CN104820030B - A kind of method of six kinds of phthalic acid esters in LC-MS detection drinking water - Google Patents
A kind of method of six kinds of phthalic acid esters in LC-MS detection drinking water Download PDFInfo
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Abstract
The invention discloses a kind of method that LC-MS detects six kinds of phthalic acid esters in drinking water, belongs to drinking water detection technique field.Which comprises the steps：(1) guard column is installed additional；(2) condition determination and mode；(3) Criterion working curve；(4) drinking water detection to be measured.The detection method of the present invention; without the need for carrying out pre-treatment to sample; energy direct injected; so as to rapidly to drinking water in six kinds of phthalic acid esters (DMP, DEP, DBP, BBP, DEHP and DNOP) carry out qualitative and quantitative analysis; have few simple to operation, sampling quantity, low cost, favorable reproducibility, stability strong; it is applicable not only to surroundings monitoring, and the rapid screening suitable for pollutant emergent accident.
Description
Technical field
The present invention relates to a kind of detection method, more particularly to a kind of simple, quick to six kinds of phthalic acids in drinking water
The qualitative and quantitative detection method of ester, belongs to drinking water detection technique field.
Background technology
Phthalate compound (Phthalic acid esters, PAEs) is the important endocrine disruption of a class
Thing.Trace PAEs can be enriched with water body, soil, animals and plants, be difficult in the environment degrade, the internal system of human body is caused
Interference, directly affects the metabolism of human body, and plasticiser phthalic acid two (2- ethylhexyls) ester (DEHP) toxicity compares trimerization
Cyanamide is big 20 times.Research shows that plasticiser can also increase liver kidney burden, cause chronic injury to immune system, digestive system, very
To causing liver cancer.In white wine disturbance in 2012, dibutyl phthalate (DBP) the highest detection value being detected in sample reaches
1.04mg/kg.With a large amount of uses of plastic packing product, PAEs is remained and the pollution caused in transition process in the environment
Increasingly seriously, part water body and soil also suffer that PAEs pollutes.To the analysis of phthalate compound, detection in environment
The new problem faced with the control person that has been environmental monitoring work and new challenge.
EPA is by repefral (DMP), diethyl phthalate (DEP), phthalic acid two
Butyl ester (DBP), butyl benzyl phthalate (BBP) phthalic acid two (2- ethylhexyls) ester (DEHP) and adjacent benzene two
Formic acid di-n-octyl (DNOP) is classified as priority pollutants.Wherein, DMP, DBP and DNOP are also listed in Environment Priority by China
Pollutant blacklist.
At present, the instrument analytical method of PAEs is mainly using gas-chromatography (GC) and liquid chromatogram (LC) method, and sample
Pre-treatment is the key for determining PAEs detection sensitivities.The sample-pretreating method of PAEs is different with sample substrate and presence is poor
Different.Liquid-liquid extraction method (LLE) is the conventional pre-treating methods of PAEs in the simple matrix liquid sample such as water, white wine, beverage, Chang Cai
It is extractant with n-hexane and dichloromethane.Its advantage be simple to operate, but there is also organic solvent consumption big, to environment
Cause secondary pollution, time-consuming the longer, rate of recovery is relatively low, emulsion is serious, be difficult to realization the deficiency such as is automatically brought into operation.In recent years,
Solid-phase Microextraction (SPME), dispersive liquid-liquid microextraction method (DLLME), dispersive liquid-liquid microextraction-floating solvent cures method
(DLLME-SFO), emerging extraction and the purification techniques such as cloud point extraction method (CPE), due to fast etc. with easy to operate, rate of extraction
Feature, the extraction and purification of the PAEs being also applied in the samples such as water, soil, but its sample pre-treatments are generally required with reference to super
Sound assists extraction (UAE), Microwave assisted extraction method (MAE) or solid phase extraction (SPE).Wherein, solid phase extraction (SPE) tool
Have that solvent load is few, enrichment and good purification, simple to operate the features such as, but the bioaccumulation efficiency of different batches adsorbent is different,
The repeatability of analysis result is influenced whether, if irreversible absorption occurs can cause the loss of object in sample, sometimes even
The phenomenons such as superficial degradation reaction, adsorbent blocking duct can occur.Further, since various PAEs have height phase in structure
Like property, and content generally in the sample is relatively low, the qualitative and poor AAS of quantitation capabilities substantially without practical value,
It is not suitable for the measure of PAEs in environmental sample.
