CN109374769A - A kind of method of a variety of organophosphorus esters in ultra performance liquid chromatography-mass spectroscopy surface water - Google Patents
A kind of method of a variety of organophosphorus esters in ultra performance liquid chromatography-mass spectroscopy surface water Download PDFInfo
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Abstract
The invention discloses the method for a variety of organophosphorus esters in a kind of ultra performance liquid chromatography-mass spectroscopy surface water, key step includes: that (1) prepares gradient standard hybrid working liquid；(2) sample liquid-liquid extraction pre-treatment；(3) with ultra performance liquid chromatography-mass spectroscopy titer and sample liquid；(4) standard curve of organic phosphoric acid ester monomer is obtained with titer detection data, the content of organophosphorus ester in sample is obtained by standard curve with sample liquid detection data.Sample pre-treatments are simple in the present invention, can effectively avoid pillar blockage problem, while small column polarity range of choice is wide；Qualitative, quantitative is carried out to 11 kinds of organophosphorus esters using ultra performance liquid chromatography-mass spectrum, the good separation of all organophosphorus esters is realized in 17min, object blank recovery of standard addition is 70%-120% (except triethyl phosphate is 63%), and detection is limited to 0.08-1.8ng/L.
Description
Technical field
The present invention relates to the method for a variety of organophosphorus esters in measurement surface water more particularly to a kind of ultra high efficiency liquid phase colors
The method of a variety of organophosphorus esters in spectrum-mass spectroscopy surface water.
Background technique
Organophosphorus ester (organophosphate esters, OPEs) is a kind of artificial synthesized novel organic matter,
It is cheap, there is preferable compatibility with high molecular material, frequently as additive flame retardant and plasticizer.Organophosphorus ester according to
Its structure can be divided into three classes with purposes: alkyl-substituted organophosphorus ester is mainly used as plasticizer, defoaming agent and additive；
The organophosphorus ester that halogenated alkyl replaces and aryl replaces is mainly used as furniture, textile, mattress, electronic product and children's phase
The fire retardant of product (stroller, nightwear, infant-wear) is closed, such organophosphorus ester has persistence, in the environment difficult drop
Solution, it is easy to left behind in the environment.According to the data statistics of European fire retardant association, from 2001 to 2006, as resistance
The organophosphorus ester of agent is fired, demand increases year by year with output, mainly in a manner of chemistry addition and other compounds
Mixing links together not by the mode of chemical bonding with other pollutants, therefore is easy to release in various transport process
It is put into environment, with the increase of its Environment release amount, caused environmental problem just gradually causes to pay close attention to, to organophosphorus ester
Detection technique still need to further develop with it is perfect.
Current study show that: organophosphorus ester is not a kind of Environmental security substance, and a variety of organophosphorus esters have toxicity.
Compared to non-halogenated organophosphorus ester, halogenated organophosphorus ester has stronger carcinogenicity, neurotoxicity and genotoxicity.2006
The risk draft of European Union's publication thinks that TCEP has carcinogenicity, high toxicity and environmental persistence, the World Health Organization in 1998
Research shows that TDCPP has carcinogenicity, TCEP and TDCPP have potential neurotoxicity, and have to aqueous bio acute
Or chronic adverse effect.TCPP is a kind of suspicious carcinogenic substance.TCEP is classified as the second class priority pollutant by European Union, by TCPP
Be classified as the 4th class priority pollutant with TDCPP, Europe in the 1990s mid-term oneself be forbidden to use TCEP, and with TCPP come
Instead of using TCEP.For non-halogenated organophosphorus ester, TMP has genetoxic, and TnBP has neurotoxicity.TPhP and
EHDPP has potential source biomolecule enriching and genotoxic potential to aquatic ecosystem.TPhP can inhibit the intracorporal carboxy-lesterase of people, from
And dermatitis is easily caused, furthermore the substance in house dust can inhibit hormone level in human body and significantly reduce male's essence
Liquid is horizontal.
Since the hydrogen substituent group of organophosphorus ester is different, cause the physics and chemistry of different classes of substituent group organophosphorus ester special
Gender gap is very big, such as polarity, volatility, water solubility, octanol-water partition coefficient, therefore examines to the analysis of organophosphorus ester
Survey also brings very big puzzlement.Currently, the pre-treating method of organophosphorus ester is mainly Solid Phase Extraction in water body, this method can
Object in less water body is interfered preferably to extract the impurity such as drinking water and underground well water, but this for river
Impurity interferes more serious water body, is likely to result in clogging, impurity serious interference；The polarity of solid phase extraction column retains
It is limited in scope, the extraction work of more organophosphorus esters cannot be completed；Furthermore extraction cannot with purification in pretreatment process
One step is completed, complicated for operation, and sensitivity and selectivity are poor.
