CN114705784A - Online detection method for organic phosphate in environmental water - Google Patents
Online detection method for organic phosphate in environmental water Download PDFInfo
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- CN114705784A CN114705784A CN202210386690.3A CN202210386690A CN114705784A CN 114705784 A CN114705784 A CN 114705784A CN 202210386690 A CN202210386690 A CN 202210386690A CN 114705784 A CN114705784 A CN 114705784A
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- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 claims description 4
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
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- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
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Abstract
An online detection method of organic phosphate in environmental water comprises the following steps: filtering an environmental water sample, injecting the filtered environmental water sample into an online solid-phase extraction column by using a first automatic sample injector, and enriching and purifying organic phosphate in the environmental water sample under the optimized online solid-phase extraction condition; eluting the enriched and purified organic phosphate from the on-line solid phase extraction column, and directly injecting the organic phosphate into a high performance liquid chromatography device for separation; directly injecting the separated organic phosphate into a tandem mass spectrometry device for mass spectrometry detection; the optimized online solid-phase extraction conditions comprise the type of an online solid-phase extraction column, the sample loading volume, the sample loading rate and the sample loading time of an environmental water sample, and are obtained by optimizing through a single-factor test method by taking the mass spectrum peak intensity of organic phosphate in a tandem mass spectrum device as an evaluation index. The invention realizes the full-automatic large-volume sample introduction and on-line solid phase extraction processes, improves the analysis flux and sensitivity, has good accuracy, is simple and convenient to operate, saves time and improves the detection efficiency.
Description
Technical Field
The invention belongs to the fields of chemical analysis technology and environmental protection, and relates to an online detection method for determining organic phosphate in environmental water.
Technical Field
Organic Phosphates (OPEs) are artificially synthesized phosphoric acid derivatives, have low production cost and good flame retardant, plasticizing and lubricating effects, and are widely applied to consumer products such as building materials, electronic products, plastic products, home decoration, textiles, cables, insulating materials, coatings, hydraulic oil and the like as flame retardants and plasticizers. As brominated flame retardants are becoming increasingly forbidden worldwide, these have made OPEs a major alternative. The use of OPEs began in the early 20 th century, and due to their excellent performance and low cost of production, their production and usage increased at an alarming rate year by year, with the worldwide OPEs consuming about 55 million tons in 2012 and increasing to 105 million tons in 2018. With the widespread use of OPEs, they are found in many environmental media worldwide, including dust, the atmosphere, bodies of water, soils and sediments, organisms, etc., even in our daily drinking water. Humans are exposed to ops through air inhalation, dust intake, skin absorption and diet, which may have a range of health effects on humans: carcinogenicity, developmental toxicity, neurotoxicity, nephrotoxicity, skin irritation, sperm quality reduction, dermatitis, endocrine disorders, and the like.
For an environmental water sample, a solid phase extraction method (SPE) is generally adopted for pretreatment in the traditional method. The matrix of an environmental water sample is complex, and the occurrence of trace OPEs in the environment is low, so that the environmental water sample needs to be pretreated firstly, pollutants to be detected are extracted from the complex matrix, the interference of the matrix and coexisting substances to the detection is eliminated, and the effect of enriching and concentrating the detected trace components (ppb and ppt levels) is further realized. However, the traditional offline sample pretreatment method has the defects of complex process, long consumption time, easy pollution and degradation of samples in the treatment process, and the offline SPE cartridge is a disposable consumable, uses a toxic solvent and has a large amount of required samples and solvents, so the traditional offline sample pretreatment method does not accord with the trend of green analytical chemistry at present.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide an online detection method for organophosphates in environmental water, so as to at least partially solve at least one of the above technical problems.
