CN105067723B - A kind of method of organophosphate ester flame retardant in gas-chromatography QQ-TOF mass spectrometry analysis soils/sediments - Google Patents
A kind of method of organophosphate ester flame retardant in gas-chromatography QQ-TOF mass spectrometry analysis soils/sediments Download PDFInfo
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- CN105067723B CN105067723B CN201510471622.7A CN201510471622A CN105067723B CN 105067723 B CN105067723 B CN 105067723B CN 201510471622 A CN201510471622 A CN 201510471622A CN 105067723 B CN105067723 B CN 105067723B
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Abstract
The present invention relates to a kind of analysis method of organophosphate ester flame retardant in soils/sediments, detects 8 kinds of organophosphorus esters in the solid phase samples such as soils/sediments, belongs to the quantitative analysis method of organic pollution in analytical chemistry field.Sample is freeze-dried, is stored in glass sample bottle after grinding sieving（4℃）.Pre-treatment is carried out using vibration+ultrasonic method extraction, Florisil column purifications.Sample pre-treatments are simple to operate in the present invention, and the time is shorter, and solvent consumption is few, and qualitative, quantitatives are carried out to 8 kinds of organophosphorus esters using gas-chromatography QQ-TOF mass spectrometry instrument, realize the good separation of all target substances in 19min, the object rate of recovery 80% 120%（Except triethyl phosphate is 72.9%）, detection limit has good precision and the degree of accuracy up to 0.31 64.51ng/L.
Description
Technical field
The invention belongs to analytical chemistry field, is a kind of quantitative analysis method of organic pollution.Specifically, it is a kind of
With organophosphorus ester in vibration+ultrasonic extraction soils/sediments, through Florisil column purifications, with gas-chromatography-series connection level Four
The method that bar GC-MS carries out qualitative and quantitative analysis to 8 kinds of organophosphorus esters.
Background technology
Organophosphorus ester（Organophosphate esters, OPEs）It is by different hydrocarbons substituent（Alkyl, alkyl chloride
Base, aromatic radical）The compound for substituting the hydrogen on phosphoric acid molecules and being formed.Due to excellent OPEs fire resistance and PBBs
Ethers fire retardant is worldwide gradually disabled, and outputs of the OPEs in the whole world is stepped up.Research both domestic and external shows,
OPEs is sufficiently stable, and alkyl and aryl OPEs have strong biological effect.Wherein triphenyl phosphate（Triphenyl
Phosphate, TPhP/TPP）And tributyl phosphate（Tri-n-butyl phosphate, TnBP）It is considered to have Nervous toxicity
Property, tricresyl phosphate（1,3- bis- chloro- 1- propyl group）Ester（Tri (dichloropropyl) phosphate, TDCP）, tricresyl phosphate（2- chlorine
Ethyl）Ester（Tri (2-chloroethyl) phosphate, TCEP）, tricresyl phosphate（2- chloro isopropyls）Ester（Tri
(chloropropyl) phosphate, TCPP）, tricresyl phosphate（2- butoxyethyl groups）Ester（Tris(2-butoxyethyl)
Phosphate, TBEP）There is carcinogenicity to animal.In view of chloro OPEs has stronger biological toxicity and environmental persistence,
TCEP is included in second batch in nineteen ninety-five and pays high attention to material by European Union, and TCPP, TDCP are included in into the 4th batch of height in 2000
Pay close attention to material.OPEs is mainly bonded as a kind of additive flame retardant with chemical material, it is easy to it is discharged into surrounding environment,
At present, detected in a variety of surrounding mediums of multiple countries and regions.
At present, in sample mainly there is the detection method of organophosphorus ester：Gas chromatography（GC-NPD）, gaschromatographic mass spectrometry
Method（GC-MS）And liquid chromatography tandem mass spectrometry（LC-MS/MS）.GC-NPD is for phosphorus-containing compound in spite of higher sensitive
Degree, but its less stable；GC-MS can produce excessive fragment when analyzing, when especially analyzing three ester of aliphatic, these OPEs warps
McLafferty rearrangement three times is gone through, low quality ion can be disturbed；Although LC-MS/MS can use Selective reaction monitoring pattern, common
Disturbed by sample substrate substantially, so as to influence sensitivity in electron spray ionisation source.Gas-chromatography-QQ-TOF mass spectrometry combination（GC-
MS/MS）With more preferable applicability and reliability, LC-MS/MS electron spray ionisation is compared using electron bombardment ionization source ionization mode
Source, influenceed by matrix smaller；Gas-chromatography disengaging time is typically short compared with liquid chromatogram；GC- is compared using Selective reaction monitoring pattern
MS has higher sensitivity.