The detection method of organophosphorus ester mainly has gas chromatography and liquid chromatography at present, and gas chromatography is main
There are two kinds of gas phase-nitrogen phosphorous detector method (GC-NPD) and gas chromatography-mass spectrography (GC-EI-MS), although the method pair of GC-NPD
Phosphorus-containing compound has preferable selectivity, but this method stability is poor, needs to regularly replace the rubidium pearl in detector；GC-
The method of EI-MS can weaken influence of the matrix effect to dosing process, but Bjorklund J etc. was in Rapid in 2004
Communications in Mass Spectrometry Rcm mono- the article pointed out can be generated when being analyzed using GC-MS it is excessive broken
When piece, especially analysis three ester of aliphatic, these OPEs can generate 3 McLafferty rearrangements, so that EI-MS spectral signal is considerably
Weak, base peak m/z99 is consistent with the phosphate radical of protonation, so matrix components can interfere low quality ion.Liquid chromatography master
There is liquid chromatography-mass spectrometry (LC-MS), there is higher selectivity and sensitive compared to GC-MS with this method detection OPEs
Degree, can directly detect the OPEs in water sample, not need for object to be transferred in organic solvent, and can measure other polarity simultaneously
Stronger compound, however there are two defects for the method for the LC-MS developed at present: first is that the organophosphorus ester that can be analyzed simultaneously
Type it is less, second is that the analysis time of sample is too long, even up to 30 minutes average 20 minutes, therefore the extraction about OPEs
Take-analysis determining method still needs to continuously improve.
Summary of the invention
The purpose of the present invention is to overcome the disadvantages of the prior art, provides a kind of ultra high efficiency liquid of simple and fast time-saving and efficiency
The method that phase chromatography-mass spectroscopy measures a variety of organophosphorus esters in surface water.
The technical scheme adopted by the invention is that:
A kind of method of a variety of organophosphorus esters in ultra performance liquid chromatography-mass spectroscopy surface water, comprising the following steps:
(1) standard hybrid working liquid is prepared:
(a) triethyl phosphate that the concentration of 10 μ L is 100mg/L, tricresyl phosphate positive third are drawn respectively with 10 μ L micropipette rifles
Ester, TRI N BUTYL PHOSPHATE, triisooctyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (2- ethylhexyl diphenyl)
Ester, tricresyl phosphate (butoxyethyl group) ester, tricresyl phosphate (2- chloroethyl) ester, tricresyl phosphate (2- chloropropyl) ester, tricresyl phosphate (1,3- dichloro
Isopropyl) ester standard reserving solution, it then instills in a 2ml chromatogram bottle and mixes, then be added 890 μ L's in 2ml chromatogram bottle
Methanol, oscillation obtain the standard hybrid working liquid of the 1mg/L of 1ml；
(b) 0.5 μ L, 1 μ L, 2 μ L, 5 μ L, 10 μ L, 20 μ L, 50 μ L, 200 μ L, 500 μ L are drawn respectively with micropipette rifle
The standard hybrid working liquid of 1mg/L, obtains the standard hybrid working liquid of nine kinds of volumes, each personal methanol dilution to 1ml, and oscillation mixes
The even standard hybrid working liquid for obtaining nine kinds of various concentrations: 0.5 μ g/L, 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50
μ g/L, 200 μ g/L, 500 each 1ml of μ g/L standard hybrid working liquid；
(2) sample pretreatment:
Water sample of the 500ml by filtering is measured, substitute is added into water sample, extracts water sample two with the extractant of 50ml
Secondary, combining extraction liquid, with the dry extract liquor of desiccant anhydrous sodium sulfate, the extract liquor rotary evaporation after drying is concentrated into 1ml, dense
Contracting liquid is transferred to chromatogram bottle, repeatedly washs revolving bottle on a small quantity with methylene chloride, and cleaning solution is transferred in 2ml chromatogram bottle, nitrogen is used
Air-blowing sweeps concentrate and instills HPLC grades of methanol 0.5ml constant volumes in 2ml chromatogram bottle to nearly dry doubling as sample solution；
(3) with ultra performance liquid chromatography-tandem mass spectrum measurement standard hybrid working liquid and sample solution；
(4) using standard hybrid working liquid concentration as abscissa, chromatographic peak face corresponding with the standard hybrid working liquid concentration
Product is that ordinate establishes a standard curve, then measures sample solution by ultra performance liquid chromatography-tandem mass spectrum, obtains sample
The chromatographic peak area of product solution obtains the actual concentrations of sample liquid by the standard curve of standard hybrid working liquid.
Compared with prior art, the invention has the following advantages:
Target compound in surface water is extracted using liquid-liquid extraction method, it is easy to operate, time-consuming short；Use ultra high efficiency
The method of liquid chromatography-mass spectrography establishes the qualitative analysis and quantitative detecting method of 11 kinds of organophosphorus esters, by optimizing liquid phase
Condition and Mass Spectrometry Conditions solve the problems, such as that conventional method analysis time is longer, and this method is made to have better choice and sensitive
Degree, the quantitative determination of organophosphorus ester can be realized with this method.
The present invention extracts the organophosphorus ester in surface water using the method for liquid-liquid extraction, can extract to avoid solid phase
During taking due to impurity it is more caused by pillar blockage problem, while extractant polarity range of choice used is wide, can be complete
At the extraction compared with multiple types organophosphorus ester.
This method optimizes ultra performance liquid chromatography condition, effectively reduces analysis time, improves analysis rate, tie simultaneously
It closes concatenated triple level four bars mass spectrums and measures organophosphorus ester under quantitative reaction monitoring pattern, substantially increase analysis method
Sensitivity and selectivity, reduce detection limit, the quantitative detection suitable for Environmental Trace organophosphorus ester.