According to an embodiment of the invention, an online detection method of organic phosphate in environmental water is provided, which comprises the following steps: step A: filtering an environmental water sample, injecting the filtered environmental water sample into an online solid-phase extraction column by using a first automatic sample injector, and enriching and purifying organic phosphate in the environmental water sample under an optimized online solid-phase extraction condition; and B, step B: eluting the enriched and purified organic phosphate from the online solid-phase extraction column, and directly injecting the organic phosphate into a high performance liquid chromatography device through a second automatic sample injector for separation; and C: directly injecting the separated organic phosphate into a tandem mass spectrometry device, and carrying out mass spectrometry detection on the organic phosphate in a multi-reaction monitoring mode under a positive ion mode; the optimized online solid-phase extraction conditions comprise the type of an online solid-phase extraction column, the sample loading volume, the sample loading rate and the sample loading time of the environmental water sample, and are obtained by optimizing through a single-factor test method by taking the mass spectrum peak intensity of the organic phosphate in the tandem mass spectrum device as an evaluation index.
Based on the technical scheme, the online detection method for the organic phosphate in the environmental water at least has one or part of the following beneficial effects:
(1) the invention establishes an online solid-phase extraction-high performance liquid chromatography-tandem mass spectrometry (namely online SPE-HPLC-MS/MS) method for OPEs in an environmental water sample, based on the online detection method, the environmental water sample can be directly tested on a machine after being filtered, any pretreatment process is not needed, complex processes such as concentration and constant volume in offline sample treatment are avoided, the solvent consumption and the organic solvent waste liquid treatment cost can be reduced, the system can be automatically carried out, and the sample preparation time is reduced, only 2ml of water sample is needed in the method, and the detection of 22 OPEs can be completed within 22 minutes;
(2) compared with an offline mode, the method can transfer the whole extract on an online solid-phase extraction column (namely an online SPE column) to a high performance liquid chromatography (namely HPLC) analysis column in the online mode, so that the sample flux is increased, and stronger OPEs mass spectrum peak intensity is obtained based on the optimized online solid-phase extraction condition, so that the sensitivity is improved, and the detection limit range of 22 OPEs is 0.06-1.22 ng/L; meanwhile, the precision and the accuracy are improved, the relative standard deviation RSD is 2.9-16%, and the reproducibility is good;
(3) based on the online detection method provided by the invention, the environment sample can be directly detected on the computer after being filtered, so that the sample is prevented from contacting the environment in the detection process, the risks of sample pollution and analyte degradation can be reduced, and the loss of the analyte is reduced or eliminated;
(4) the online SPE column can be reused generally;
(5) the present invention uses reduced amounts of solvent and reduces the risk of operator exposure to infectious agents or toxic solvents.
Drawings
Fig. 1 is a flowchart of a development process of an online detection method for OPEs according to embodiment 1 of the present invention.
FIG. 2 is a plot of the selection of the on-line SPE cartridges in example 1-1 of the present invention as a function of the peak intensity of the OPEs (normalized to 50 ng/L).
FIG. 3 is a graph showing the relationship between the sample loading volume and the peak intensity of OPEs (at a loading concentration of 50ng/L) in examples 1-2 of the present invention.
FIG. 4 is a graph showing the relationship between the sample loading rate and the peak intensity of OPEs (50ng/L) in examples 1 to 3 of the present invention.
FIG. 5 is a graph showing the relationship between the sample loading time and the peak intensity of OPEs (50ng/L) in examples 1-4 of the present invention.
FIGS. 6A-6C are on-line SPE-HPLC-MS/MS chromatographic separation profiles of OPEs in example 2 of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention establishes an online SPE-HPLC-MS/MS method of the OPEs, an environmental water sample can be directly and automatically detected on a machine after being filtered, sample pretreatment is not needed, solvent consumption and waste liquid treatment cost are reduced, in the process of realizing the invention, the online solid phase extraction condition has obvious influence on the peak intensity of the OPEs detected by the online SPE-HPLC-MS/MS, and stronger OPEs mass spectrum peak intensity can be obtained by optimizing the online solid phase extraction condition, so that the sensitivity is improved, the detection limit of the OPEs in 22 is greatly reduced, the precision and the accuracy are improved, and the method has good reproducibility.
Specifically, according to some embodiments of the present invention, an online detection method for OPEs in environmental water is provided, which includes steps A to C.