The content of the invention
The present invention is big for solvent consumption in experimentation, and time length, operation sequence is complicated, and matrix interference is serious, spirit
Sensitivity is low etc., there is provided point of organophosphorus ester in a kind of solid phase environment medium such as soils/sediments of time saving and energy saving efficiently and accurately
Analysis method.The present invention is using object in vibration+ultrasonic method extraction sample, and simple to operate, usage time is short, and solvent consumption is few；
Florisil column purifications can effectively remove the organic interfering substance matter in matrix, and commercialized degree is high, easily obtain, and operate letter
Single, solvent usage amount is few.GC-MS/MS has relatively low test limit and high selectivity and sensitivity, has suitable for Determination of Trace Volatile
The detection of organic pollutants.
Organophosphorus ester hinders in a kind of gas-chromatography proposed by the present invention-QQ-TOF mass spectrometry analysis soils/sediments
The method of agent is fired, is comprised the following steps that：
（1）Soils/sediments sample is freeze-dried, ground 80-100 mesh sieves；
（2）Every time step is weighed with assay balance（1）Gained sample 2.0g, then add 10ng and substitute mark, with 20mL bodies
Product is than being 1:The mixed solution of 1 acetone and n-hexane composition extracts, and first vibrates 1min, ultrasonic 10min with eddy oscillating device,
10min is centrifuged under 3000 rpm rotating speeds；Extraction 1 time is repeated, solution is extracted in merging twice, with Rotary Evaporators concentration and solvent
N-hexane is replaced to 0.8-1.2ml；
（3）To step（2）Obtained solution is using activation copper sulphur removal；
（4）Purified using Florisil solid phase extraction columns, by step（3）Obtained extract solution crosses post, and ethyl acetate is washed
De- post, elution liquid nitrogen is blown and concentrates and be replaced as hexane solution；
（5）Using gas-chromatography-QQ-TOF mass spectrometry determination step（4）Organophosphorus ester in resulting solution；
（5.1）Its testing conditions is：
Chromatographic parameter：DB-5MS（30m×0.25mm×0.25μm）Capillary chromatographic column, carrier gas are high-purity helium, constant current
Pattern, column flow are 1 mL/min, not shunted, sample size 1uL, 250 DEG C of injector temperature, heating schedule：Column temperature is initially 50
℃（Keep 1min）, 25 DEG C/min rises to 200 DEG C（Keep 1 min）, 2 DEG C/min rises to 210 DEG C（Keep 1 min）, so
25 DEG C/min is warming up to 250 DEG C afterwards（Keep 1 min）, 2 DEG C/min is raised to 260 DEG C, and last 25 DEG C/min is warming up to 300
℃（Keep 2 min）；
Mass spectrometry parameters：250 DEG C of ion source temperature, 280 DEG C of transmission line temperature, EI sources（70 eV）, Selective reaction monitoring
（SRM）Pattern, collision gas are high-purity argon gas, collision atmospheric pressure 1.0 mTorr；
（5.2）Internal standard method is used to be calculated with chromatographic peak area under each Compound Retention time organic in soils/sediments
The concentration of phosphate.
In the present invention, the organophosphorus ester analyzed includes triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, phosphoric acid
Three（2- chloroethyls）Ester, tricresyl phosphate（2- chloro isopropyls）Ester, tricresyl phosphate（The chloro- 2- propyl group of 1,3- bis-）Ester, triphenyl phosphate or phosphorus
Acid three（2- ethylhexyls）It is one or more of in ester.
In the present invention, selected alternate standard product and internal standard are respectively deuterated TRI N BUTYL PHOSPHATE（TnBP-D27）With it is deuterated
Triphenyl phosphate（TPhP-D15）.
In the present invention, step（1）In, after soils/sediments sample is freeze-dried, it is ground with native machine is ground, and
Cross 80 mesh sieves.
In the present invention, step（3）In, copper will be activated in right amount and will be added in extract solution, be stood 8-12 hours, be activated the addition of copper
Amount is it is ensured that copper will not all be vulcanized.
In the present invention, step（4）In, it is 500 mg/3 mL from Florisil solid phase extraction columns specification, it is first during purification
Florisil pillars are activated with 5 mL methanol, 5 mL n-hexanes respectively, extract solution is flowed through into pillar, are eluted with 3 mL n-hexanes,
Pillar is eluted with 8 mL ethyl acetate respectively, solution is concentrated and solvent is replaced as n-hexane.
