CN104849373A - Method for testing residual amount of perfluoro caprylic acid in leather based on precolumn derivatization-high performance liquid chromatography-fluorescence detector - Google Patents
Method for testing residual amount of perfluoro caprylic acid in leather based on precolumn derivatization-high performance liquid chromatography-fluorescence detector Download PDFInfo
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- CN104849373A CN104849373A CN201510277666.6A CN201510277666A CN104849373A CN 104849373 A CN104849373 A CN 104849373A CN 201510277666 A CN201510277666 A CN 201510277666A CN 104849373 A CN104849373 A CN 104849373A
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Abstract
The invention provides a method for testing the residual amount of perfluoro caprylic acid (PFOA) in leather based on a precolumn derivatization-high performance liquid chromatography-fluorescence detector. The method specifically comprises the following steps: performing ultrasonic extraction on a sample, concentrating a sample extraction liquid, performing derivatization reaction on PFOA in the extract, filtering into a sample bottle by using a membrane, testing and verifying by using a high performance liquid chromatography-fluorescence detector, at the same time implementing blank experiment, and quantitatively testing target compounds of the sample liquid by using an external standard method. High performance liquid chromatography testing parameters and testing steps are reasonably selected, a fluorescence detector is selected, and the external standard method is adopted to quantify the content, so that precise testing on the residual amount of perfluoro caprylic acid (PFOA) in leather, artificial leather and products of leather and artificial leather can be achieved. The method has the characteristics of being economic and effective, high in precision, high in anti-interference property and low in detection limit.
Description
Technical field
The present invention relates to Product checking analysis field, be specifically related to a kind of column front derivation
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid (PFOA) residual quantity in leather.
Background technology
Perfluoro caprylic acid (Perfluorooctanic acid, PFOA) molecular formula is CF
3(CF
2)
6cOOH is one of representative member in PFCs family.There is due to it performances such as excellent hydrophobic oleophobic performance, high thermal stability, high chemical stability and high surface, be widely used in leather production as " three prevent " surface finishing agent.But, there are some researches show that PFOA is extensively present in biosome and in ecologic environment, and there is the multiple toxicity such as genotoxicity, genetoxic, development toxicity, immunotoxicity and hepatotoxicity, become a kind of novel lasting organic contaminant (POPs) drawn attention.Within 2004, domestic and international paid close attention to " Du Pont's non-stick pan event " is exactly caused by PFOA.In european union directive, PFOA has similar harmfulness to PFOS also will be listed in limited thing because of under a cloud, and pollution control management office of Norway carried out limiting the quantity using to PFOA in 2013.Therefore, in leather and leather products, the detection analysis of PFOA content has important practical significance and necessity.
So far, detection analysis for PFOA in leather and leather products there is no unification of the motherland standard, and the provincial standard DB33/T 479-2009 mensuration Liquid Chromatography-Tandem Mass Spectrometry of PFOS and PFOA " in textile, the leather " that Zhejiang Province issues can detect PFOA content in leather.The PFOA detection method that other industry or subject have developed mainly contains HPLC-MS method, HPLC-MS/MS method, GC-MS method etc.In view of though these method detection sensitivities are high, the high-end resolution instrument of main dependence, testing cost is high, is difficult to popularize.Select suitable derivatization reagent and simple pre-treating method, exploitation does not rely on expensive instrument, and analysis cost is low, and the analyzing detecting method being easy to operate and popularize is one of important research direction of Environmental Analytical Chemistry.
The object of the invention is the deficiency for prior art existence and defect, combine by means of column front derivation-high performance liquid chromatography-fluorescence technology, provide one can measure the detection method of perfluoro caprylic acid (PFOA) in leather, leatheret and goods thereof.Detection method provided by the present invention is realized by column front derivation-High Performance Liquid Chromatography with Fluorescence Detection, and be intended to solve existing method and mostly depend on high-end analysis and detecting instrument, testing cost is high, and method is difficult to the problem of popularization and application.This method is by choose reasonable high-performance liquid chromatogram determination parameter and testing procedure, employing fluorescence detector detects, quantified by external standard method, can realize the mensuration of PFOA content in leather, leatheret and goods thereof, has economical and effective, precision is high, antijamming capability is strong and detectability is low feature.So far, the detection method adopting column front derivation-high performance liquid chromatography-fluorescence device analysis to measure PFOA in leather and leather products both at home and abroad detects and there is not yet document and patent report.
