CN116718681A - Sampler for organic phosphate and metabolite thereof in indoor air and sampling and measuring method thereof - Google Patents
Sampler for organic phosphate and metabolite thereof in indoor air and sampling and measuring method thereof Download PDFInfo
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- CN116718681A CN116718681A CN202310473974.0A CN202310473974A CN116718681A CN 116718681 A CN116718681 A CN 116718681A CN 202310473974 A CN202310473974 A CN 202310473974A CN 116718681 A CN116718681 A CN 116718681A
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- solid phase
- phase extraction
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- methanol
- ethyl acetate
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- 238000005070 sampling Methods 0.000 title claims abstract description 45
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 40
- 239000010452 phosphate Substances 0.000 title claims abstract description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002207 metabolite Substances 0.000 title claims abstract description 23
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 77
- 238000012856 packing Methods 0.000 claims abstract description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 174
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 159
- 239000003365 glass fiber Substances 0.000 claims description 45
- 239000000945 filler Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 30
- 239000003480 eluent Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001514 detection method Methods 0.000 claims description 20
- 238000010813 internal standard method Methods 0.000 claims description 14
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 33
- 150000003014 phosphoric acid esters Chemical class 0.000 description 25
- 239000000126 substance Substances 0.000 description 22
- 235000018087 Spondias lutea Nutrition 0.000 description 16
- 238000011084 recovery Methods 0.000 description 16
- 238000010828 elution Methods 0.000 description 8
- -1 bis (2-hydroxyethyl) 2- (3-hydroxybutoxy) ethyl Chemical group 0.000 description 7
- 238000011109 contamination Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 5
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 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 3
- WBRNMKRNLOPRGC-UHFFFAOYSA-N 2,2-dibutoxyethyl dihydrogen phosphate Chemical compound CCCCOC(COP(O)(O)=O)OCCCC WBRNMKRNLOPRGC-UHFFFAOYSA-N 0.000 description 2
- PMGHIGLOERPWGC-UHFFFAOYSA-N Bis-(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(O)OCCCl PMGHIGLOERPWGC-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UQSRKBXTCXVEJL-UHFFFAOYSA-N bis(2-butoxyethyl) 2-hydroxyethyl phosphate Chemical compound CCCCOCCOP(=O)(OCCO)OCCOCCCC UQSRKBXTCXVEJL-UHFFFAOYSA-N 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- HQYOAUQRZRQVDY-UHFFFAOYSA-M dibenzoyl phosphate Chemical compound C=1C=CC=CC=1C(=O)OP(=O)([O-])OC(=O)C1=CC=CC=C1 HQYOAUQRZRQVDY-UHFFFAOYSA-M 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 2
- PXZZRISEDBDRLY-UHFFFAOYSA-N (2-tert-butylphenyl) dihydrogen phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(O)(O)=O PXZZRISEDBDRLY-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UXEXPVAWQLGFAP-UHFFFAOYSA-N CC(Cl)COP(O)(=O)OCC(C)Cl Chemical compound CC(Cl)COP(O)(=O)OCC(C)Cl UXEXPVAWQLGFAP-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- AUUWEOBTRZWTTC-UHFFFAOYSA-N bis(1-chloropropan-2-yl) 1-hydroxypropan-2-yl phosphate Chemical compound OCC(C)OP(=O)(OC(C)CCl)OC(C)CCl AUUWEOBTRZWTTC-UHFFFAOYSA-N 0.000 description 1
- OHRCKPRYDGSBRN-UHFFFAOYSA-N bis(2-methylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC=C1OP(O)(=O)OC1=CC=CC=C1C OHRCKPRYDGSBRN-UHFFFAOYSA-N 0.000 description 1
- PLUDEAUQZKPAIN-UHFFFAOYSA-N bis(4-methylphenyl) hydrogen phosphate Chemical compound C1=CC(C)=CC=C1OP(O)(=O)OC1=CC=C(C)C=C1 PLUDEAUQZKPAIN-UHFFFAOYSA-N 0.000 description 1
- NXMAGNXUXORQMR-UHFFFAOYSA-N butan-2-yloxy ethyl hydrogen phosphate Chemical compound P(=O)(OOC(C)CC)(O)OCC NXMAGNXUXORQMR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HDFFVHSMHLDSLO-UHFFFAOYSA-M dibenzyl phosphate Chemical compound C=1C=CC=CC=1COP(=O)([O-])OCC1=CC=CC=C1 HDFFVHSMHLDSLO-UHFFFAOYSA-M 0.000 description 1
- LJBNHONKIDIOPD-UHFFFAOYSA-N dibutyl 3-hydroxybutyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCC(C)O LJBNHONKIDIOPD-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002038 ethyl acetate fraction Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002032 methanolic fraction Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical class OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- MGEISCKTUGVOHN-UHFFFAOYSA-N tris(2-hydroxyethyl) phosphate Chemical compound OCCOP(=O)(OCCO)OCCO MGEISCKTUGVOHN-UHFFFAOYSA-N 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a sampler for organic phosphate and metabolites thereof in indoor air and a sampling and measuring method thereof. The invention takes CNWBONDHC-C18 packing and CNWBONDCN packing as packing of the solid phase extraction column, and the CNWBONDHC-C18 packing and the CNWBOND CN packing have higher selectivity and higher adsorption capacity on organic phosphate and metabolites thereof. Moreover, the sampler provided by the invention has the advantages of simple structure and convenience in use, and is suitable for wide application.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a sampler for organic phosphate and metabolites thereof in indoor air and a sampling and measuring method thereof.
