CN104820030A - Method for detecting six phthalates in drinking water through liquid chromatography-mass spectrometry - Google Patents
Method for detecting six phthalates in drinking water through liquid chromatography-mass spectrometry Download PDFInfo
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Abstract
The invention discloses a method for detecting six phthalates in drinking water through liquid chromatography-mass spectrometry, and belongs to the technical field of drinking water detection. The method comprises the following steps: (1) additionally arranging a protection column; (2) measuring conditions and a mode; (3) establishing a standard working curve; (4) detecting to-be-detected drinking water. According to the detection method, a sample is not required to be pretreated and can be directly fed, so that the six phthalates (DMP (Dimethyl Phthalate), DEP (Diethyl Phthalate), DBP (Dibutyl Phthalate), BBP (Benzyl Butyl Phthalate), DEHP (Di 2-Ethyl Hexyl Phthalate) and DNOP (Di N Octyl Phthalate)) in the drinking water are qualitatively and quantitatively analyzed at high speed; the method has the advantages of easiness and convenience in operation, less sampling quantity, low cost, good reproducibility, high stability and the like, is not only suitable for daily environment monitoring and is also suitable for quick screening of pollutants in emergency accidents.
Description
Technical field
The present invention relates to a kind of detection method, particularly relate to a kind of simple, quick detection method to six kinds of phthalic ester quantitative and qualitative analysis in potable water, belong to potable water detection technique field.
Background technology
Phthalate compound (Phthalic acid esters, PAEs) is the important incretion interferent of a class.Trace PAEs can enrichment in water body, soil, animals and plants, be difficult to degraded in the environment, interference is caused to the internal system of human body, the direct metabolism affecting human body, large 20 times of plasticiser phthalic acid two (2-ethylhexyl) ester (DEHP) toxicity ratio melamine.Research shows, plasticiser also can increase liver kidney burden, causes chronic injury, even cause liver cancer to immune system, digestive system.In white wine disturbance in 2012, dibutyl phthalate (DBP) Supreme Procuratorate be detected in sample goes out value and reaches 1.04mg/kg.Along with a large amount of uses of plastic packing product, PAEs in the environment residual with transition process in the pollution that causes also day by day serious, part water body and soil also suffer that PAEs pollutes.The new problem that the analysis of phthalate compound in environment, the Detection & Controling person that has been environmental monitoring work is faced and new challenge.
Repefral (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP) phthalic acid two (2-ethylhexyl) ester (DEHP) and di-n-octyl phthalate (DNOP) are classified as priority pollutants by EPA.Wherein, DMP, DBP and DNOP are also listed in priority pollutant blacklist by China.
At present, the instrument analytical method of PAEs mainly adopts gas chromatography (GC) and liquid chromatography (LC) method, and sample pre-treatments is the key determining PAEs detection sensitivity.The sample-pretreating method of PAEs there are differences with sample substrate difference.Liquid-liquid extraction method (LLE) is the pre-treating method that in the simple matrix liquid sample such as water, white wine, beverage, PAEs is conventional, and normal employing normal hexane and methylene chloride are extraction solvent.Its advantage is simple to operate, but also exist organic solvent-oil ratio large, environment caused secondary pollution, consuming time longer, the recovery is lower, emulsion is serious, be difficult to realize the deficiencies such as automatic operation.In recent years, Solid-phase Microextraction (SPME), dispersive liquid-liquid microextraction method (DLLME), dispersive liquid-liquid microextraction-emerging extraction and purification techniques such as floating solvent cures method (DLLME-SFO), cloud point extraction method (CPE), owing to having the features such as easy and simple to handle, rate of extraction is fast, also be applied to the extraction and cleanup of the PAEs in the sample such as water, soil, but its sample pre-treatments often needs in conjunction with ultrasonic assistance extraction (UAE), Microwave assisted extraction method (MAE) or solid phase extraction (SPE).Wherein, solid phase extraction (SPE) has the features such as solvent load is few, accumulation and purification is effective, simple to operate, but the bioaccumulation efficiency of different batches adsorbent is different, the repeatability of analysis result can be had influence on, if there is the loss that irreversible absorption can cause object in sample, the phenomenon such as superficial degradation reaction, adsorbent blocking duct sometimes even can be there is.In addition, because various PAEs structurally also exists high similarity, and usually content is in the sample to which lower, and the poor spectrophotometric method of quantitative and qualitative analysis ability does not have practical value substantially, is not suitable for the mensuration of PAEs in environmental sample.