Summary of the invention
A kind of based on column front derivation
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid residual quantity in leather; it is characterized in that the assay method of described perfluoro caprylic acid (PFOA) residual quantity is by 3-(acetyl bromide) cumarin (3-BrAC) column front derivation-high performance liquid chromatography-fluorescence device mensuration, assay method specifically comprises the following steps:
(1) testing sample is shredded be placed in container, be placed in ultrasonic washing instrument ultrasonic extraction 0.5h ~ 1h after adding organic solvent again, leach filtrate; Add organic solvent again, re-extract 1 time, ultrasonic time shortens to 10 min ~ 20min, again filters, and merges twice filtrate, the extract that Rotary Evaporators must concentrate;
(2) extract revolving and steam in bottle is dissolved with acetonitrile, be settled to 1 mL ~ 3 mL, vortex oscillation 3 min ~ 10min, accurately pipette in 10mL test tube with liquid-transfering gun, add 50 μ L ~ 200 μ L derivatization reagents, after sealing, at 50 ~ 80 DEG C, 2h ~ 5h is reacted in jolting, derivatization reaction terminates to be cooled to room temperature rapidly afterwards, be placed in fuming cupboard and balance 1 min ~ 5 min, through 0.45 μm of organic membrane filtration in sample bottle, must sample measuring liquid be treated;
(3) according to the content situation treating PFOA derivative products in sample measuring liquid, the standard working solution of selected concentration comparable, standard working solution and treat PFOA in sample measuring liquid response all should instrument detect the range of linearity in, measure with high performance liquid chromatography-fluorescence device, if there is peak to occur in sample liquid in identical retention time with standard solution, then need confirmation; Chromatographic peak retention time through confirmatory analysis measured matter is consistent with standard substance, then judge in testing sample containing PFOA;
(4) detect blank sample with high performance liquid chromatography-fluorescence device by step (1), (2) simultaneously;
(5) with external standard method drawing standard curve, the content of PFOA in sample is calculated as follows:
x=(C-C
0)*
f /m
In formula: the content of PFOA in x-sample, unit is mg/kg;
The concentration of PFOA in the sample liquid of C-obtained by typical curve, unit is μ g/mL;
C
0the concentration of PFOA in the-blank test that obtained by typical curve, unit is μ g/mL;
The final dilution ratio of f-detection liquid;
The quality of the sample representated by m-detection liquid, unit is g.
Described a kind of column front derivation
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid residual quantity in leather, it is characterized in that described ultrasonic extraction organic solvent is the potpourri of one or more in methyl alcohol, ethanol, acetone, ethyl acetate, methenyl choloride, methylene chloride, phenixin and acetonitrile.
Described a kind of column front derivation
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid residual quantity in leather, it is characterized in that described derivatization reagent is 3-(acetyl bromide) cumarin (3-BrAC).
Described a kind of column front derivation
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid residual quantity in leather, it is characterized in that Parameter Conditions when described high performance liquid chromatography-fluorescence device measures is as follows:
A) chromatographic column: C18 chromatographic column (4.6 × 250 mm, 5 μm);
B) chromatogram column temperature: 20 DEG C ~ 40 DEG C;
C) fluorescence detector: excitation wavelength 306 nm, emission wavelength 420 nm;
D) mobile phase: 60 % acetonitrile and acetonitriles, elution program is as shown in table 1;
E) flow velocity: 0.8 ~ 1.8 mL/min;
F) sample size: 10 μ L;
Table 1 Gradient Elution program
| Time/min | 60% acetonitrile/% | Acetonitrile/% |
| 0 | 100 | 0 |
| 5 | 100 | 0 |
| 20 | 0 | 100 |
| 25 | 100 | 0 |
| 27 | 100 | 0 |
Claims (4)
1. one kind based on column front derivation
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid residual quantity in leather; it is characterized in that the assay method of described perfluoro caprylic acid (PFOA) residual quantity is measured by 3-(acetyl bromide) cumarin (3-BrAC) column front derivation-high performance liquid chromatography-fluorescence device, assay method specifically comprises the following steps:
(1) testing sample is shredded be placed in container, be placed in ultrasonic washing instrument ultrasonic extraction 0.5h ~ 1h after adding organic solvent again, leach filtrate; Add organic solvent again, re-extract 1 time, ultrasonic time shortens to 10 min ~ 20min, again filters, and merges twice filtrate, the extract that Rotary Evaporators must concentrate;
(2) extract revolving and steam in bottle is dissolved with acetonitrile, be settled to 1 mL ~ 3 mL, vortex oscillation 3 min ~ 10min, accurately pipette in 10mL test tube with liquid-transfering gun, add 50 μ L ~ 200 μ L derivatization reagents, after sealing, at 50 ~ 80 DEG C, 2h ~ 5h is reacted in jolting, derivatization reaction terminates to be cooled to room temperature rapidly afterwards, be placed in fuming cupboard and balance 1 min ~ 5 min, through 0.45 μm of organic membrane filtration in sample bottle, must sample measuring liquid be treated;
(3) according to the content situation treating PFOA derivative products in sample measuring liquid, the standard working solution of selected concentration comparable, standard working solution and treat PFOA in sample measuring liquid response all should instrument detect the range of linearity in, measure with high performance liquid chromatography-fluorescence device, if there is peak to occur in sample liquid in identical retention time with standard solution, then need confirmation; Chromatographic peak retention time through confirmatory analysis measured matter is consistent with standard substance, then judge in testing sample containing PFOA;
(4) detect blank sample with high performance liquid chromatography-fluorescence device by step (1), (2) simultaneously;
(5) with external standard method drawing standard curve, the content of PFOA in sample is calculated as follows:
x=(C-C
0)*
f /m
In formula: the content of PFOA in x-sample, unit is mg/kg;
The concentration of PFOA in the sample liquid of C-obtained by typical curve, unit is μ g/mL;
C
0the concentration of PFOA in the-blank test that obtained by typical curve, unit is μ g/mL;
The final dilution ratio of f-detection liquid;
The quality of the sample representated by m-detection liquid, unit is g.