In consideration of it, being necessary that research is a kind of without the need for carrying out pre-treatment, energy fast qualitative and quantitative determination drinking water to sample
In six kinds of phthalic acid esters new detection method.LC-MS (HPLC-MS) technology is with high performance liquid chromatography as separating
Means, a kind of separate analytical technique with mass spectrum as Identification Tools efficiently separate ability and mass spectrographic height with liquid chromatogram
Sensitivity, extremely strong qualitative exclusive specificity.But at present, there is not yet HPLC-MS is used for six kinds of phthalic acid esters of drinking water
The report of qualitative and quantitative analysis.Therefore, set up six kinds of phthalic acid ester Qualitative and quantitative analysis methods of efficient drinking water to use
Six kinds of phthalic acid esters in monitoring drinking water are significant.
Content of the invention
Present invention aim to address the deficiencies in the prior art, there is provided six kinds of adjacent benzene in a kind of LC-MS detection drinking water
The method of dicarboxylic acid esters.The detection method of the present invention, without the need for carrying out pre-treatment to sample, energy direct injected, so as to rapidly right
Six kinds of phthalic acid esters (DMP, DEP, DBP, BBP, DEHP and DNOP) in drinking water carry out qualitative and quantitative analysis.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：Six kinds of adjacent benzene in a kind of LC-MS detection drinking water
The method of dicarboxylic acid esters, comprises the steps：
(1) guard column is installed additional：Install chromatographic column additional guard column；
(2) condition determination and mode:The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, liquid phase is used
Chromatogram-series connection quadrupole rod mass spectrum is measured, and instrument parameter condition is shown in Table 1, Selective reaction monitoring parent ion, daughter ion and collision
Energy is shown in Table 2；
The mass spectrographic instrument parameter of 1 liquid chromatography-tandem level Four bar of table
2 Selective reaction monitoring parent ion of table, daughter ion and collision energy and scan mode
(3) Criterion working curve：The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, respectively
Standard liquid described in accurately drawing 25 μ l, is settled to 10mL respectively with pure water, respectively obtains 6 kinds of phthalic ester concentrations and be
The standard solution of 0.5 μ g/mL；0,10,20,40,80,160,200,400,800,1600 μ l above-mentioned standards use is taken respectively
Liquid, is settled to 10mL respectively with pure water, obtains the series standard liquid of 0,0.5,1,2,4,8,10,20,40,80 μ g/l, using step
Suddenly experimental condition sample introduction listed by Tables 1 and 2 in (2), respectively obtains the peak area of 6 kinds of phthalic acid esters, then with peak area is
Ordinate, concentration are abscissa, draw calibration curve respectively, respectively obtain the calibration curve of 6 kinds of phthalic acid esters, Ran Houfen
Linear regression analysis is not carried out；
(4) drinking water detection to be measured：Drinking Water Samples to be measured are taken, using experimental condition listed by Tables 1 and 2 in step (2)
Sample introduction, obtains the peak area of Drinking Water Samples to be measured, and then the peak area with above-mentioned Drinking Water Samples to be measured is brought into as ordinate
The calibration curve of 6 kinds of phthalic acid esters of step (3) gained, obtain final product Drinking Water Samples to be measured 6 kinds of phthalic acid esters dense
Angle value.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, step (1) method that installs additional that protects is：Connected using connecting tube in the front end of the chromatographic column
Install guard column additional, the entrance connection injection port of the guard column, outlet connection chromatographic column, the two ends of the connecting tube have hollow
Screw and sealing pressure ring.
Further, 2mL8mm standard mouth screw thread mouth sample bottles are adopted, during analysis sample during determination sample described in step (2)
Only use bottle cap, the flow velocity be 0.2mL/min, the column temperature be 30 DEG C, the sample size be 5 μ L, the capillary voltage
For 4000V, the atomization gas pressure is 40psi, and the atomization gas flow velocity is 10L/min, and the atomization gas temperature is 350 DEG C.