Given this, be necessary to study a kind of new detection method without the need to carrying out six kinds of phthalic esters in pre-treatment, energy fast qualitative and quantitative detection potable water to sample.LC-MS (HPLC-MS) technology is separation means with high performance liquid chromatography, take mass spectrum as a kind of separate analytical technique of Identification Tools, have efficient separating power and mass spectrographic high sensitivity, the extremely strong qualitative exclusive specificity of liquid chromatography.But at present, there is not yet the report of HPLC-MS for the qualitative and quantitative analysis of potable water six kinds of phthalic esters.Therefore, efficient potable water six kinds of phthalic ester Qualitative and quantitative analysis methods are set up significant for six kinds of phthalic esters of monitoring in potable water.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art, provide a kind of LC-MS to detect the method for six kinds of phthalic esters in potable water.Detection method of the present invention, without the need to carrying out pre-treatment to sample, energy direct injected, thus rapidly qualitative and quantitative analysis is carried out to kind of the phthalic ester of six in potable water (DMP, DEP, DBP, BBP, DEHP and DNOP).
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of LC-MS detects the method for six kinds of phthalic esters in potable water, comprises the steps:
(1) guard column is installed additional: install chromatographic column additional guard column;
(2) condition determination and mode: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, measure with liquid chromatography-tandem quadrupole rod mass spectrum, instrument parameter condition is in table 1, and Selective reaction monitoring parent ion, daughter ion and collision energy are in table 2;
The mass spectrographic instrument parameter of table 1 liquid chromatography-tandem level Four bar
Table 2 Selective reaction monitoring parent ion, daughter ion and collision energy and scan mode
(3) Criterion working curve: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, accurately draw standard solution described in 25 μ l respectively, be settled to 10mL respectively with pure water, obtain the standard solution that 6 kinds of phthalic ester concentrations are 0.5 μ g/mL respectively; Get the above-mentioned standard solution of 0,10,20,40,80,160,200,400,800,1600 μ l respectively, 10mL is settled to respectively with pure water, obtain the series standard liquid of 0,0.5,1,2,4,8,10,20,40,80 μ g/l, adopt test condition sample introduction listed by the middle table 1 of step (2) and table 2, obtain the peak area of 6 kinds of phthalic esters respectively, be ordinate again with peak area, concentration is horizontal ordinate, drawing standard curve respectively, obtain the typical curve of 6 kinds of phthalic esters respectively, then carry out linear regression analysis respectively;
(4) potable water to be measured detects: get Drinking Water Samples to be measured, adopt test condition sample introduction listed by the middle table 1 of step (2) and table 2, obtain the peak area of Drinking Water Samples to be measured, then with the peak area of above-mentioned Drinking Water Samples to be measured for ordinate, bring the typical curve of step (3) gained 6 kinds of phthalic esters into, obtain the concentration value of 6 kinds of phthalic esters of Drinking Water Samples to be measured.
On the basis of technique scheme, the present invention can also do following improvement.
Further; the method that installs additional protected described in step (1) is: use connecting pipe series connection to install guard column additional in the front end of described chromatographic column; the entrance of described guard column connects injection port, and outlet connects chromatographic column, and all there are hollow screw and sealing pressure ring in the two ends of described connecting pipe.