Background
Organic phosphates (Organophosphate esters, OPEs) are a class of triphosphate compounds having side chains substituted with alkyl, aryl or chloroalkyl groups. OPEs are used in large amounts as flame retardants or plasticizers and are widely used in various household and industrial products due to their excellent properties in terms of reducing the flammability or increasing the plasticity of polymers. Whereas most OPEs are routinely added rather than chemically bound to the product, they are easily released into the environment by volatilization, abrasion or leaching.
At present, the collection of OPEs in the atmosphere mainly adopts a high-flow sampler for active sampling, specifically, the high-flow sampler uses polyurethane foam (PUF) and polystyrene ion exchange resin filler (XAD-2) as enrichment media, and uses a glass fiber filter membrane (glass fiber filter, GFF) or a quartz fiber filter membrane (quartz fiber filter, QFF) to collect the interception particle phase compound, but the high-flow sampler is widely applied to the collection of outdoor low-concentration atmospheric samples, and has the advantages of larger volume, more energy consumption and poor portability.
The method has the advantages of low energy consumption, portability and high efficiency when the enrichment capacity meets the quantitative analysis, can reflect the short-time change trend of concentration, and is more suitable for indoor air sample collection. At present, for collecting OPEs in indoor air, the existing small-flow sampler generally enriches samples based on PUF and XAD-2 resin fillers, and then adopts solvent consumption methods such as a Soxhlet extraction method, a rotary evaporator or an ultrasonic extraction method to extract the OPEs adsorbed in the fillers, and then sequentially carries out solid phase extraction column purification, nitrogen blowing concentration and sample injection detection.
Disclosure of Invention
In view of the above, the present invention aims to provide a sampler for organic phosphate and its metabolites in indoor air and a sampling and measuring method thereof. The sampler provided by the invention remarkably simplifies the sampling process of organic phosphate and metabolites thereof in indoor air, and reduces the interference of uncertainty factors on sampling measurement results.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a sampler for organic phosphate and metabolites thereof in indoor air, which comprises:
a plurality of solid phase extraction columns 1 connected in parallel;
each solid phase extraction column 1 is internally provided with a glass fiber sieve plate 1-3, a glass fiber sieve plate 1-4 and a glass fiber sieve plate 1-5;
packing for packing the solid phase extraction column 1, the packing comprising CNWBOND HC-C18 packing 1-1 and CNWBOND CN packing 1-2; the glass fiber sieve plate 1-3 divides the filler into an upper layer and a lower layer; the CNWBOND HC-C18 filler 1-1 is positioned above the glass fiber screen plate 1-3 and below the glass fiber screen plate 1-4; the CNWBOND CN filler 1-2 is positioned below the glass fiber screen plate 1-3 and above the glass fiber screen plate 1-5;
a flowmeter 2 connected with the outlet of the solid phase extraction column 1 through a pipeline;
and a diaphragm vacuum pump 3 connected with the outlet of the flowmeter 2 through a pipeline.
Preferably, the inner diameter of the solid phase extraction column is 12.5-13 mm, and the height is 65-70 mm.
Preferably, the particle sizes of the CNWBOND HC-C18 filler 1-1 and the CNWBOND CN filler 1-2 are independently 40-63 μm.
Preferably, the volume ratio of the CNWBOND HC-C18 packing 1-1 to the single solid phase extraction cartridge is 250mg: 8.5-9 mL; the volume ratio of CNWBOND CN packing 1-2 to single solid phase extraction cartridge was 250mg: 8.5-9 mL.
The invention also provides a method for collecting organic phosphate and metabolites thereof in indoor air by using the sampler, which comprises the following steps:
after the solid phase extraction column 1 is activated, a sampler is placed in a room to be tested, and a diaphragm vacuum pump 3 is started for sampling; during the sampling, the height of the solid phase extraction column 1 in the sampler from the ground is more than or equal to 1m.
Preferably, the activation is methanol activation and ethyl acetate activation which are sequentially performed.
Preferably, the sampling rate is 3.5-4.5L/min, and the sampling time is 8-12 h.