2. a kind of column front derivation according to claim 1
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid residual quantity in leather, it is characterized in that described ultrasonic extraction organic solvent is the potpourri of one or more in methyl alcohol, ethanol, acetone, ethyl acetate, methenyl choloride, methylene chloride, phenixin and acetonitrile.
3. a kind of column front derivation according to claim 1
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid residual quantity in leather, it is characterized in that described derivatization reagent is 3-(acetyl bromide) cumarin (3-BrAC).
4. a kind of column front derivation according to claim 1
-high performance liquid chromatography-fluorescence device measures the detection method of perfluoro caprylic acid residual quantity in leather, it is characterized in that Parameter Conditions when described high performance liquid chromatography-fluorescence device measures is as follows:
A) chromatographic column: C18 chromatographic column (4.6 × 250 mm, 5 μm);
B) chromatogram column temperature: 20 DEG C ~ 40 DEG C
C) fluorescence detector: excitation wavelength 306 nm, emission wavelength 420 nm;
D) mobile phase: 60 % acetonitrile and acetonitriles, elution program is as shown in table 1; ;
E) flow velocity: 0.8 ~ 1.8 mL/min
F) sample size: 10 μ L;
Table 1 Gradient Elution program
。
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| CN105334284A (en) * | 2015-12-04 | 2016-02-17 | 国家环境分析测试中心 | Method for recognizing and eliminating interference of carboxylic acids in detection of perfluorobutyric acid |
| CN108144572A (en) * | 2017-12-28 | 2018-06-12 | 江苏大学 | A kind of application of graphite phase carbon nitride perfluoro caprylic acid in water removal is gone |
| CN108169380A (en) * | 2018-01-19 | 2018-06-15 | 浙江工业大学 | A kind of deriving method for high performance liquid chromatography detection perfluoro caprylic acid |
| CN108387665A (en) * | 2018-01-19 | 2018-08-10 | 浙江工业大学 | A kind of deriving method detecting perfluoro caprylic acid with UV-HPLC |
| CN109001345A (en) * | 2018-10-19 | 2018-12-14 | 重庆大学 | Measure the High Performance Liquid Chromatography with Fluorescence Detection of perfluoro caprylic acid concentration in landfill leachate |
| CN109682895A (en) * | 2018-12-18 | 2019-04-26 | 福建省产品质量检验研究院 | A kind of quantitative detecting method of additive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105334284A (en) * | 2015-12-04 | 2016-02-17 | 国家环境分析测试中心 | Method for recognizing and eliminating interference of carboxylic acids in detection of perfluorobutyric acid |
| CN108144572A (en) * | 2017-12-28 | 2018-06-12 | 江苏大学 | A kind of application of graphite phase carbon nitride perfluoro caprylic acid in water removal is gone |
| CN108169380A (en) * | 2018-01-19 | 2018-06-15 | 浙江工业大学 | A kind of deriving method for high performance liquid chromatography detection perfluoro caprylic acid |
| CN108387665A (en) * | 2018-01-19 | 2018-08-10 | 浙江工业大学 | A kind of deriving method detecting perfluoro caprylic acid with UV-HPLC |
| CN109001345A (en) * | 2018-10-19 | 2018-12-14 | 重庆大学 | Measure the High Performance Liquid Chromatography with Fluorescence Detection of perfluoro caprylic acid concentration in landfill leachate |
| CN109001345B (en) * | 2018-10-19 | 2022-06-17 | 重庆大学 | High performance liquid chromatography fluorescence detection method for determining concentration of perfluorooctanoic acid in landfill leachate |
| CN109682895A (en) * | 2018-12-18 | 2019-04-26 | 福建省产品质量检验研究院 | A kind of quantitative detecting method of additive |
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