Further, described in step (3), pure water is plus alkali redistilled water, the preparation method of described plus alkali redistilled water
For：Take 400mL brand-new distilled water to be put in cucurbit, add zeolite and 5 grams of NaOH, the uniform placement 1 hour of shaking to heat,
Cast out 50mL front-end volatiles, take stage casing 250mL and collect 1 hour, obtain final product.
The invention has the beneficial effects as follows：
1., without the need for carrying out pre-treatment to sample, direct injected, with simple to operation, sampling for the detection method of the present invention
Amount less, low cost, favorable reproducibility, strong stability the advantages of.
2. the detection method of the present invention significantly improves detection efficiency, and once experiment can be quickly and accurately to drinking water
In six kinds of phthalic acid esters carry out qualitative and quantitative analysis, substantial saving in the working time of testing staff.
3. the detection method of the present invention adopts C18 chromatographic columns, LC-MS (HPLC-MS) technology, with higher sensitive
Degree, detection limit are less than 0.6 μ g/L, it is sufficient to ensure the monitoring requirement of daily drunk water, and install additional before sample enters chromatographic column
Guard column, plays a part of to purify sample, protection chromatographic column.
4. the blank water of the present invention is adopted plus alkali redistilled water, than ultra-pure water, deionized water, brand-new distilled water, color
Spectrum pure water and acid adding redistilled water, the mass spectrum little, blank value of response are minimum, similar with the performance of chromatogram pure water, and cost is lower.
5. the detection method of the present invention has a extensive future, and is applicable not only to surroundings monitoring, and is applied to emergent
The rapid screening of pollutant in accident.
Description of the drawings
Fig. 1 is mass spectrum multiple-reaction monitoring figure (MRM) of the repefral (DMP) of the present invention.
Fig. 2 is mass spectrum multiple-reaction monitoring figure (MRM) of the diethyl phthalate (DEP) of the present invention.
Fig. 3 is mass spectrum multiple-reaction monitoring figure (MRM) of the dibutyl phthalate (DBP) of the present invention.
Fig. 4 is mass spectrum multiple-reaction monitoring figure (MRM) of the butyl benzyl phthalate (BBP) of the present invention.
Fig. 5 is mass spectrum multiple-reaction monitoring figure (MRM) of the phthalic acid two (2- ethylhexyls) ester (DEHP) of the present invention.
Fig. 6 is mass spectrum multiple-reaction monitoring figure (MRM) of the dioctyl phthalate (DNOP) of the present invention.
Specific embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
Non- for limiting the scope of the present invention.
Embodiment 1
(1) guard column is installed additional：Guard column, protection column inlet connection sample introduction are installed in chromatographic column front end additional using connecting tube series connection
Mouthful, outlet connection chromatographic column, there are hollow screw and sealing pressure ring in the two ends of connecting tube；
(2) condition determination and mode:The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, liquid phase is used
Chromatogram-series connection quadrupole rod mass spectrum is measured, and instrument parameter condition is shown in Table 3, Selective reaction monitoring parent ion, daughter ion and collision
Energy is shown in Table 2；Using 2mL8mm standard mouth screw thread mouth sample bottles during the determination sample, only using bottle cap during analysis sample；
The mass spectrographic instrument parameter of 3 liquid chromatography-tandem level Four bar of table
2 Selective reaction monitoring parent ion of table, daughter ion and collision energy and scan mode
(3) Criterion working curve：The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, respectively
Standard liquid described in accurately drawing 25 μ l, is settled to 10mL respectively with pure water, respectively obtains 6 kinds of phthalic ester concentrations and be
The standard solution of 0.5 μ g/mL；The pure water is plus alkali redistilled water that the preparation method of described plus alkali redistilled water is：
Take 400mL brand-new distilled water to be put in cucurbit, add zeolite and 5 grams of NaOH, the uniform placement 1 hour of shaking to heat, house
50mL front-end volatiles are removed, stage casing 250mL is taken and is collected 1 hour, obtain final product；10,20,40,80,160,200,400,800,1600 are taken respectively
μ l above-mentioned standards use liquid, are settled to 10mL respectively with pure water, obtain the series mark of 0.5,1,2,4,8,10,20,40,80 μ g/l
Quasi- liquid, using table 3 in step (2) and experimental condition sample introduction listed by table 2, how anti-the mass spectrum for respectively obtaining 6 kinds of phthalic acid esters is
Should monitor figure (MRM) (as shown in Figures 1 to 6) and peak area, then with peak area as ordinate, concentration as abscissa, paint respectively
Calibration curve processed, respectively obtains the calibration curve of 6 kinds of phthalic acid esters, then carries out linear regression analysis respectively, linear system
Number R>0.9900 can be used as calibration curve, as shown in table 4；
The calibration curve of 46 kinds of phthalic acid esters of table
The intercept and slope value of contrast standard curve, 6 kinds of phthalic acid esters are linearly good in 0～80 μ g/L concentration ranges
Good, calibration curve meets quantitative calculating needs.