The invention has the advantages that：
The present invention is extracted using vibration and the method for combination of ultrasound to target substance, extractant can be made to be obtained with sample
To abundant contact, than only having large increase, Florisil column purification efficiency highs, whole pre-treatment with the efficiency of ultrasonic extraction
Journey is simple to operate, saves the time, and solvent consumption is reduced.
The SRM of the gas-chromatography that the present invention uses-QQ-TOF mass spectrometry combined instrument has higher selectivity and sensitive
Degree, while detection limit is relatively low, suitable for the detection and analysis of organic micro-pollutant.
The present invention can be effectively separated to surveying 10 kinds of OPEs, and accurate qualitative and accurate quantification, the rate of recovery is in 80%-
120%（Except triethyl phosphate is 72.9%）, test limit is up to 0.31-64.51ng/L.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the present invention；
Fig. 2 be GC-MS/MS bioassay standard samples in organophosphorus ester chromatogram total figure, 1.TEP 2.TPrP 3.TnBP-
d27 4.TnBP 5.TCEP 6.TCPP 7.TDCP 8.TPhP-d15 9.TPhP 10.TEHP。
Embodiment
With reference to specific embodiment, the present invention is further elaborated, these embodiments be merely to illustrate the present invention without
For limiting the scope of the present invention.
Embodiment 1：
With analysis of the present invention to organophosphorus ester in the deposit of the Hefei City pool Xihe River, appropriate deposit is taken to be freeze-dried
48h, 80-100 mesh sieves are crossed after native machine is ground using grinding.With three parts of electronic balance weighing 2.0g sediment samples, put respectively
Enter in three 30mL glass centrifuge tubes, 10ng TnBP-D27 are added into sample, add 20mL acetone：N-hexane（V:V=1：
1）Extraction solvent, the centrifugation mouth of pipe is sealed with aluminium foil, ultrasonic 10min in Ultrasound Instrument is put into, then centrifuges at 3,000 rpm
10min, separate in supernatant extract solution to boiling flask；Repeat extraction once, mix extract solution twice.Extract solution is steamed in rotation
Concentrated and be transferred in screw thread mouth test tube on hair instrument, with 3mL n-hexane wash bottle walls, washed 3 times, washing lotion transposition screw thread oral examination
Pipe, nitrogen are blown to about 1mL.Activation copper is put into extract solution, stands a night, activating the amount of copper need to can ensure that copper will not be by whole sulphur
Change.
Respectively with 5mL methanol and 5mL n-hexanes activation Florisil posts；Extract solution is flowed through into pillar, washed with 1mL n-hexanes
Tube wall, washing lotion cross pillar；Post is eluted with 3mL n-hexanes, removes non polar impurities；Pillar finally is eluted with 8mL ethyl acetate,
This process only collects eluent.Elution liquid nitrogen is blown to 1mL, is transferred to sample injection bottle.5ng internal standards are added, are settled to 1mL.
The sample handled well is analyzed with GC-Ms/Ms and detected, testing conditions are：
Chromatographic parameter：Chromatographic column is DB-5MS（30m×0.25mm×0.25μm）Capillary column, carrier gas are high-purity helium,
Using constant current mode, column flow is 1 mL/min, no shunt mode, auto injection amount 1uL, 250 DEG C of injector temperature；Heat up journey
Sequence：Column temperature is initially 50 DEG C（Keep 1min）, 25 DEG C/min rises to 200 DEG C（Keep 1 min）, 2 DEG C/min rises to 210 DEG C
（Keep 1 min）, then 25 DEG C/min be warming up to 250 DEG C（Keep 1 min）, 2 DEG C/min is raised to 260 DEG C, last 25 DEG C/
Min is warming up to 300 DEG C（Keep 2 min）；
Mass spectrometry parameters：Ion source temperature is 250 DEG C, and transmission line temperature is 280 DEG C；Ion gun is EI sources（70 eV）, use
Selective reaction monitoring（SRM）Pattern, collision gas are argon gas；Impact pressure is 1.0 mTorr.
Chemical classes are determined according to appearance time, calculate the content of each material using internal standard method according to peak area.
