CN113533554A - Method and device for measuring 4-branched-chain nonyl phenol and bisphenol A in water - Google Patents
Method and device for measuring 4-branched-chain nonyl phenol and bisphenol A in water Download PDFInfo
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Abstract
The embodiment of the invention discloses a method and a device for measuring 4-branched-chain nonyl phenol and bisphenol A in water. The method for measuring 4-branched nonyl phenol and bisphenol A in water quality comprises the following steps: performing solid phase extraction on a water sample to be detected to obtain a concentrated solution; performing derivatization treatment on the concentrated solution to obtain a sample to be detected; performing gas chromatography-mass spectrometry on a sample to be detected based on the calibration curve by adopting gas chromatography reference conditions and mass spectrometry reference conditions which are the same as those for drawing the calibration curve; and acquiring a mass concentration detection result of the target compound in the sample to be detected according to the mass concentration of the internal standard substance, the average relative response factor of the target compound, the response value of the quantitative ions of the target compound obtained by gas chromatography-mass spectrometry and the response value of the internal standard quantitative ions corresponding to the target compound. By applying the method, the measurement accuracy of the 4-branched-chain nonyl phenol and the bisphenol A can be improved.
Description
Technical Field
The invention relates to an environmental monitoring technology, in particular to a method and a device for measuring 4-branched-chain nonyl phenol and bisphenol A in water.
Background
Bisphenol A (BPA) is one of the most widely used industrial compounds in the world and is mainly used for producing various high polymer materials such as polycarbonate, epoxy resin, polysulfone resin, polyphenyl ether resin, unsaturated polyester resin and the like. BPA is an environmental Endocrine Disrupting substance (EDC) with estrogenic activity, which binds to intracellular estrogen receptors after entering the body and produces a pseudo-estrogen or antiestrogen effect through various mechanisms, thereby Disrupting the normal function of the Endocrine system and exerting multifaceted effects on the body.
Nonyl Phenol (NPs) is also one of the environmental endocrine disruptors, has estrogenic activity and can mimic estrogen behaviour, thereby disrupting normal functioning of the hormonal system and leading to potential reproductive problems. The estrogenic activity of the industrial nonyl phenol is 1/3168-1/54825 times that of 17 beta-estradiol (17 beta-estradiol, E2). As environmental hormones, NPs can compete for binding sites of estradiol receptors, bind to androgen receptors through a series of complex steps, and play a role in endocrine disruption, including synthesis, secretion, transportation, binding, biological effects and elimination of hormones, so that endocrine dysregulation is caused, normal regulation and control functions of immune, nervous and reproductive development systems and the like are changed, abnormal development of animal gonads, reproductive capacity reduction and immunity reduction are caused, meanwhile, the NPs can influence other multiple systems such as cardiovascular, digestive and nervous systems, and the estrogen effect of the NPs is a main factor of organism injury caused by the NPs.
The content of Nonyl Phenol (NPs) and bisphenol a in water directly affects the safety of water resource utilization, and thus, the content of bisphenol a and alkylphenol in water needs to be monitored.
At present, most of methods for extracting bisphenol A and nonyl phenol in water are concentrated on liquid-liquid extraction and solid-phase extraction, and in the analysis method, gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry are generally adopted for direct measurement, but in the analysis process, a test sample containing bisphenol A and nonyl phenol is easy to cause serious tailing of peak shape and serious reduction of column efficiency, and particularly when the test sample has impurity interference, the measurement precision is low.
Disclosure of Invention
In view of this, the embodiment of the present invention provides a method and an apparatus for measuring 4-branched nonyl phenol and bisphenol a in water, so as to improve the measurement accuracy of 4-branched nonyl phenol and bisphenol a.