The invention also provides a method for measuring the organic phosphate and the metabolite thereof in the indoor air, which is characterized by comprising the following steps:
adding an organic phosphate internal standard and an organic phosphate metabolite internal standard into the sampled solid-phase extraction column 1, and then eluting with ethyl acetate and methanol in sequence to obtain an ethyl acetate eluent and a methanol eluent respectively;
combining the ethyl acetate eluates to obtain ethyl acetate to-be-detected liquid;
combining the methanol eluents to obtain methanol to-be-detected liquid;
and blowing the liquid nitrogen to be tested of the ethyl acetate to be near dry, re-dissolving the liquid nitrogen with methanol, performing high performance liquid chromatography-tandem mass spectrometry detection, and calculating by an internal standard method to obtain the concentration of the organic phosphate in the indoor air.
Directly performing high performance liquid chromatography-tandem mass spectrometry detection on the methanol to-be-detected liquid, and calculating by an internal standard method to obtain the concentration of the organic phosphate metabolite in the indoor air;
the sampled solid phase extraction column 1 is the solid phase extraction column 1 obtained by sampling according to the method in the technical scheme.
Preferably, the mass ratio of the volume of the methanol for elution to the packing in the single solid phase extraction small column is 4-5 mL:500mg.
Preferably, the mass ratio of the volume of the methanol for ethyl acetate to the packing in the single solid phase extraction column is 4-5 mL:500mg.
The invention provides a sampler for organic phosphate and metabolites thereof in indoor air, which comprises: a plurality of solid phase extraction columns 1 connected in parallel; each solid phase extraction column 1 is internally provided with a glass fiber sieve plate 1-3, a glass fiber sieve plate 1-4 and a glass fiber sieve plate 1-5; packing for packing the solid phase extraction column 1, the packing comprising CNWBOND HC-C18 packing 1-1 and CNWBOND CN packing 1-2; the glass fiber sieve plate 1-3 divides the filler into an upper layer and a lower layer; the CNWBOND HC-C18 filler 1-1 is positioned above the glass fiber screen plate 1-3 and below the glass fiber screen plate 1-4; the CNWBOND CN filler 1-2 is positioned below the glass fiber screen plate 1-3 and above the glass fiber screen plate 1-5; a flowmeter 2 connected with the outlet of the solid phase extraction column 1 through a pipeline; and a diaphragm vacuum pump 3 connected with the outlet of the flowmeter 2 through a pipeline. The invention takes CNWBOND HC-C18 filler and CNWBOND CN filler as filling filler of the solid phase extraction column, and the CNWBOND HC-C18 filler and the CNWBOND CN filler have higher selectivity and higher adsorption capacity on organic phosphate and metabolites thereof. Moreover, the sampler provided by the invention has the advantages of simple structure and convenience in use, and is suitable for wide application.
The invention also provides a method for measuring the organic phosphate and the metabolite thereof in the indoor air, which comprises the following steps: adding an organic phosphate internal standard and an organic phosphate metabolite internal standard into the sampled solid-phase extraction column 1, and then eluting with ethyl acetate and methanol in sequence to obtain an ethyl acetate eluent and a methanol eluent respectively; combining the ethyl acetate eluates to obtain ethyl acetate to-be-detected liquid; combining the methanol eluents to obtain methanol to-be-detected liquid; blowing ethyl acetate to be detected into liquid nitrogen to be near dry, re-dissolving the ethyl acetate with methanol, performing high performance liquid chromatography-tandem mass spectrometry detection, and calculating by an internal standard method to obtain the concentration of the organic phosphate in indoor air; directly performing high performance liquid chromatography-tandem mass spectrometry detection on the methanol to-be-detected liquid, and calculating by an internal standard method to obtain the concentration of the organic phosphate metabolite in the indoor air; the sampled solid phase extraction column 1 is the solid phase extraction column 1 obtained by sampling by the method. The invention directly elutes the sampled solid phase extraction column, the obtained eluent can be directly sampled for detection after concentration, compared with the prior art, the invention does not need the steps of solvent extraction and purification, thereby not only reducing the solvent consumption and simplifying the sampling flow, but also gradually eluting the organic phosphate and the metabolites thereof step by step, and simultaneously reducing the interference of uncertainty factors on the sampling and measuring result.
Drawings
FIG. 1 shows a sampler provided by the invention, wherein a 1-solid phase extraction column, a 1-1-CNWBOND HC-C18 filler, a 1-2-CNWBOND CN filler, a 1-3-1-5 glass fiber sieve plate, a 2-flowmeter and a 3-diaphragm vacuum pump are adopted.
Detailed Description
The invention provides a sampler for organic phosphate and metabolites thereof in indoor air, which comprises:
a plurality of solid phase extraction columns 1 connected in parallel;
each solid phase extraction column 1 is internally provided with a glass fiber sieve plate 1-3, a glass fiber sieve plate 1-4 and a glass fiber sieve plate 1-5;
packing for packing the solid phase extraction column 1, the packing comprising CNWBOND HC-C18 packing 1-1 and CNWBOND CN packing 1-2; the glass fiber sieve plate 1-3 divides the filler into an upper layer and a lower layer; the CNWBOND HC-C18 filler 1-1 is positioned above the glass fiber screen plate 1-3 and below the glass fiber screen plate 1-4; the CNWBOND CN filler 1-2 is positioned below the glass fiber screen plate 1-3 and above the glass fiber screen plate 1-5;
a flowmeter 2 connected with the outlet of the solid phase extraction column 1 through a pipeline;
and a diaphragm vacuum pump 3 connected with the outlet of the flowmeter 2 through a pipeline.
