CN106908549B - It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously - Google Patents
It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously Download PDFInfo
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Abstract
The present invention relates to the determination techniques fields of organophosphorus ester in soil, are specifically related to a kind of while measuring 12 kinds of remaining methods of OPEs in pedotheque.The present invention utilizes 12 kinds of remaining methods of phosphate compounds in high performance liquid chromatography-mass spectrometry technology combination liquid-liquid extraction and Solid Phase Extraction detection soil.Pedotheque is through liquid-liquid extraction and Solid Phase Extraction, with high performance liquid chromatography-mass spectrometry instrument MRM monitoring ion mode analysis, quantified by external standard method.For method of the invention for most of OPEs, detection limit is low, and stability is good, and detection sensitivity is high, for the rapid screening of OPEs in soil, can satisfy 12 kinds of remaining testing requirements of OPEs in soil substantially.
Description
Technical field
The present invention relates to the determination techniques fields of organophosphorus ester in soil, are specifically related to a kind of while measuring soil-like
12 kinds of remaining methods of OPEs in product.
Background technique
In recent years, due to the bio-toxicity and environmental risk of polybrominated diphenyl ethers (PBDEs) based flame retardant, countries in the world are
Gradually limit and forbid the production and application of polybrominated diphenyl ethers.Organophosphorus ester (organophosphate esters, OPEs)
As the main substitute of brominated flame-retardant, it is widely used in plastics, textile, electronic equipment and household items, and
Yield and dosage are significantly increased.Since OPEs is mainly added in product with simple physics mode, in its production, make
With inevitably entering in environment via various approach in, disposal process, has detection in agricultural land soil at present.With
PBDEs is compared, and OPEs totality lipophilicity is weaker, and bioconcentration is relatively weak, but environmental risk is small unlike PBDEs.Biology
Toxicologic study shows that OPEs has neurotoxicity, carcinogenicity, endocrine disrupting, causes potential threat to human health.
Therefore, for OPEs as a kind of emerging pollutant, problem of environmental pollution has caused the concern of global scholar.
Currently, the detection method of OPEs mainly has gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), gas
Phase chromatography-other joint technology (GC-NPD, GC-EI-MS etc., liquid chromatography (HPLC), Liquid Chromatography-Mass Spectrometry
(HPLC-MS/MS) etc., being related to sample includes house dust, air, water sample, deposit, soil, biology etc..Due to residual in soil
The OPEs stayed mostly exists with trace level, and many kinds of, in addition, soil constituent is more complex, has to OPEs detection larger dry
It disturbs.
For the above status, the present inventor is quasi- using high performance liquid chromatography-tandem mass detection method and in conjunction with liquid-liquid extraction
With the pre-treating method of Solid Phase Extraction, a kind of 12 kinds of OPEs residual quantitative analysis method of trace in soil is established, it can be basic
Meet rapid screening and testing requirements.Liquid Chromatography-Mass Spectrometry is because having highly sensitive and highly selective, anti-interference ability
By force, the effective tool of OPEs residual qualitative and quantitative analysis can be become.
Summary of the invention
The purpose of the present invention is having some limitations for existing detection method, sensitivity is not high enough, anti-interference
The problems such as ability is poor provides a kind of while measuring 12 kinds of remaining methods of OPEs in pedotheque, and this method detection limit is low, stablizes
Property is good, can satisfy 12 kinds of remaining testing requirements of OPEs in soil substantially.
