CN104155295B - A kind of chromic method in Solid phase extraction-Continuous Flow Analysis instrument Fast Measurement paper wrapper - Google Patents
A kind of chromic method in Solid phase extraction-Continuous Flow Analysis instrument Fast Measurement paper wrapper Download PDFInfo
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- CN104155295B CN104155295B CN201410435882.4A CN201410435882A CN104155295B CN 104155295 B CN104155295 B CN 104155295B CN 201410435882 A CN201410435882 A CN 201410435882A CN 104155295 B CN104155295 B CN 104155295B
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Abstract
The invention belongs to Determination of Hexavalent Chromium technical field in paper wrapper, specifically a kind of chromic method in Solid phase extraction-Continuous Flow Analysis instrument Fast Measurement paper wrapper, it is characterized in that: adopt the dipotassium hydrogen phosphate cushioning liquid of pH=7.5～8.0 to extract the Cr VI in paper wrapper, after filtration, remove the color in sample extraction liquid with solid-phase extraction column, then use the content of 6-valence Cr ions in Continuous Flow Analysis instrument Fast Measurement extract. The invention has the advantages that: can remove the interfering material that affects measurement result, QB with prior art? the analytical method of 2930.2-2008 is compared, and sample, through purified treatment, does not need to deduct sample background blank, thereby improve sensitivity of analytical method, detection limit has been improved to 4 times; After sample treatment completes, detect automatically, make operation more easy; Sample determination speed is fast, and repeatability and the rate of recovery of experiment are fine, are applicable to the analysis of batch samples.
Description
Technical field
The present invention relates to Determination of Hexavalent Chromium technical field in paper package material, be specifically a kind of Solid phase extraction-Chromic method in Continuous Flow Analysis instrument Fast Measurement paper wrapper. The method adopts the phosphoric acid of pH=7.5～8.0Cr VI in hydrogen dipotassium cushioning liquid extraction paper wrapper, removes through solid phase extraction column the chaff interference that impact is measuredMatter, then uses the content of 6-valence Cr ions in Continuous Flow Analysis instrument Fast Measurement extract.
Background technology
Cr VI (Cr6＋) be a kind of important environmental contaminants, there is extremely strong carcinogenic and mutagenicity, easily penetration cellFilm and in human body absorptivity high, EPA (EPA) is defined as one of toxicant of 17 kinds of highly dangerous. MirrorIn Cr VI (Cr6＋) endanger hugely, the states such as the World Health Organization, Europe, the U.S. and China more and more pay close attention to chromicHarm, more strict restriction is containing the discharge standard of hexavalent chromium wastewater. At present at water quality, electric, leather, printing-ink, bagThe industries such as dress printed matter have clearly limited chromic residual quantity, as Cr VI limitation in paper food packaging materialsFor 0.5mg/kg.
Cr VI detects main method and comprises: AAS, Using Flow Injection Analysis, flow analysis, the chromatography of ions, changeLearn luminescence method, atomic spectroscopy, polarography and liquid chromatogram-inductivity coupled plasma mass spectrometry coupling method (HPLC-ICP-MS connectionBy technology) etc., the feature such as wherein AAS height easy and simple to handle, selective, testing cost be lower, and extensively become every profession and tradeThe standard method of Determination of Hexavalent Chromium, as: " Waterquality--Determinationofchromium(VI)--Methodusingflowanalysis（FIAandCFA）andspectrometricdetection》（ISO23913-2006), " the mensuration Part III of textile heavy metal: Cr VI AAS " (GB/T17593.3-2006), " limitation of some harmful element and assay method in ink " standard method such as (QB2930.2-2008). At present, closeIn paper products, the bioassay standard method of Cr VI residual quantity is mainly QB2930.2-2008, this standard adopt strong base solution andHigh temperature extracts, and sample coloring matter is very easily dissolved in extraction solution, brings very large interference to spectrophotometry; Method detectsLimit for height, can not low content sample, so this standard method has larger limitation. For realizing in Rapid Photometric Determination paper productsCr VI.