As shown in fig. 1, the sampler provided by the invention comprises a plurality of solid-phase extraction columns 1 connected in parallel. The number of the solid phase extraction columns 1 is particularly preferably 2 in the embodiment; in the embodiment of the invention, the inner diameter of the solid phase extraction small column 1 is particularly preferably 12.8mm, the outer diameter is preferably 14.7mm, and the height is preferably 68mm. Each solid phase extraction small column 1 is internally provided with a glass fiber sieve plate 1-3, a glass fiber sieve plate 1-4 and a glass fiber sieve plate 1-5. In the invention, the solid phase extraction columns are connected in parallel, so that the sampling rate can be increased.
In the invention, the packing of the solid phase extraction column comprises CNWBOND HC-C18 packing 1-1 and CNWBOND CN packing 1-2; in the present invention, the particle size of the CNWBOND HC-C18 filler 1-1 and the CNWBOND CN filler 1-2 is preferably 40 to 63. Mu.m. In the present invention, the volume ratio of the CNWBOND HC-C18 packing 1-1 to the single solid phase extraction cartridge is preferably 250mg: 8.5-9 mL. In the present invention, the volume ratio of the CNWBOND CN packing 1-2 to the single solid phase extraction cartridge was 250mg: 8.5-9 mL. In the present invention, the CNWBOND HC-C18 filler and CNWBOND CN filler are preferably purchased from CNW company, germany.
In the invention, the glass fiber screen plate 1-3 divides the filler into an upper layer and a lower layer, and the CNWBOND HC-C18 filler 1-1 is positioned above the glass fiber screen plate 1-3 and below the glass fiber screen plate 1-4. The CNWBOND CN filler 1-2 is located below the glass fiber screen 1-3 and above the glass fiber screen 1-5. In the present invention, the glass fiber sieve plate is not particularly limited, and a glass fiber sieve plate which is well known to those skilled in the art and is matched with the solid phase extraction column 1 may be used.
In the invention, the glass fiber sieve plate can prevent materials from mixing and leaking.
The sampler provided by the invention comprises a flowmeter 2 connected with the outlet of the solid phase extraction small column 1 through a pipeline. In the present invention, the flow meter 2 is not particularly limited, and a flow meter well known to those skilled in the art may be used to satisfy the range requirement. In the present invention, the flowmeter 2 is used to display the sampling rate.
The sampler provided by the invention comprises a diaphragm vacuum pump 3 connected with the outlet of the flowmeter 2 through a pipeline. In the present invention, the pumping rate of the diaphragm vacuum pump 3 is preferably 4.0L/min. The present invention is not particularly limited, and the diaphragm vacuum pump 3, which is well known to those skilled in the art, may be used to satisfy the pumping rate requirement. In the present invention, the diaphragm vacuum pump 3 is used to control the sampling rate.
In the present invention, the piping is preferably a silicone tube. The silica gel tube is not particularly limited, and silica gel tubes well known to those skilled in the art may be used.
The invention also provides a method for collecting organic phosphate and metabolites thereof in indoor air by using the sampler, which comprises the following steps:
after the solid phase extraction column 1 is activated, a sampler is placed in a room to be tested, and a diaphragm vacuum pump 3 is started for sampling.
In the present invention, the organic phosphate esters include diphenyl 2-ethylhexyl phosphate (EHDPP), tris (2-butoxyethyl) phosphate (TBOEP), tris (2-chloroethyl) phosphate (TCEP), tris (2-chloropropyl) phosphate (TCIPP), tricresyl phosphate (TCRP), tris (1, 3-dichloro-2-propyl) phosphate (TDCIPP, tris (2-ethylhexyl) phosphate (TEHP), triethyl phosphate (TEP), tri-n-butyl phosphate (TNBP), triisobutyl phosphate (TIBP), triphenyl phosphate (TPHP), triphenyl phosphate (TPP), bis (1-chloro-2-propyl) 1-hydroxy-2-propyl phosphate (BCIPP), bis (2-butoxyethyl) 2-hydroxyethyl phosphate (BBOEHEP), bis (3-hydroxybutyl) dibutyl phosphate (3-OH-BP), bis (2-hydroxyethyl) 2- (3-hydroxybutoxy) ethyl phosphate (3-OH-OEP) and di (OEP) 2-hydroxyethyl phosphate (BBOH) in the present invention, or the products of the present invention may be metabolized in the di-butoxyethyl phosphate (OEP) or in the di-butoxyethyl phosphate (OEP) of the present invention, one or more of (2-butoxy) ethyl phosphate (BOEP), bis (2-chloroethyl) phosphate (BCEP), bis (2-chloropropyl) phosphate (BCIPP), bis (1, 3-dichloro) isopropyl phosphate (BDCIPP), bis (2-ethylhexyl) phosphate (BEHP), dibutyl phosphate (DNBP), diphenyl phosphate (DPHP), di-o-tolyl phosphate (DoCP), di-p-tolyl phosphate (DpCP), dibenzyl phosphate (DTP), dibenzoyl phosphate (MDPP) and t-butylphenyl phosphate (tb-PPP).