The embodiment of the invention provides a method for measuring 4-branched-chain nonyl phenol and bisphenol A in water, which comprises the following steps:
performing solid phase extraction on a water sample to be detected to obtain a concentrated solution;
performing derivatization treatment on the concentrated solution to obtain a sample to be detected, wherein the derivatization treatment comprises the following steps: transferring the concentrated solution into a 1ml volumetric flask, washing a concentration tube or a concentration flask for containing the concentrated solution with a small amount of dichloromethane, and combining the washing solution into the volumetric flask; sequentially adding 100 mul of internal standard substance use solution and 100 mul of derivative reagent, and fixing the volume to 1ml by using dichloromethane to obtain a fixed volume solution; deriving the constant volume solution at room temperature for 1h to obtain a sample to be detected;
performing gas chromatography-mass spectrometry on a sample to be detected based on the calibration curve by adopting gas chromatography reference conditions and mass spectrometry reference conditions which are the same as those for drawing the calibration curve;
and acquiring a mass concentration detection result of the target compound in the sample to be detected according to the mass concentration of the internal standard substance, the average relative response factor of the target compound, the response value of the quantitative ions of the target compound obtained by gas chromatography-mass spectrometry and the response value of the internal standard quantitative ions corresponding to the target compound.
Preferably, the solid-phase extraction is performed on the water sample to be detected to obtain a concentrated solution, and the method comprises the following steps:
activating the solid phase extraction column by using 10ml of acetone, 10ml of dichloromethane, 10ml of methanol and 10ml of water in sequence;
weighing 500ml of water sample to be detected, adding 100 mul of substitute using solution, uniformly mixing, passing through the activated solid phase extraction column at the flow rate of 5.0ml/min, and blowing the solid phase extraction column to be nearly dry by using nitrogen after the sampling is finished;
eluting the solid phase extraction column with 5.0ml acetone and 15ml dichloromethane in sequence at a flow rate of 1.0ml/min, collecting the eluate, adding a small amount of n-hexane into the eluate, dehydrating with anhydrous sodium sulfate, and concentrating the dehydrated eluate to 0.5ml with a concentrating device.
Preferably, the packing of the solid phase extraction column adopts styrene/divinylbenzene polymer.
Preferably, the substitute use solution is bisphenol A-d16, and the mass concentration is rho-1 mu g/ml.
Preferably, the internal standard substance using liquid comprises: phenanthrene-d 10 and pyrene-d 10, rho 1 mug/ml; the derivatization reagent is N, O-bis (trimethylsilyl) trifluoroacetamide.
Preferably, the gas chromatography reference conditions are:
sample inlet temperature: no shunt sampling at 300 ℃;
temperature programming: keeping the column temperature at 50 deg.C for 2min, heating to 100 deg.C at 20 deg.C/min, heating to 200 deg.C at 10 deg.C/min, and heating to 300 deg.C at 20 deg.C/min for 5 min;
sample introduction amount: 1 mul;
the mass spectrum reference conditions are as follows:
transmission line temperature: 280 ℃;
temperature of the quadrupole rods: 150 ℃;
ion source temperature: 230 ℃;
ionization energy: 70 eV;
the mass range is as follows: 35-400 amu;
the data acquisition mode is as follows: and (4) scanning the ions.
Preferably, said plotting a calibration curve comprises:
respectively transferring predetermined amounts of standard stock solution and substitute stock solution, and placing in a series of 1ml volumetric flasks;
respectively adding 100 mul of internal standard substance using liquid and 100 mul of derivative reagent into each volumetric flask, and using dichloromethane to fix the volume to 1 ml;
preparing calibration series with target concentration of 5.0. mu.g/L, 20.0. mu.g/L, 40.0. mu.g/L, 80.0. mu.g/L, 200. mu.g/L, 500. mu.g/L and 1000. mu.g/L respectively, deriving for 1h at room temperature, sequentially measuring from low concentration to high concentration according to gas chromatography reference condition and mass spectrum reference condition, and recording retention time and quantitative ion response value of each target compound and corresponding internal standard in the calibration series.
Preferably, the performing gas chromatography-mass spectrometry on the sample to be tested based on the calibration curve by using the same gas chromatography reference condition and mass spectrometry reference condition as the calibration curve, includes:
taking a sample to be tested, and determining according to the gas chromatography reference condition and the mass spectrum reference condition which are the same as those for drawing a calibration curve;
in the measuring process, when the concentration of the sample to be measured exceeds the highest point of the calibration curve, a proper amount of the sample to be measured is diluted in the volumetric flask and then measured.