The technical scheme is that
It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously, comprising the following steps:
S1: mixed standard solution is prepared:
A. prepare single standard reserving solution (10mg/L): accurately weighing 12 kinds of each 0.01g of OPEs, with methanol dissolution constant volume in
In 10mL volumetric flask, it is made into the standard reserving solution that mass concentration is 1000mg/L；100 μ L (1000mg/L) standard inventories are taken respectively
Liquid, with methanol dilution to scale, prepares the standard reserving solution that mass concentration is 10mg/L, is stored in 4 DEG C in 10mL volumetric flask
In refrigerator；
B. prepare hybrid standard stock solution (200 μ g/L): it is accurate draw each single standard reserving solution (10mg/L) of 200 μ L in
In 10mL volumetric flask, with methanol dilution to scale, the hybrid standard stock solution that mass concentration is 200 μ g/L is prepared, is protected at 4 DEG C
It deposits；
C. use methanol as solvent, it is dense to be made into quality after above-mentioned hybrid standard stock solution (200 μ g/L) is diluted in proportion
Degree is respectively the mixed standard solution of 0.2,1,2,5,10,20,50,100 μ g/L, is saved at 4 DEG C；
S2: standard curve is drawn:
12 kinds of OPEs hybrid standards that mass concentration is respectively 0.2,1,2,5,10,20,50 and 100 μ g/L are prepared with methanol
Solution draws standard curve with mass concentration (x) of the peak area (y) to object；
S3: sample acquisition:
Pedotheque is acquired in sampled point, impurity removing is removed, is placed in stainless steel box, be freeze-dried, ground 60 mesh ,-
20 DEG C of preservations are to be measured；
S4: sample pre-treatments:
After freeze-dried ground 60 mesh of above-mentioned pedotheque, 5g pedotheque is weighed respectively and is centrifuged in 100mL
Guan Zhong is added 30mL organic solvent and is used as extractant, after ultrasonic extraction 30min, with 8000r/min centrifugation 5min, by supernatant
Be placed in chicken heart bottle, repeat the above steps 1 time, merge supernatant, rotary evaporation to 10mL hereinafter, be diluted to 100mL with ultrapure water,
It is filtered through 0.45 μm of glass fiber filter, Oasis HLB pillar is passed through with the flow velocity of 4mL/min.Before loading, 5mL second is successively used
Acetoacetic ester, 5mL methanol, 5mL ultrapure water activate pillar.After loading, is eluted with 5mL deionized water, discard leacheate, negative pressure is drained
10min, then eluted 2 times with 5mL ethyl acetate, and keeping elution flow rate is 1mL/min.The eluent of collection through rotary evaporation extremely
It is dry, with methanol constant volume to 1mL, analyzed to HPLC-MS/MS；
S5: high performance liquid chromatography mass spectrometer MRM monitoring ion mode analysis:
A. high-efficient liquid phase chromatogram condition: chromatographic column: Agilent ZORBAX Eclipse Plus C18 (150mm ×
2.1mm,3.5um)；Mobile phase: 0.2% (V/V) formic acid (A) and methanol (B)；Flow velocity is 0.3mL/min；Column temperature: 30 DEG C；Sample introduction
Volume: 5uL；Gradient elution program: when 0~8min, mobile phase is formic acid 30%, methanol 70%；When 8~8.1min, mobile phase
For formic acid 5%, methanol 95%；When 8.1~16min, mobile phase is formic acid 5%, methanol 95%；When 16~20min, mobile phase is
Formic acid 30%, methanol 70%；
B. Mass Spectrometry Conditions: selection electron spray ion (ESI) source positive ion mode scanning, using semi-automatic input mode, with 5
The standard reserving solution of 500 μ g/L is injected separately into ion source by the flow velocity of μ L/min；Monitoring pattern is the monitoring of more reactive ions
(MRM)；Corresponding parent ion peak is chosen, second mass analysis is carried out to its daughter ion, obtains fragment ion information；
S6: quantified by external standard method: after monitoring ion mode analysis by high performance liquid chromatography mass spectrometer MRM, according to drawing
The chromatogram of system calculates the peak area of sample solution, and is calculated in sample solution by standard curve described in step S2
The concentration of 12 kinds of OPEs, object is in good linear relationship within the scope of 1~100 μ g/L, with signal-to-noise ratio S/N=3 calculating instrument
Device method detection limit (LOD), S/N=10 is as instrumental method quantitative limit (LOQ).It is continuous to the standard solution of 100 μ g/L simultaneously
Measurement 3 days, daily measurement 3 times, calculates in a few days and day to day precision；It the results are shown in Table 1.
