CN102841162A - Method for simultaneously and quickly determining contents of multiple organic phosphate fire retardants in drinking water - Google Patents
Method for simultaneously and quickly determining contents of multiple organic phosphate fire retardants in drinking water Download PDFInfo
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- 239000003651 drinking water Substances 0.000 title claims abstract description 11
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- 229910019142 PO4 Inorganic materials 0.000 title abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 4
- 239000010452 phosphate Substances 0.000 title abstract description 4
- 235000020188 drinking water Nutrition 0.000 title abstract 2
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- 238000012360 testing method Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
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- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012453 solvate Substances 0.000 claims 1
- 238000001819 mass spectrum Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
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- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
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- 238000004128 high performance liquid chromatography Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 15
- 238000001514 detection method Methods 0.000 description 8
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 7
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 description 5
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 5
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 description 4
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 4
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- -1 brominated substituted alkyl OPEs Chemical class 0.000 description 2
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 2
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005477 standard model Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000001284 gas chromatography-nitrogen--phosphorus detection Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
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- XDEPVFFKOVDUNO-UHFFFAOYSA-N pentafluorobenzyl bromide Chemical compound FC1=C(F)C(F)=C(CBr)C(F)=C1F XDEPVFFKOVDUNO-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
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- 239000002349 well water Substances 0.000 description 1
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Abstract
The invention provides a method for simultaneously and quickly determining contents of multiple organic phosphate fire retardants in drinking water and belongs to the field of the determination for the organic phosphate fire retardants. The method mainly comprises the following steps of: performing solid-phase column extraction; eluting with solvents; concentrating and fixing volume; and determining a to-be-determined sample by using a high performance liquid chromatography-triple quadrupole rod mass spectrum combined meter. According to the method provided by the invention, the high performance liquid chromatography and tandem mass spectrum condition parameters are established and optimized, so that the simultaneous determination for three types (halogen-free, chloro-free and bromo-free) of ten organic phosphates can be realized; the determining method is excellent in selectivity and sensitivity, realizes the quick, accurate and quantitative determination for the contents of multiple organic phosphates under water condition by using the advantage in determined compound nature of the two-level mass spectrum, and overcomes the defects of the prior art in the field.
Description
Technical field
The invention belongs to machine phosphate flame retardant content detection field, the method for multiple organophosphorus ester flame-proof agent content in a kind of while fast measuring potable water of saying so more specifically.
Background technology
(organophosphate esters is that (organophosphorus flameretardants OPFRs), has been widely used in industries such as chemical industry, weaving, building materials and electronics to a type of important organophosphorous fire retardant at present OPEs) to organophosphate.Because several kinds of PBDE based flame retardants are forbidden at world wide gradually, organophosphate has also all had significantly increase because of its outstanding flame retardant effect demand and turnout worldwide.According to statistics, global annual turnout is up to 200,000 tons, and China produced 70,000 tons in 2007, export 40,000 surplus ton.Since organophosphate mainly with addition manner but not the chemical bonding mode join in the material, so this has just increased the probability that it gets into surrounding environment.Bibliographical information all has organophosphate to detect in Germany, Australia, Japan, Italy, Spain and the Chinese surface water.The detection of organophosphate and few in the potable water at present also detect in wherein German underground water, Italian well water, the Spain's tap water, but method still is in the development phase.
