CN106908549A - It is a kind of while the method for determining 12 kinds of OPEs residual in pedotheque - Google Patents
It is a kind of while the method for determining 12 kinds of OPEs residual in pedotheque Download PDFInfo
- Publication number
- CN106908549A CN106908549A CN201710211513.0A CN201710211513A CN106908549A CN 106908549 A CN106908549 A CN 106908549A CN 201710211513 A CN201710211513 A CN 201710211513A CN 106908549 A CN106908549 A CN 106908549A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- opes
- kinds
- methyl alcohol
- standard
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
- G01N2030/126—Preparation by evaporation evaporating sample
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The present invention relates to the determination techniques field of organophosphorus ester in soil, it is specifically related to a kind of while the method that 12 kinds of OPEs are remained in determining pedotheque.The present invention is using 12 kinds of methods of phosphate compounds residual in high performance liquid chromatography mass spectrometric hyphenated technique combination liquid-liquid extraction and SPE detection soil.Pedotheque is monitored ion mode and is analyzed through liquid-liquid extraction and SPE, with high performance liquid chromatography GC-MS MRM, quantified by external standard method.The method of the present invention is for most of OPEs, and detection limit is low, and good stability, detection sensitivity is high, for the rapid screening of OPEs in soil, 12 kinds of detection requirements of OPEs residuals in soil is disclosure satisfy that substantially.
Description
Technical field
The present invention relates to the determination techniques field of organophosphorus ester in soil, a kind of measure soil-like simultaneously is specifically related to
12 kinds of methods of OPEs residuals in product.
Background technology
In recent years, due to the bio-toxicity and environmental risk of PBDE (PBDEs) based flame retardant, countries in the world are
Progressively limit and forbid the production and application of PBDE.Organophosphorus ester (organophosphate esters, OPEs)
As the main substitute of brominated flame-retardant, it is widely used in plastics, textile, electronic equipment and household articles, and
Yield and consumption are significantly increased.Because OPEs is mainly added in product with simple physics mode, thus its production, make
Inevitably entered in environment via various approach with, disposal process, detected in agricultural land soil at present.With
PBDEs is compared, and OPEs totality lipophilicitys are weaker, and its bioconcentration is relatively weak, but environmental risk is small unlike PBDEs.It is biological
Toxicologic study shows that OPEs has neurotoxicity, carcinogenicity, endocrine disrupting, and potential threat is caused to health.
Therefore, used as a kind of emerging pollutant, its problem of environmental pollution has caused the concern of global scholar to OPEs.
At present, the detection method of OPEs mainly has gas chromatography (GC), GC-MS (GC-MS), gas
Phase chromatogram-other GC-MS (GC-NPD, GC-EI-MS etc., liquid chromatography (HPLC), Liquid Chromatography-Mass Spectrometries
(HPLC-MS/MS) etc., it is related to sample including house dust, air, water sample, deposit, soil, biology etc..Due to residual in soil
The OPEs for staying is more with the presence of trace level, and species is various, additionally, soil constituent is more complicated, OPEs detections is had larger dry
Disturb.
For above present situation, the present inventor intends using high performance liquid chromatography-tandem mass detection method and combines liquid-liquid extraction
With the pre-treating method of SPE, a kind of 12 kinds of OPEs residual quantitative analysis methods of trace in soil are set up, can be basic
Meet rapid screening and detection is required.Liquid Chromatography-Mass Spectrometry is because with high sensitivity and high selectivity, antijamming capability
By force, the effective tool that OPEs remains qualitative and quantitative analysis can be turned into.
The content of the invention
The purpose of the present invention is directed to existing detection method and has some limitations, and insufficient sensitivity is high, anti-interference
The problems such as ability, there is provided a kind of while determining 12 kinds of methods of OPEs residuals in pedotheque, the method detection limit is low, stabilization
Property it is good, 12 kinds of detection requirements of OPEs residuals in soil are disclosure satisfy that substantially.