In the step A, filtering an environmental water sample, injecting the filtered environmental water sample into an online solid-phase extraction column by using a first automatic sample injector, and enriching and purifying the OPEs in the environmental water sample under the optimized online solid-phase extraction condition; in the step B, directly injecting the enriched and purified OPEs into a high performance liquid chromatography device for separation after eluting the OPEs from the online solid phase extraction column; in the step C, directly injecting the separated OPEs into a tandem mass spectrum device, and carrying out mass spectrum detection on the OPEs in a multi-reaction monitoring mode in a positive ion mode; the optimized online solid-phase extraction conditions comprise the types of online solid-phase extraction columns, the sample loading volume, the sample loading rate and the sample loading time of an environmental water sample, and the mass spectrum peak intensity of the OPEs in the tandem mass spectrum device is used as an evaluation index to be obtained through optimization by a single-factor test method.
It should be noted that the sample loading volume of the environmental water sample refers to the sample loading amount of the environmental water sample, that is, the volume of the environmental water sample loaded to the first autosampler; the sample loading rate refers to the flow rate of the extraction pump at the loading position, namely the rate of loading the environmental water sample from the first automatic sample injector to the online solid-phase extraction column; the sample loading time refers to the time when the extraction pump is switched to the elution position, that is, the time when the environmental water sample is loaded from the first automatic sample injector to the on-line solid-phase extraction column.
According to the embodiment of the invention, the online solid-phase extraction condition is optimized, and the online SPE-HPLC-MS/MS method of the OPEs in the environmental water is established. The method improves the analysis flux and sensitivity, has good accuracy, is simple and convenient to operate, saves time and improves the detection efficiency.
In some embodiments, the online detection method of the present invention can be used for online detection of 22 OPEs, where the 22 OPEs are: trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPrP), tri-n-butyl phosphate (TnBP), triisobutyl phosphate (TiBP), tris (2-ethylhexyl) phosphate (TEHP), tributoxyethyl phosphate (TBOEP), tris (1-chloro-2-propyl) phosphate (TCIPP), tris (2-chloroethyl) phosphate (TCEP), tris (1, 3-dichloro-2-propyl) phosphate (TDCPP), triphenyl phosphate (TPHP), tricresyl phosphate (TMPP), cresyldiphenyl phosphate (CDPP), 2-ethylhexyl diphenyl phosphate (DPP), resorcinol tetraphenyl diphosphate (RDP), bisphenol A bis (diphenyl phosphate) (BABP), 2, 2-bis (chloromethyl) trimethylene bis (2-chloroethyl) phosphate) (V6), tris (2, 4-di-tert-butylphenyl) phosphate (TDTBPP), 3-isopropylphenylphenylphosphate (3IPPDPP), bis (3-isopropylphenyl) phenyl phosphate (B3IPPPP), 3-tert-butylphenyl diphenylphosphate (3tBPDPP), bis (3-tert-butylphenyl) phenyl phosphate (B3 tBPPP).
In some embodiments, the optimized on-line solid phase extraction conditions comprise:
an online solid phase extraction column: an Xbridge C8 Direct Connect HP column, particle size 10 μm, internal diameter × column length 2.1mm × 30 mm;
mobile phase: phase A is ultrapure water, phase B is acetonitrile containing 0.1 vol% formic acid, and gradient elution is carried out;
sample loading volume: 1.5-2 ml;
sample loading rate: 1.0-2.5 ml/min;
sample loading time: 1.0-1.5 min.
In some embodiments, the optimized on-line solid phase extraction conditions comprise:
an online solid phase extraction column: an Xbridge C8 Direct Connect HP column, particle size 10 μm, internal diameter × column length 2.1mm × 30 mm;
mobile phase: phase A is ultrapure water, phase B is acetonitrile containing 0.1 vol% formic acid, and gradient elution is carried out;
sample loading volume: 2 ml;
sample loading rate: 2.0 ml/min;
sample loading time: 1.0 min.
In some embodiments, the liquid chromatography conditions comprise:
HPLC analytical column: an Acclaim Mixed-Mode HILIC-1 column with the particle size of 5 mu m, the inner diameter multiplied by the column length of 2.1mm multiplied by 150 mm;
mobile phase: phase A is ultrapure water, phase B is acetonitrile, gradient elution is carried out;
column temperature: 25-35 ℃.