Further, 2mL8mm standard mouth screw thread mouth sample bottle is adopted during working sample described in step (2), only bottle cap is used when analyzing sample, described flow velocity is 0.2mL/min, and described column temperature is 30 DEG C, and described sample size is 5 μ L, described capillary voltage is 4000V, described atomization gas pressure is 40psi, and described atomization gas flow velocity is 10L/min, and described atomization gas temperature is 350 DEG C.
Further, described in step (3), pure water is for adding alkali redistilled water, the described preparation method adding alkali redistilled water is: get 400mL brand-new distilled water and put into cucurbit, add zeolite and 5 grams of NaOH, heating in 1 hour is evenly placed in jolting, cast out 50mL front-end volatiles, get stage casing 250mL and collect 1 hour, to obtain final product.
The invention has the beneficial effects as follows:
1. detection method of the present invention is without the need to carrying out pre-treatment to sample, direct injected, has the advantages such as simple to operation, sampling quantity is few, cost is low, favorable reproducibility, stability are strong.
2. detection method of the present invention significantly improves detection efficiency, and once experiment can carry out qualitative and quantitative analysis to kind of the phthalic ester of six in potable water quickly and accurately, substantial saving in the working time of testing staff.
3. detection method of the present invention adopts C18 chromatographic column, LC-MS (HPLC-MS) technology; there is higher sensitivity; detection limit is all no more than 0.6 μ g/L; be enough to the monitoring requirement ensureing daily potable water; and guard column is installed additional before sample enters chromatographic column, play the effect of purification sample, protection chromatographic column.
4. blank hydromining of the present invention is with adding alkali redistilled water, and than ultrapure water, deionized water, brand-new distilled water, chromatogram pure water and acid adding redistilled water, mass spectrum response is little, blank value is minimum, similar with the performance of chromatogram pure water, and cost is lower.
5. detection method of the present invention has a extensive future, and is not only applicable to surroundings monitoring, and is applicable to the rapid screening of pollutant in emergent accident.
Accompanying drawing explanation
Fig. 1 is the mass spectrum multiple-reaction monitoring figure (MRM) of repefral of the present invention (DMP).
Fig. 2 is the mass spectrum multiple-reaction monitoring figure (MRM) of diethyl phthalate of the present invention (DEP).
Fig. 3 is the mass spectrum multiple-reaction monitoring figure (MRM) of dibutyl phthalate of the present invention (DBP).
Fig. 4 is the mass spectrum multiple-reaction monitoring figure (MRM) of butyl benzyl phthalate of the present invention (BBP).
Fig. 5 is the mass spectrum multiple-reaction monitoring figure (MRM) of phthalic acid two (2-ethylhexyl) ester (DEHP) of the present invention.
Fig. 6 is the mass spectrum multiple-reaction monitoring figure (MRM) of dioctyl phthalate of the present invention (DNOP).
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
(1) guard column is installed additional: use connecting pipe series connection to install guard column additional in chromatographic column front end, guard column entrance connects injection port, and outlet connects chromatographic column, and all there are hollow screw and sealing pressure ring in the two ends of connecting pipe;
(2) condition determination and mode: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, measure with liquid chromatography-tandem quadrupole rod mass spectrum, instrument parameter condition is in table 3, and Selective reaction monitoring parent ion, daughter ion and collision energy are in table 2; Adopt 2mL8mm standard mouth screw thread mouth sample bottle during described working sample, when analyzing sample, only use bottle cap;
The mass spectrographic instrument parameter of table 3 liquid chromatography-tandem level Four bar
Table 2 Selective reaction monitoring parent ion, daughter ion and collision energy and scan mode
(3) Criterion working curve: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, accurately draw standard solution described in 25 μ l respectively, be settled to 10mL respectively with pure water, obtain the standard solution that 6 kinds of phthalic ester concentrations are 0.5 μ g/mL respectively, described pure water for adding alkali redistilled water, described in add alkali redistilled water preparation method be: get 400mL brand-new distilled water and put into cucurbit, add zeolite and 5 grams of NaOH, heating in 1 hour is evenly placed in jolting, cast out 50mL front-end volatiles, get stage casing 250mL and collect 1 hour, to obtain final product, get 10 respectively, 20, 40, 80, 160, 200, 400, 800, the above-mentioned standard solution of 1600 μ l, 10mL is settled to respectively with pure water, obtain 0.5, 1, 2, 4, 8, 10, 20, 40, the series standard liquid of 80 μ g/l, adopt test condition sample introduction listed by the middle table 3 of step (2) and table 2, obtain mass spectrum multiple-reaction monitoring figure (MRM) (as shown in Figures 1 to 6) and the peak area of 6 kinds of phthalic esters respectively, be ordinate again with peak area, concentration is horizontal ordinate, drawing standard curve respectively, obtain the typical curve of 6 kinds of phthalic esters respectively, then linear regression analysis is carried out respectively, namely linear coefficient R>0.9900 can be used as typical curve, as shown in table 4,
The typical curve of table 46 kinds of phthalic esters
The intercept of contrast standard curve and slope value, 6 kinds of phthalic esters are good in 0 ~ 80 μ g/L concentration range internal linear, and typical curve meets and quantitatively calculates needs.