The linear equation of table 1:12 kind OPEs, related coefficient, in a few days with day to day precision, detection limit and quantitative limit
Further, in the above scheme, 12 kinds of OPEs include trimethyl phosphate (Trimethyl phosphate,
TMP), triethyl phosphate (Triethyl phosphate, TEP), TRI N BUTYL PHOSPHATE (Tri-n-butyl phosphate,
TnBP), tricresyl phosphate (2- butoxyethyl group) ester (Tributoxyethyl phosphate, TBEP), tricresyl phosphate (2- chlorine isopropyl
Base) ester (Tri (chloropropyl) phosphate, TCPP), tricresyl phosphate (the chloro- 2- propyl of 1,3- bis-) ester (Tri
(dichloropropyl) phosphate, TDCP), triphenyl phosphate (Triphenyl phosphate, TPhP), tripotassium phosphate
Phenyl ester (Tricresyl phosphate, TCrP), tricresyl phosphate (2- chloroethyl) ester (Tri (2-chloroethyl)
Phosphate, TCEP), tri-2-ethylhexyl phosphate (Tri (2-ethylhexyl) phosphate, TEHP), tricresyl phosphate
(2,3- dibromopropyl) ester (tris (2,3-Dibromopropyl) phosphate, TDBPP), 2- ethylhexyl diphenylphosphoric acid
Ester (2-Ethylhexyl diphenyl phosphate, EHDPP).
Further, in the above scheme, the extractant is acetonitrile.
Further, in the above scheme, in the mass spectral analysis, ion source temperature: 500 DEG C, ionspray electricity
Pressure: 5500V；Gas curtain gas (curtain gas, CUR) pressure is 206851.8Pa；Spraying gas (ion source gas 1, GS1)
Pressure is 241327.1Pa；Auxiliary heating gas (ion source gas 2, GS2) pressure is 275802.4Pa.Obtain fragment from
After sub-information, then the mass spectrometry parameters such as CE, DP, EP, CXP of target compound second order ms are optimized, mass spectrum reacts more
Monitoring parameters are shown in Table 2.
The parameter and its LC-MS detection parameters of table 2:12 kind OPEs
* quota ion is indicated
The beneficial effects of the present invention are: the present invention using high performance liquid chromatography-mass spectrometry technology combination liquid-liquid extraction with
Solid Phase Extraction detects 12 kinds of remaining methods of phosphate compounds in pedotheque simultaneously, and pedotheque is through liquid-liquid extraction and admittedly
It mutually extracts, with high performance liquid chromatography-mass spectrometry instrument MRM monitoring ion mode analysis, quantified by external standard method, method pair of the invention
For most of OPEs, detection limit is low, and stability is good, and detection sensitivity is high, for the rapid screening of OPEs in pedotheque,
Substantially 12 kinds of remaining testing requirements of OPEs in pedotheque be can satisfy.
Detailed description of the invention
Fig. 1 is the total ion chromatogram of the different lower 12 kinds of OPEs mixed standard solutions of mobile phase (100 μ g/L)；
Wherein, 1a: acetonitrile-aqueous solution；1b: methanol-water solution；1c: -0.2% aqueous formic acid of methanol；Wherein, 1: phosphorus
Sour trimethyl；2: triethyl phosphate；3: tricresyl phosphate (2- chloroethyl) ester；4: tricresyl phosphate (chloropropyl) ester；5: tricresyl phosphate (dichloro third
Base) ester；6: three-(2,3- dibromopropyl) phosphates；7: triphenyl phosphate；8: TRI N BUTYL PHOSPHATE；9: tricresyl phosphate butoxy second
Ester；10: phosphoric acid 2- ethylhexyl diphenyl ester；11: tricresyl phosphate；12: tri-2-ethylhexyl phosphate.