(4) detection limit is determined：20 blank water samples are taken, is entered using table 3 in step (2) and experimental condition listed by table 2 successively
Sample, determines detection limit with the standard deviation of 6 kinds of phthalic acid ester peak areas.According to IUPAC
(IUPAC) regulation to detection limit：The standard deviation of D.L=K'Sb/k, K'=3, wherein Sb for peak area, k is calibration curve
Slope, the detection limit of 6 kinds of phthalic acid esters is respectively：Repefral (DMP) is 0.62 μ g/L, O-phthalic
Diethyl phthalate (DEP) is 0.77 μ g/L, dibutyl phthalate (DBP) is 0.15 μ g/L, butyl benzyl phthalate
(BBP) for 0.098 μ g/L, phthalic acid two (2- ethylhexyls) ester (DEHP) be 0.23 μ g/L, dioctyl phthalate
(DNOP) it is 0.0086 μ g/L.According to《Water environment quality standard》(GB3838-2002) regulation：Two fourth of phthalic acid
Ester (DBP) standard limited value is 3 μ g/L, phthalic acid two (2- ethylhexyls) ester standard limited value is 8 μ g/L, and remaining 4 kinds are not then
Do standard and limit regulation.As can be seen here, in the method for the present invention, the detection limit of 6 kinds of phthalic acid esters is well below standard
Specified in limit value, it is sufficient to ensure the environmental monitoring requirement of daily drunk water.Therefore, the method for the present invention can apply to concentrate
The rapid screening of formula drinking water sources water phthalate pollutant.
(5) method precision and recovery of standard addition：Respectively 6 kinds of phthalic acid esters of preparation steps (2) gained 0.5,2,
8th, the series standard liquid of 4 concentration of 40 μ g/L, each 7 samples of each concentration, is respectively adopted in step (2) listed by Tables 1 and 2
Experimental condition sample introduction, examines or check the precision of method with sample peak area and the relative standard deviation for being calculated concentration.To blank
Add the mixed standard solution of 6 kinds of phthalic acid esters in water sample, obtain the standard liquid after mark-on, for simulated environment water
Sample, direct injection analysis.To concentration be 0.5,2,8,40 μ g/L mark-on after each 7 samples of standard liquid adopt step (2)
Middle table 3 and experimental condition listed by table 2 are measured, and as a result show, 6 kinds of phthalic acid esters are in 0～80 μ g/L concentration ranges
Method precision is good, the equal ＜ 5% of quantitative result relative standard deviation.For quick analysis, the precision of the method reaches
Arrive test request；In terms of recovery of standard addition, 4 kinds of concentration mark-on results of 6 kinds of phthalic acid esters are controlled 85～120%
In the range of, can also meet test request.
(6) drinking water detection to be measured：Water factory of Qu Mou cities Drinking Water Samples 1, using the 2 listed examination of table 3 in step (2) and table
Condition sample introduction is tested, the peak area of Drinking Water Samples to be measured is obtained, then with the peak area of above-mentioned Drinking Water Samples to be measured as vertical seat
Mark, brings the calibration curve of 6 kinds of phthalic acid esters of step (3) gained into, obtains 6 kinds of phthalic acids of Drinking Water Samples to be measured
The concentration of ester is respectively：Repefral (DMP) is 1.25 μ g/L, diethyl phthalate (DEP) is 1.48 μ g/
L, dibutyl phthalate are 0.29 μ g/L, butyl benzyl phthalate (BBP) is 0.37 μ g/L, phthalic acid two
(2- ethylhexyls) ester (DEHP) is 0.15 μ g/L, dioctyl phthalate (DNOP) is 0.12 μ g/L.