Though organophosphate all is to have replaced three hydrogen on the phosphate group by three groups; But the difference of substituted radical just; Cause the physicochemical property between the different organophosphates to have very big-difference; Comprise polarity, volatility, water-disintegrable etc., this has also brought very big difficulty to analyzing and testing.Mainly contain two kinds to multiple organophosphate method for measuring simultaneously in the potable water at present; Vapor-phase chromatography and liquid chromatography mass coupling method; GC-NPD and GC-EI-MS are two kinds of main detection methods of gas phase, and NPD's is stable bad, and the EI-MS matrix interference is apparent in view; In addition, some OPEs (like TEHP) boiling point is higher, is difficult to volatilization; Therefore gas phase process is improper, often needs complicated pre-treatment program, but also has many documents to attempt; Schindler literary composition in Journal of Chromatography B in 2009 is mentioned, and utilizes PFBBR bromine (PFBBr) to make derivatization reagent, thereby has realized the detection of TCEP, TPP etc.; But complex steps, and influence reappearance; LC-MS/MS shows excellent adaptability and reliability, and the selectivity of SRM and sensitivity detect than GC-MS and all wants high, and the multiple choices of ioning method can be the selection that offers the best of reduction matrix effect.Yet there are much identical deficiencies in the LC-MS/MS detection method to OPEs in the potable water with gas phase process at present, comprising: a, length consuming time (average more than 20 minutes, have in addition want more than 30 minute); B, target OPEs limited (generally contain a small amount of several kinds of alkyl replacement and chloro alkyl and replace OPEs, not brominated substituted alkyl OPEs).In the recent period the Liu Jing of Chinese Academy of Sciences richness developed a kind of method can be than the harmonic analysis time, but this analysis speed still remains raising, and this method do not insert bromo alkyl OPEs, influences its range of application to a certain extent.
Summary of the invention
1, invents the technical matters that will solve
The object of the present invention is to provide the method for multiple organophosphorus ester flame-proof agent content in a kind of while fast measuring potable water.Use Ultra Performance Liquid Chromatography-triple quadrupole bar mass spectrum to set up and optimize three major types (Halogen generation, chloro, bromo) totally 10 kinds of organophosphates (TPP, TCPP, TDCPP, TDBPP, TCEP, TEHP, TBEP, TBP, EHDPP, d27-TBP; Wherein d27-TBP is the substitute standard specimen) second order ms (MS/MS) detection method; Make this method that good selectivity and sensitivity can be arranged the detection method of target compound through optimization to liquid chromatography, tandem mass spectrum conditional parameter; And utilize the advantage of second order ms on compound is qualitative, realize the content of multiple organophosphate in quick, the accurate detection by quantitative water environment.
2, technical scheme
For realizing above-mentioned purpose, reach above-mentioned effect, the present invention realizes through following technical scheme:
The method of multiple organophosphorus ester flame-proof agent content the steps include: in a kind of while fast measuring potable water
(1) the little column extracting of solid phase: utilize solid phase extraction column that organophosphate contained in the water sample is carried out enrichment;
(2) wash-out: object is eluted from solid-phase extraction column with acetonitrile;
(3) concentrate: eluent is concentrated, and solvent replacing is constant volume again, is transferred in the sample introduction bottle to preserve;
(4) go up machine testing: sample is measured through Ultra Performance Liquid Chromatography-triple quadrupole bar GC-MS.
Said solid phase extraction column, adopt Supelco the C18 pillar (specification: 1g/6mL), before the use respectively with 10 mL acetonitriles and the activation cleaning successively of 10mL deionized water.
Said elution process is carried out wash-out with twice acetonitrile solution, one time 6 mL.
Said Ultra Performance Liquid Chromatography-mass spectrum condition is:
Ultra Performance Liquid Chromatography appearance: the ACQUITY UPLC of Waters company; Chromatographic column: Waters BEH phenyl post (2.1 mm * 100 mm, 1.7 μ m), column temperature is set to 40 ℃; Moving phase: A: water, B: methyl alcohol all adds the formic acid of 0.1% (v/v); Flow velocity is set 0.4mL/min; Eluent gradient is set by following the description: 5% (B) rises to 100% (B) in 8 minutes, drops to 5% (B) then in 1 minute, keeps 1 minute.Sampling volume is 10 μ L.