Specific embodiment
By taking 25 sampled point pedotheques collected being arranged in Jiangsu Province farmland as an example, carries out while measuring soil
Following 12 kinds of OPEs residual, 12 kinds of OPEs include including trimethyl phosphate (Trimethyl phosphate, TMP), phosphorus in sample
Triethylenetetraminehexaacetic acid ester (Triethyl phosphate, TEP), TRI N BUTYL PHOSPHATE (Tri-n-butyl phosphate, TnBP), phosphorus
Sour three (2- butoxyethyl group) esters (Tributoxyethyl phosphate, TBEP), tricresyl phosphate (2- chloro isopropyl) ester (Tri
(chloropropyl) phosphate, TCPP), tricresyl phosphate (the chloro- 2- propyl of 1,3- bis-) ester (Tri (dichloropropyl)
Phosphate, TDCP), triphenyl phosphate (Triphenyl phosphate, TPhP), tricresyl phosphate (Tricresyl
Phosphate, TCrP), tricresyl phosphate (2- chloroethyl) ester (Tri (2-chloroethyl) phosphate, TCEP), tricresyl phosphate
(2- ethylhexyl) ester (Tri (2-ethylhexyl) phosphate, TEHP), tricresyl phosphate (2,3- dibromopropyl) ester (tris
(2,3-Dibromopropyl) phosphate, TDBPP), 2- ethylhexyl diphenyl phosphate (2-Ethylhexyl
diphenyl phosphate,EHDPP)；Measuring method the following steps are included:
It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously, comprising the following steps:
S1: mixed standard solution is prepared:
A. prepare single standard reserving solution (10mg/L): accurately weighing 12 kinds of each 0.01g of OPEs, with methanol dissolution constant volume in
In 10mL volumetric flask, it is made into the standard reserving solution that mass concentration is 1000mg/L；100 μ L (1000mg/L) standard inventories are taken respectively
Liquid, with methanol dilution to scale, prepares the standard reserving solution that mass concentration is 10mg/L, is stored in 4 DEG C in 10mL volumetric flask
In refrigerator；
B. prepare hybrid standard stock solution (200 μ g/L): it is accurate draw each single standard reserving solution (10mg/L) of 200 μ L in
In 10mL volumetric flask, with methanol dilution to scale, the hybrid standard stock solution that mass concentration is 200 μ g/L is prepared, is protected at 4 DEG C
It deposits；
C. use methanol as solvent, it is dense to be made into quality after above-mentioned hybrid standard stock solution (200 μ g/L) is diluted in proportion
Degree is respectively the mixed standard solution of 0.2,1,2,5,10,20,50,100 μ g/L, is saved at 4 DEG C；
S2: standard curve is drawn:
12 kinds of OPEs hybrid standards that mass concentration is respectively 0.2,1,2,5,10,20,50 and 100 μ g/L are prepared with methanol
Solution draws standard curve with mass concentration (x) of the peak area (y) to object；
S3: sample acquisition:
Pedotheque is acquired in sampled point, impurity removing is removed, is placed in stainless steel box, be freeze-dried, ground 60 mesh ,-
20 DEG C of preservations are to be measured；
S4: sample pre-treatments:
After freeze-dried ground 60 mesh of above-mentioned pedotheque, 5g pedotheque is weighed respectively and is centrifuged in 100mL
Guan Zhong is added 30mL organic solvent and is used as extractant, after ultrasonic extraction 30min, with 8000r/min centrifugation 5min, by supernatant
Be placed in chicken heart bottle, repeat the above steps 1 time, merge supernatant, rotary evaporation to 10mL hereinafter, be diluted to 100mL with ultrapure water,
It is filtered through 0.45 μm of glass fiber filter, Oasis HLB pillar is passed through with the flow velocity of 4mL/min.Before loading, 5mL second is successively used
Acetoacetic ester, 5mL methanol, 5mL ultrapure water activate pillar.After loading, is eluted with 5mL deionized water, discard leacheate, negative pressure is drained
10min, then eluted 2 times with 5mL ethyl acetate, and keeping elution flow rate is 1mL/min.The eluent of collection through rotary evaporation extremely
It is dry, with methanol constant volume to 1mL, analyzed to HPLC-MS/MS；
S5: high performance liquid chromatography mass spectrometer MRM monitoring ion mode analysis:
A. high-efficient liquid phase chromatogram condition: chromatographic column: Agilent ZORBAX Eclipse Plus C18 (150mm ×
2.1mm,3.5um)；Mobile phase: 0.2% (V/V) formic acid (A) and methanol (B)；Flow velocity is 0.3mL/min；Column temperature: 30 DEG C；Sample introduction
Volume: 5uL；Gradient elution program: when 0~8min, mobile phase is formic acid 30%, methanol 70%；When 8~8.1min, mobile phase
For formic acid 5%, methanol 95%；When 8.1~16min, mobile phase is formic acid 5%, methanol 95%；When 16~20min, mobile phase is
Formic acid 30%, methanol 70%；
B. Mass Spectrometry Conditions: selection electron spray ion (ESI) source positive ion mode scanning, using semi-automatic input mode, with 5
The standard reserving solution of 500 μ g/L is injected separately into ion source by the flow velocity of μ L/min；Monitoring pattern is the monitoring of more reactive ions
(MRM)；Ion source temperature: 500 DEG C, ion spray voltage: 5500V；Gas curtain gas (curtain gas, CUR) pressure is
206851.8Pa；Spraying gas (ion source gas 1, GS1) pressure is 241327.1Pa；Auxiliary heating gas (ion source
Gas 2, GS2) pressure be 275802.4Pa.Corresponding parent ion peak is chosen, second mass analysis is carried out to its daughter ion, is obtained
Fragment ion information；Then the mass spectrometry parameters such as CE, DP, EP, CXP of target compound second order ms are optimized, mass spectrum is more
Reaction monitoring parameter is shown in Table 2.