Embodiment 2
(1) guard column is installed additional：Guard column, protection column inlet connection sample introduction are installed in chromatographic column front end additional using connecting tube series connection
Mouthful, outlet connection chromatographic column, there are hollow screw and sealing pressure ring in the two ends of connecting tube；
(2) condition determination and mode:The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, liquid phase is used
Chromatogram-series connection quadrupole rod mass spectrum is measured, and instrument parameter condition is shown in Table 5, Selective reaction monitoring parent ion, daughter ion and collision
Energy is shown in Table 2；Using 2mL8mm standard mouth screw thread mouth sample bottles during the determination sample, only using bottle cap during analysis sample；
The mass spectrographic instrument parameter of 5 liquid chromatography-tandem level Four bar of table
2 Selective reaction monitoring parent ion of table, daughter ion and collision energy and scan mode
(3) Criterion working curve：The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, respectively
Standard liquid described in accurately drawing 25 μ l, is settled to 10mL respectively with pure water, respectively obtains 6 kinds of phthalic ester concentrations and be
The standard solution of 0.5 μ g/mL；The pure water is plus alkali redistilled water that the preparation method of described plus alkali redistilled water is：
Take 400mL brand-new distilled water to be put in cucurbit, add zeolite and 5 grams of NaOH, the uniform placement 1 hour of shaking to heat, house
50mL front-end volatiles are removed, stage casing 250mL is taken and is collected 1 hour, obtain final product；10,20,40,80,160,200,400,800,1600 are taken respectively
μ l above-mentioned standards use liquid, are settled to 10mL respectively with pure water, obtain the series mark of 0.5,1,2,4,8,10,20,40,80 μ g/l
Quasi- liquid, using table 5 in step (2) and experimental condition sample introduction listed by table 2, how anti-the mass spectrum for respectively obtaining 6 kinds of phthalic acid esters is
Should monitor figure (MRM) (as shown in Figures 1 to 6) and peak area, then with peak area as ordinate, concentration as abscissa, paint respectively
Calibration curve processed, respectively obtains the calibration curve of 6 kinds of phthalic acid esters, then carries out linear regression analysis respectively, linear system
Number R>0.9900 can be used as calibration curve, as shown in table 6；
The calibration curve of 66 kinds of phthalic acid esters of table
The intercept and slope value of contrast standard curve, 6 kinds of phthalic acid esters are linearly good in 0～80 μ g/L concentration ranges
Good, calibration curve meets quantitative calculating needs.
(3) detection limit is determined：20 blank water samples are taken, is entered using table 5 in step (2) and experimental condition listed by table 2 successively
Sample, determines detection limit with the standard deviation of 6 kinds of phthalic acid ester peak areas.According to IUPAC
(IUPAC) regulation to detection limit：The standard deviation of D.L=K'Sb/k, K'=3, wherein Sb for peak area, k is calibration curve
Slope, the detection limit of 6 kinds of phthalic acid esters is respectively：Repefral (DMP) is 0.54 μ g/L, O-phthalic
Diethyl phthalate (DEP) is 0.59 μ g/L, dibutyl phthalate (DBP) is 0.11 μ g/L, butyl benzyl phthalate
(BBP) for 0.061 μ g/L, phthalic acid two (2- ethylhexyls) ester (DEHP) be 0.15 μ g/L, dioctyl phthalate
(DNOP) it is 0.0043 μ g/L.According to《Water environment quality standard》(GB3838-2002) regulation：Two fourth of phthalic acid
Ester (DBP) standard limited value is 3 μ g/L, phthalic acid two (2- ethylhexyls) ester standard limited value is 8 μ g/L, and remaining 4 kinds are not then
Do standard and limit regulation.As can be seen here, in the method for the present invention, the detection limit of 6 kinds of phthalic acid esters is well below standard
Specified in limit value, it is sufficient to ensure the environmental monitoring requirement of daily drunk water.Therefore, the method for the present invention can apply to concentrate
The rapid screening of formula drinking water sources water phthalate pollutant.