The technical scheme is that：
It is a kind of while the method for determining 12 kinds of OPEs residual in pedotheque, comprises the following steps：
S1：Prepare mixed standard solution：
A. single standard reserving solution (10mg/L) is prepared：Accurately weigh 12 kinds of each 0.01g of OPEs, with methyl alcohol dissolve constant volume in
In 10mL volumetric flasks, the standard reserving solution that mass concentration is 1000mg/L is made into；100 μ L (1000mg/L) standard inventories are taken respectively
In 10mL volumetric flasks, with methanol dilution to scale, it is the standard reserving solution of 10mg/L to prepare mass concentration to liquid, is stored in 4 DEG C
In refrigerator；
B. hybrid standard storing solution (200 μ g/L) is prepared：It is accurate draw each single standard reserving solutions (10mg/L) of 200 μ L in
In 10mL volumetric flasks, with methanol dilution to scale, the hybrid standard storing solution that mass concentration is 200 μ g/L is prepared, in guarantor at 4 DEG C
Deposit；
C. it is made into quality as solvent, after above-mentioned hybrid standard storing solution (200 μ g/L) is diluted in proportion with methyl alcohol dense
Degree is respectively the mixed standard solution of 0.2,1,2,5,10,20,50,100 μ g/L, in preservation at 4 DEG C；
S2：Draw standard curve：
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 methyl alcohol
Solution, standard curve is drawn with peak area (y) to the mass concentration (x) of object；
S3：Sample collection：
Pedotheque is gathered in sampled point, impurity removing is removed, is placed in stainless steel box, freeze-drying, ground 60 mesh sieve ,-
20 DEG C of preservations are to be measured；
S4：Sample pre-treatments：
After by freeze-dried ground 60 mesh sieve of above-mentioned pedotheque, 5g pedotheques are weighed respectively and is centrifuged in 100mL
Guan Zhong, adds 30mL organic solvents as extractant, after ultrasonic extraction 30min, 5min is centrifuged with 8000r/min, by supernatant
Heart bottle is placed in, is repeated the above steps 1 time, merge supernatant, rotary evaporation to below 10mL is diluted to 100mL with ultra-pure water,
Filtered through 0.45 μm of glass fiber filter, Oasis HLB pillars are passed through with the flow velocity of 4mL/min.Before loading, 5mL second is used successively
Acetoacetic ester, 5mL methyl alcohol, 5mL ultra-pure waters activation pillar.After loading, with 5mL deionized water drip washing, leacheate is discarded, negative pressure is drained
10min, then eluted 2 times with 5mL ethyl acetate, and it is 1mL/min to keep elution flow rate.The eluent of collection is rotated to be evaporated to
It is dry, with methanol constant volume to 1mL, treat that HPLC-MS/MS is analyzed；
S5：High performance liquid chromatography GC-MS MRM monitoring ion mode analyses：
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 methyl alcohol (B)；Flow velocity is 0.3mL/min；Column temperature：30℃；Sample introduction
Volume：5uL；Gradient elution program：During 0~8min, mobile phase is formic acid 30%, methyl alcohol 70%；During 8~8.1min, mobile phase
It is formic acid 5%, methyl alcohol 95%；During 8.1~16min, mobile phase is formic acid 5%, methyl alcohol 95%；During 16~20min, mobile phase is
Formic acid 30%, methyl alcohol 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 gun by the flow velocity of μ L/min；Monitoring pattern is monitored for many reactive ions
(MRM)；Corresponding parent ion peak is chosen, second mass analysis are carried out to its daughter ion, obtain fragment ion information；
S6：Quantified by external standard method：Monitored after ion mode analyzes by high performance liquid chromatography GC-MS MRM, according to painting
The chromatogram of system calculates the peak area of sample solution, and by the standard curve described in step S2 calculates sample solution
12 kinds of concentration of OPEs, object is in good linear relationship in the range of 1~100 μ g/L, with signal to noise ratio S/N=3 calculating instruments
Device method detection limit (LOD), S/N=10 is used as instrumental method quantitative limit (LOQ).It is simultaneously continuous to the standard liquid of 100 μ g/L
Determine 3 days, determine 3 times daily, calculate in a few days and day to day precision；The results are shown in Table 1.
Table 1：12 kinds of linear equations of OPEs, coefficient correlation, in a few days with day to day precision, detection limit and quantitative limit
Further, in such 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 groups) ester (Tributoxyethyl phosphate, TBEP), tricresyl phosphate (2- chlorine isopropyls
Base) ester (Tri (chloropropyl) phosphate, TCPP), tricresyl phosphate (the chloro- 2- propyl group of 1,3- bis-) ester (Tri
(dichloropropyl) phosphate, TDCP), triphenyl phosphate (Triphenyl phosphate, TPhP), tripotassium phosphate
Phenyl ester (Tricresyl phosphate, TCrP), tricresyl phosphate (2- chloroethyls) ester (Tri (2-chloroethyl)
Phosphate, TCEP), tri-2-ethylhexyl phosphate (Tri (2-ethylhexyl) phosphate, TEHP), tricresyl phosphate
(2,3- dibromopropyls) ester (tris (2,3-Dibromopropyl) phosphate, TDBPP), 2- ethylhexyl diphenylphosphoric acids
Ester (2-Ethylhexyl diphenyl phosphate, EHDPP).