(4) measure detection limit: get 20 blank water samples, adopt test condition sample introduction listed by the middle table 3 of step (2) and table 2 successively, measure detection limit with the standard deviation of 6 kinds of phthalic ester peak areas.According to IUPAC (IUPAC) to the regulation of detection limit: D.L=K'Sb/k, K'=3, wherein Sb is the standard deviation of peak area, k is the slope of typical curve, the detection limit of 6 kinds of phthalic esters is respectively: repefral (DMP) is 0.62 μ g/L, diethyl phthalate (DEP) is 0.77 μ g/L, dibutyl phthalate (DBP) is 0.15 μ g/L, butyl benzyl phthalate (BBP) is 0.098 μ g/L, phthalic acid two (2-ethylhexyl) ester (DEHP) is 0.23 μ g/L, dioctyl phthalate (DNOP) is 0.0086 μ g/L.Regulation according to " water environment quality standard " (GB3838-2002): dibutyl phthalate (DBP) standard limited value is 3 μ g/L, phthalic acid two (2-ethylhexyl) ester standard limited value is 8 μ g/L, all the other 4 kinds are not then done criteria limit regulation.As can be seen here, in method of the present invention, the limit value that the detection limit of 6 kinds of phthalic esters all specifies in standard, is enough to the environmental monitoring requirement ensureing daily potable water.Therefore, method of the present invention can apply to the rapid screening of centralized drinking water sources water phthalate pollutant.
(5) method precision and recovery of standard addition: the series standard liquid of 4 concentration of 0.5,2,8,40 μ g/L of preparation steps (2) gained 6 kinds of phthalic esters respectively, each 7 samples of each concentration, adopt test condition sample introduction listed by table 1 and table 2 in step (2) respectively, with sample peak area and the precision of relative standard deviation examination method calculating concentration.In blank water sample, add the mixed standard solution of 6 kinds of phthalic esters, obtain the standard solution after mark-on, for analog environmental water, direct injection analysis.To concentration be 0.5,2,8, each 7 samples of standard solution after the mark-on of 40 μ g/L adopt test condition listed by table 3 and table 2 in step (2) to measure, result shows, 6 kinds of phthalic esters method precision in 0 ~ 80 μ g/L concentration range is good, the equal < 5% of quantitative result relative standard deviation.For express-analysis, the precision of the method reaches test request; Recovery of standard addition aspect, 4 kinds of concentration mark-on results of 6 kinds of phthalic esters all control, in the scope of 85 ~ 120%, also can meet test request.