(4) method precision and recovery of standard addition：Respectively 6 kinds of phthalic acid esters of preparation steps (2) gained 0.5,2,
8th, the series standard liquid of 4 concentration of 40 μ g/L, each 7 samples of each concentration are respectively adopted in step (2) listed by table 5 and table 2
Experimental condition sample introduction, examines or check the precision of method with sample peak area and the relative standard deviation for being calculated concentration.To blank
Add the mixed standard solution of 6 kinds of phthalic acid esters in water sample, obtain the standard liquid after mark-on, for simulated environment water
Sample, direct injection analysis.To concentration be 0.5,2,8,40 μ g/L mark-on after each 7 samples of standard liquid adopt step (2)
Experimental condition listed by middle Tables 1 and 2 is measured, and as a result shows, 6 kinds of phthalic acid esters are in 0～80 μ g/L concentration ranges
Method precision is good, the equal ＜ 5% of quantitative result relative standard deviation.For quick analysis, the precision of the method reaches
Arrive test request；In terms of recovery of standard addition, 4 kinds of concentration mark-on results of 6 kinds of phthalic acid esters are controlled 85～120%
In the range of, can also meet test request.
(5) drinking water detection to be measured：Water factory of Qu Mou cities Drinking Water Samples 2, using the 2 listed examination of table 5 in step (2) and table
Condition sample introduction is tested, the peak area of Drinking Water Samples to be measured is obtained, then with the peak area of above-mentioned Drinking Water Samples to be measured as vertical seat
Mark, brings the calibration curve of 6 kinds of phthalic acid esters of step (3) gained into, obtains 6 kinds of phthalic acids of Drinking Water Samples to be measured
The concentration of ester is respectively：Repefral (DMP) is 1.22 μ g/L, diethyl phthalate (DEP) is 1.35 μ g/
L, dibutyl phthalate are 0.35 μ g/L, butyl benzyl phthalate (BBP) is 0.24 μ g/L, phthalic acid two
(2- ethylhexyls) ester (DEHP) is 0.13 μ g/L, dioctyl phthalate (DNOP) is 0.085 μ g/L.
Embodiment 3
(1) guard column is installed additional：Guard column, protection column inlet connection sample introduction are installed in chromatographic column front end additional using connecting tube series connection
Mouthful, outlet connection chromatographic column, there are hollow screw and sealing pressure ring in the two ends of connecting tube；
(2) condition determination and mode:The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, liquid phase is used
Chromatogram-series connection quadrupole rod mass spectrum is measured, and instrument parameter condition is shown in Table 7, Selective reaction monitoring parent ion, daughter ion and collision
Energy is shown in Table 2；Using 2mL8mm standard mouth screw thread mouth sample bottles during the determination sample, only using bottle cap during analysis sample；
The mass spectrographic instrument parameter of 7 liquid chromatography-tandem level Four bar of table
2 Selective reaction monitoring parent ion of table, daughter ion and collision energy and scan mode
(3) Criterion working curve：The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, respectively
Standard liquid described in accurately drawing 25 μ l, is settled to 10mL respectively with pure water, respectively obtains 6 kinds of phthalic ester concentrations and be
The standard solution of 0.5 μ g/mL；The pure water is plus alkali redistilled water that the preparation method of described plus alkali redistilled water is：
Take 400mL brand-new distilled water to be put in cucurbit, add zeolite and 5 grams of NaOH, the uniform placement 1 hour of shaking to heat, house
50mL front-end volatiles are removed, stage casing 250mL is taken and is collected 1 hour, obtain final product；10,20,40,80,160,200,400,800,1600 are taken respectively
μ l above-mentioned standards use liquid, are settled to 10mL respectively with pure water, obtain the series mark of 0.5,1,2,4,8,10,20,40,80 μ g/l
Quasi- liquid, using table 7 in step (2) and experimental condition sample introduction listed by table 2, how anti-the mass spectrum for respectively obtaining 6 kinds of phthalic acid esters is
Should monitor figure (MRM) (as shown in Figures 1 to 6) and peak area, then with peak area as ordinate, concentration as abscissa, paint respectively
Calibration curve processed, respectively obtains the calibration curve of 6 kinds of phthalic acid esters, then carries out linear regression analysis respectively, linear system
Number R>0.9900 can be used as calibration curve, as shown in table 8；
The calibration curve of 86 kinds of phthalic acid esters of table
The intercept and slope value of contrast standard curve, 6 kinds of phthalic acid esters are linearly good in 0～80 μ g/L concentration ranges
Good, calibration curve meets quantitative calculating needs.