The present invention can be effectively separated 11 kinds of organophosphorus esters, accurate qualitative and accurate quantification, and 11 kinds organic phosphorus
The range of linearity of acid esters is 2-200 μ g/L, the related coefficient (R of standard curve2) it is all larger than 0.99, recovery of standard addition 70%-
120% (except triethyl phosphate is 63%), detection is limited to 0.08-1.8ng/L.
Detailed description of the invention
Fig. 1 is the method for a variety of organophosphorus esters in a kind of ultra performance liquid chromatography-mass spectroscopy surface water of the invention
Flow diagram；
Fig. 2 is the chromatogram of TEP；
Fig. 3 is the chromatogram of TPrP；
Fig. 4 is the chromatogram of TnBP；
Fig. 5 is the chromatogram of TEHP；
Fig. 6 is the chromatogram of TCEP；
Fig. 7 is the chromatogram of TCPP；
Fig. 8 is the chromatogram of TDCPP；
Fig. 9 is the chromatogram of TPhP；
Figure 10 is the chromatogram of TCrP；
Figure 11 is the chromatogram of EHDPP；
Figure 12 is the chromatogram of TBEP.
Specific embodiment
The present invention is illustrated in the following with reference to the drawings and specific embodiments.
A variety of organophosphorus esters in a kind of ultra performance liquid chromatography-mass spectroscopy surface water of the invention as shown in drawings
Method, comprising the following steps:
(1) standard hybrid working liquid is prepared:
(a) the triethyl phosphate TEP, tricresyl phosphate that the concentration of 10 μ L is 100mg/L are drawn respectively with 10 μ L micropipette rifles
N-propyl TPrP, TRI N BUTYL PHOSPHATE TnBP, triisooctyl phosphate TEHP, triphenyl phosphate TPhP, tricresyl phosphate TCrP,
Tricresyl phosphate (2- ethylhexyl diphenyl) ester EHDPP, tricresyl phosphate (butoxyethyl group) ester TBEP, tricresyl phosphate (2- chloroethyl) ester
TCEP, tricresyl phosphate (2- chloropropyl) ester TCPP, tricresyl phosphate (1,3- bis- chloro isopropyl) ester TDCPP standard reserving solution, then drip
Enter and mixed in a 2ml chromatogram bottle, then the methanol of 890 μ L is added in 2ml chromatogram bottle, oscillation obtains the standard of the 1mg/L of 1ml
Hybrid working liquid；
(b) 0.5 μ L, 1 μ L, 2 μ L, 5 μ L, 10 μ L, 20 μ L, 50 μ L, 200 μ L, 500 μ L are drawn respectively with micropipette rifle
The standard hybrid working liquid of 1mg/L, obtains the standard hybrid working liquid of nine kinds of volumes, each personal methanol dilution to 1ml, and oscillation mixes
The even standard hybrid working liquid for obtaining nine kinds of various concentrations: 0.5 μ g/L, 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50
μ g/L, 200 μ g/L, 500 each 1ml of μ g/L standard hybrid working liquid.
(2) sample pretreatment:
Water sample of the 500ml by filtering is measured, substitute is added into water sample, extracts water sample two with the extractant of 50ml
Secondary, combining extraction liquid, with the dry extract liquor of desiccant anhydrous sodium sulfate, the extract liquor rotary evaporation after drying is concentrated into 1ml, dense
Contracting liquid is transferred to chromatogram bottle, repeatedly washs revolving bottle on a small quantity with methylene chloride, and cleaning solution is transferred in 2ml chromatogram bottle, nitrogen is used
Air-blowing sweeps concentrate and instills HPLC grades of methanol 0.5ml constant volumes in 2ml chromatogram bottle to nearly dry doubling as sample solution.
(3) with ultra performance liquid chromatography-tandem mass spectrum measurement standard hybrid working liquid and sample solution, liquid chromatogram-string
Join the instrument that mass spectrograph uses mark ultra high efficiency commercially available.
(4) certain chromatographic peak area is obtained based on certain density standard hybrid working liquid, by measuring various concentration
The available a series of chromatographic peak area of standard hybrid working liquid, using standard hybrid working liquid concentration as abscissa, with this
The corresponding chromatographic peak area of standard hybrid working liquid concentration is that ordinate can establish a standard curve, then passes through ultra high efficiency
Liquid chromatography tandom mass spectrometry determination sample solution obtains the chromatographic peak area of sample solution, passes through the mark of standard hybrid working liquid
Directrix curve obtains the actual concentrations of sample liquid.
The organophosphorus ester of the analysis includes four kinds of alkyl for organophosphorus ester: triethyl phosphate, tricresyl phosphate propyl ester, phosphorus
Sour tri-n-butyl, triisooctyl phosphate；Three kinds of chloro alkyl are for organophosphorus ester: tricresyl phosphate (2- chloroethyl) ester, tricresyl phosphate (2-
Chloropropyl) ester, tricresyl phosphate (1,3- bis- chloro isopropyl) ester；Three kinds of aryl are for organophosphorus ester: triphenyl phosphate, phosphate trimethylbenzene
Ester, tricresyl phosphate (2- ethylhexyl diphenyl) ester and tricresyl phosphate (butoxyethyl group) ester.
Step (2) filtering preferably uses 0.45 μm of filtering with microporous membrane.
Step (2) substitute refer to deuterated triphenyl phosphate, deuterated TRI N BUTYL PHOSPHATE, deuterated triethyl phosphate,
One of deuterated tricresyl phosphate (2- chloroethyl) ester, preferably deuterated triphenyl phosphate, advantage be it is from a wealth of sources, price is just
Preferably.