Further, in such scheme, the extractant is acetonitrile.
Further, in such 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 mses are optimized, reacted mass spectrum more
Monitoring parameter is shown in Table 2.
Table 2：12 kinds of parameters and its LC-MS detection parameters of OPEs
* quota ion is represented
The beneficial effects of the invention are as follows：The present invention using HPLC-MS technology combination liquid-liquid extraction with
SPE detects 12 kinds of methods of phosphate compounds residual in pedotheque simultaneously, and pedotheque is through liquid-liquid extraction and admittedly
Mutually extract, monitor ion mode with HPLC-MS instrument MRM and analyze, quantified by external standard method, the method for the present invention pair
For most of OPEs, detection limit is low, and good stability, detection sensitivity is high, for the rapid screening of OPEs in pedotheque,
Substantially 12 kinds of detection requirements of OPEs residuals in pedotheque be disclosure satisfy that.
Brief description of the drawings
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：The aqueous formic acid of methyl alcohol -0.2%；Wherein, 1：Phosphorus
Sour trimethyl；2：Triethyl phosphate；3：Tricresyl phosphate (2- chloroethyls) ester；4：Tricresyl phosphate (chloropropyl) ester；5：Tricresyl phosphate (dichloro third
Base) ester；6：Three-(2,3- dibromopropyls) phosphates；7：Triphenyl phosphate；8：TRI N BUTYL PHOSPHATE；9：Tricresyl phosphate butoxy second
Ester；10：Phosphoric acid 2- ethylhexyl diphenyl esters；11：Tricresyl phosphate；12：Tri-2-ethylhexyl phosphate.
Specific embodiment
By taking the pedotheque that 25 sampled points set in Jiangsu Province farmland are gathered as an example, carry out determining soil simultaneously
Following 12 kinds of OPEs residuals in sample, 12 kinds of OPEs include trimethyl phosphate (Trimethyl phosphate, TMP), phosphorus
Triethylenetetraminehexaacetic acid ester (Triethyl phosphate, TEP), TRI N BUTYL PHOSPHATE (Tri-n-butyl phosphate, TnBP), phosphorus
Sour three (2- butoxyethyl groups) esters (Tributoxyethyl phosphate, TBEP), tricresyl phosphate (2- chloro isopropyls) ester (Tri
(chloropropyl) phosphate, TCPP), tricresyl phosphate (the chloro- 2- propyl group of 1,3- bis-) ester (Tri (dichloropropyl)
Phosphate, TDCP), triphenyl phosphate (Triphenyl phosphate, TPhP), tricresyl phosphate (Tricresyl
Phosphate, TCrP), tricresyl phosphate (2- chloroethyls) ester (Tri (2-chloroethyl) phosphate, TCEP), tricresyl phosphate
(2- ethylhexyls) ester (Tri (2-ethylhexyl) phosphate, TEHP), tricresyl phosphate (2,3- dibromopropyls) ester (tris
(2,3-Dibromopropyl) phosphate, TDBPP), 2- ethylhexyl diphenyl phosphates (2-Ethylhexyl
diphenyl phosphate,EHDPP)；Assay method is comprised the following steps：
It is a kind of while the method for determining 12 kinds of OPEs residual in pedotheque, comprises the following steps：
S1：Prepare mixed standard solution：
A. single standard reserving solution (10mg/L) is prepared：Accurately weigh 12 kinds of each 0.01g of OPEs, with methyl alcohol dissolve constant volume in
In 10mL volumetric flasks, the standard reserving solution that mass concentration is 1000mg/L is made into；100 μ L (1000mg/L) standard inventories are taken respectively
In 10mL volumetric flasks, with methanol dilution to scale, it is the standard reserving solution of 10mg/L to prepare mass concentration to liquid, is stored in 4 DEG C
In refrigerator；
B. hybrid standard storing solution (200 μ g/L) is prepared：It is accurate draw each single standard reserving solutions (10mg/L) of 200 μ L in
In 10mL volumetric flasks, with methanol dilution to scale, the hybrid standard storing solution that mass concentration is 200 μ g/L is prepared, in guarantor at 4 DEG C
Deposit；
C. it is made into quality as solvent, after above-mentioned hybrid standard storing solution (200 μ g/L) is diluted in proportion with methyl alcohol dense
Degree is respectively the mixed standard solution of 0.2,1,2,5,10,20,50,100 μ g/L, in preservation at 4 DEG C；
S2：Draw standard curve：