(6) potable water to be measured detects: water factory of Qu Mou city Drinking Water Samples 1, adopt test condition sample introduction listed by the middle table 3 of step (2) and table 2, obtain the peak area of Drinking Water Samples to be measured, then with the peak area of above-mentioned Drinking Water Samples to be measured for ordinate, bring the typical curve of step (3) gained 6 kinds of phthalic esters into, the concentration obtaining 6 kinds of phthalic esters of Drinking Water Samples to be measured is respectively: repefral (DMP) is 1.25 μ g/L, diethyl phthalate (DEP) is 1.48 μ g/L, dibutyl phthalate is 0.29 μ g/L, butyl benzyl phthalate (BBP) is 0.37 μ g/L, phthalic acid two (2-ethylhexyl) 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: use connecting pipe series connection to install guard column additional in chromatographic column front end, guard column entrance connects injection port, and outlet connects chromatographic column, and all there are hollow screw and sealing pressure ring in the two ends of connecting pipe;
(2) condition determination and mode: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, measure with liquid chromatography-tandem quadrupole rod mass spectrum, instrument parameter condition is in table 5, and Selective reaction monitoring parent ion, daughter ion and collision energy are in table 2; Adopt 2mL8mm standard mouth screw thread mouth sample bottle during described working sample, when analyzing sample, only use bottle cap;
The mass spectrographic instrument parameter of table 5 liquid chromatography-tandem level Four bar
Table 2 Selective reaction monitoring parent ion, daughter ion and collision energy and scan mode
(3) Criterion working curve: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, accurately draw standard solution described in 25 μ l respectively, be settled to 10mL respectively with pure water, obtain the standard solution that 6 kinds of phthalic ester concentrations are 0.5 μ g/mL respectively, described pure water for adding alkali redistilled water, described in add alkali redistilled water preparation method be: get 400mL brand-new distilled water and put into cucurbit, add zeolite and 5 grams of NaOH, heating in 1 hour is evenly placed in jolting, cast out 50mL front-end volatiles, get stage casing 250mL and collect 1 hour, to obtain final product, get 10 respectively, 20, 40, 80, 160, 200, 400, 800, the above-mentioned standard solution of 1600 μ l, 10mL is settled to respectively with pure water, obtain 0.5, 1, 2, 4, 8, 10, 20, 40, the series standard liquid of 80 μ g/l, adopt test condition sample introduction listed by the middle table 5 of step (2) and table 2, obtain mass spectrum multiple-reaction monitoring figure (MRM) (as shown in Figures 1 to 6) and the peak area of 6 kinds of phthalic esters respectively, be ordinate again with peak area, concentration is horizontal ordinate, drawing standard curve respectively, obtain the typical curve of 6 kinds of phthalic esters respectively, then linear regression analysis is carried out respectively, namely linear coefficient R>0.9900 can be used as typical curve, as shown in table 6,
The typical curve of table 66 kinds of phthalic esters
The intercept of contrast standard curve and slope value, 6 kinds of phthalic esters are good in 0 ~ 80 μ g/L concentration range internal linear, and typical curve meets and quantitatively calculates needs.
(3) measure detection limit: get 20 blank water samples, adopt test condition sample introduction listed by the middle table 5 of step (2) and table 2 successively, measure detection limit with the standard deviation of 6 kinds of phthalic ester peak areas.According to IUPAC (IUPAC) to the regulation of detection limit: D.L=K'Sb/k, K'=3, wherein Sb is the standard deviation of peak area, k is the slope of typical curve, the detection limit of 6 kinds of phthalic esters is respectively: repefral (DMP) is 0.54 μ g/L, diethyl phthalate (DEP) is 0.59 μ g/L, dibutyl phthalate (DBP) is 0.11 μ g/L, butyl benzyl phthalate (BBP) is 0.061 μ g/L, phthalic acid two (2-ethylhexyl) ester (DEHP) is 0.15 μ g/L, dioctyl phthalate (DNOP) is 0.0043 μ g/L.Regulation according to " water environment quality standard " (GB3838-2002): dibutyl phthalate (DBP) standard limited value is 3 μ g/L, phthalic acid two (2-ethylhexyl) ester standard limited value is 8 μ g/L, all the other 4 kinds are not then done criteria limit regulation.As can be seen here, in method of the present invention, the limit value that the detection limit of 6 kinds of phthalic esters all specifies in standard, is enough to the environmental monitoring requirement ensureing daily potable water.Therefore, method of the present invention can apply to the rapid screening of centralized drinking water sources water phthalate pollutant.