In the present invention, the activation is preferably methanol activation and ethyl acetate activation which are sequentially performed. In the invention, the volume of the methanol and the mass ratio of the packing in the single solid phase extraction column are preferably 4-5 mL when the methanol is activated: 500mg. In the invention, when the ethyl acetate is activated, the mass ratio of the volume of the ethyl acetate to the filler in the single solid-phase extraction column is preferably 4-5 mL:500mg.
In the invention, after the solid phase extraction column 1 is activated, the activated solid phase extraction column 1 is preferably wrapped by aluminum foil and then sealed in a polypropylene bag, and then a sampler is carried into a room to be detected for sampling.
In the invention, during the sampling, the height of the solid phase extraction column 1 in the sampler from the ground is preferably more than or equal to 1m, and more preferably 1.2-1.5 m. In the present invention, the sampling rate controlled by the diaphragm vacuum pump 3 is preferably 3.5 to 4.5L/min, more preferably 4.0L/min, and the sampling time is preferably 8 to 12h, more preferably 10h.
The invention also provides a method for measuring the organic phosphate and the metabolite thereof in the indoor air, which comprises the following steps:
adding an organic phosphate internal standard and an organic phosphate metabolite internal standard into the sampled solid-phase extraction column 1, and then eluting with ethyl acetate and methanol in sequence to obtain an ethyl acetate eluent and a methanol eluent respectively;
combining the ethyl acetate eluates to obtain ethyl acetate to-be-detected liquid;
combining the methanol eluents to obtain methanol to-be-detected liquid;
blowing ethyl acetate to be detected into liquid nitrogen to be near dry, re-dissolving the ethyl acetate with methanol, performing high performance liquid chromatography-tandem mass spectrometry detection, and calculating by an internal standard method to obtain the concentration of the organic phosphate in indoor air;
directly performing high performance liquid chromatography-tandem mass spectrometry detection on the methanol to-be-detected liquid, and calculating by an internal standard method to obtain the concentration of the organic phosphate metabolite in the indoor air;
in the invention, the addition amount of the organic phosphate internal standard and the organic phosphate metabolite internal standard is preferably 5ng; in the invention, the ratio of the eluted ethyl acetate to the packing in the single solid phase extraction column is preferably 4-5 mL:500mg. In the present invention, the elution rate of the ethyl acetate is preferably 0.5 to 1 drop/sec. In the invention, the mass ratio of the volume of the methanol for elution to the packing in the single solid phase extraction column is preferably 4-5 mL:500mg, the eluting rate of the methanol is preferably 0.5 to 1 drop/sec.
In the present invention, after the combined ethyl acetate eluent and methanol eluent are obtained, the method preferably further comprises the steps of blowing, concentrating and fixing the volume of the combined eluent by liquid nitrogen, wherein in the embodiment of the present invention, the reagent for fixing the volume is preferably methanol, and the volume for fixing the volume is preferably 200 μl.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Device and method for controlling the same
As shown in fig. 1, the sampler consists of two parallel solid phase extraction columns; the inner diameter of the single solid phase extraction is 12.8mm, the outer diameter is 14.7mm, and the height is 68mm; the single solid phase extraction column is filled with 250mg of CNWBOND HC-C18 packing and 250mg of CNWBOND CN packing, and the CNWBOND HC-C18 packing and the CNWBOND CN packing are separated into an upper layer and a lower layer by a glass fiber sieve plate; the particle size of the CNWBOND HC-C18 filler and the CNWBOND CN filler is 40-63 μm.
A flowmeter connected with the outlet of the solid phase extraction column through a silica gel tube;
and a diaphragm vacuum pump communicated with the outlet of the flowmeter through a silica gel tube.
(2) Sample collection
Indoor air samples are collected in dormitories of men and women in a plurality of dormitory buildings of universities of south China.
Before sample collection, the solid phase extraction column is activated with 4mL of methanol and 4mL of ethyl acetate in sequence, wrapped with aluminum foil paper and sealed in a polypropylene bag for storage, and then carried to a sampling site. The sampling device is placed at a height of 1.2m from the ground, the sampling rate is about 4.0L/min, and the sample collection time is 10h. After the sampling is finished, the solid phase extraction column is still wrapped in aluminum foil, sealed in a polypropylene bag, transported back to a laboratory as soon as possible, and stored in a refrigerator at-20 ℃ for treatment.