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 methyl alcohol
Solution, standard curve is drawn with peak area (y) to the mass concentration (x) of object；
S3：Sample collection：
Pedotheque is gathered in sampled point, impurity removing is removed, is placed in stainless steel box, freeze-drying, ground 60 mesh sieve ,-
20 DEG C of preservations are to be measured；
S4：Sample pre-treatments：
After by freeze-dried ground 60 mesh sieve of above-mentioned pedotheque, 5g pedotheques are weighed respectively and is centrifuged in 100mL
Guan Zhong, adds 30mL organic solvents as extractant, after ultrasonic extraction 30min, 5min is centrifuged with 8000r/min, by supernatant
Heart bottle is placed in, is repeated the above steps 1 time, merge supernatant, rotary evaporation to below 10mL is diluted to 100mL with ultra-pure water,
Filtered through 0.45 μm of glass fiber filter, Oasis HLB pillars are passed through with the flow velocity of 4mL/min.Before loading, 5mL second is used successively
Acetoacetic ester, 5mL methyl alcohol, 5mL ultra-pure waters activation pillar.After loading, with 5mL deionized water drip washing, leacheate is discarded, negative pressure is drained
10min, then eluted 2 times with 5mL ethyl acetate, and it is 1mL/min to keep elution flow rate.The eluent of collection is rotated to be evaporated to
It is dry, with methanol constant volume to 1mL, treat that HPLC-MS/MS is analyzed；
S5：High performance liquid chromatography GC-MS MRM monitoring ion mode analyses：
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 methyl alcohol (B)；Flow velocity is 0.3mL/min；Column temperature：30℃；Sample introduction
Volume：5uL；Gradient elution program：During 0~8min, mobile phase is formic acid 30%, methyl alcohol 70%；During 8~8.1min, mobile phase
It is formic acid 5%, methyl alcohol 95%；During 8.1~16min, mobile phase is formic acid 5%, methyl alcohol 95%；During 16~20min, mobile phase is
Formic acid 30%, methyl alcohol 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 gun by the flow velocity of μ L/min；Monitoring pattern is monitored for many 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 are carried out to its daughter ion, obtained
Fragment ion information；Then the mass spectrometry parameters such as CE, DP, EP, CXP of target compound second order mses are optimized, mass spectrum is more
Reaction monitoring parameter is shown in Table 2.
Table 2：12 kinds of parameters and its LC-MS detection parameters of OPEs
* quota ion is represented
S6：Quantified by external standard method：Monitored after ion mode analyzes by high performance liquid chromatography GC-MS MRM, according to painting
The chromatogram of system calculates the peak area of sample solution, and by the standard curve described in step S2 calculates sample solution
12 kinds of concentration of OPEs, object is in good linear relationship in the range of 0.2~100 μ g/L, is calculated with signal to noise ratio S/N=3
Instrumental method detection limit (LOD), S/N=10 is used as instrumental method quantitative limit (LOQ).The standard liquid to 100 μ g/L connects simultaneously
It is continuous to determine 3 days, determine 3 times daily, calculate in a few days and day to day precision；The results are shown in Table 1.
Table 1：12 kinds of linear equations of OPEs, coefficient correlation, in a few days with day to day precision, detection limit and quantitative limit
Experimental verification：
1. the selection of mobile phase：Generally, can be improved under acid condition compound [M+H]+cation response, this
Experiment uses ESI+ patterns, respectively with acetonitrile-aqueous solution, methanol-water solution, the aqueous formic acid of methyl alcohol -0.2% as flowing
Phase, the separating effect to 12 kinds of OPEs (100 μ g/L) is compared, and its TIC is shown in Fig. 1.Result is found 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 object is divided
It is little (see Fig. 1 c) from influence, but can be the response for improving partial target thing, therefore select the aqueous formic acid of methyl alcohol -0.2%
It is mobile phase.