(4) method precision and recovery of standard addition: the series standard liquid of 4 concentration of 0.5,2,8,40 μ g/L of preparation steps (2) gained 6 kinds of phthalic esters respectively, each 7 samples of each concentration, adopt test condition sample introduction listed by table 5 and table 2 in step (2) respectively, with sample peak area and the precision of relative standard deviation examination method calculating concentration.In blank water sample, add the mixed standard solution of 6 kinds of phthalic esters, obtain the standard solution after mark-on, for analog environmental water, direct injection analysis.To concentration be 0.5,2,8, each 7 samples of standard solution after the mark-on of 40 μ g/L adopt test condition listed by table 1 and table 2 in step (2) to measure, result shows, 6 kinds of phthalic esters method precision in 0 ~ 80 μ g/L concentration range is good, the equal < 5% of quantitative result relative standard deviation.For express-analysis, the precision of the method reaches test request; Recovery of standard addition aspect, 4 kinds of concentration mark-on results of 6 kinds of phthalic esters all control, in the scope of 85 ~ 120%, also can meet test request.
(5) potable water to be measured detects: water factory of Qu Mou city Drinking Water Samples 2, adopt test condition sample introduction listed by the middle table 5 of step (2) and table 2, obtain the peak area of Drinking Water Samples to be measured, then with the peak area of above-mentioned Drinking Water Samples to be measured for ordinate, bring the typical curve of step (3) gained 6 kinds of phthalic esters into, the concentration obtaining 6 kinds of phthalic esters of Drinking Water Samples to be measured is respectively: repefral (DMP) is 1.22 μ g/L, diethyl phthalate (DEP) is 1.35 μ g/L, dibutyl phthalate is 0.35 μ g/L, butyl benzyl phthalate (BBP) is 0.24 μ g/L, phthalic acid two (2-ethylhexyl) 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: use connecting pipe series connection to install guard column additional in chromatographic column front end, guard column entrance connects injection port, and outlet connects chromatographic column, and all there are hollow screw and sealing pressure ring in the two ends of connecting pipe;
(2) condition determination and mode: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, measure with liquid chromatography-tandem quadrupole rod mass spectrum, instrument parameter condition is in table 7, and Selective reaction monitoring parent ion, daughter ion and collision energy are in table 2; Adopt 2mL8mm standard mouth screw thread mouth sample bottle during described working sample, when analyzing sample, only use bottle cap;
The mass spectrographic instrument parameter of table 7 liquid chromatography-tandem level Four bar
Table 2 Selective reaction monitoring parent ion, daughter ion and collision energy and scan mode
(3) Criterion working curve: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, accurately draw standard solution described in 25 μ l respectively, be settled to 10mL respectively with pure water, obtain the standard solution that 6 kinds of phthalic ester concentrations are 0.5 μ g/mL respectively, described pure water for adding alkali redistilled water, described in add alkali redistilled water preparation method be: get 400mL brand-new distilled water and put into cucurbit, add zeolite and 5 grams of NaOH, heating in 1 hour is evenly placed in jolting, cast out 50mL front-end volatiles, get stage casing 250mL and collect 1 hour, to obtain final product, get 10 respectively, 20, 40, 80, 160, 200, 400, 800, the above-mentioned standard solution of 1600 μ l, 10mL is settled to respectively with pure water, obtain 0.5, 1, 2, 4, 8, 10, 20, 40, the series standard liquid of 80 μ g/l, adopt test condition sample introduction listed by the middle table 7 of step (2) and table 2, obtain mass spectrum multiple-reaction monitoring figure (MRM) (as shown in Figures 1 to 6) and the peak area of 6 kinds of phthalic esters respectively, be ordinate again with peak area, concentration is horizontal ordinate, drawing standard curve respectively, obtain the typical curve of 6 kinds of phthalic esters respectively, then linear regression analysis is carried out respectively, namely linear coefficient R>0.9900 can be used as typical curve, as shown in table 8,
The typical curve of table 86 kinds of phthalic esters
The intercept of contrast standard curve and slope value, 6 kinds of phthalic esters are good in 0 ~ 80 μ g/L concentration range internal linear, and typical curve meets and quantitatively calculates needs.