Material appearance time order is surveyed in standard liquid is（min）：TEP 5.17；TPrP 6.69；TnBP-d27
8.16；TnBP 8.29；TCEP 9.33；TCPP 9.65；TDCP 16.70；TPhP-d15 17.48；TPhP 17.60；TEHP
18.28。
Embodiment 2
Analysis to organophosphorus ester in the Wulihe deposit of Hefei City ten, appropriate deposit freeze-drying 48h is taken, is utilized
Grind and 80-100 mesh sieves are crossed after native machine is ground.With three parts of electronic balance weighing 2.0g sediment samples, three are respectively put into
In 30mL glass centrifuge tubes, 10ng TnBP-D27 are added into sample, add 20mL acetone：N-hexane（V:V=1：1）Extraction
Solvent, the centrifugation mouth of pipe is sealed with aluminium foil, ultrasonic 10min in Ultrasound Instrument is put into, then centrifuges 10min at 3,000 rpm, is separated
In supernatant extract solution to boiling flask；Repeat extraction once, mix extract solution twice.Extract solution is carried out on a rotary evaporator
Concentrate and be transferred in screw thread mouth test tube, with 3mL n-hexane wash bottle walls, wash 3 times, washing lotion transposition screw thread mouth test tube, nitrogen is blown to about
1mL.Activation copper is put into extract solution, stands a night, activating the amount of copper need to can ensure that copper will not all be vulcanized.Use respectively
5mL methanol and 5mL n-hexanes activation Florisil posts；Extract solution is flowed through into pillar, tube wall, washing lotion mistake are washed with 1mL n-hexanes
Pillar；Post is eluted with 3mL n-hexanes, goes the removal of impurity；Finally eluent is only collected with 8mL ethyl acetate elution pillar, this process.
Elution liquid nitrogen is blown to 1mL, is transferred to sample injection bottle.5ng internal standards are added, are settled to 1mL.
The sample handled well is analyzed with GC-Ms/Ms and detected, testing conditions are：
Chromatographic parameter：Chromatographic column is DB-5MS（30m×0.25mm×0.25μm）Capillary column, carrier gas are high-purity helium,
Using constant current mode, column flow is 1 mL/min, no shunt mode, auto injection amount 1uL, 250 DEG C of injector temperature；Heat up journey
Sequence：Column temperature is initially 50 DEG C（Keep 1min）, 25 DEG C/min rises to 200 DEG C（Keep 1 min）, 2 DEG C/min rises to 210 DEG C
（Keep 1 min）, then 25 DEG C/min be warming up to 250 DEG C（Keep 1 min）, 2 DEG C/min is raised to 260 DEG C, last 25 DEG C/
Min is warming up to 300 DEG C（Keep 2 min）；
Mass spectrometry parameters：Ion source temperature is 250 DEG C, and transmission line temperature is 280 DEG C；Ion gun is EI sources（70 eV）, use
Selective reaction monitoring（SRM）Pattern, collision gas are argon gas；Impact pressure is 1.0 mTorr.
Chemical classes are determined according to appearance time, calculate the content of each material using internal standard method according to peak area.
Above-described embodiment is easy for the those skilled in the art and understood and applied the invention, for the art
For those of ordinary skill, under the premise without departing from the principles of the invention, some improvements and modifications can also be made.
Claims (6)
1. the method for organophosphate ester flame retardant in a kind of gas-chromatography-QQ-TOF mass spectrometry analysis soils/sediments, it is special
Sign is to comprise the following steps that：
（1）Soils/sediments sample is freeze-dried, ground 80-100 mesh sieves；
（2）Every time step is weighed with assay balance（1）Gained sample 2.0g, then add 10ng and substitute mark, with 20mL volume ratios
For 1:The mixed solution of 1 acetone and n-hexane composition extracts, and first vibrates 1min, ultrasonic 10min, 3000 with eddy oscillating device
10min is centrifuged under rpm rotating speeds；Extraction 1 time is repeated, solution is extracted in merging twice, is replaced with Rotary Evaporators concentration and solvent
N-hexane is to 0.8-1.2ml；
（3）To step（2）Obtained solution is using activation copper sulphur removal；
（4）By step（3）Obtained solution ethyl acetate elution post, will elute liquid nitrogen by Florisil solid phase extraction columns
Blow and concentrate and be replaced as hexane solution；
（5）Using gas-chromatography-QQ-TOF mass spectrometry determination step（4）Organophosphorus ester in resulting solution；
（5.1）Its testing conditions is：
Chromatographic parameter：DB-5MS, 30m × 0.25mm × 0.25 μm capillary chromatographic column, carrier gas be high-purity helium, constant current mode,
The mL/min of column flow 1, do not shunt, sample size 1uL, 250 DEG C of injector temperature, heating schedule：Column temperature is initially 50 DEG C, keeps
1min, 25 DEG C/min rise to 200 DEG C, keep 1 min, 2 DEG C/min to rise to 210 DEG C, keep 1 min, then 25 DEG C/min
250 DEG C are warming up to, keeps 1 min, 2 DEG C/min to be raised to 260 DEG C, last 25 DEG C/min is warming up to 300 DEG C, keeps 2 min；
Mass spectrometry parameters：250 DEG C of ion source temperature, 280 DEG C of transmission line temperature, EI sources, 70 eV, Selective reaction monitoring SRM patterns,
Collision gas is high-purity argon gas, collision atmospheric pressure 1.0 mTorr；
（5.2）Internal standard method is used to calculate organic phosphoric acid in soils/sediments with chromatographic peak area under each Compound Retention time
The content of ester.