2. the selection of Extraction solvent：5 kinds of organic solvent (n-hexane-methyl alcohol (2:1, V/V), methanol-acetonitrile (1:4, V/V),
Methyl alcohol, acetonitrile and n-hexane-ethyl acetate (2:5, V/V)) extracting method is below 55% to the TMP rate of recovery, this be probably by
Caused by TMP is preferably water-soluble and volatile；The TCEP rate of recovery is also relatively poor, in the range from 24.14%~58.60%,
It is probably because complicated deposit matrix is to the substrate inhibition effect of TCEP.Additionally, 5 kinds of organic solvents only have acetonitrile as extraction
When taking agent, TCPP, TCrP can reach the preferable rate of recovery, and respectively 72.82%, 119.5%, and remaining 4 kinds of extractant is to it
The rate of recovery is below 5%.Comparatively speaking, effect of extracting when acetonitrile makees Extraction solvent is preferable.Therefore, subsequent experimental selection acetonitrile
As optimal extractant.
3. the rate of recovery and precision：
With the extremely low soil of object as a control group, and using its concentration the baseline value for being controlled as blank.Add respectively
Low (5 μ g/kg), in (10 μ g/kg), (50 μ g/kg) 3 objects of various concentrations high, each concentration sets 3 Duplicate Samples,
Testing result deducts the baseline value for substituting sample.In pedotheque 12 kinds of average recovery of standard addition of OPEs be 31.24%~
116.63%.Experimental result is shown in Table 3.
Table 3：12 kinds of rate of recovery and precision of OPEs in pedotheque
4. 12 kinds of detection and analysis of target compound in 25 pedotheques of sampled point that pair farmland is set, the results are shown in Table
4。
Table 4：The exposure concentrations (μ g/kg) of 12 kinds of OPEs in agricultural land soil
5.nda:Do not detect；The single OPE total concentrations of b account for the percentage of all OPEs total concentrations.
6. conclusion：The high performance liquid chromatography-tandem mass (HPLC-MS/MS) that the present invention sets up is while determine agricultural land soil
In 12 kinds of OPEs residual analysis methods.Generally, for major part OPEs in text, the method detection limit is low, good stability,
But cause its rate of recovery in soil relatively low because it is preferably water-soluble and volatile for trimethyl phosphate (TMP), for
For tricresyl phosphate (2- chloroethyls) ester (TCEP), it may be possible to due to the depression effect that the complicated matrix of deposit is produced, cause back
Yield is relatively low.But for the rapid screening of OPEs in agricultural land soil, this method disclosure satisfy that 12 kinds of OPEs in agricultural land soil substantially
The detection requirement of residual.
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
The present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
Modified with to the technical scheme described in previous embodiment, or equivalent is carried out to which part technical characteristic；And
These modifications are replaced, and do not make the spirit and model of the essence disengaging embodiment of the present invention technical scheme of appropriate technical solution
Enclose.
Claims (4)
1. a kind of while the method for determining 12 kinds of OPEs residual in pedotheque, it is characterised in that comprise the following steps：
S1：Prepare mixed standard solution：
A. single standard reserving solution is prepared：12 kinds of each 0.01g of OPEs accurately are weighed, with methyl alcohol dissolving constant volume in 10mL volumetric flasks,
It is made into the standard reserving solution that mass concentration is 1000mg/L；100 μ L standard reserving solutions are taken respectively in 10mL volumetric flasks, use methyl alcohol
Scale is diluted to, it is the standard reserving solution of 10mg/L to prepare mass concentration, is stored in 4 DEG C of refrigerators；
B. hybrid standard storing solution is prepared：Accurate each single standard reserving solutions of 200 μ L of drawing use methanol dilution in 10mL volumetric flasks