In some embodiments, a high performance liquid chromatography apparatus configured with a dual ternary gradient pump, a second autosampler, an HPLC analytical column, and a column oven is used, wherein the dual ternary gradient pump comprises: the extraction pump is connected to the first automatic sample injector and is used for pumping the mobile phase into the online solid-phase extraction column; and an analysis pump connected to the second autosampler for pumping the mobile phase to the liquid chromatography column. The column temperature box is used for placing the HPLC analytical column so as to adjust the column temperature of the HPLC analytical column. More specifically, the first and second auto-injectors are both six-way valve injectors.
In some examples, the analytical pump used ultrapure water (phase a) and acetonitrile (phase B) as mobile phases, and the extraction pump used ultrapure water (phase a) and 0.1% formic acid-acetonitrile (phase B) as mobile phases. Gradient elution was performed using an analytical pump and an extraction pump, respectively, and the gradient elution procedure is shown in table 1.
Table 1 HPLC gradient elution conditions for OPEs
Note: the extraction pump is switched to the elution position at 1min and to the load position at 14min
In some embodiments, the tandem mass spectrometry apparatus is a triple quadrupole tandem mass spectrometer equipped with an electrospray ion source (ESI) and operating software, wherein the electrospray source is in positive ion mode (ESI +); the detection mode is multi-reaction monitoring (MRM).
The mass spectrum detection conditions are as follows: the air pressure of the air curtain is 10psi, the collision air pressure is 9psi, the spraying voltage of the ion source is 5500V, the temperature is 600 ℃, the atomizing air is 50psi, and the auxiliary atomizing air is 50 psi. Alternatively, the gas curtain pressure is 10psi, the collision pressure is 9psi, the ion source spray voltage is 5500V, the temperature is 600 ℃, the atomizing gas is 50psi, and the assisting atomizing gas is 50 psi.
In some embodiments, ion pair and mass spectral parameters of the ops, such as declustering voltage (DP), Collision Energy (CE), collision exit voltage (CXP), are as shown in table 2 below, and the ops can be detected qualitatively and quantitatively using the ion pair and mass spectral parameters shown in table 2.
Specifically, 22 kinds of OPEs can be quantitatively detected by using a mixed internal standard substance based on an internal standard method, wherein the mixed internal standard substance comprises TCIPP-d18, TCEP-d12, TMP-d9, TEP-d15, TPrP-d21, TnBP-d27, TPHP-d15, TEHP-d51, TBOEP-d21 and TDCPP-d15, and the mass spectrum peak area corresponding to each OPE and the internal standard substance can be determined based on the ion pairs and the mass spectrum parameters of the 22 kinds of OPEs and the mixed internal standard substance in the table 2. It should be noted that the present invention is not limited to this, and the quantitative detection of 22 OPEs can be similarly achieved by the external standard method.
TABLE 2 ion Pair and Mass Spectrometry parameters for OPEs
In some embodiments, when the OPEs are quantitatively detected based on an internal standard method, a mixed internal standard substance is added into an environmental water sample, and the online detection method further comprises the steps D to F.
In the step D, detecting a series of standard sample solutions with different standard adding concentrations by using the operations of the steps A to C, wherein the series of standard sample solutions comprise a plurality of organic phosphate esters and mixed internal standard substances, and each internal standard substance in the mixed internal standard substances is respectively corresponding to at least one organic phosphate ester for quantification; in the step E, performing regression analysis on the ratio of the mass spectrum peak area of each organic phosphate to the mass spectrum peak area of the corresponding internal standard substance and the standard addition concentration of the organic phosphate according to the detection result of the series of standard sample solutions to obtain a working curve of each organic phosphate; and F, determining the content of each organic phosphate in the environmental water sample according to the detection result and the working curve of the environmental water sample. It can be understood that the spiking concentrations of the mixed internal standard in the serial standard sample solution and the environmental water sample are the same.