The parameter and its LC-MS detection parameters of table 2:12 kind OPEs
* quota ion is indicated
S6: quantified by external standard method: after monitoring ion mode analysis by high performance liquid chromatography mass spectrometer MRM, according to drawing
The chromatogram of system calculates the peak area of sample solution, and is calculated in sample solution by standard curve described in step S2
The concentration of 12 kinds of OPEs, object are in good linear relationship within the scope of 0.2~100 μ g/L, with signal-to-noise ratio S/N=3 calculating
Instrumental method detection limit (LOD), S/N=10 is as instrumental method quantitative limit (LOQ).The standard solution of 100 μ g/L is connected simultaneously
Continuous measurement 3 days, daily measurement 3 times calculate in a few days and day to day precision；It the results are shown in Table 1.
The linear equation of table 1:12 kind OPEs, related coefficient, in a few days with day to day precision, detection limit and quantitative limit
Experimental verification:
1. the selection of mobile phase: can be improved under normal circumstances, under acid condition compound [M+H]+cation response, this
Experiment use ESI+ mode, use respectively acetonitrile-aqueous solution, methanol-water solution, -0.2% aqueous formic acid of methanol as flow
Phase is compared the separating effect of 12 kinds of OPEs (100 μ g/L), and total ion chromatogram is shown in Fig. 1.As a result, it has been found that with first
The mass spectrum response at object peak and separating degree are more preferable (see Fig. 1 b) when alcohol-water is mobile phase, and add formic acid and divide object
Less (see Fig. 1 c) from influence, but the response of partial target object can be improved, therefore selects -0.2% aqueous formic acid of methanol
For mobile phase.
2. the selection of Extraction solvent: 5 kinds of organic solvents (n-hexane-methanol (2:1, V/V), methanol-acetonitrile (1:4, V/V),
Methanol, acetonitrile and n-hexane-ethyl acetate (2:5, V/V)) extracting method is below 55% to the TMP rate of recovery, this may be by
It is preferable water-soluble and volatile caused in TMP；The TCEP rate of recovery is also relatively poor, in the range of 24.14%~58.60%,
It may be the substrate inhibition effect due to complicated deposit matrix to TCEP.In addition, 5 kinds of organic solvents only have acetonitrile as extraction
When taking agent, TCPP, TCrP can reach the preferable rate of recovery, respectively 72.82%, 119.5%, and remaining 4 kinds of extractant is to it
The rate of recovery is below 5%.In comparison, effect of extracting when acetonitrile makees Extraction solvent is preferable.Therefore, subsequent experimental selects acetonitrile
As optimal extractant.
3. the rate of recovery and precision:
As a control group with the extremely low soil of object, and the baseline value that its concentration is controlled as blank.It adds respectively
Low (5 μ g/kg), in (10 μ g/kg), high (50 μ g/kg) 3 various concentrations object, 3 Duplicate Samples are arranged in each concentration,
Testing result deducts the baseline value of substitution sample.In pedotheque the average recovery of standard addition of 12 kinds of OPEs be 31.24%~
116.63%.Experimental result is shown in Table 3.
Table 3: the rate of recovery and precision of 12 kinds of OPEs in pedotheque
4. the detection and analysis of 12 kinds of target compounds, the results are shown in Table in the pedotheque of 25 sampled points of pair farmland setting
4。
Exposure concentrations (μ g/kg) of the table 4:12 kind OPEs in agricultural land soil
5.nda: it is not detected；The single OPE total concentration of b accounts for the percentage of all OPEs total concentrations.