To scale, the hybrid standard storing solution that mass concentration is 200 μ g/L is prepared, in preservation at 4 DEG C；
C. with methyl alcohol as solvent, be made into after above-mentioned hybrid standard storing solution is diluted in proportion mass concentration be respectively 0.2,1,
2nd, the mixed standard solution of 5,10,20,50,100 μ g/L, in preservation at 4 DEG C；
S2：Draw standard curve：
12 kinds of OPEs hybrid standards for being respectively 0.2,1,2,5,10,20,50 and 100 μ g/L with methyl alcohol preparation mass concentration are molten
Liquid, standard curve is drawn with peak area (y) to the mass concentration (x) of object；
S3：Sample collection：
Pedotheque is gathered in sampled point, impurity removing is removed, is placed in stainless steel box, freeze-drying, ground 60 mesh sieve, -20 DEG C
Preserve to be measured；
S4：Sample pre-treatments：
After by freeze-dried ground 60 mesh sieve of above-mentioned pedotheque, 5g pedotheques are weighed respectively in 100mL centrifuge tubes,
30mL organic solvents are added as extractant, after ultrasonic extraction 30min, 5min is centrifuged with 8000r/min, supernatant is placed in chicken
Heart bottle, repeats the above steps 1 time, merges supernatant, and rotary evaporation to below 10mL is diluted to 100mL with ultra-pure water, through 0.45
The filtering of μm glass fiber filter, Oasis HLB pillars are passed through with the flow velocity of 4mL/min.Before loading, successively with 5mL ethyl acetate,
5mL methyl alcohol, 5mL ultra-pure waters activation pillar.After loading, with 5mL deionized water drip washing, leacheate is discarded, negative pressure drains 10min,
Eluted 2 times with 5mL ethyl acetate again, and it is 1mL/min to keep elution flow rate.The eluent of collection is rotated to be evaporated to dryness, and is used
Methanol constant volume treats that HPLC-MS/MS is analyzed to 1mL；
S5：High performance liquid chromatography GC-MS MRM monitoring ion mode analyses：
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 methyl alcohol (B)；Flow velocity is 0.3mL/min；Column temperature：30℃；Sampling volume：
5uL；Gradient elution program：During 0~8min, mobile phase is formic acid 30%, methyl alcohol 70%；During 8~8.1min, mobile phase is formic acid
5%th, methyl alcohol 95%；During 8.1~16min, mobile phase is formic acid 5%, methyl alcohol 95%；During 16~20min, mobile phase is formic acid
30%th, methyl alcohol 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 gun by the flow velocity of min；Monitoring pattern is many reactive ions monitoring (MRM)；Choosing
Corresponding parent ion peak is taken, second mass analysis are carried out to its daughter ion, obtain fragment ion information；
S6：Quantified by external standard method：After high performance liquid chromatography GC-MS MRM monitors ion mode analysis, according to what is drawn
Chromatogram calculates the peak area of sample solution, and 12 kinds in sample solution are calculated by the standard curve described in step S2
The concentration of OPEs, with signal to noise ratio S/N=3 computing equipment methods detection limit (LOD), S/N=10 is used as instrumental method quantitative limit
(LOQ)。
2. according to claim 1 a kind of while determining the analysis method of 12 kinds of OPEs residual in soil, it is characterised in that
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 groups)
Ester (Tributoxyethyl phosphate, TBEP), tricresyl phosphate (2- chloro isopropyls) ester (Tri (chloropropyl)
Phosphate, TCPP), tricresyl phosphate (the chloro- 2- propyl group of 1,3- bis-) ester (Tri (dichloropropyl) phosphate, TDCP),
Triphenyl phosphate (Triphenyl phosphate, TPhP), tricresyl phosphate (Tricresyl phosphate, TCrP),
Tricresyl phosphate (2- chloroethyls) ester (Tri (2-chloroethyl) phosphate, TCEP), tri-2-ethylhexyl phosphate (Tri
(2-ethylhexyl) phosphate, TEHP), tricresyl phosphate (2,3- dibromopropyls) ester (tris (2,3-Dibromopropyl)
Phosphate, TDBPP), 2- ethylhexyl diphenyl phosphates (2-Ethylhexyl diphenyl phosphate,
EHDPP)。
3. according to claim 1 a kind of while determining the analysis method of 12 kinds of OPEs residual in soil, it is characterised in that
The extractant is acetonitrile.