Step (2) extractant is one of methylene chloride, n-hexane, ethyl acetate, preferably dichloromethane
Alkane, advantage be it is cheap, it is good to the effect of extracting of analyte.
Step (3) ultra performance liquid chromatography-Mass Spectrometry Conditions are as follows:
Liquid phase chromatogram condition: 6420 highly effective liquid phase chromatographic system of Agilent Infinity；
Chromatographic column: Zorbax Eclipse Plus C18Column, column temperature are 40 DEG C, column specification size are as follows: 2.1mm × 50mm；
i.d,1.8μm；
Mobile phase: A: volume ratio is the aqueous formic acid of 1:1000, B: pure methanol, flow rate of mobile phase 0.4mL/min.Stream
Dynamic phase gradient elution requirement is as follows: keeping volume ratio A:B=60%:40% in 0-3min, keeps volume ratio A:B in 3-4.5min
Volume ratio A:B=45%:55% is kept in=50%:50%, 6.5-8.5min, keeps volume ratio A:B=in 8.5-9min
Volume ratio A:B=20%:80% is kept in 30%:70%, 9-11min, keeps volume ratio A:B=10% in 11-12min:
Volume ratio A:B=0%:100% is kept in 90%, 12-15.5min, keeps volume ratio A:B=60% in 15.5-18.5min:
40%.
Sampling volume is 10 μ L.
Mass Spectrometry Conditions:
The triple level four bars mass detectors of Agilent 6460；
Ion source: ion source temperature: ESI 300 DEG C, ionizes mode: positive ion mode；Dry gas stream speed: 7l/min；Mist
Change device pressure: 45psi；Sheath temperature degree: 350 DEG C, sheath gas: 11l/min；Collision voltage: 3.5kV；Spray nozzle voltage: 0kV；It adopts
Mode set: quantitative reaction monitoring pattern.
Ultra performance liquid chromatography-mass spectrometry parameters in relation to each organic phosphoric acid ester monomer are as follows:
When measuring tricresyl phosphate (2- chloroethyl) ester: mother ion mass-to-charge ratio 285, the mass-to-charge ratio of quantitative daughter ion is 99, fixed
The mass-to-charge ratio of temper ion is 63.1；
When measuring tricresyl phosphate (2- chloropropyl) ester: mother ion mass-to-charge ratio 327, the mass-to-charge ratio of quantitative daughter ion is 99, fixed
The mass-to-charge ratio of temper ion is 174.9；
When measuring tricresyl phosphate (1,3- bis- chloro isopropyl) ester: mother ion mass-to-charge ratio 428.9, the mass-to-charge ratio of quantitative daughter ion
It is 99.1, the mass-to-charge ratio of qualitative daughter ion is 208.9；
When measuring triethyl phosphate: mother ion mass-to-charge ratio 183, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative daughter ion
Mass-to-charge ratio be 126.9；
When measuring tricresyl phosphate propyl ester: mother ion mass-to-charge ratio 225.3, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative son from
The mass-to-charge ratio of son is 140.9；
When measuring TRI N BUTYL PHOSPHATE: mother ion mass-to-charge ratio 267.3, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative son
The mass-to-charge ratio of ion is 211；
When measuring triisooctyl phosphate: mother ion mass-to-charge ratio 435.4, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative son
The mass-to-charge ratio of ion is 113；
When measuring tricresyl phosphate: mother ion mass-to-charge ratio 369.1, the mass-to-charge ratio of quantitative daughter ion is 91.1, qualitative
The mass-to-charge ratio of daughter ion is 165；
When measuring triphenyl phosphate: mother ion mass-to-charge ratio 327, the mass-to-charge ratio of quantitative daughter ion are 77.1, qualitative son from
The mass-to-charge ratio of son is 214.9；
When measuring tricresyl phosphate (2- ethylhexyl diphenyl) ester: mother ion mass-to-charge ratio 363.2, the matter lotus of quantitative daughter ion
Than being 251, the mass-to-charge ratio of qualitative daughter ion is 77.1；
When measuring tricresyl phosphate (butoxyethyl group) ester: the mass-to-charge ratio of mother ion mass-to-charge ratio 399.3, quantitative daughter ion is
199, the mass-to-charge ratio of qualitative daughter ion is 299.1.
Embodiment 1
The organophosphorus ester in the water body of Tianjin Haihe River mainstream is analyzed with the present invention.
1. preparing standard working solution:
(a) the triethyl phosphate TEP, tricresyl phosphate that the concentration of 10 μ L is 100mg/L are drawn respectively with 10 μ L micropipette rifles
N-propyl TPrP, TRI N BUTYL PHOSPHATE TnBP, triisooctyl phosphate TEHP, triphenyl phosphate TPhP, tricresyl phosphate TCrP,
Tricresyl phosphate (2- ethylhexyl diphenyl) ester EHDPP, tricresyl phosphate (butoxyethyl group) ester TBEP, tricresyl phosphate (2- chloroethyl) ester
TCEP, tricresyl phosphate (2- chloropropyl) ester TCPP, tricresyl phosphate (1,3- bis- chloro isopropyl) ester TDCPP standard reserving solution, they are dripped
Enter and mixed in 2ml chromatogram bottle, then the methanol of 890 μ L is added in 2ml chromatogram bottle, oscillation obtains the standard mixing of the 1mg/L of 1ml
Working solution；
(b) 0.5 μ L, 1 μ L, 2 μ L, 5 μ L, 10 μ L, 20 μ L, 50 μ L, 200 μ L, 500 μ L are drawn respectively with micropipette rifle
The standard hybrid working liquid of 1mg/L, obtains the standard hybrid working liquid of nine kinds of volumes, each personal methanol dilution to 1ml, and oscillation mixes
The even standard hybrid working liquid for obtaining nine kinds of various concentrations: 0.5 μ g/L, 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50
μ g/L, 200 μ g/L, 500 each 1ml of μ g/L standard hybrid working liquid.