Summary of the invention
Main purpose of the present invention is to measure Cr VI residual quantity in paper products, and set up a kind of Solid phase extraction-The method of Cr VI residual quantity in Continuous Flow Analysis instrument Fast Measurement paper products. The present invention adopts the buffering of pH=7.5～8.0Cr VI in solution oscillation extraction paper products, after filtration, by the color in solid-phase extraction column removal sample extraction solution, thenWith content of 6-valence Cr ions in Continuous Flow Analysis instrument Fast Measurement extraction solution.
The object of the invention is to realize by following steps:
A kind of chromic method in Solid phase extraction-Continuous Flow Analysis instrument Fast Measurement paper wrapper, adoptsWith the Cr VI in the dipotassium hydrogen phosphate cushioning liquid extraction paper wrapper of pH=7.5～8.0, after filtration, use SPEPost is removed the color in sample extraction liquid, then uses the content of 6-valence Cr ions in Continuous Flow Analysis instrument Fast Measurement extract, toolBody step is as follows:
(1) Cr VI extracts: paper products are cut into 5mm × 5mm fragment, take 0.5～2.0g sample, and then with 10The cushioning liquid oscillation extraction of～50mLpH=7.5～8.0, filters, and obtains Cr VI extraction solution;
(2) extract purifies: pipette 3～8mL Cr VI extraction solution in pretreated solid-phase extraction column, wait to extract moltenAfter liquid flows out completely, then add the drip washing of 1～5mL cushioning liquid once, efflux and leacheate are incorporated in 10mL volumetric flask, useCushioning liquid is settled to scale, shakes up, and obtains Cr VI solution to be measured;
(3) Determination of Hexavalent Chromium: first the test pipeline of analyzer is transformed, made on the glass four-way on analyzerThe pump line that inlet a is 0.32ml/min by a flow imports air, and inlet c is 0.23ml/min by a flowPump line import developer, pump line that inlet b is 1.20ml/min by a flow imports sample solution, glass four-wayLiquid outlet d mixes circle with 20 circles and is connected, thereby realizes sample solution and chromogenic reagent solution importing and carry out chromogenic reaction, thenCarry out standard liquid and sample analysis, obtain chromic content in solution to be measured, then by calculating sexavalence in paper productsThe residual quantity of chromium.
The oscillation extraction time in step (1) is 10～60min.
Filtration in step (1) is to filter with middling speed qualitative filter paper.
The pretreatment of the solid-phase extraction column in step (2) refers to the pigment solid particle of removing in sample extraction solutionThing; Preprocess method: with 5mL methanol solution drip washing pillar, and then rinse once with 5mL water, finally use 5mLpH=7.5～8.0 cushioning liquid again drip washing is once for subsequent use.
Chromogenic reagent solution liquid in step (3) is for containing 1.20mol/L sulfuric acid, 0.4mol/L phosphoric acid and 0.5g/L hexicholThe chromogenic reagent solution of base phosphinylidyne two hydrazines.
Agents useful for same configures in the following manner:
(1) pH=7.5～8.0 cushioning liquid: take 22.8g dipotassium hydrogen phosphate and be dissolved in 200mL water, after dissolving completely,Proceed in 1000mL volumetric flask, be then settled to scale, shake up, then with acidometer, pH value is adjusted to 7.5～8.0.
(2) preparation of chromogenic reagent solution: take 0.4g diphenyl phosphinylidyne two hydrazines in 1L beaker, then add 200mL differentPropyl alcohol, stirs diphenyl phosphinylidyne two hydrazines is dissolved completely, adds 500mL water, then under agitation adds respectively the 60mL concentrated sulfuric acidWith 20mL SPA, be cooled to after room temperature, then be settled to 1000mL.
