CN105021745A - Purification and enrichment pretreatment technology of food organic pollutants hydroxylated polybrominated diphenyl ethers - Google Patents
Purification and enrichment pretreatment technology of food organic pollutants hydroxylated polybrominated diphenyl ethers Download PDFInfo
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- CN105021745A CN105021745A CN201410155460.1A CN201410155460A CN105021745A CN 105021745 A CN105021745 A CN 105021745A CN 201410155460 A CN201410155460 A CN 201410155460A CN 105021745 A CN105021745 A CN 105021745A
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Abstract
The invention belongs to the field of a purification and enrichment pretreatment technology of food organic pollutants hydroxylated polybrominated diphenyl ethers. The technology comprises the following steps: activating a silica gel solid-phase extraction column with dichloromethane and n-hexane and then loading a sample, leaching with an n-hexane solution, eluting with dichloromethane, blow-drying an eluate with nitrogen, redissolving residues with acetonitrile, filtering and conducting liquid chromatographic-tandem mass spectrometric detection. By the pretreatment technology, recovery rate of the seven hydroxylated polybrominated diphenyl ethers (3-OH-BDE-47, 5-OH-BDE-47, 6-OH-BDE-47, 2'-OH-BDE-68, 4-OH-BDE-42, 6-OH-BDE-85 and 6'-OH-BDE-99) is 82.83%-99.83%, relative deviation is lower than 10%, and accuracy and precision are good.
Description
Technical field
The invention belongs to the purification enrichment preconditioning technique field of food organic contaminant hydroxyl PBDE, particularly relate to a kind of purification enrichment technical method using Solid-Phase Extraction.
Background technology
Hydroxyl PBDE (OH-PBDEs) is a class persistence organic pollutant, and source mainly comprises two aspects, and one is the Spontaneous release of marine algae, and one is that the biology of PBDEs transforms.OH-PBDEs is except having except similar toxic action with PBDEs, also have and affect estradiol synthesis, interference oxidative phosphorylation (OXPHOS) effect waits toxicological characteristics, if 6-OH-BDE-47 is under 25nmol/L concentration, there is deformity in zebrafish embryo, even can suppress to grow under more high dose and occur dead, and the disorder of OXPHOS in mitochondria can be caused in nanomole concentration range.OH-PBDEs is also proved to be and can accumulates in organic blood.Therefore, the hydroxyl PBDE monitored in food is extremely important.The main detection means of current hydroxyl PBDE is chromatographic tandem mass spectrometry method, because in actual food product system, hydroxyl PBBs ether content is lower, the ppm level of hundreds of is generally arrived tens, therefore, before carrying out chromatographic tandem Mass Spectrometer Method, need to carry out purifying, enrichment and the pre-service such as concentrated.
Solid-Phase Extraction have simple to operate, solvent consumption is few, save time, the advantage such as laborsaving and widely applicable, be suitable in the preprocessing process of contaminant trace species, and the selection of solid phase extraction column stuffing is most important, it is the key of relation purifying, enrichment success or failure to the adsorption effect of hydroxyl PBDE; Suitable leacheate can remove some impurity, reduces interference; Suitable eluent then can effective wash-out object, improves the recovery.Therefore, the present invention is directed to food organic contaminant hydroxyl PBDE, select suitable solid-phase extraction column, leacheate and eluent, reach the object of effective purifying and enrichment.
Summary of the invention
The object of the invention is the purification enrichment preconditioning technique method providing 7 kinds of OH-PBDEs in a kind of easy, efficient food.Technical scheme of the present invention is as follows:
(1) activation of solid phase extraction column: add 5mL methylene chloride in Solid-Phase Extraction silica gel pillar, vacuum filtration drip washing, discards efflux; Add 5mL normal hexane again, vacuum filtration drip washing, discards efflux;
(2) loading: 5mL is contained OH-PBDEs (3-hydroxyl-2, 2 ', 4, 4 '-tetrabromo Biphenyl Ether (3-OH-BDE-47), 5-hydroxyl-2, 2 ', 4, 4 '-tetrabromo Biphenyl Ether (5-OH-BDE-47), 6-hydroxyl-2, 2 ', 4, 4 '-tetrabromo Biphenyl Ether (6-OH-BDE-47), 2 '-hydroxyl-2, 3 ', 4, 5 '-tetrabromo Biphenyl Ether (2 '-OH-BDE-68), 4-hydroxyl-2, 2 ', 3, 4 '-tetrabromo Biphenyl Ether (4-OH-BDE-42), 6-hydroxyl-2, 2 ', 3, 4, 4 '-pentabromo-Biphenyl Ether (6-OH-BDE-85), 6 '-hydroxyl-2, 2 ', 4, 4 ' 5-pentabromo-Biphenyl Ether (6 '-OH-BDE-99)) solution slowly join in the solid phase extraction column of activation, vacuum filtration, coutroi velocity is about 2mL/min, discard efflux,
(3) drip washing: after the solution containing OH-PBDEs is all by solid phase extraction column, adds 5mL leacheate, and vacuum filtration drip washing, discards efflux;
(4) wash-out: add 6mL eluent in solid phase extraction column, vacuum filtration, collects eluent in test tube;
(5) concentrated: eluent slowly blows to dry with nitrogen at 40 DEG C, obtains residue;
(6) redissolve: in residue, add 1mL acetonitrile, shake test tube gently, to transparent;
(7) filter: transparency liquid 0.22 μm of organic membrane filtration, collect filtrate, obtain the sample that can be used for the detection of liquid phase tandem mass spectrum.