4. according to a kind of while determining the analysis method that 12 kinds of OPEs in soil are remained described in claim 1, it is characterised in that institute
In stating mass spectral analysis, ion source temperature：500 DEG C, ion spray voltage：5500V；Gas curtain gas (curtain gas, CUR)
Pressure is 206 851.8Pa；Spraying gas (ion source gas 1, GS1) pressure is 241 327.1Pa；Auxiliary heating gas
(ion source gas 2, GS2) pressure is 275802.4Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710211513.0A CN106908549B (en) | 2017-03-31 | 2017-03-31 | It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710211513.0A CN106908549B (en) | 2017-03-31 | 2017-03-31 | It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106908549A true CN106908549A (en) | 2017-06-30 |
| CN106908549B CN106908549B (en) | 2019-07-19 |
Family
ID=59195302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710211513.0A Expired - Fee Related CN106908549B (en) | 2017-03-31 | 2017-03-31 | It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106908549B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108507821A (en) * | 2018-06-20 | 2018-09-07 | 温州新鸿检测技术有限公司 | A kind of soil pollution detection method |
| CN108519451A (en) * | 2018-03-09 | 2018-09-11 | 沈阳大学 | A method of utilizing matrix solid phase dispersion extractive analysis plant organophosphorus ester |
| CN108872429A (en) * | 2018-06-29 | 2018-11-23 | 江苏亿科检测技术服务有限公司 | The detection method of 2- ethylhexyl diphenyl phosphate in a kind of leather |
| CN109374769A (en) * | 2018-11-14 | 2019-02-22 | 天津大学 | A kind of method of a variety of organophosphorus esters in ultra performance liquid chromatography-mass spectroscopy surface water |
| CN109668981A (en) * | 2018-12-25 | 2019-04-23 | 广东省东莞市质量监督检测中心 | A kind of method of phosphor-containing flame-proof agent content and the amount of migration in measurement toy |
| CN111983069A (en) * | 2020-08-11 | 2020-11-24 | 深圳市环境科学研究院 | Detection method for determining phosphorus flame retardant and degradation product thereof in surface water |
| CN112229936A (en) * | 2020-12-14 | 2021-01-15 | 南京市产品质量监督检验院 | Method for simultaneously detecting 33 plastic additives in food contact material |
| CN112362772A (en) * | 2020-10-29 | 2021-02-12 | 实朴检测技术(上海)股份有限公司 | Method for detecting residual organic solvent in soil |
| 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 |
| CN113899836A (en) * | 2021-08-27 | 2022-01-07 | 中国科学院烟台海岸带研究所 | Rapid high-throughput detection method for antibiotics in soil sample and sediment sample |
| 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 |
| 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 |
| CN115598263A (en) * | 2022-11-25 | 2023-01-13 | 国科大杭州高等研究院（Cn） | Method for simultaneously determining contents of organic phosphate and conversion product thereof |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-03-31 CN CN201710211513.0A patent/CN106908549B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| ALESSANDRO BACALONI ET AL.: "Liquid chromatography/tandem mass spectrometry determination of organophosphorus flame retardants and plasticizers in drinking and surface waters", 《RAPID COMMUNICATIONS IN MASS SPECTROMETRY》 * |
| 刘静 等: "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", 《生态毒理学报》 * |
| 秦宏兵 等: "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", 《分析科学学报》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108519451A (en) * | 2018-03-09 | 2018-09-11 | 沈阳大学 | A method of utilizing matrix solid phase dispersion extractive analysis plant organophosphorus ester |
| CN108507821A (en) * | 2018-06-20 | 2018-09-07 | 温州新鸿检测技术有限公司 | A kind of soil pollution detection method |
| CN108872429A (en) * | 2018-06-29 | 2018-11-23 | 江苏亿科检测技术服务有限公司 | The detection method of 2- ethylhexyl diphenyl phosphate in a kind of leather |
| CN109374769A (en) * | 2018-11-14 | 2019-02-22 | 天津大学 | A kind of method of a variety of organophosphorus esters in ultra performance liquid chromatography-mass spectroscopy surface water |
| CN109668981A (en) * | 2018-12-25 | 2019-04-23 | 广东省东莞市质量监督检测中心 | A kind of method of phosphor-containing flame-proof agent content and the amount of migration in measurement toy |
| CN111983069A (en) * | 2020-08-11 | 2020-11-24 | 深圳市环境科学研究院 | Detection method for determining phosphorus flame retardant and degradation product thereof in surface water |
| CN111983069B (en) * | 2020-08-11 | 2021-11-23 | 深圳市环境科学研究院 | Detection method for determining phosphorus flame retardant and degradation product thereof in surface water |
| CN112362772A (en) * | 2020-10-29 | 2021-02-12 | 实朴检测技术(上海)股份有限公司 | Method for detecting residual organic solvent in soil |
| CN112229936B (en) * | 2020-12-14 | 2021-03-19 | 南京市产品质量监督检验院 | Method for simultaneously detecting 33 plastic additives in food contact material |
| CN112229936A (en) * | 2020-12-14 | 2021-01-15 | 南京市产品质量监督检验院 | Method for simultaneously detecting 33 plastic additives in food contact material |