For example, in step D, a series of ultrapure water mixed standard sample solutions with different standard addition concentrations (such as 1.0ng/L, 5.0ng/L, 10.0ng/L, 25.0ng/L, 50.0ng/L, 100.0ng/L, 200.0ng/L and 500.0ng/L) are prepared, 25.0ng/L of mixed internal standard substance is added, and 25.0ng/L of mixed internal standard substance is added to the environmental water sample, and the series of ultrapure water standard sample solutions and the environmental water sample are respectively subjected to on-machine analysis according to the operations of the steps A to C in the on-line detection method of the invention, and each mass concentration is measured in parallel for 5 times. And step E, performing regression analysis on the ratio y of the mass spectrum peak areas of the OPEs and the corresponding internal standard substance and the spiking concentration x of the corresponding OPEs to establish a working curve. And F, determining the content of each OPE in the environmental water sample according to the mass spectrum peak area ratio of each OPE to the corresponding internal standard substance in the detection result of the environmental water sample and the working curve.
The technical solutions of the present invention are described in detail below by using preferred embodiments, and it should be noted that the following specific embodiments are only examples and are not intended to limit the present invention. The experimental procedures used in the following examples are, unless otherwise specified, conventional procedures; the materials, reagents, instruments and the like used are commercially available unless otherwise specified.
Example 1: optimizing on-line solid phase extraction conditions
In this embodiment, an online solid-phase extraction-high performance liquid chromatography-tandem mass spectrometry method is adopted to detect ops in water, 22 ops are selected as target objects, 50.0ng/L of 22 ops mixed standard solution is prepared by using ultrapure water, and 25.0ng/L of mixed internal standard solution is added to obtain a sample to be detected containing the target objects, so that online solid-phase extraction conditions are optimized, as shown in fig. 1.
The on-line solid phase extraction-high performance liquid chromatography-tandem mass spectrometry system comprises: an online solid-phase extraction device provided with a six-way valve sample injector and an online solid-phase extraction column; a high performance liquid chromatograph (Ultimate 3000 HPLC, Thermo Fisher Scientific, USA) equipped with a double ternary gradient pump, a six-way valve sample injector, and a column oven; and a triple quadrupole tandem mass spectrometer (API 4500, Applied Biosystems/MDS SCIEX, US) configured with electrospray ion source (ESI) and analysis 1.4.2 working software.
The online solid phase extraction conditions are as follows:
an online solid phase extraction column: experiments were performed using two online SPE columns, an Xbridge C18Direct Connect HP column (10 μm, 2.1mm x 30mm, Waters, USA) and an Xbridge C8 Direct Connect HP column (10 μm, 2.1mm x 30mm, Waters, USA) to examine the effect of the online SPE columns on OPEs peak intensity.
Mobile phase: phase A is ultrapure water, phase B is acetonitrile containing 0.1 vol% formic acid, and gradient elution is carried out;
sample loading volume: sample loading volumes of 0.5, 1, 1.5, 2, 2.5ml were selected to examine the effect of loading volume on the peak intensities of OPEs.
Sample loading rate: sample loading rates of 0.5, 1.0, 2.0, 2.5, 3.0mL/min were selected to examine the effect of loading rate on the peak intensity of ops.
Sample loading time: sample loading times of 0.5, 1.0, 2.0, 3.0min were selected to examine the effect of loading time on the peak intensity of OPEs.
Liquid chromatography conditions:
HPLC analytical column: acclaim Mixed-Mode HILIC-1 analytical column (5 μm, 2.1 mm. times.150 mm, Thermo Fisher Scientific, USA);
mobile phase: phase A is ultrapure water, phase B is acetonitrile, and gradient elution is carried out according to the procedure shown in Table 1;
flow rate: 0.25 mL/min;
column temperature: 25-35 ℃.
Mass spectrum detection conditions:
an electrospray source: positive ion mode (ESI +);
the detection mode is as follows: multiple Reaction Monitoring (MRM), gas curtain pressure of 10psi, collision pressure of 9psi, ion source spray voltage of 5500V, temperature of 600 ℃, atomizing gas of 50psi, assisted atomizing gas of 50 psi.
Examples 1 to 1
This example compares the mass spectral peak intensities of OPEs using different SPE cartridges.