2. organophosphorus ester hinders in gas-chromatography according to claim 1-QQ-TOF mass spectrometry analysis soils/sediments
Fire agent method, it is characterised in that the organophosphorus ester analyzed include triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate,
Tricresyl phosphate（2- chloroethyls）Ester, tricresyl phosphate（2- chloro isopropyls）Ester, tricresyl phosphate（The chloro- 2- propyl group of 1,3- bis-）Ester, triphenyl phosphate
Or tricresyl phosphate（2- ethylhexyls）It is one or more of in ester.
3. organophosphorus ester hinders in gas-chromatography according to claim 1-QQ-TOF mass spectrometry analysis soils/sediments
Fire the method for agent, it is characterised in that selected alternate standard product and internal standard are respectively deuterated TRI N BUTYL PHOSPHATE and deuterated tricresyl phosphate
Phenyl ester.
4. organophosphorus ester hinders in gas-chromatography according to claim 1-QQ-TOF mass spectrometry analysis soils/sediments
Fire the method for agent, it is characterised in that step（1）In, after soils/sediments sample is freeze-dried, ground with native machine is ground
Mill, and cross 80 mesh sieves.
5. organophosphorus ester hinders in gas-chromatography according to claim 1-QQ-TOF mass spectrometry analysis soils/sediments
Fire the method for agent, it is characterised in that step（3）In, copper will be activated in right amount and will be added in extract solution, be stood 8-12 hours, be activated copper
Addition is it is ensured that copper will not all be vulcanized.
6. organophosphorus ester hinders in gas-chromatography according to claim 1-QQ-TOF mass spectrometry analysis soils/sediments
Fire the method for agent, it is characterised in that step（4）In, it is 500 mg/3 mL from Florisil pillars specification, first distinguishes during purification
With 5 mL methanol, 5 mL n-hexanes activation Florisil pillars, extract solution is flowed through into pillar, eluted with 3 mL n-hexanes, respectively
Pillar is eluted with 8 mL ethyl acetate, solution is concentrated and solvent is replaced as n-hexane.
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| 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 |
| CN105699527A (en) * | 2016-02-02 | 2016-06-22 | 环境保护部华南环境科学研究所 | Detection method of content of brominated flame retardant and phosphorus-based flame retardant in blood serum |
| CN106596786B (en) * | 2016-12-26 | 2019-12-17 | 上海微谱化工技术服务有限公司 | Detection method for detecting organophosphate flame retardant in ABS plastic |
| CN106908549B (en) * | 2017-03-31 | 2019-07-19 | 环境保护部南京环境科学研究所 | It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously |
| CN107255680B (en) * | 2017-06-02 | 2019-12-24 | 沈阳大学 | Method for simultaneously and rapidly detecting multiple organic phosphate flame retardants in soil |
| CN108195981A (en) * | 2017-11-16 | 2018-06-22 | 吉贵祥 | The method for quantitatively detecting tricresyl phosphate (bis- chloro- 2- propyl of 1,3-) ester in Fine Particles PM2.5 |
| CN107991397A (en) * | 2017-12-12 | 2018-05-04 | 中国水产科学研究院珠江水产研究所 | Organic contamination object detecting method in a kind of deposit |
| CN108663455B (en) * | 2018-06-14 | 2019-11-12 | 南京大学 | It is a kind of based on statistics strategy deposit in the non-targeted analysis method of organic pollutant and application |
| CN109115902B (en) * | 2018-07-23 | 2021-06-15 | 苏州科技大学 | Method for detecting organic phosphorus flame retardant in grains |
| CN111983068A (en) * | 2020-08-11 | 2020-11-24 | 深圳市环境科学研究院 | Method for detecting phosphorus flame retardant and degradation product thereof in sediment |
| CN112067730A (en) * | 2020-10-15 | 2020-12-11 | 合肥学院 | Method for detecting polybrominated diphenyl ethers in deposition column core |
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| CN103616469A (en) * | 2013-12-13 | 2014-03-05 | 中华人民共和国北京出入境检验检疫局 | Method for detecting organophosphate flame retardant |
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