(4) measure detection limit: get 20 blank water samples, adopt test condition sample introduction listed by the middle table 7 of step (2) and table 2 successively, measure detection limit with the standard deviation of 6 kinds of phthalic ester peak areas.According to IUPAC (IUPAC) to the regulation of detection limit: D.L=K'Sb/k, K'=3, wherein Sb is the standard deviation of peak area, k is the slope of typical curve, the detection limit of 6 kinds of phthalic esters is respectively: repefral (DMP) is 0.57 μ g/L, diethyl phthalate (DEP) is 0.66 μ g/L, dibutyl phthalate (DBP) is 0.18 μ g/L, butyl benzyl phthalate (BBP) is 0.084 μ g/L, phthalic acid two (2-ethylhexyl) ester (DEHP) is 0.17 μ g/L, dioctyl phthalate (DNOP) is 0.0064 μ g/L.Regulation according to " water environment quality standard " (GB3838-2002): dibutyl phthalate (DBP) standard limited value is 3 μ g/L, phthalic acid two (2-ethylhexyl) ester standard limited value is 8 μ g/L, all the other 4 kinds are not then done criteria limit regulation.As can be seen here, in method of the present invention, the limit value that the detection limit of 6 kinds of phthalic esters all specifies in standard, is enough to the environmental monitoring requirement ensureing daily potable water.Therefore, method of the present invention can apply to the rapid screening of centralized drinking water sources water phthalate pollutant.
(5) method precision and recovery of standard addition: the series standard liquid of 4 concentration of 0.5,2,8,40 μ g/L of preparation steps (2) gained 6 kinds of phthalic esters respectively, each 7 samples of each concentration, adopt test condition sample introduction listed by table 7 and table 2 in step (2) respectively, with sample peak area and the precision of relative standard deviation examination method calculating concentration.In blank water sample, add the mixed standard solution of 6 kinds of phthalic esters, obtain the standard solution after mark-on, for analog environmental water, direct injection analysis.To concentration be 0.5,2,8, each 7 samples of standard solution after the mark-on of 40 μ g/L adopt test condition listed by table 7 and table 2 in step (2) to measure, result shows, 6 kinds of phthalic esters method precision in 0 ~ 80 μ g/L concentration range is good, the equal < 5% of quantitative result relative standard deviation.For express-analysis, the precision of the method reaches test request; Recovery of standard addition aspect, 4 kinds of concentration mark-on results of 6 kinds of phthalic esters all control, in the scope of 85 ~ 120%, also can meet test request.