Mass spectrometer: the Quattro Ultima of Waters company triple quadrupole bar mass spectrum; Ion gun: ESI; Ionization pattern: positive ion mode; Atomization gas is selected high purity nitrogen and high-purity argon respectively with collision gas; Capillary voltage: 4.0kV; Ion gun and probe temperature are respectively 100 ℃ and 300 ℃; Taper hole blowback air flow: 150L/h; Desolventizing air-flow: 700L/h; Acquisition mode: SRM.The Ultra Performance Liquid Chromatography of each organophosphate-mass spectrometer parameter is seen table 1;
Table 1:
3, beneficial effect
This method provides the method for multiple organophosphorus ester flame-proof agent content in a kind of while fast measuring potable water, adopts Ultra Performance Liquid Chromatography-triple quadrupole bar mass spectrometry combination method.These method characteristics are that Ultra Performance Liquid Chromatography has improved instrumental analysis speed greatly; Shortened the time of instrumental analysis; Utilize triple quadrupole bar mass spectrum effectively to reduce background interference simultaneously, simplified the loaded down with trivial details step of sample pre-treatments simultaneously, reduced the method detectability in conjunction with solid phase extraction techniques.
Experiment shows: the instrument detecting limit (being defined as three times of signal to noise ratio (S/N ratio)s) through optimizing the final multiple organophosphate of confirming is 0.005-0.368ug/L, and method quantitatively is limited to 0.5-1ng/L.Typical curve related coefficient (R
2) between 0.9934-0.9992, satisfy and analyze requirement.
Description of drawings:
Fig. 1 is the chromatographic peak figure of 10 kinds of organophosphates among the embodiment 2.
Embodiment:
The present invention will be described below in conjunction with specifically executing example.Employed Ultra Performance Liquid Chromatography-mass spectrum condition is consistent with technical scheme.
Embodiment 1
1, the preparation of typical curve sample: use methyl alcohol to be mixed with the mixing standard specimen storing solution that concentration is 1 mg/L 10 kinds of organophosphate standard items (TPP, TCPP, TDCPP, TDBPP, TCEP, TEHP, TBEP, TBP, EHDPP, d27-TBP), utilize the hybrid standard use liquid of this storing solution preparation gradient for 1-500 ng/L;
2, the drafting of typical curve: utilize Ultra Performance Liquid Chromatography-triple quadrupole bar GC-MS; Use liquid to detect by instrument condition described in the summary of the invention to each concentration gradient hybrid standard; To select the ion pair chromatographic peak area is ordinate, and corresponding concentration is a horizontal ordinate drawing standard curve.The result shows: typical curve related coefficient (R
2) between 0.9934-0.9992, the instrument detecting limit of confirming thus (being defined as three times of signal to noise ratio (S/N ratio)s) is 0.005-0.368 ug/L, instrument quantitatively is limited to 1-2 ug/L.
Embodiment 2
1, gets 6 parts of 1L tap water; Wherein 3 parts add organophosphate hybrid standard sample (TPP, TCPP, TDCPP, TDBPP, TCEP, TEHP, TBEP, TBP, EHDPP, d27-TBP) the 50 μ L that concentration is 1 mg/L respectively; Promptly being made into concentration is the mixed mark tap water sample of 50 ng/L, and other 3 parts only add d27-TBP standard model use liquid 5 uL that concentration is 10 mg/L.
2, sample preparation: the C18 pillar good with prior activation processing carries out SPE, and flow velocity keeps being about 5 mL/min, and whole process notices guaranteeing that pillar is moistening, and be after water sample has been crossed, that the SPE pillar is dry; The method wash-out in the summary of the invention is pressed in dry back; Twice eluent is collected in the same receiving flask; Utilize Rotary Evaporators that effluent volume is reduced to below 1 mL, clean the transfer back and slowly blow near dried, solvent replacing is become methyl alcohol with high purity nitrogen; Final constant volume is transferred in the sample introduction bottle to 0.5 mL, is kept in-20 ℃ of refrigerators to be measured.
3, Instrument measuring and qualitative, quantitative: right according to retention time and characteristic ion, confirm the chromatographic peak (see figure 1) of 10 kinds of organophosphates; According to peak area, utilize external standard method calculation sample concentration.All between 90%-100%, other material does not detect for three parts of blank sample substitute recovery, and the recovery of other three duplicate samples is all at (remove TEHP 64.08%, EHDPP 19.26%) more than 80%.