2. sample pretreatment: the separatory funnel of 500ml being placed on separating funnel stand, the earth's surface of 500ml is measured with beaker
Water water sample is added thereto, and the deuterated triphenyl phosphate of 20ng is added with micropipette rifle, with the methylene chloride liquid-liquid extraction two of 50ml
Secondary, extraction, which should sufficiently be vibrated, every time shakes up, and merges organic phase, and after anhydrous sodium sulfate drying, extract liquor is transferred to 250ml's
In revolving bottle, rotary evaporation to 1ml, concentrate is transferred to chromatogram bottle, repeatedly washs revolving bottle, cleaning solution on a small quantity with methylene chloride
It is transferred in chromatogram bottle, the concentration liquid nitrogen in chromatogram bottle, which is blown to, closely to be done, and with methanol constant volume to 0.5ml, obtains sample solution.
3. with ultra performance liquid chromatography-mass spectroscopy standard working solution and sample solution:
Liquid phase chromatogram condition: 6420 highly effective liquid phase chromatographic system of Agilent Infinity；Chromatographic column: Zorbax
Eclipse Plus C18Column, column temperature are 40 DEG C, mobile phase: A: volume ratio is 0.1% aqueous formic acid, B: pure methanol, mobile phase
Flow velocity is 0.4mL/min.Eluent gradient elution requirement is as follows: volume ratio A:B=60%:40%, 3- are kept in 0-3min
Volume ratio A:B=50%:50% is kept in 4.5min, keeps volume ratio A:B=45%:55%, 8.5- in 6.5-8.5min
Volume ratio A:B=30%:70% is kept in 9min, and volume ratio A:B=20%:80% is kept in 9-11min, is protected in 11-12min
Volume ratio A:B=10%:90% is held, volume ratio A:B=0%:100% is kept in 12-15.5min, is protected in 15.5-18.5min
Hold volume ratio A:B=60%:40%.Sampling volume is 10 μ L.
Mass Spectrometry Conditions: the triple level four bars mass detectors of Agilent 6460；Ion source: ESI, ion source temperature: 300
DEG C, ionize mode: positive ion mode；Dry gas stream speed: 7l/min；Nebulizer pressure: 45psi；Sheath temperature degree: 350 DEG C, sheath gas
Flow velocity: 11l/min；Collision voltage: 3.5kV；Spray nozzle voltage: 0kV；Acquisition mode: quantitative reaction monitoring pattern.
After standard hybrid working liquid sample introduction, obtain the corresponding chromatogram of each organic phosphoric acid ester monomer, with chromatogram be according to
According to being quantified.The chromatogram of triethyl phosphate is as shown in Figure 2: retention time 3.220min, response 6.3 × 102；Phosphoric acid
The chromatogram of three propyl ester is as shown in Figure 3: retention time 9.899min, response 2.8 × 104；The chromatogram of TRI N BUTYL PHOSPHATE
It is as shown in Figure 4: retention time 13.075min, response 2.2 × 104；The chromatogram of triisooctyl phosphate is as shown in Figure 5: protecting
Staying the time is 16.370min, response 7.8 × 103；The chromatogram of tricresyl phosphate (2- chloroethyl) ester is as shown in Figure 6: retention time
For 5.314min, response 0.98 × 103；The chromatogram of tricresyl phosphate (2- chloropropyl) ester is as shown in Figure 7: retention time is
10.245min, response 1.5 × 103；The chromatogram of tricresyl phosphate (bis- chloro isopropyl of 1,3-) ester is as shown in Figure 8: retention time is
12.382min, response 3.6 × 102；The chromatogram of tricresyl phosphate is as shown in Figure 9: retention time 13.928min, rings
It should value 4.6 × 103；The chromatogram of triphenyl phosphate is as shown in Figure 10: retention time 12.464min, response 5.3 × 103；
Tricresyl phosphate (2- ethylhexyl diphenyl) is as shown in figure 11: retention time 14.283min, response 2.3 × 103；Tricresyl phosphate
(butoxyethyl group) ester is as shown in figure 12: retention time 13.441min, response 9.8 × 103。
4. obtaining certain chromatographic peak area based on certain density standard hybrid working liquid, pass through measurement various concentration
The available a series of chromatographic peak area of standard hybrid working liquid, using standard hybrid working liquid concentration as abscissa, with the mark
The corresponding chromatographic peak area of quasi- hybrid working liquid concentration is that ordinate can establish a standard curve, then passes through ultra high efficiency liquid
Phase chromatography-tandem mass spectrum measures sample solution, obtains the chromatographic peak area of sample solution, passes through the standard of standard hybrid working liquid
Curve obtains the actual concentrations of organophosphorus ester in Main Stream of Haihe River sample.