| 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 |
| CN113899836A (en) * | 2021-08-27 | 2022-01-07 | 中国科学院烟台海岸带研究所 | Rapid high-throughput detection method for antibiotics in soil sample and sediment sample |
| 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 |
| 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 |
| CN115598263A (en) * | 2022-11-25 | 2023-01-13 | 国科大杭州高等研究院（Cn） | Method for simultaneously determining contents of organic phosphate and conversion product thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106908549B (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106908549A (en) | It is a kind of while the method for determining 12 kinds of OPEs residual in pedotheque | |
| CN106841471B (en) | It is a kind of to measure 12 kinds of remaining methods of OPEs in water sample and deposit simultaneously | |
| Giulivo et al. | Analysis of organophosphorus flame retardants in environmental and biotic matrices using on-line turbulent flow chromatography-liquid chromatography-tandem mass spectrometry | |
| Canellas et al. | Atmospheric pressure gas chromatography coupled to quadrupole-time of flight mass spectrometry as a powerful tool for identification of non intentionally added substances in acrylic adhesives used in food packaging materials | |
| CN106053703B (en) | It is a kind of at the same detect food in various plants growth regulator method | |
| CN103713062B (en) | The method for quick of Determination of Residual Organic Solvents is limited the use of in a kind of textile | |
| Cervera et al. | Determination of volatile organic compounds in water by headspace solid-phase microextraction gas chromatography coupled to tandem mass spectrometry with triple quadrupole analyzer | |
| Bridoux et al. | Quantitative analysis of phosphoric acid esters in aqueous samples by isotope dilution stir-bar sorptive extraction combined with direct analysis in real time (DART)-Orbitrap mass spectrometry | |
| Nan et al. | Novel and rapid method for determination of organophosphorus pesticide residues in edible fungus using direct gas purge microsyringe extraction coupled on-line with gas chromatography–mass spectrometry | |
| Celano et al. | Liquid chromatography quadrupole time-of-flight mass spectrometry quantification and screening of organophosphate compounds in sludge | |
| Lorenzo et al. | Determination of organophosphate flame retardants in soil and fish using ultrasound‐assisted extraction, solid‐phase clean‐up, and liquid chromatography with tandem mass spectrometry | |
| CN103698462B (en) | Method for detecting plurality of residual pesticides in tobacco simultaneously | |
| Tsao et al. | Microwave-assisted headspace solid-phase microextraction for the rapid determination of organophosphate esters in aqueous samples by gas chromatography-mass spectrometry | |
| Zushi et al. | Nontarget approach for environmental monitoring by GC× GC-HRTOFMS in the Tokyo Bay basin | |
| CN108469482B (en) | Method for simultaneously determining phosphorus flame retardant and bromine flame retardant in PVC (polyvinyl chloride) by GC-MS (gas chromatography-Mass spectrometer) | |
| CN109374769A (en) | A kind of method of a variety of organophosphorus esters in ultra performance liquid chromatography-mass spectroscopy surface water | |
| van Stee et al. | Identification of non-target compounds using gas chromatography with simultaneous atomic emission and mass spectrometric detection (GC-AED/MS): analysis of municipal wastewater | |
| Sánchez-Brunete et al. | Determination of polybrominated diphenyl ethers in soil by ultrasonic assisted extraction and gas chromatography mass spectrometry | |
| Godfrey et al. | Use of QuEChERS as a manual and automated high-throughput protocol for investigating environmental matrices | |
| Tao et al. | A natural environmental chamber study on the emissions and fate of organophosphate esters in the indoor environment | |
| Wang et al. | Determination of ultra-trace organic acids in Masson pine (Pinus massoniana L.) by accelerated solvent extraction and liquid chromatography–tandem mass spectrometry | |
| Castro et al. | Determination of human metabolites of chlorinated phosphorous flame retardants in wastewater by N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide-derivatization and gas chromatography-high resolution mass spectrometry | |
| Yang et al. | Determination of swainsonine in the endophytic Undifilum fungi by high-performance liquid chromatography with evaporative light-scattering detector | |
| CN106442787B (en) | The foundation of liquid chromatogram retention index and its application in terms of compound characterization | |
| CN107255680A (en) | While a variety of organophosphate ester flame retardant methods in quick detection soil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190719 Termination date: 20200331 |