Advantage of the present invention and beneficial effect are: adopt purification enrichment preconditioning technique of the present invention, the recovery is high, and energy pre-service simultaneously 7 kinds of OH-PBDEs, can be used for extensive sample detection, be suitable for standardization.
Accompanying drawing explanation
Fig. 1 HPLC-ESI-MS/MS detects the chromatogram that 7 kinds of OH-PBDEs mix mark solution.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details, but the present invention is not limited only to following embodiment.
Embodiment 1
Adopt HPLC-ESI-MS/MS to detect 7 kinds of OH-PBDEs (3-OH-BDE-47,5-OH-BDE-47,6-OH-BDE-47,2 '-OH-BDE-68,4-OH-BDE-42,6-OH-BDE-85,6 '-OH-BDE-99), liquid phase selects chromatographic column to be C simultaneously
18(150mm × 2.00mm, 3 μm); Column temperature: 35 DEG C; Sample size: 10 μ L; Mobile phase: 0.1% formic acid and acetonitrile; Gradient elution program is in table 1; Flow velocity: 0.25mL/min.
Mass spectrum adopts electron spray, Negative electrospray ionization scan pattern (ESI
-), multiple reaction monitoring (MRM); Ion spray voltage: 4500V; Ion source temperature T:500 DEG C; Atomization gas Gas1:25; Atomization gas Gas2:20.
The chromatic graph spectrum of 7 kinds of OH-PBDEs is shown in accompanying drawing 1, and quantitation curves regression equation is in table 2.
Table 1 condition of gradient elution
Table 2HPLC-ESI-MS/MS detects the parameter of 7 kinds of hydroxyl PBDEs
Embodiment 2
Accurately measure 7 kinds of each 100 μ L of standard solution in the brown volumetric flask of 10mL, be settled to 10mL with acetonitrile, be mixed with the OH-PBDEs hybrid standard storing solution of 100ng/mL.By silica gel SPE pillar (1g/6mL) 5mL methylene chloride and the activation of 5mL normal hexane, the 5mL10ng/mL standard solution be configured to the OH-PBDEs hybrid standard storing solution of 100ng/mL is slowly joined in the solid phase extraction column of activation, after the solution containing OH-PBDEs is all by solid phase extraction column, add the drip washing of 5mL normal hexane, vacuum filtration leacheate, discards efflux; In pillar, add 6mL dichloromethane eluant afterwards, vacuum filtration, collect eluent in test tube; At 40 DEG C, nitrogen slowly dries up, then with 1mL acetonitrile redissolve residue, with 0.22 μm of organic membrane filtration acetonitrile solution, carry out HPLC-ESI-MS/MS detection, condition determination is as embodiment 1.The checking recovery and standard deviation (R.S.D), complete 3 parallel laboratory tests.Analysis result is in table 3
As shown in Table 3, the recovery of 7 kinds of hydroxyl PBDEs is between 82.83% ~ 99.83%, and relative standard deviation is all lower than 10%, and veracity and precision is good.
The veracity and precision of table 37 kind of hydroxyl PBDE
Above preferred embodiment is only for illustration of content of the present invention; in addition; the present invention also has other embodiments; in every case those skilled in the art are because of technology involved in the present invention enlightenment, and the technical scheme adopting equivalent replacement or equivalent deformation mode to be formed all drops in protection scope of the present invention.
Claims (7)
1. a purification enrichment preconditioning technique for food organic contaminant hydroxyl PBDE, is characterized in that: comprise the steps:
(1) activation of solid phase extraction column: add 5mL methylene chloride in Solid-Phase Extraction silica gel pillar, vacuum filtration drip washing, discards efflux; Add 5mL normal hexane again, vacuum filtration drip washing, discards efflux;
(2) loading: solution 5mL being contained OH-PBDEs slowly joins in the solid phase extraction column of activation, vacuum filtration, and coutroi velocity is about 2mL/min, discards efflux;
(3) drip washing: after the solution containing OH-PBDEs is all by solid phase extraction column, adds 5mL leacheate, and vacuum filtration drip washing, discards efflux;
(4) wash-out: add eluent in solid phase extraction column, vacuum filtration, collects eluent in test tube;
(5) concentrated: eluent slowly blows to dry with nitrogen at 40 DEG C, obtains residue;
(6) redissolve: in residue, add 1mL acetonitrile, shake test tube gently, to transparent;
(7) filter: transparency liquid 20.22 μm of organic membrane filtrations, collect filtrate, obtain the bar product that can be used for the detection of liquid phase tandem mass spectrum.