5. acquiring water sample in 25 places altogether along Haihe River, each place acquires 1L water sample, by each place of acquisition
Water sample repeats the above steps 2-4 respectively, obtains 25 sample concentration values, these sample concentrations is first summed it up then divided by sample number
Amount, obtains the average value of Haihe River sample；Concentration range is arranged 25 sample concentration values are ascending, most with both ends
Value expression, as shown in the table.
Table: the concentration level of organophosphorus ester in Main Stream of Haihe River surface water
By this experiment it follows that the main species of Haihe River organophosphorus ester pollution are that have in chloro alkyl generation
Machine phosphate TCEP (67.45ng/L), TCPP (78.48ng/L) and alkyl are for organophosphorus ester TEP (63.15ng/L), TnBP
(86.58ng/L), these two types of organophosphorus esters are difficult to degrade in the environment due to persistence, not facile hydrolysis, photodissociation and biology
Degradation, therefore be easy to left behind in water body, water pollution is caused, should be drawn attention, the supervision for reinforcing relative region is arranged
It applies；Aryl is very low for the water body concentration of organophosphorus ester, such organophosphorus ester half-life period is very short, it is easy to degrade, it is not easy to
Cause water pollution.
2 method blank value of embodiment and the experiment of the blank rate of recovery.
1. preparing standard working solution:
(a) the triethyl phosphate TEP, tricresyl phosphate that the concentration of 10 μ L is 100mg/L are drawn respectively with 10 μ L micropipette rifles
N-propyl TPrP, TRI N BUTYL PHOSPHATE TnBP, triisooctyl phosphate TEHP, triphenyl phosphate TPhP, tricresyl phosphate TCrP,
Tricresyl phosphate (2- ethylhexyl diphenyl) ester EHDPP, tricresyl phosphate (butoxyethyl group) ester TBEP, tricresyl phosphate (2- chloroethyl) ester
TCEP, tricresyl phosphate (2- chloropropyl) ester TCPP, tricresyl phosphate (1,3- bis- chloro isopropyl) ester TDCPP standard reserving solution, they are dripped
Enter and mixed in 2ml chromatogram bottle, then the methanol of 890 μ L is added in 2ml chromatogram bottle, oscillation obtains the standard mixing of the 1mg/L of 1ml
Working solution；
(b) 0.5 μ L, 1 μ L, 2 μ L, 5 μ L, 10 μ L, 20 μ L, 50 μ L, 200 μ L, 500 μ L are drawn respectively with micropipette rifle
The standard hybrid working liquid of 1mg/L, obtains the standard hybrid working liquid of nine kinds of volumes, each personal methanol dilution to 1ml, and oscillation mixes
The even standard hybrid working liquid for obtaining nine kinds of various concentrations: 0.5 μ g/L, 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50
μ g/L, 200 μ g/L, 500 each 1ml of μ g/L standard hybrid working liquid.
2. sample pretreatment: the separatory funnel of 500ml being placed on separating funnel stand, the distillation of 500ml is measured with beaker
Water water sample is added thereto, and the deuterated triphenyl phosphate of 20ng is added with micropipette rifle, with the methylene chloride liquid-liquid extraction two of 50ml
Secondary, extraction, which should sufficiently be vibrated, every time shakes up, and merges organic phase, and after anhydrous sodium sulfate drying, extract liquor is transferred to 250ml's
In revolving bottle, rotary evaporation to 1ml or so, concentrate is transferred to chromatogram bottle, repeatedly washs revolving bottle on a small quantity with methylene chloride, washes
It washs liquid to be transferred in chromatogram bottle, the concentration liquid nitrogen in chromatogram bottle, which is blown to, closely to be done, and with methanol constant volume to 0.5ml, obtains sample solution.
3. with ultra performance liquid chromatography-mass spectroscopy standard working solution and sample solution:
Liquid phase chromatogram condition: 6420 highly effective liquid phase chromatographic system of Agilent Infinity；Chromatographic column: Zorbax
Eclipse Plus C18 column, column temperature are 40 DEG C, mobile phase: A: volume ratio is 0.1% aqueous formic acid, B: pure methanol, flowing
Phase flow velocity is 0.4mL/min.Eluent gradient elution requirement is as follows: volume ratio A:B=60%:40%, 3- are kept in 0-3min
Volume ratio A:B=50%:50% is kept in 4.5min, keeps volume ratio A:B=45%:55%, 8.5- in 6.5-8.5min
Volume ratio A:B=30%:70% is kept in 9min, and volume ratio A:B=20%:80% is kept in 9-11min, is protected in 11-12min
Volume ratio A:B=10%:90% is held, volume ratio A:B=0%:100% is kept in 12-15.5min, is protected in 15.5-18.5min
Hold volume ratio A:B=60%:40%.Sampling volume is 10 μ L.
Mass Spectrometry Conditions: the triple level four bars mass detectors of Agilent 6460；Ion source: ESI, ion source temperature: 300
DEG C, ionize mode: positive ion mode；Dry gas stream speed: 7l/min；Nebulizer pressure: 45psi；Sheath temperature degree: 350 DEG C, sheath gas
Flow velocity: 11l/min；Collision voltage: 3.5kV；Spray nozzle voltage: 0kV；Acquisition mode: quantitative reaction monitoring pattern.