The retention effect of the two on-line SPE columns, XBridge C18 and XBridge C8, was compared according to the peak intensity of ops. As shown in fig. 2, when XBridge C18 was used as an on-line SPE column, it was found that the extraction efficiency was low for long-chain ops such as TEHP, RDP, BABP, and short-chain TMP. However, the choice of XBridge C8 for the long chain compound is much better, so XBridge C8 is preferred as the online SPE column.
Examples 1 to 2
This example selects different loading volumes to compare the mass spectral peak intensities of OPEs.
0.5 ml, 1 ml, 1.5 ml, 2ml and 2.5ml (the maximum volume of a quantitative ring of a six-way valve sample injector in the on-line solid phase extraction device used in the invention is 2.5ml) are selected as sample loading volumes, the sample loading volumes are optimized according to the peak intensity of OPEs, the peak intensity of OPEs is firstly increased and then decreased along with the increase of the sample loading volumes, the sample loading volumes have good mass spectrum response intensity when being 1.5-2 ml, and the peak intensity is the highest when being 2ml (as shown in FIG. 3), so that 2ml is preferably selected as the sample loading volumes.
Examples 1 to 3
Different loading rates were selected to compare the mass spectral peak intensities of the OPEs.
And (3) respectively carrying out sample loading at the speed of 0.5, 1.0, 2.0, 2.5 and 3.0mL/min to investigate the concentration effect of the SPE column on the target substance, and optimizing the sample loading rate according to the peak intensity of the OPEs. As shown in FIG. 4, the OPEs peak response intensity increases and then decreases with the increase of the sample loading rate, the sample loading rate has good mass spectrum response intensity at 1.0-2.5 mL/min, and the peak response intensity is the highest at 2.0mL/min, so 2.0mL/min is selected as the preferred sample loading rate.
Examples 1 to 4
Different loading times were selected to compare the mass spectral peak intensities of the OPEs.
And selecting 0.5, 1.0, 2.0 and 3.0min as the sample loading time, and inspecting the loading condition of the online SPE column on the OPEs. As shown in fig. 5, the results indicate that the peak response of the detected ops increased significantly when the loading time was changed from 0.5min to 1.0 min; however, the peak intensity of OPEs decreased sharply when the loading time was 2.0 and 3.0 min. When the sample loading time is 1.0-1.5 min, the loading capacity of OPEs is better, and more preferably 1min is used as the sample loading time.
Based on the foregoing examples, determining optimized on-line solid phase extraction conditions includes: an online solid phase extraction column: an XBridge C8 Direct Connect HP column having a particle size of 10 μm, an internal diameter x column length of 2.1mm x 30 mm; mobile phase: phase A was ultrapure water, phase B was acetonitrile containing 0.1 vol% formic acid, and gradient elution was performed according to the procedure shown in Table 1; sample loading volume: 2 ml; sample loading rate: 2.0 ml/min; sample loading time: 1.0 min. On the basis, an online SPE-HPLC-MS/MS method of OPEs is established.
Example 2: detecting OPEs in environmental water
1) Establishing a working curve
Based on the online solid phase extraction conditions determined in example 1, a working curve was established and method performance parameters were investigated. Serial ultrapure water standard sample solutions with different standard adding concentrations (1.0ng/L, 5.0ng/L, 10.0ng/L, 25.0ng/L, 50.0ng/L, 100.0ng/L, 200.0ng/L and 500.0ng/L) are prepared, a mixed internal standard substance concentration of 25.0ng/L is added, the OPEs established according to the embodiment 1 of the invention are analyzed on the computer according to the online SPE-HPLC-MS/MS method, and each mass concentration is measured for 5 times in parallel. And (4) carrying out regression analysis on the peak area ratio y of each analyte and the corresponding internal standard and the corresponding concentration x to establish a working curve.
As shown in Table 3, the method has a good linear relation in the range of 1-500ng/L, and the linear correlation coefficients (R) of 22 OPEs are all larger than 0.99. Under the condition of 2ml sample injection, the detection Limit (LOD) of 22 targets is 0.06-1.22ng/L, and the detection limit of the method is lower. The precision of the method was evaluated by measuring the relative standard deviation (RSD, reproducibility), which was 2.9-16%, indicating that the method has good reproducibility.