(6) potable water to be measured detects: water factory of Qu Mou city Drinking Water Samples 3, adopt test condition sample introduction listed by the middle table 1 of step (2) and table 2, obtain the peak area of Drinking Water Samples to be measured, then with the peak area of above-mentioned Drinking Water Samples to be measured for ordinate, bring the typical curve of step (3) gained 6 kinds of phthalic esters into, the concentration obtaining 6 kinds of phthalic esters of Drinking Water Samples to be measured is respectively: repefral (DMP) is 1.30 μ g/L, diethyl phthalate (DEP) is 1.32 μ g/L, dibutyl phthalate is 0.44 μ g/L, butyl benzyl phthalate (BBP) is 0.29 μ g/L, phthalic acid two (2-ethylhexyl) ester (DEHP) is 0.15 μ g/L, dioctyl phthalate (DNOP) is 0.091 μ g/L.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. LC-MS detects a method for six kinds of phthalic esters in potable water, it is characterized in that, comprises the steps:
(1) guard column is installed additional: install chromatographic column additional guard column;
(2) condition determination and mode: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, measure with liquid chromatography-tandem quadrupole rod mass spectrum, instrument parameter condition is in table 1, and Selective reaction monitoring parent ion, daughter ion and collision energy are in table 2;
The mass spectrographic instrument parameter of table 1 liquid chromatography-tandem level Four bar
Table 2 Selective reaction monitoring parent ion, daughter ion and collision energy and scan mode
(3) Criterion working curve: get the standard solution that 6 kinds of phthalic ester concentrations are 200 μ g/mL, accurately draw standard solution described in 25 μ l respectively, be settled to 10mL respectively with pure water, obtain the standard solution that 6 kinds of phthalic ester concentrations are 0.5 μ g/mL respectively; Get the above-mentioned standard solution of 0,10,20,40,80,160,200,400,800,1600 μ l respectively, 10mL is settled to respectively with pure water, obtain the series standard liquid of 0,0.5,1,2,4,8,10,20,40,80 μ g/l, adopt test condition sample introduction listed by the middle table 1 of step (2) and table 2, obtain the peak area of 6 kinds of phthalic esters respectively, be ordinate again with peak area, concentration is horizontal ordinate, drawing standard curve respectively, obtain the typical curve of 6 kinds of phthalic esters respectively, then carry out linear regression analysis respectively;
(4) potable water to be measured detects: get Drinking Water Samples to be measured, adopt test condition sample introduction listed by the middle table 1 of step (2) and table 2, obtain the peak area of Drinking Water Samples to be measured, then with the peak area of above-mentioned Drinking Water Samples to be measured for ordinate, bring the typical curve of step (3) gained 6 kinds of phthalic esters into, obtain the concentration value of 6 kinds of phthalic esters of Drinking Water Samples to be measured.
2. a kind of LC-MS according to claim 1 detects the method for six kinds of phthalic esters in potable water; it is characterized in that; the method that installs additional protected described in step (1) is: use connecting pipe series connection to install guard column additional in the front end of described chromatographic column; the entrance of described guard column connects injection port; outlet connects chromatographic column, and all there are hollow screw and sealing pressure ring in the two ends of described connecting pipe.
3. a kind of LC-MS according to claim 1 detects the method for six kinds of phthalic esters in potable water, it is characterized in that, 2mL8mm standard mouth screw thread mouth sample bottle is adopted during working sample described in step (2), only bottle cap is used when analyzing sample, described flow velocity is 0.2mL/min, described column temperature is 30 DEG C, described sample size is 5 μ L, described capillary voltage is 4000V, described atomization gas pressure is 40psi, described atomization gas flow velocity is 10L/min, and described atomization gas temperature is 350 DEG C.
4. a kind of LC-MS according to claim 1 detects the method for six kinds of phthalic esters in potable water, it is characterized in that, described in step (3), pure water is for adding alkali redistilled water, the described preparation method adding alkali redistilled water is: get 400mL brand-new distilled water and put into cucurbit, add zeolite and 5 grams of NaOH, heating in 1 hour is evenly placed in jolting, casts out 50mL front-end volatiles, get stage casing 250mL and collect 1 hour, to obtain final product.
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| CN112903884B (en) * | 2019-11-19 | 2022-07-12 | 中国科学院深圳先进技术研究院 | Method for simultaneously detecting phthalate compounds and metabolites thereof and application thereof |
| CN110988189A (en) * | 2019-12-23 | 2020-04-10 | 舟山市食品药品检验检测研究院 | Method for rapidly determining phthalate plasticizer in beverage |
| 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 |
| CN115598263B (en) * | 2022-11-25 | 2023-04-18 | 国科大杭州高等研究院 | Method for simultaneously determining contents of organic phosphate and conversion product thereof |
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