Embodiment 3
1, gets 6 portions of 1L mineral waters; Wherein 3 parts add organophosphate hybrid standard sample (TPP, TCPP, TDCPP, TDBPP, TCEP, TEHP, TBEP, TBP, EHDPP, d27-TBP) the 50 μ L that concentration is 1 mg/L respectively; Promptly being made into concentration is the mixed mark mineral water sample of 50 ng/L, and other 3 parts only add d27-TBP standard model use liquid 5 uL that concentration is 10 mg/L.
2, carry out sample preparation like embodiment 1, all between 90%-100%, other material does not detect for three parts of blank sample substitute recovery, and the recovery of three duplicate samples is all at (remove TEHP 34.47%, EHDPP 18.93%) more than 80%.
Claims (7)
1. the method for multiple organophosphorus ester flame-proof agent content in the fast measuring potable water simultaneously the steps include:
(1) the little column extracting of solid phase: utilize solid phase extraction column that organophosphate contained in the water sample is carried out enrichment;
(2) wash-out: object is eluted from solid-phase extraction column with acetonitrile;
(3) concentrate: eluent is concentrated, and solvent replacing is constant volume again, is transferred in the sample introduction bottle to preserve;
(4) go up machine testing: sample is measured through Ultra Performance Liquid Chromatography-triple quadrupole bar GC-MS.
2. according to right 1 described assay method, it is characterized in that solid phase extraction column is the C18 pillar of Supelco in the step (1), flow velocity should keep being about 5 mL/min, and whole process guarantees that pillar is moistening.
3. according to right 1 described assay method, it is characterized in that the said solvent replacing of step (3) is meant original acetonitrile solvent is replaced to methanol solvate.
4. according to right 1 described assay method, it is characterized in that the first alcohol and water that adds 0.1% (v/v) formic acid when said Ultra Performance Liquid Chromatography-triple quadrupole bar GC-MS is measured carries out gradient elution as moving phase.
5. according to right 4 described assay methods, it is characterized in that, adopt Waters BEH phenyl column liquid chromatographic post to analyze when said Ultra Performance Liquid Chromatography-triple quadrupole bar GC-MS is measured as separating column.
6. according to right 4 described assay methods, it is characterized in that, is ion gun with ESI when said Ultra Performance Liquid Chromatography-triple quadrupole bar GC-MS is measured, and the ionization pattern is a positive ion mode.
7. according to each described assay method in right 5 or 6, it is characterized in that detecting scan mode SRM with choice reaction when said high performance liquid chromatography-triple quadrupole bar GC-MS is measured is data acquisition modes.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104049049A (en) * | 2014-07-09 | 2014-09-17 | 南京大学 | Method for synchronously detecting plurality of organophosphorus fire retardants in bottom mud |
| CN105403650A (en) * | 2015-12-07 | 2016-03-16 | 中华人民共和国临沂出入境检验检疫局 | Determination method for chlorophosphate flame retardant in wood product |
| CN107422048A (en) * | 2017-04-10 | 2017-12-01 | 中国水产科学研究院黑龙江水产研究所 | Water sample level Four bar flight time mass spectrum method for combined use is identified without standard items rapid screening |
| CN107843666A (en) * | 2017-11-07 | 2018-03-27 | 山西农业大学 | A kind of quick determination method of organic pollutants |
| CN109374769A (en) * | 2018-11-14 | 2019-02-22 | 天津大学 | A kind of method of a variety of organophosphorus esters in ultra performance liquid chromatography-mass spectroscopy surface water |
| CN110806451A (en) * | 2019-10-16 | 2020-02-18 | 生态环境部南京环境科学研究所 | Method for measuring content of phosphodiester metabolites of OPEs in plasma |
| CN111044643A (en) * | 2019-12-31 | 2020-04-21 | 中国环境科学研究院 | Detection method of organic phosphate |
| CN115598263A (en) * | 2022-11-25 | 2023-01-13 | 国科大杭州高等研究院（Cn） | Method for simultaneously determining contents of organic phosphate and conversion product thereof |
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