TABLE 3 OPE linearity, limit of detection (LOD) and Relative Standard Deviation (RSD) of analytical methods
2) Performing labeling recovery determination on OPEs in environmental water
The on-line SPE-HPLC-MS/MS method established in example 1 was used to perform a spiking recovery experiment on tap water from Beijing. The OPEs mixed standard solution was added to tap water and tested for spiked recovery of OPEs at three concentration levels (10, 50 and 200 ng/L). As shown in Table 4, the normalized recovery (RRs) is the average of 5 replicates, with RRs being able to be between 80 and 120% for most OPEs. After on-line measurement under the optimal conditions, the on-line SPE-HPLC-MS/MS chromatographic separation chart of 22 OPEs is shown in FIGS. 6A-6C, wherein target OPEs are simultaneously measured, but the chromatogram is separately presented according to the peak emergence time and the peak response intensity for clearer differentiation and display.
Wherein, in FIGS. 6A-6C, 1.TMP, 2.TEP, 3.TPrP, 4.TCIPP, 5.V6, 6.TiBP, 7.TnBP, 8.TBOEP, 9. TPHP; TCEP, 11.TDCPP, 12.CDPP, 13.3IPPDPP, 14.TMPP, 15.RDP, 16.3 tBBDPP, 17.EHDPP, 18.B3IPPPP, 19.B3 tPPP, 20.BABP, 21.TDTBPP, 22.TEHP, 23.d9-TMP, 24.d15-TEP, 25.d12-TCEP, 26.d21-TPRP, 27.d18-TCIPP, 28.d15-TDCPP, 29.d27-TnBP, 30.d27-TBOEP, 31.d15-TPHP, 32.d 51-TEHP.
TABLE 4 samples of tap water OPEs normalized recovery (RRs) and Relative Standard Deviation (RSD)
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An online detection method of organic phosphate in environmental water comprises the following steps:
step A: filtering an environmental water sample, injecting the filtered environmental water sample into an online solid-phase extraction column by using a first automatic sample injector, and enriching and purifying organic phosphate in the environmental water sample under an optimized online solid-phase extraction condition;
and B: eluting the enriched and purified organic phosphate from the online solid-phase extraction column, and directly injecting the organic phosphate into a high performance liquid chromatography device for separation;
and C: directly injecting the separated organic phosphate into a tandem mass spectrometry device, and carrying out mass spectrometry detection on the organic phosphate in a multi-reaction monitoring mode under a positive ion mode;
the optimized online solid-phase extraction conditions comprise the type of an online solid-phase extraction column, the sample loading volume, the sample loading rate and the sample loading time of the environmental water sample, and are obtained by optimizing through a single-factor test method by taking the mass spectrum peak intensity of the organic phosphate in the tandem mass spectrum device as an evaluation index.
2. The on-line detection method according to claim 1, wherein the optimized on-line solid phase extraction conditions comprise:
an Xbridge C8 Direct Connect HP column with the particle size of 10 mu m, the inner diameter multiplied by the column length by 2.1mm multiplied by 30mm is used as an online solid phase extraction column;
selecting ultrapure water and acetonitrile containing 0.1 vol% formic acid as a mobile phase for gradient elution;
the sample loading volume of the environmental water sample is 1.5-2 ml, the sample loading speed is 1.0-2.5 ml/min, and the sample loading time is 1.0-1.5 min.
3. The on-line detection method according to claim 2, wherein in the optimized on-line solid phase extraction conditions, ultrapure water is used as phase A, acetonitrile containing 0.1 vol% formic acid is used as phase B, and the gradient elution procedure is as follows: 0-1 min, 100 vol% A, and the flow rate is 2 ml/min; 1.2-13.8 min, 100 vol% A and the flow rate of 0.25 ml/min; 14-20 min, 0 vol% A and the flow rate of 0.75 ml/min; 20.2-22 min, 100 vol% A and the flow rate of 2 ml/min.