In the present invention, design pump line is to be mainly canbe used on line chromogenic reaction, can reduce using amount of reagent, and operation moreAdd easy, reduce testing cost; Strengthen sample size and can improve reaction sensitivity.
Compared with the analytical method of the inventive method and the QB2930.2-2008 of prior art, sample is through purified treatment, noNeed to deduct sample background blank, thereby improve sensitivity of analytical method, detection limit is improved to 4 times; After sample treatment completes,Detect automatically, make operation more easy; Sample determination speed is fast, and repeatability and the rate of recovery of experiment are fine, are applicable to large quantities ofThe analysis of amount sample.
Brief description of the drawings
Fig. 1 is Continuous Flow Analysis instrument detection module configuration (testing pipeline) connection diagram of the present invention.
Sequence number in figure: the 1st, wash pin liquid, the 2nd, air, the 3rd, sample solution, the 4th, chromogenic reagent solution, the 5th, flow 2.0mL/minPump line, the 6th, flow 0.32mL/min pump line, the 7th, flow 1.20mL/min pump line, the 8th, flow 0.23mL/min pump line, 9 is 320 circles mix circle, the 10th, 1cm colorimetric pool (with 540nm optical filter), the 11st, glass four-way, the 12nd, waste liquid.
Detailed description of the invention
The present invention is described further below in conjunction with instantiation:
Example 1
According to experimental procedure and QB2930.2-2008 method regulation step, this invention and QB2930.2-are investigated respectively2008 method detection limits, this inventive method detects and is limited to 0.87 μ g/L, is quantitatively limited to 2.90 μ g/L, QB2930.2-2008 methodDetect and be limited to 4.30 μ g/L, be quantitatively limited to 14.3 μ g/L; The former detection limit is the latter's 1/5, thereby shows that this invention significantly carriesThe high detection limit of method, is conducive to the Accurate Determining of low content sample.
Example 2
Choose the paper printed matter of 4 different packaged foods, be cut into 5mm × 5mm fragment, take 1.0g in 100mLIn triangular flask, (do 2 parallel determinations), add the cushioning liquid oscillation extraction 30min of 50mLpH=7.5～8.0, fixed by middling speedProperty Filter paper filtering, obtains Cr VI extraction solution; Pipette 5mL extraction solution in pretreated polyamide solid phase extraction cartridge, treatAfter extraction solution flows out completely, then add the drip washing of 4mL cushioning liquid once, efflux and leacheate are incorporated in 10mL volumetric flaskIn, be settled to scale with cushioning liquid, shake up, obtain Cr VI solution to be measured; And then with design continuous flow method detectModule is carried out assay. Meanwhile, sample also carries out content of 6-valence Cr ions mensuration, result according to QB2930.2-2008 standard methodAs follows:
Result shows, this inventive method can be carried out Accurate Determining to low content Cr VI in paper products, and QB2930.2-2008 standard method does not detect; In paper products, two method testing results of high-load Cr VI are basically identical.
Example 3
Take pre-cut and become 5mm × 5mm sweet wrapper fragment 0.5g (to do 2 parallel determinations) in 100mL triangular flask,Add the cushioning liquid oscillation extraction 20min of 25mLpH=7.5～8.0, with the filtration of middling speed qualitative filter paper, obtain Cr VI extractionSolution; Pipette 6mL extraction solution in pretreated polyamide solid phase extraction cartridge, after extraction solution flows out completely, then addOnce, efflux and leacheate are incorporated in 10mL volumetric flask the drip washing of 3mL cushioning liquid, are settled to scale with cushioning liquid, shakeEven, obtain Cr VI solution to be measured; And then with design continuous flow method detection module carry out assay, this sugar as calculatedIn fruit paper, Cr VI does not detect (lower than food wrapper limitation 0.05mg/kg).