(2) Sample processing
Before the solid phase extraction small column is eluted, 5ng of OPEs internal standard substance and 5ng of mOPEs internal standard substance are respectively added into the upper layer of the small column packing, then 4mL of ethyl acetate and 4mL of methanol are sequentially adopted for eluting, and ethyl acetate eluent and methanol eluent are respectively collected.
Combining the ethyl acetate eluates to obtain ethyl acetate to-be-detected liquid;
combining the methanol eluents to obtain methanol to-be-detected liquid;
blowing ethyl acetate to be detected into liquid nitrogen to be near dry, re-dissolving the ethyl acetate with methanol, performing high performance liquid chromatography-tandem mass spectrometry detection, and calculating by an internal standard method to obtain the concentration of the organic phosphate in indoor air;
and directly performing high performance liquid chromatography-tandem mass spectrometry detection on the methanol to-be-detected liquid, and calculating by an internal standard method to obtain the concentration of the organic phosphate metabolite in the indoor air.
The ratio of the amount of the substance of the OPEs internal standard substance, the amount of the substance of the mOPEs internal standard substance to the original contamination level (i.e. the amount of the substance added respectively) in the measurement result is respectively recorded as the sampling recovery rate of the sampler to the OPEs and the mOPEs, and the real concentration level of the organic phosphate in the sampling space can be obtained by dividing the amount of all the detected OPEs and the mOPEs (non-internal standard substance) by the sampling recovery rate of the corresponding internal standard substance.
Table 1 shows the sampling recovery rate of the sampler for OPEs and mOPEs in the indoor air of the dormitory; table 2 shows concentration levels of OPEs and mOPEs in the air in a dormitory room.
Table 1 sampler samples recovery rates of OPEs and mOPEs in students' dormitory indoor air (%)
| Contaminants (S) | Dormitory A | Dormitory B | Dormitory C | Dormitory D |
| TEP | 87.5 | 120 | 90.1 | 90.2 |
| TPP | 89.2 | 111 | 98.7 | 87.5 |
| TCIPP | 79.4 | 101 | 85.9 | 72.1 |
| DNBP | 88.3 | 106 | 78.3 | 69.9 |
| DoCP | 82.3 | 109 | 90.9 | 79.3 |
| BDCIPP | 81.0 | 113 | 98.3 | 72.4 |
TABLE 2 concentration levels of OPEs and mOPEs in part of dormitory indoor air (ng/m) 3 )
| Contaminants (S) | Internal standard | Dormitory A | Dormitory B | Dormitory C | Dormitory D |
| TEP | TEP-D15 | 8.28 | 34.7 | 28.5 | 58.2 |
| TPP | TPP-D12 | 0.06 | 0.01 | N.D. | 0.06 |
| TCIPP | TPP-D12 | 4.29 | 6.05 | 2.35 | 4.60 |
| DNBP | DNBP-D18 | N.D. | N.D. | 0.02 | N.D. |
| DoCP | DoCP-D12 | 0.05 | N.D. | N.D. | N.D. |
| BDCIPP | BDCIPP-D10 | N.D. | 0.27 | N.D. | N.D. |
Note that: N.D. in Table 2 shows that no detection or a detection concentration of less than 0.01ng/m 3 。
Example 2
(1) Sample collection
Indoor air samples are collected in a plurality of server machine rooms in the south-school zone of the jin of the university of south China.
Before sample collection, the solid phase extraction column is activated with 4mL of methanol and 4mL of ethyl acetate in sequence, wrapped with aluminum foil paper and sealed in a polypropylene bag for storage, and then carried to a sampling site. The sampling device is placed at a height of 1.2m from the ground, the sampling rate is about 4.0L/min, and the sample collection time is 10h. After the sampling is finished, the solid phase extraction column is still wrapped in aluminum foil, sealed in a polypropylene bag, transported back to a laboratory as soon as possible, and stored in a refrigerator at-20 ℃ for treatment.
(2) Sample processing
Before the solid phase extraction small column is eluted, 5ng of OPEs internal standard substance and 5ng of mOPEs internal standard substance are respectively added into the upper layer of the small column packing, then 4mL of ethyl acetate and 4mL of methanol are sequentially adopted for eluting, and ethyl acetate eluent and methanol eluent are respectively collected.
Combining the ethyl acetate eluates to obtain ethyl acetate to-be-detected liquid;
combining the methanol eluents to obtain methanol to-be-detected liquid;
blowing ethyl acetate to be detected into liquid nitrogen to be near dry, re-dissolving the ethyl acetate with methanol, performing high performance liquid chromatography-tandem mass spectrometry detection, and calculating by an internal standard method to obtain the concentration of the organic phosphate in indoor air;
and directly performing high performance liquid chromatography-tandem mass spectrometry detection on the methanol to-be-detected liquid, and calculating by an internal standard method to obtain the concentration of the organic phosphate metabolite in the indoor air.