After standard hybrid working liquid sample introduction, obtain the corresponding chromatogram of each organic phosphoric acid ester monomer, with chromatogram be according to
According to being quantified.The chromatogram of triethyl phosphate is as shown in Figure 2: retention time 3.220min, response 6.3 × 102；Phosphoric acid
The chromatogram of three propyl ester is as shown in Figure 3: retention time 9.899min, response 2.8 × 104；The chromatogram of TRI N BUTYL PHOSPHATE
It is as shown in Figure 4: retention time 13.075min, response 2.2 × 104；The chromatogram of triisooctyl phosphate is as shown in Figure 5: protecting
Staying the time is 16.370min, response 7.8 × 103；The chromatogram of tricresyl phosphate (2- chloroethyl) ester is as shown in Figure 6: retention time
For 5.314min, response 0.98 × 103；The chromatogram of tricresyl phosphate (2- chloropropyl) ester is as shown in Figure 7: retention time is
10.245min, response 1.5 × 103；The chromatogram of tricresyl phosphate (bis- chloro isopropyl of 1,3-) ester is as shown in Figure 8: retention time is
12.382min, response 3.6 × 102；The chromatogram of tricresyl phosphate is as shown in Figure 9: retention time 13.928min, rings
It should value 4.6 × 103；The chromatogram of triphenyl phosphate is as shown in Figure 10: retention time 12.464min, response 5.3 × 103；
Tricresyl phosphate (2- ethylhexyl diphenyl) is as shown in figure 11: retention time 14.283min, response 2.3 × 103；Tricresyl phosphate
(butoxyethyl group) ester is as shown in figure 12: retention time 13.441min, response 9.8 × 103。
4. obtaining certain chromatographic peak area based on certain density standard hybrid working liquid, pass through measurement various concentration
The available a series of chromatographic peak area of standard hybrid working liquid, using standard hybrid working liquid concentration as abscissa, with the mark
The corresponding chromatographic peak area of quasi- hybrid working liquid concentration is that ordinate can establish a standard curve, then passes through ultra high efficiency liquid
Phase chromatography-tandem mass spectrum measures sample solution, obtains the chromatographic peak area of sample solution, passes through the standard of standard hybrid working liquid
Curve can show that each organophosphorus ester content of monomer, content of monomer at this time are in the distilled water obtained with this method extraction and determination
For blank value.
5. repeating step 2-4, and 50 are additionally added with outside the micropipette rifle addition deuterated triphenyl phosphate of 20ng at step 2
At this moment the 500 μ g/L standard hybrid working liquid of μ L can be obtained by the standard curve of standard hybrid working liquid and be extracted with this method
Obtained each organophosphorus ester content of monomer is measured, with the concentration value measured at this time divided by theoretically dense in chromatogram bottle before sample introduction
Spending the 50 obtained ratios of μ g/L is blank recovery of standard addition.
Table: method blank value and blank recovery of standard addition (n=5)
By this experiment it can be seen that the blank value of each organic phosphoric acid ester monomer is very low or even be not detected, it was demonstrated that with should
Introduced method interference is very low when the monitoring of kind method progress organic phosphoric acid ester monomer, can ignore；Furthermore this method is used
Various types of organophosphorus ester is measured, the rate of recovery is all larger than 60%, it was demonstrated that this kind of method reliability is very high, can promote the use of.
Claims (4)
1. the method for a variety of organophosphorus esters in a kind of ultra performance liquid chromatography-mass spectroscopy surface water, it is characterised in that including
Following steps:
(1) standard hybrid working liquid is prepared:
(a) with 10 μ L micropipette rifles draw respectively the triethyl phosphate that the concentration of 10 μ L is 100mg/L, tricresyl phosphate n-propyl,
TRI N BUTYL PHOSPHATE, triisooctyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (2- ethylhexyl diphenyl) ester,
Tricresyl phosphate (butoxyethyl group) ester, tricresyl phosphate (2- chloroethyl) ester, tricresyl phosphate (2- chloropropyl) ester, (1,3- dichloro is different for tricresyl phosphate
Propyl) ester standard reserving solution, it then instills in a 2ml chromatogram bottle and mixes, then the first of 890 μ L is added in 2ml chromatogram bottle
Alcohol, oscillation obtain the standard hybrid working liquid of the 1mg/L of 1ml；
(b) 1mg/ of 0.5 μ L, 1 μ L, 2 μ L, 5 μ L, 10 μ L, 20 μ L, 50 μ L, 200 μ L, 500 μ L are drawn respectively with micropipette rifle
The standard hybrid working liquid of L, obtains the standard hybrid working liquid of nine kinds of volumes, each personal methanol dilution to 1ml, and oscillation mixes
To the standard hybrid working liquid of nine kinds of various concentrations: 0.5 μ g/L, 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/
L, 200 μ g/L, 500 each 1ml of μ g/L standard hybrid working liquid；
(2) sample pretreatment:
Water sample of the 500ml by filtering is measured, substitute is added into water sample, extracts water sample twice with the extractant of 50ml,
Combining extraction liquid, with the dry extract liquor of desiccant anhydrous sodium sulfate, the extract liquor rotary evaporation after drying is concentrated into 1ml, is concentrated
Liquid is transferred to chromatogram bottle, repeatedly washs revolving bottle on a small quantity with methylene chloride, and cleaning solution is transferred in 2ml chromatogram bottle, nitrogen is used
Purging concentrate instills HPLC grades of methanol 0.5ml constant volumes to nearly dry doubling as sample solution in 2ml chromatogram bottle；
(3) with ultra performance liquid chromatography-tandem mass spectrum measurement standard hybrid working liquid and sample solution；
(4) using standard hybrid working liquid concentration as abscissa, chromatographic peak area corresponding with the standard hybrid working liquid concentration is
Ordinate establishes a standard curve, then measures sample solution by ultra performance liquid chromatography-tandem mass spectrum, it is molten to obtain sample
The chromatographic peak area of liquid obtains the actual concentrations of sample liquid by the standard curve of standard hybrid working liquid.