Claims (4)
1. a chromic method in Solid phase extraction-Continuous Flow Analysis instrument Fast Measurement paper wrapper, its spyLevy and be: adopt the dipotassium hydrogen phosphate cushioning liquid of pH=7.5～8.0 to extract the Cr VI in paper wrapper, after filtration,Remove the color in sample extraction liquid with solid-phase extraction column, then use the sexavalence in Continuous Flow Analysis instrument Fast Measurement extractChromium content, concrete steps are as follows:
(1) Cr VI extracts: paper products are cut into 5mm × 5mm fragment, take 0.5～2.0g sample, and then with 10～The cushioning liquid oscillation extraction of 50mLpH=7.5～8.0, filters, and obtains Cr VI extraction solution;
(2) extract purifies: pipette 3～8mL Cr VI extraction solution in pretreated solid-phase extraction column, treat that extraction solution is completeAfter full outflow, then add the drip washing of 1～5mL cushioning liquid once, efflux and leacheate are incorporated in 10mL volumetric flask, by bufferingSolution is settled to scale, shakes up, and obtains Cr VI solution to be measured; Described pretreatment refers to the look of removing in sample extraction solutionElement solid particulate matter; Preprocess method: with 5mL methanol solution drip washing pillar, and then rinse once with 5mL water, finally useThe cushioning liquid of 5mLpH=7.5～8.0 again drip washing is once for subsequent use;
(3) Determination of Hexavalent Chromium: first the test pipeline of analyzer is transformed, made the feed liquor on the glass four-way on analyzerThe pump line that mouth a is 0.32ml/min by a flow imports air, the pump that inlet c is 0.23ml/min by a flowPipe imports developer, and the pump line that inlet b is 1.20ml/min by a flow imports sample solution, the fluid of glass four-wayMouth d mixes circle with 20 circles and is connected, thereby realizes sample solution and chromogenic reagent solution importing and carry out chromogenic reaction, then carries outStandard liquid and sample analysis, obtain chromic content in solution to be measured, more chromic by calculating in paper productsResidual quantity.
2. in Solid phase extraction-Continuous Flow Analysis instrument Fast Measurement paper wrapper according to claim 1 sixThe method of valency chromium, is characterized in that: the oscillation extraction time in step (1) is 10～60min.
3. in Solid phase extraction-Continuous Flow Analysis instrument Fast Measurement paper wrapper according to claim 1 sixThe method of valency chromium, is characterized in that: the filtration in step (1) is to filter with middling speed qualitative filter paper.
4. in Solid phase extraction-Continuous Flow Analysis instrument Fast Measurement paper wrapper according to claim 1 sixThe method of valency chromium, is characterized in that: the chromogenic reagent solution in step (3) is for containing 1.20mol/L sulfuric acid, 0.4mol/L phosphoric acidChromogenic reagent solution with 0.5g/L diphenyl phosphinylidyne two hydrazines.
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| CN104677849A (en) * | 2015-03-18 | 2015-06-03 | 浙江正安检测技术有限公司 | Improved measurement method for chromic acid mist in stationary source emission |
| CN105651773A (en) * | 2016-02-29 | 2016-06-08 | 云南同创检测技术股份有限公司 | Method for measuring content of cellulose in tobacco through potassium dichromate oxidation by means of continuous flow analyzer |
| CN108519338A (en) * | 2018-02-12 | 2018-09-11 | 云南中烟工业有限责任公司 | A kind of high-throughput Continuous Flow Analysis method for water-soluble sugar in tobacco gene editor's material |
| CN111487331B (en) * | 2019-01-25 | 2022-07-12 | 南开大学 | Quantitative detection method for trace nylon 6 and nylon 66 in environmental sample |
| CN113758888A (en) * | 2021-09-08 | 2021-12-07 | 中国烟草总公司郑州烟草研究院 | Method for measuring titanium dioxide content in food and test pipeline |
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| CN101294898B (en) * | 2008-06-23 | 2010-04-14 | 中国烟草总公司郑州烟草研究院 | Method for measuring chromium content in smoke tipping paper |
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