The ratio of the amount of the substance of the OPEs internal standard substance, the amount of the substance of the mOPEs internal standard substance to the original contamination level (i.e. the amount of the substance added respectively) in the measurement result is respectively recorded as the sampling recovery rate of the sampler to the OPEs and the mOPEs, and the real concentration level of the organic phosphate and the metabolites thereof in the sampling space can be obtained by dividing the amount of all the detected OPEs and the mOPEs (non-internal standard substance) by the sampling recovery rate of the corresponding internal standard substance.
Table 3 shows the sampling recovery rate of the sampler for the OPEs and the mOPEs in the indoor air of the server room; table 4 shows concentration levels of OPEs and mmopes in the air in the server room.
Table 3 sampler samples recovery rates of OPEs and mOPEs in indoor air of server room (%)
| Contaminants (S) | Machine room A | Machine room B | Machine room C |
| TEP | 79.5 | 91.4 | 124 |
| TDCIPP | 99.3 | 89.3 | 130 |
| TCIPP | 88.4 | 99.8 | 151 |
| DNBP | 97.2 | 78.8 | 136 |
| DPHP | 70.4 | 86.1 | 149 |
| BDCIPP | 91.8 | 102 | 127 |
Table 4 concentration levels of OPEs and minopes in partial server room indoor air
Note that: N.D. in Table 4 shows that no detection or a detected concentration of less than 0.01ng/m 3 。
Example 3
The invention also evaluates the sampling accuracy and reliability of the sampler, and the specific experiment is as follows:
a plurality of samplers are randomly selected, the samplers are the same as that of the embodiment 1, 4mL of methanol and 4mL of ethyl acetate are sequentially used for activating the solid phase extraction column, the column is wrapped by aluminum foil paper and sealed in a polypropylene bag for storage, and the operation is carried out respectively as follows.
1' elution test: the method comprises the steps of (1) dying the toxic organic phosphate and 10ng of each substance of the metabolite of the toxic organic phosphate on a solid phase extraction column, and directly eluting;
2' air extraction test: on a solid phase extraction column, 10ng of each substance of toxic organic phosphate and metabolite thereof is absorbed and pumped for 2m 3 The elution was then carried out at a pumping rate of about 4.0L/min.
3' penetration test: air is sequentially passed through a blank column (small column without contamination for removing background pollution), a contamination column (each material of the contamination organic phosphate and its metabolite 10 ng), a penetration blank column (the organic phosphate which is not reserved in the contamination column and is taken away by air is received), and the total volume of air suction is 2m 3 (the pumping speed is about 4.0L/min), and the blank column, the contamination column and the penetrating blank column are eluted;
the above elution was performed and measured as follows:
eluting with 4mL of ethyl acetate and 4mL of methanol in sequence, and collecting an ethyl acetate eluent and a methanol eluent respectively. Combining the ethyl acetate eluates to obtain ethyl acetate to-be-detected liquid; and combining the obtained methanol eluates to obtain the methanol to-be-detected liquid. And blowing the liquid nitrogen to be tested of the ethyl acetate to be near dry, adding an internal standard substance, re-dissolving the internal standard substance by using methanol, and then performing high performance liquid chromatography-tandem mass spectrometry detection, and calculating by using an internal standard method to obtain the recovery rate and the relative standard deviation of the organic phosphate in the indoor air. And adding an internal standard into the methanol to-be-detected liquid, and then directly performing high performance liquid chromatography-tandem mass spectrometry detection, and calculating by an internal standard method to obtain the recovery rate and the relative standard deviation of the organic phosphate metabolite in the indoor air. Table 5 shows recovery rates and relative standard deviations of OPEs and mOPEs using solid phase extraction columns.
TABLE 5 recovery (%) and relative standard deviation (%)
Note that: e represents the elution recovery of the ethyl acetate fraction; m represents the elution recovery of the methanol fraction; r represents the overall recovery (recovery); RSD represents the relative standard deviation (relative standard deviation), BT represents penetration (reflecting the presence or absence of entrapment on the blank penetration column).
As can be seen from Table 5, the sampler provided by the invention is used for collecting OPEs and mOPEs in indoor air, and has good accuracy and reliability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A sampler, comprising:
a plurality of solid phase extraction columns (1) connected in parallel;
each solid phase extraction column (1) is internally provided with a glass fiber sieve plate (1-3), a glass fiber sieve plate (1-4) and a glass fiber sieve plate (1-5);
packing for packing a solid phase extraction column (1), the packing comprising CNWBONDHC-C18 packing (1-1) and CNWBONDCN packing (1-2); the glass fiber sieve plate (1-3) divides the filler into an upper layer and a lower layer; the CNWBONDHC-C18 filler (1-1) is located above the fiberglass screen (1-3) and below the fiberglass screen (1-4); the CNWBOND CN filler (1-2) is positioned below the glass fiber screen plate (1-3) and above the glass fiber screen plate (1-5);
a flowmeter (2) connected with the outlet of the solid phase extraction column (1) through a pipeline;
and a diaphragm vacuum pump (3) connected with the outlet of the flowmeter (2) through a pipeline.