6. conclusion: high performance liquid chromatography-tandem mass (HPLC-MS/MS) that the present invention establishes while measuring agricultural land soil
In 12 kinds of remaining analysis methods of OPEs.Generally, for major part OPEs in text, this method detection limit is low, and stability is good,
But for trimethyl phosphate (TMP) because it is preferable water-soluble and volatile, cause its rate of recovery in the soil relatively low, for
For tricresyl phosphate (2- chloroethyl) ester (TCEP), it may be possible to due to the depression effect that the matrix of deposit complexity generates, cause back
Yield is relatively low.But for the rapid screening of OPEs in agricultural land soil, this method can satisfy 12 kinds of OPEs in agricultural land soil substantially
Remaining testing requirements.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and model of technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (2)
1. a kind of measure 12 kinds of remaining methods of organophosphorus ester in pedotheque simultaneously, which comprises the following steps:
S1: mixed standard solution is prepared:
A. it prepares single standard reserving solution: accurately weighing each 0.01 g of 12 kinds of organophosphorus esters, held with methanol dissolution constant volume in 10 mL
In measuring bottle, it is made into the standard reserving solution that mass concentration is 1000 mg/L；Take 100 μ L standard reserving solutions in 10 mL capacity respectively
In bottle, with methanol dilution to scale, the standard reserving solution that mass concentration is 10 mg/L is prepared, is stored in 4 DEG C of refrigerators；
B. prepare hybrid standard stock solution: accurate each single standard reserving solution of 200 μ L of drawing is dilute with methanol in 10mL volumetric flask
It releases to scale, prepares the hybrid standard stock solution that mass concentration is 200 μ g/L, saved at 4 DEG C；
C. use methanol as solvent, be made into after above-mentioned hybrid standard stock solution is diluted in proportion mass concentration be respectively 0.2,1,
2, the mixed standard solution of 5,10,20,50,100 μ g/L, saves at 4 DEG C；
S2: standard curve is drawn:
12 kinds of organic phosphoric acids that mass concentration is respectively 0.2,1,2,5,10,20,50 and 100 μ g/L are prepared with methanol
Ester mixed standard solution draws standard curve with mass concentration x of the peak area y to object；
S3: sample acquisition:
Pedotheque is acquired in sampled point, impurity removing is removed, is placed in stainless steel box, be freeze-dried, ground 60 mesh, -20 DEG C
It saves to be measured；
S4: sample pre-treatments:
After freeze-dried ground 60 mesh of above-mentioned pedotheque, 5 g pedotheques are weighed respectively in 100 mL centrifuge tubes
In, 30 mL organic solvents are added and are used as extractant, after 30 min of ultrasonic extraction, with 8000 r/min, 5 min of centrifugation, by supernatant
Liquid is placed in chicken heart bottle, repeats the above steps 1 time, merges supernatant, rotary evaporation is to 10 mL hereinafter, being diluted to 100 with ultrapure water
ML is filtered through 0.45 μm of glass fiber filter, passes through Oasis HLB pillar with the flow velocity of 4 mL/min；Before loading, successively with 5
ML ethyl acetate, 5 mL methanol, 5 mL ultrapure waters activate pillar；After loading, is eluted with 5 mL deionized waters, discards leacheate,
Negative pressure drains 10 min, then is eluted 2 times with 5 mL ethyl acetate, and keeping elution flow rate is 1 mL/min；The eluent of collection
It is analyzed with methanol constant volume to 1 mL to HPLC-MS/MS through rotary evaporated to dryness；The extractant is acetonitrile；
S5: high performance liquid chromatography mass spectrometer MRM monitoring ion mode analysis:
A. high-efficient liquid phase chromatogram condition: chromatographic column: Agilent ZORBAX Eclipse Plus C18,150 mm × 2.1 mm,
3.5 um；Mobile phase: 0.2% V/V formic acid A and methanol B；Flow velocity is 0.3 mL/min；Column temperature: 30 DEG C；Sampling volume: 5 uL；
