarette mainstream flue gas, Cr(III with in mobile phase extracting directly flue gas) 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 to measure with ICP-MS
52cr, thus realize Cr(III in cigarette smoke) and Cr(VI) quantitative test.Sample pre-treatments is easy, quick, and can complete Cr(III in 10 min) and Cr(VI) quantitative measurement, thus provide technical support for the harmfulness of heavy metal chromium to human body and environment in accurate evaluation of flue gas.
Description
Technical field
The present invention relates to chromium element morphology extraction and isolation analytical approach in cigarette smoke, chromium element different shape in concrete finger buffer solution extraction flue gas, use chromium element morphology in high performance liquid chromatography and inductivity coupled plasma mass spectrometry (HPLC-ICP-MS) coupling technique compartment analysis cigarette smoke again, can the burst size of different shape chromium element in quantitative test flue gas.
Background technology
Chromium is a kind of metal with silvery white gloss, and chemical property is very stable, usually with Cr
+ 3to Cr
+ 6the state of oxidation exist, wherein Cr
+ 3for Essential metal elements of human, the estimation range of the cr intake that the adult that NRC CFN determined in 1989 is applicable to every day is 50 ~ 200 μ g.The current Cr that also not evidence show
+ 3cr can be changed in biology system
+ 6.High concentration Cr
+ 6expose the damage mainly causing acute renal glomerulus and renal tubule.Chronic exposure Cr
+ 6respiratory tumor can be caused.Cr
+ 61 class carcinogenic substance is decided to be by IARC.Therefore, in order to accurate evaluation heavy metal in flue gas chromium is to the harmfulness of human body and environment, also its existing forms must be analyzed.
Sexavalent chrome, usually adopts spectrophotometric method to carry out analysis and measures.Along with the industries such as food, water quality, toy and cosmetics have formulated comparatively strict sexavalent chrome limitation requirement, the method sensitivity can not meet sexavalent chrome and detect needs.Therefore, to research and develop 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 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 signals change, be widely used in food, environment, medicine and biological sample etc. at present, utilize the chromium morphological analysis in the samples such as HPLC-ICP-MS coupling technique analysis natural water as people such as Wolf, the people such as Kuo then carry out morphological analysis to chromium element in soil and plant body.Current tobacco business mainly pays close attention to the total volume of chromium element in cigarette mainstream flue gas, does not relate to the morphological analysis of chromium element in cigarette smoke; In view of chromic harmfulness, be necessary the existing forms studying chromium element in main flume, at home and abroad there is no the morphological analysis research report of chromium element in flue gas at present.
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, in accurate evaluation of flue gas, the harmfulness of heavy metal chromium to human body and environment provides technical support.
The object of the invention realizes by following technical scheme:
Cr(III in a kind of cigarette smoke) and Cr(VI) extraction and isolation and analytical approach, it is characterized in that: concrete steps are as follows:
1, the trapping of chromium in cigarette smoke
Experiment cigarette balances 48 h in the environment of temperature (22 ± 1) DEG C, relative humidity (60 ± 5) %.Prop up by cigarette average quality ± 0.02 g/ and prop up sorting with average resistance to suction ± 49 Pa/, flue gas gas gas-phase objects is trapped with 1 ~ 10 mmol/L EDTA solution (pH=7.0) of rotating disk smoking machine Electrostatic method trapping Smoke Particulate and 10 ~ 40 mL, be make trivalent chromium and EDTA complexing by the object of this solution, thus trivalent chromium is separated with sexavalent chrome on separating column.
2, the process of flue gas gas gas-phase objects and granule phase substance
With the EDTA solution trapping gas gas-phase objects, the granule phase substance on Electrostatic pipe is all rinsed in 50 mL volumetric flasks, after constant volume at 40 ~ 80 DEG C water-bath 0.5 ~ 4 h, make trivalent chromium and the complete complexing of 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
Connected by 50 cm PEEK pipes between HPLC and ICP-MS: 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 rotating disk smoking machine-Electrostatic method trapping can trap DIFFERENT Cr element morphology in cigarette mainstream flue gas, Cr(III with in mobile phase extracting directly flue gas) 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 to measure with ICP-MS
52cr, thus 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, thus provide technical support for the harmfulness of heavy metal chromium to human body and environment in accurate evaluation of flue gas.
Accompanying drawing explanation
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; Aspirate 20 certain commercially available Virginian-type cigarettes with rotating disk smoking machine, trap Smoke Particulate by electrostatic catcher, trap flue gas gas gas-phase objects with the EDTA solution (pH=7.0) of 30 mL 8 mmol/L; Then use granule phase substance in gas gas-phase objects absorbing liquid drip washing Electrostatic pipe in 50m L volumetric flask, through constant volume, be placed in 60 DEG C of water-bath water-bath 2 h again, get 5 mL sample solution 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; Aspirate 20 certain commercially available blended type cigarettes with rotating disk smoking machine, trap Smoke Particulate by electrostatic catcher, trap flue gas gas gas-phase objects with the EDTA solution (pH=7.0) of 40 mL 8 mmol/L; Then use granule phase substance in gas gas-phase objects absorbing liquid drip washing Electrostatic pipe in 50 mL volumetric flasks, through constant volume, be placed in 80 DEG C of water-bath water-bath 1 h again, get 5 mL sample solution 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 a certain amount of Cr(III respectively) 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.Linear regression is carried out according to concentration of standard solution and each peak area, obtain standard working curve and linearly dependent coefficient, be 1 μ g/L mixed standard solution continuous sample introduction 10 times with concentration, 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 calibration 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; Aspirate 20 certain commercially available fire-cured tobacco type and blended type cigarettes with rotating disk smoking machine, trap Smoke Particulate by electrostatic catcher, trap flue gas gas gas-phase objects with the EDTA solution (pH=7.0) of 30 mL 8 mmol/L; Then use granule phase substance in gas gas-phase objects absorbing liquid drip washing Electrostatic pipe in 50 mL volumetric flasks, through constant volume, be placed in 60 DEG C of water-bath water-bath 2 h again, get 5 mL sample solution 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 to measure 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 :/expression does not detect.
Claims (2)
1. Cr(III in cigarette smoke) and Cr(VI) extraction and isolation and an analytical approach, it is characterized in that: concrete steps are as follows:
1) trapping of chromium in cigarette smoke
Choose experiment cigarette, trap flue gas gas gas-phase objects with 1 ~ 10 mmol/L EDTA pH value of solution=7.0 of rotating disk smoking machine Electrostatic method trapping Smoke Particulate and 10 ~ 40 mL;
2) process of flue gas gas gas-phase objects and granule phase substance
With the EDTA solution trapping gas gas-phase objects, the granule phase substance on Electrostatic pipe is all rinsed in 50 mL volumetric flasks, 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
Connected by 50 cm PEEK pipes between HPLC and ICP-MS: 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, sample determination can be carried out;
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.
2. Cr(III in cigarette smoke according to claim 1) and Cr(VI) extraction and isolation and analytical approach, it is characterized in that: experiment cigarette balances 48 h in the environment of temperature (22 ± 1) DEG C, relative humidity (60 ± 5) %, props up prop up sorting with average resistance to suction ± 49 Pa/ by cigarette average quality ± 0.02 g/.
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| 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 |
| CN106984065B (en) * | 2017-03-14 | 2019-12-20 | 中国地质大学（武汉） | Method for separating chromium form on site |
| 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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