4. The on-line detection method according to claim 1, wherein the liquid chromatography conditions in step B include:
an Acclaim Mixed-Mode HILIC-1 column with the particle size of 5 mu m, the inner diameter multiplied by the column length of 2.1mm multiplied by 150mm is used as a liquid chromatography analysis column;
selecting ultrapure water and acetonitrile as mobile phases to carry out gradient elution;
the column temperature is 25-35 ℃.
5. The on-line detection method according to claim 4, wherein in the liquid chromatography condition, ultrapure water is used as phase A, acetonitrile is used as phase B, and the gradient elution procedure is as follows: 0-2 min, 60 vol% A, and the flow rate is 0.25 ml/min; 6min, 40 vol% A, flow rate 0.25 ml/min; 9-14 min, 0 vol% A, and the flow rate of 0.25 ml/min; 14.2-22 min, 60 vol% A, and the flow rate is 0.25 ml/min.
6. The on-line detection method according to claim 1, wherein the high performance liquid chromatography apparatus is provided with a second autosampler, a liquid chromatography column, and a dual ternary gradient pump, wherein the dual ternary gradient pump comprises:
an extraction pump connected to the first autosampler for pumping mobile phase to the on-line solid phase extraction column; and
an analysis pump connected to the second autosampler for pumping mobile phase to the liquid chromatography column;
wherein the first and second auto-injectors are each preferably a six-way valve injector.
7. The on-line detection method of claim 1, wherein the tandem mass spectrometry device is a triple quadrupole tandem mass spectrometer equipped with an electrospray ion source, and the mass spectrometry detection conditions comprise: the air pressure of the air curtain is 10psi, the collision air pressure is 9psi, the spraying voltage of the ion source is 5500V, the temperature is 600 ℃, the atomizing air is 50psi, and the auxiliary atomizing air is 50 psi.
8. The on-line detection method according to claim 1, wherein a mixed internal standard substance is added to the environmental water sample; the online detection method further comprises the following steps:
step D: detecting a series of standard sample solutions with different standard adding concentrations by using the operations of the steps A to C, wherein the series of standard sample solutions comprise a plurality of organic phosphate esters and the mixed internal standard substances, and each internal standard substance in the mixed internal standard substances is respectively corresponding to at least one organic phosphate ester for quantification;
step E: carrying out regression analysis on the ratio of the mass spectrum peak area of each organic phosphate to the mass spectrum peak area of the corresponding internal standard substance and the additive standard concentration of the organic phosphate according to the detection result of the series of standard sample solutions to obtain a working curve of each organic phosphate;
step F: and determining the content of each organic phosphate in the environmental water sample according to the mass spectrum detection result of the environmental water sample and the working curve.
9. The on-line detection method according to claim 8, wherein the organic phosphate ester comprises trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, tributoxyethyl phosphate, tris (1-chloro-2-propyl) phosphate, tris (2-chloroethyl) phosphate, tris (1, 3-dichloro-2-propyl) phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, 2-ethylhexyl diphenyl phosphate, resorcinol tetraphenyl diphosphate, bisphenol A bis (diphenyl phosphate), 2, 2-bis (chloromethyl) trimethylenebis (bis (2-chloroethyl) phosphate), tris (2, 4-di-t-butylphenyl) phosphate, 3-isopropylphenyl diphenyl phosphate, bis (3-isopropylphenyl) phenyl phosphate, 3-tert-butylphenyl diphenyl phosphate, bis (3-tert-butylphenyl) phenyl phosphate.
10. The on-line detection method according to claim 9, wherein the mixed internal standard substance comprises: TCIPP-d18, TCEP-d12, TMP-d9, TEP-d15, TPrP-d21, TnBP-d27, TPHP-d15, TEHP-d51, TBOEP-d21 and TDCPP-d 15.
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| 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 |
| CN116399983A (en) * | 2023-06-09 | 2023-07-07 | 天津辰欣药物研究有限公司 | Method for detecting residual quantity of di-tert-butyl chloromethyl phosphate by using GC-MS method |
| CN116399983B (en) * | 2023-06-09 | 2023-08-15 | 天津辰欣药物研究有限公司 | Method for detecting residual quantity of di-tert-butyl chloromethyl phosphate by using GC-MS method |
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