Gradient elution program: when 0~8min, mobile phase is formic acid 30%, methanol 70%；When 8~8.1min, mobile phase be formic acid 5%,
Methanol 95%；When 8.1~16min, mobile phase is formic acid 5%, methanol 95%；When 16~20min, mobile phase be formic acid 30%,
Methanol 70%；
B. Mass Spectrometry Conditions: selection electron spray ion (ESI) source positive ion mode scanning, using semi-automatic input mode, with 5 μ L/
The standard reserving solution of 500 μ g/L is injected separately into ion source by the flow velocity of min；Monitoring pattern is that more reactive ions monitor (MRM)；
Corresponding parent ion peak is chosen, second mass analysis is carried out to its daughter ion, obtains fragment ion information；
S6: quantified by external standard method: after monitoring ion mode analysis by high performance liquid chromatography mass spectrometer MRM, according to drafting
Chromatogram calculates the peak area of sample solution, and calculates by standard curve described in step S2 12 kinds in sample solution
The concentration of organophosphorus ester, with the computing equipment method detection limit of signal-to-noise ratio S/N=3 (LOD), S/N=10 is fixed as instrumental method
Amount limit (LOQ)；
12 kinds of organophosphorus esters include trimethyl phosphate (Trimethyl phosphate), triethyl phosphate (Triethyl
Phosphate), TRI N BUTYL PHOSPHATE (Tri-n-butyl phosphate), tricresyl phosphate (2- butoxyethyl group) ester
(Tributoxyethyl phosphate), tricresyl phosphate (2- chloro isopropyl) ester (Tri (chloropropyl)
Phosphate), tricresyl phosphate (the chloro- 2- propyl of 1,3- bis-) ester (Tri (dichloropropyl) phosphate), phosphoric acid triphen
Ester (Triphenyl phosphate), tricresyl phosphate (Tricresyl phosphate), tricresyl phosphate (2- chloroethyl)
Ester (Tri (2-chloroethyl) phosphate), tri-2-ethylhexyl phosphate (Tri (2-ethylhexyl)
Phosphate), tricresyl phosphate (2,3- dibromopropyl) ester (tris (2,3-Dibromopropyl) phosphate), 2- ethyl hexyl
Base diphenyl phosphoester (2-Ethylhexyl diphenyl phosphate).
2. one kind according to claim 1 measures 12 kinds of remaining methods of organophosphorus ester in pedotheque simultaneously, special
Sign is, in the mass spectral analysis, ion source temperature: and 500 DEG C, ion spray voltage: 5500V；Gas curtain gas (curtain
Gas) pressure is 206 851.8Pa；Spray pressure power is 241 327.1 Pa；Auxiliary heating atmospheric pressure is 275 802.4 Pa.
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| CN113203804A (en) * | 2021-04-07 | 2021-08-03 | 清华大学深圳国际研究生院 | Method for detecting organic phosphate in soil/sediment |
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| CN113970609B (en) * | 2021-11-02 | 2023-05-23 | 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) | Sediment organic phosphate and metabolite LC-MS/MS analysis method |
| CN115032293A (en) * | 2022-05-09 | 2022-09-09 | 天津大学 | Method for detecting migration behavior of organic phosphate in vertical direction of soil |
| CN115598263B (en) * | 2022-11-25 | 2023-04-18 | 国科大杭州高等研究院 | Method for simultaneously determining contents of organic phosphate and conversion product thereof |
| CN116718681A (en) * | 2023-04-27 | 2023-09-08 | 南开大学 | Sampler for organic phosphate and metabolite thereof in indoor air and sampling and measuring method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105067723A (en) * | 2015-09-30 | 2015-11-18 | 同济大学 | Gas chromatography-tandem quadrupole mass spectrometry analysis method of soil / sediment organophosphate flame retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (3)
| Title |
|---|
| Liquid chromatography/tandem mass spectrometry determination of organophosphorus flame retardants and plasticizers in drinking and surface waters;Alessandro Bacaloni et al.;《RAPID COMMUNICATIONS IN MASS SPECTROMETRY》;20071231;第21卷;摘要，第1125页，第1127页右栏，图1，表1 |
| 固相萃取-气相色谱／质谱法测定水中６种有机磷酸酯类阻燃剂和增塑剂;秦宏兵 等;《分析科学学报》;20140430;第30卷(第2期);全文 |
| 珠江主干和东江河流表层沉积物中有机磷酸酯阻燃剂／增塑剂分布;刘静 等;《生态毒理学报》;20161231;第11卷(第2期);全文 |
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