2. the purification enrichment preconditioning technique of a kind of food organic contaminant hydroxyl PBDE according to claim 1, it is characterized in that: the hydroxyl PBDE related to is: 3-hydroxyl-2, 2 ', 4, 4 '-tetrabromo Biphenyl Ether (3-OH-BDE-47), 5-hydroxyl-2, 2 ', 4, 4 '-tetrabromo Biphenyl Ether (5-OH-BDE-47), 6-hydroxyl-2, 2 ', 4, 4 '-tetrabromo Biphenyl Ether (6-OH-BDE-47), 2 '-hydroxyl-2, 3 ', 4, 5 '-tetrabromo Biphenyl Ether (2 '-OH-BDE-68), 4-hydroxyl-2, 2 ', 3, 4 '-tetrabromo Biphenyl Ether (4-OH-BDE-42), 6-hydroxyl-2, 2 ', 3, 4, 4 '-pentabromo-Biphenyl Ether (6-OH-BDE-85), 6 '-hydroxyl-2, 2 ', 4, 4 ' 5-pentabromo-Biphenyl Ether (6 '-OH-BDE-99).
3. the purification enrichment preconditioning technique of a kind of food organic contaminant hydroxyl PBDE according to claim 1, is characterized in that: the solid phase extraction column selected in described step (1)-(4) is silica gel pillar.
4. the purification enrichment preconditioning technique of a kind of food organic contaminant hydroxyl PBDE according to claim 1, is characterized in that: the leacheate selected in described step (3) is normal hexane.
5. the purification enrichment preconditioning technique of a kind of food organic contaminant hydroxyl PBDE according to claim 1, is characterized in that: the eluent selected in described step (4) is methylene chloride.
6. the purification enrichment preconditioning technique of a kind of food organic contaminant hydroxyl PBDE according to claim 1, is characterized in that: the effluent volume selected in described step (4) is 6mL.
7. the purification enrichment preconditioning technique of a kind of food organic contaminant hydroxyl PBDE according to claim 1, is characterized in that: the recovery of 7 kinds of hydroxyl PBDEs is between 82.83% ~ 99.83%, and relative standard deviation is all lower than 10%.
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Cited By (3)
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| CN105699526A (en) * | 2016-02-02 | 2016-06-22 | 环境保护部华南环境科学研究所 | Method for detecting contents of brominated flame retardant and phosphorus-based flame retardant in hairs |
| CN105891358A (en) * | 2016-04-05 | 2016-08-24 | 中国科学院生态环境研究中心 | Method for simultaneously detecting 21 hydroxyl polybrominated diphenyl ethers (OH-PBDEs) in soil |
| CN111257439A (en) * | 2019-11-20 | 2020-06-09 | 浙江省海洋水产研究所 | Method for detecting hydroxyl polybrominated diphenyl ethers in aquatic products by solid-phase extraction-ultra-high performance liquid chromatography tandem mass spectrometry |
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| CN103869016A (en) * | 2014-03-26 | 2014-06-18 | 昆山洛丹伦生物科技有限公司 | Method for detecting PBDEs (Poly Brominated Diphenyl Ethers) in plastic components of electronic components and devices |
| CN104007210A (en) * | 2013-02-27 | 2014-08-27 | 上海宝钢工业技术服务有限公司 | Extraction and purification method for polybrominated biphenyls and polybrominated diphenyl ethers in coating sample |
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| CN104007210A (en) * | 2013-02-27 | 2014-08-27 | 上海宝钢工业技术服务有限公司 | Extraction and purification method for polybrominated biphenyls and polybrominated diphenyl ethers in coating sample |
| CN103869016A (en) * | 2014-03-26 | 2014-06-18 | 昆山洛丹伦生物科技有限公司 | Method for detecting PBDEs (Poly Brominated Diphenyl Ethers) in plastic components of electronic components and devices |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105699526A (en) * | 2016-02-02 | 2016-06-22 | 环境保护部华南环境科学研究所 | Method for detecting contents of brominated flame retardant and phosphorus-based flame retardant in hairs |
| CN105891358A (en) * | 2016-04-05 | 2016-08-24 | 中国科学院生态环境研究中心 | Method for simultaneously detecting 21 hydroxyl polybrominated diphenyl ethers (OH-PBDEs) in soil |
| CN111257439A (en) * | 2019-11-20 | 2020-06-09 | 浙江省海洋水产研究所 | Method for detecting hydroxyl polybrominated diphenyl ethers in aquatic products by solid-phase extraction-ultra-high performance liquid chromatography tandem mass spectrometry |
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Application publication date: 20151104 |