(4) detection limit is determined：20 blank water samples are taken, is entered using table 7 in step (2) and experimental condition listed by table 2 successively
Sample, determines detection limit with the standard deviation of 6 kinds of phthalic acid ester peak areas.According to IUPAC
(IUPAC) regulation to detection limit：The standard deviation of D.L=K'Sb/k, K'=3, wherein Sb for peak area, k is calibration curve
Slope, the detection limit of 6 kinds of phthalic acid esters is respectively：Repefral (DMP) is 0.57 μ g/L, O-phthalic
Diethyl phthalate (DEP) is 0.66 μ g/L, dibutyl phthalate (DBP) is 0.18 μ g/L, butyl benzyl phthalate
(BBP) for 0.084 μ g/L, phthalic acid two (2- ethylhexyls) ester (DEHP) be 0.17 μ g/L, dioctyl phthalate
(DNOP) it is 0.0064 μ g/L.According to《Water environment quality standard》(GB3838-2002) regulation：Two fourth of phthalic acid
Ester (DBP) standard limited value is 3 μ g/L, phthalic acid two (2- ethylhexyls) ester standard limited value is 8 μ g/L, and remaining 4 kinds are not then
Do standard and limit regulation.As can be seen here, in the method for the present invention, the detection limit of 6 kinds of phthalic acid esters is well below standard
Specified in limit value, it is sufficient to ensure the environmental monitoring requirement of daily drunk water.Therefore, the method for the present invention can apply to concentrate
The rapid screening of formula drinking water sources water phthalate pollutant.
(5) method precision and recovery of standard addition：Respectively 6 kinds of phthalic acid esters of preparation steps (2) gained 0.5,2,
8th, the series standard liquid of 4 concentration of 40 μ g/L, each 7 samples of each concentration are respectively adopted in step (2) listed by table 7 and table 2
Experimental condition sample introduction, examines or check the precision of method with sample peak area and the relative standard deviation for being calculated concentration.To blank
Add the mixed standard solution of 6 kinds of phthalic acid esters in water sample, obtain the standard liquid after mark-on, for simulated environment water
Sample, direct injection analysis.To concentration be 0.5,2,8,40 μ g/L mark-on after each 7 samples of standard liquid adopt step (2)
Middle table 7 and experimental condition listed by table 2 are measured, and as a result show, 6 kinds of phthalic acid esters are in 0～80 μ g/L concentration ranges
Method precision is good, the equal ＜ 5% of quantitative result relative standard deviation.For quick analysis, the precision of the method reaches
Arrive test request；In terms of recovery of standard addition, 4 kinds of concentration mark-on results of 6 kinds of phthalic acid esters are controlled 85～120%
In the range of, can also meet test request.
(6) drinking water detection to be measured：Water factory of Qu Mou cities Drinking Water Samples 3, using the listed examination of Tables 1 and 2 in step (2)
Condition sample introduction is tested, the peak area of Drinking Water Samples to be measured is obtained, then with the peak area of above-mentioned Drinking Water Samples to be measured as vertical seat
Mark, brings the calibration curve of 6 kinds of phthalic acid esters of step (3) gained into, obtains 6 kinds of phthalic acids of Drinking Water Samples to be measured
The concentration of ester is respectively：Repefral (DMP) is 1.30 μ g/L, diethyl phthalate (DEP) is 1.32 μ g/
L, dibutyl phthalate are 0.44 μ g/L, butyl benzyl phthalate (BBP) is 0.29 μ g/L, phthalic acid two
(2- ethylhexyls) ester (DEHP) is 0.15 μ g/L, dioctyl phthalate (DNOP) is 0.091 μ g/L.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements that is made etc. should be included within the scope of the present invention.