2. the method for a variety of organophosphorus esters in ultra performance liquid chromatography according to claim 1-mass spectroscopy surface water,
It is characterized by: the substitute in the step (2) is deuterated triphenyl phosphate.
3. a variety of organophosphorus esters in ultra performance liquid chromatography according to claim 1 or 2-mass spectroscopy surface water
Method, it is characterised in that: the extractant in the step (2) is methylene chloride.
4. a variety of organophosphorus esters in ultra performance liquid chromatography according to claim 1 or 2-mass spectroscopy surface water
Method, it is characterised in that: step (3) ultra performance liquid chromatography-Mass Spectrometry Conditions are as follows:
Liquid phase chromatogram condition: 6420 highly effective liquid phase chromatographic system of Agilent Infinity；
Chromatographic column: Zorbax Eclipse Plus C18Column, column temperature are 40 DEG C, column specification size are as follows: 2.1mm × 50mm；i.d,
1.8μm；
Mobile phase: A: volume ratio is the aqueous formic acid of 1:1000, B: pure methanol, flow rate of mobile phase 0.4mL/min；
Eluent gradient elution requirement is as follows: volume ratio A:B=60%:40%, keeping body in 3-4.5min are kept in 0-3min
For product than A:B=50%:50%, 6.5-8.5min is interior to keep volume ratio A:B=45%:55%, keeps volume ratio in 8.5-9min
Volume ratio A:B=20%:80% is kept in A:B=30%:70%, 9-11min, keeps volume ratio A:B=in 11-12min
Volume ratio A:B=0%:100% is kept in 10%:90%, 12-15.5min, keeps volume ratio A:B=in 15.5-18.5min
60%:40%；
Sampling volume is 10 μ L；
Mass Spectrometry Conditions:
The triple level four bars mass detectors of Agilent 6460；
Ion source: ion source temperature: ESI 300 DEG C, ionizes mode: positive ion mode；Dry gas stream speed: 7l/min；Atomizer
Pressure: 45psi；Sheath temperature degree: 350 DEG C, sheath gas: 11l/min；Collision voltage: 3.5kV；Spray nozzle voltage: 0kV；Acquisition side
Formula: quantitative reaction monitoring pattern；
Ultra performance liquid chromatography-mass spectrometry parameters in relation to each organic phosphoric acid ester monomer are as follows:
When measuring tricresyl phosphate (2- chloroethyl) ester: mother ion mass-to-charge ratio 285, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative son
The mass-to-charge ratio of ion is 63.1；
When measuring tricresyl phosphate (2- chloropropyl) ester: mother ion mass-to-charge ratio 327, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative son
The mass-to-charge ratio of ion is 174.9；
When measuring tricresyl phosphate (1,3- bis- chloro isopropyl) ester: the mass-to-charge ratio of mother ion mass-to-charge ratio 428.9, quantitative daughter ion is
99.1, the mass-to-charge ratio of qualitative daughter ion is 208.9；
When measuring triethyl phosphate: mother ion mass-to-charge ratio 183, the mass-to-charge ratio of quantitative daughter ion are 99, the matter of qualitative daughter ion
Lotus ratio is 126.9；
When measuring tricresyl phosphate propyl ester: mother ion mass-to-charge ratio 225.3, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative daughter ion
Mass-to-charge ratio is 140.9；
When measuring TRI N BUTYL PHOSPHATE: mother ion mass-to-charge ratio 267.3, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative daughter ion
Mass-to-charge ratio be 211；
When measuring triisooctyl phosphate: mother ion mass-to-charge ratio 435.4, the mass-to-charge ratio of quantitative daughter ion are 99, qualitative daughter ion
Mass-to-charge ratio be 113；
When measuring tricresyl phosphate: mother ion mass-to-charge ratio 369.1, the mass-to-charge ratio of quantitative daughter ion are 91.1, qualitative son from
The mass-to-charge ratio of son is 165；
When measuring triphenyl phosphate: mother ion mass-to-charge ratio 327, the mass-to-charge ratio of quantitative daughter ion are 77.1, qualitative daughter ion
Mass-to-charge ratio is 214.9；
When measuring tricresyl phosphate (2- ethylhexyl diphenyl) ester: the mass-to-charge ratio of mother ion mass-to-charge ratio 363.2, quantitative daughter ion is
251, the mass-to-charge ratio of qualitative daughter ion is 77.1；
When measuring tricresyl phosphate (butoxyethyl group) ester: mother ion mass-to-charge ratio 399.3, the mass-to-charge ratio of quantitative daughter ion is 199, fixed
The mass-to-charge ratio of temper ion is 299.1.
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