2. The sampler according to claim 1, wherein the solid phase extraction column has an inner diameter of 12.5-13 mm and a height of 65-70 mm.
3. Sampler according to claim 1, characterized in that the particle size of the CNWBONDHC-C18 filler (1-1) and CNWBONDCN filler (1-2) is independently 40-63 μm.
4. A sampler according to claim 1 or 3, characterized in that the volume ratio of the CNWBOND HC-C18 packing (1-1) and the single solid phase extraction cartridge is 250mg: 8.5-9 mL; the volume ratio of the CNWBONDCN packing (1-2) to the single solid phase extraction cartridge was 250mg: 8.5-9 mL.
5. A method for collecting organic phosphate and metabolite thereof in indoor air by using the sampler as claimed in any one of claims 1 to 4, comprising the steps of:
after the solid phase extraction column (1) is activated, a sampler is placed in a room to be detected, and a diaphragm vacuum pump (3) is started for sampling; during sampling, the height of the solid phase extraction column (1) in the sampler from the ground is more than or equal to 1m.
6. The method according to claim 5, wherein the activation is methanol activation and ethyl acetate activation performed sequentially.
7. Method according to claim 5, characterized in that the membrane vacuum pump (3) controls the sampling rate to be 3.5-4.5L/min, the sampling time to be 8-12 h.
8. A method for measuring organic phosphate and metabolites thereof in indoor air, which is characterized by comprising the following steps:
adding an organic phosphate internal standard and an organic phosphate metabolite internal standard into the sampled solid phase extraction column (1), and eluting with ethyl acetate and methanol sequentially to obtain an ethyl acetate eluent and a methanol eluent respectively;
combining the ethyl acetate eluates to obtain ethyl acetate to-be-detected liquid;
combining the methanol eluents to obtain methanol to-be-detected liquid;
blowing ethyl acetate to be detected into liquid nitrogen to be near dry, re-dissolving the ethyl acetate with methanol, performing high performance liquid chromatography-tandem mass spectrometry detection, and calculating by an internal standard method to obtain the concentration of the organic phosphate in indoor air;
directly performing high performance liquid chromatography-tandem mass spectrometry detection on the methanol to-be-detected liquid, and calculating by an internal standard method to obtain the concentration of the organic phosphate metabolite in the indoor air;
the sampled solid phase extraction column (1) is the solid phase extraction column (1) obtained by the method of any one of claims 5-7.
9. The method according to claim 8, wherein the mass ratio of the volume of the eluting methanol to the packing in the single solid phase extraction cartridge is 4 to 5mL:500mg.
10. The method according to claim 8, wherein the mass ratio of the volume of methanol for ethyl acetate to the packing in the single solid phase extraction column is 4 to 5mL:500mg.
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| CN106908549A (en) * | 2017-03-31 | 2017-06-30 | 环境保护部南京环境科学研究所 | It is a kind of while the method for determining 12 kinds of OPEs residual in pedotheque |
| CN107543742A (en) * | 2016-06-24 | 2018-01-05 | 南开大学 | It is complete in a kind of room air（It is more）The sampler and its application method of fluoroalkyle compound |
| CN111044643A (en) * | 2019-12-31 | 2020-04-21 | 中国环境科学研究院 | Detection method of organic phosphate |
| CN111795874A (en) * | 2020-07-31 | 2020-10-20 | 南开大学 | Sampler for brominated flame retardant in indoor air and sampling and measuring method thereof |
| CN113970609A (en) * | 2021-11-02 | 2022-01-25 | 自然资源部第四海洋研究所(中国—东盟国家海洋科技联合研发中心) | LC-MS/MS analysis method for sediment organic phosphate and metabolite |
| CN115032292A (en) * | 2022-05-09 | 2022-09-09 | 天津大学 | Detection and analysis method for organic phosphate in water sample |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107543742A (en) * | 2016-06-24 | 2018-01-05 | 南开大学 | It is complete in a kind of room air（It is more）The sampler and its application method of fluoroalkyle compound |
| CN106908549A (en) * | 2017-03-31 | 2017-06-30 | 环境保护部南京环境科学研究所 | It is a kind of while the method for determining 12 kinds of OPEs residual in pedotheque |
| CN111044643A (en) * | 2019-12-31 | 2020-04-21 | 中国环境科学研究院 | Detection method of organic phosphate |
| CN111795874A (en) * | 2020-07-31 | 2020-10-20 | 南开大学 | Sampler for brominated flame retardant in indoor air and sampling and measuring method thereof |
| CN113970609A (en) * | 2021-11-02 | 2022-01-25 | 自然资源部第四海洋研究所(中国—东盟国家海洋科技联合研发中心) | LC-MS/MS analysis method for sediment organic phosphate and metabolite |
| CN115032292A (en) * | 2022-05-09 | 2022-09-09 | 天津大学 | Detection and analysis method for organic phosphate in water sample |
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