Claims (3)
1. a kind of method that LC-MS detects six kinds of phthalic acid esters in drinking water, it is characterised in that comprise the steps：
(1) guard column is installed additional：Install chromatographic column additional guard column, the method that installs additional that protects is：Before the chromatographic column
End installs guard column, the entrance connection injection port of the guard column, outlet connection chromatographic column, the connection additional using connecting tube series connection
There are hollow screw and sealing pressure ring in the two ends of pipe；
(2) condition determination and mode:Take the standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL, with liquid chromatogram-
Series connection quadrupole rod mass spectrum is measured, and instrument parameter condition is specially：Liquid phase chromatogram condition be chromatographic column C18 post, 2.1 ×
50mm, 1.8 μm；Guard column C18 posts, 2.1 × 5mm, 1.8 μm；0.05% aqueous formic acid of mobile phase with the volume ratio of acetonitrile is
5:95；0.1～0.3mL/min of flow velocity, 20～40 DEG C of column temperature；2～8 μ L of sample size；Mass Spectrometry Conditions are ion gun ESI cations；
Scan mode MRM；Monitoring mode multiple-reaction monitoring；3000～5000V of capillary voltage；Atomization gas 20～60psi of pressure；Atomization
5～15L/min of gas velocity；300～400 DEG C of atomization gas temperature；
Selective reaction monitoring parent ion, daughter ion and collision energy and scan mode are specially：Repefral, m/z1
217.2, fragmentor 76, CE 0, scan pattern MRM；Diethyl phthalate, m/z1 245.2, fragmentor
86, CE 0, scan pattern MRM；Dibutyl phthalate, m/z1 301.2, m/z2 245.2, fragmentor 98, CE
0/8, scan pattern MRM；Butyl benzyl phthalate, m/z1 335.2, m/z2 91.1, m/z3 65.2, fragmentor
92, CE 0/50/93, scan pattern MRM；Phthalic acid two (2- ethylhexyls) ester, m/z1 413.3, m/z2 301.3, m/
Z3 189.1, fragmentor 130, CE 0/13/17, scan pattern MRM；Di-n-octyl phthalate, m/z1 413.4,
M/z2 301.4, fragmentor 130, CE 0/15, scan pattern MRM；
(3) Criterion working curve：The standard liquid that 6 kinds of phthalic ester concentrations are 200 μ g/mL is taken, respectively accurately
Standard liquid described in 25 μ l is drawn, with adding alkali redistilled water to be settled to 10mL respectively, 6 kinds of phthalic acid esters is respectively obtained dense
Degree is the standard solution of 0.5 μ g/mL；0,10,20,40,80,160,200,400,800,1600 μ l above-mentioned standards are taken respectively
Using liquid, with adding alkali redistilled water to be settled to 10mL respectively, the series of 0,0.5,1,2,4,8,10,20,40,80 μ g/l is obtained
Titer, using experimental condition sample introduction listed by Tables 1 and 2 in step (2), respectively obtains the peak area of 6 kinds of phthalic acid esters,
Again with peak area as ordinate, concentration as abscissa, respectively draw calibration curve, respectively obtain the mark of 6 kinds of phthalic acid esters
Directrix curve, then carries out linear regression analysis respectively；
(4) drinking water detection to be measured：Drinking Water Samples to be measured are taken, using experimental condition sample introduction listed by Tables 1 and 2 in step (2),
The peak area of Drinking Water Samples to be measured is obtained, then the peak area with above-mentioned Drinking Water Samples to be measured brings step into as ordinate
(3) calibration curve of 6 kinds of phthalic acid esters of gained, obtains final product the concentration value of 6 kinds of phthalic acid esters of Drinking Water Samples to be measured.
2. the method that a kind of LC-MS according to claim 1 detects six kinds of phthalic acid esters in drinking water, which is special
Levy and be, using 2mL8mm standard mouth screw thread mouth sample bottles during determination sample described in step (2), only using bottle during analysis sample
Lid, the flow velocity are 0.2mL/min, and the column temperature is 30 DEG C, and the sample size is 5 μ L, and the capillary voltage is 4000V,
The atomization gas pressure is 40psi, and the atomization gas flow velocity is 10L/min, and the atomization gas temperature is 350 DEG C.
3. the method that a kind of LC-MS according to claim 1 detects six kinds of phthalic acid esters in drinking water, which is special
Levy and be, the preparation method for adding alkali redistilled water described in step (3) is：Take 400mL brand-new distilled water to be put in cucurbit,
Addition zeolite and 5 grams of NaOH, the uniform placement 1 hour of shaking are heated, and are cast out 50mL front-end volatiles, are taken stage casing 250mL collections 1 little
When, obtain final product.
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