The embodiment of the invention provides a device for measuring 4-branched-chain nonyl phenol and bisphenol A in water, which comprises:
the solid phase extraction module is used for performing solid phase extraction on a water sample to be detected to obtain a concentrated solution;
the derivatization module is used for performing derivatization treatment on the concentrated solution to obtain a sample to be tested, and comprises: transferring the concentrated solution into a 1ml volumetric flask, washing a concentration tube or a concentration flask for containing the concentrated solution with a small amount of dichloromethane, and combining the washing solution into the volumetric flask; sequentially adding 100 mul of internal standard substance use solution and 100 mul of derivative reagent, and fixing the volume to 1ml by using dichloromethane to obtain a fixed volume solution; deriving the constant volume solution at room temperature for 1h to obtain a sample to be detected;
the analysis module is used for performing gas chromatography-mass spectrometry analysis on the sample to be detected based on the calibration curve by adopting the same gas chromatography reference condition and mass spectrometry reference condition as the calibration curve;
and the mass concentration determination module is used for obtaining a mass concentration detection result of the target compound in the sample to be detected according to the mass concentration of the internal standard substance, the average relative response factor of the target compound, the response value of the target compound quantitative ion obtained by performing gas chromatography-mass spectrometry and the response value of the internal standard quantitative ion corresponding to the target compound.
The embodiment of the present invention further provides a computer device, which includes a memory, a processor, and a computer program stored in the memory and capable of running on the processor, and the processor implements the steps of the above method when executing the computer program.
The embodiment of the invention provides a method and a device for measuring 4-branched-chain nonyl phenol and bisphenol A in water, which comprises the following steps: performing solid phase extraction on a water sample to be detected to obtain a concentrated solution; performing derivatization treatment on the concentrated solution to obtain a sample to be detected, wherein the derivatization treatment comprises the following steps: transferring the concentrated solution into a 1ml volumetric flask, washing a concentration tube or a concentration flask for containing the concentrated solution with a small amount of dichloromethane, and combining the washing solution into the volumetric flask; sequentially adding 100 mul of internal standard substance use solution and 100 mul of derivative reagent, and fixing the volume to 1ml by using dichloromethane to obtain a fixed volume solution; deriving the constant volume solution at room temperature for 1h to obtain a sample to be detected; performing gas chromatography-mass spectrometry on a sample to be detected based on the calibration curve by adopting gas chromatography reference conditions and mass spectrometry reference conditions which are the same as those for drawing the calibration curve; and acquiring a mass concentration detection result of the target compound in the sample to be detected according to the mass concentration of the internal standard substance, the average relative response factor of the target compound, the response value of the quantitative ions of the target compound obtained by gas chromatography-mass spectrometry and the response value of the internal standard quantitative ions corresponding to the target compound. Therefore, the sample to be tested is obtained after derivatization by solid-phase extraction, and due to the fact that the derivatized bisphenol A and alkylphenol have lower polarity, lower boiling point and better stability compared with non-derivatized bisphenol A and alkylphenol, the anti-interference capability during analysis is stronger, and the sample can be stored for a longer time for retesting, so that the accuracy of analysis and determination can be effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow diagram of the method of the present invention for determining 4-branched nonyl phenol and bisphenol A in an aqueous medium;
FIG. 2 is a schematic structural diagram of an apparatus for measuring 4-branched nonyl phenol and bisphenol A in water according to the present invention;
fig. 3 is a schematic structural diagram of a computer device 300 according to an embodiment of the present application.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment of the invention, N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) is sampled to perform derivatization treatment on the water quality to be tested (water sample to be tested), so that the polarity and boiling point of the derivatized bisphenol A and alkylphenol can be effectively reduced, the volatility and stability are enhanced, the anti-interference capability is stronger during content analysis, and the sample can be stored for a longer time to facilitate retesting of the sample, thereby ensuring the accuracy of analysis and determination, and having the advantages of high sensitivity, low detection limit and the like.
FIG. 1 is a schematic flow diagram of the method of the present invention for measuring 4-branched nonyl phenol and bisphenol A in an aqueous medium. As shown in fig. 1, the process includes:
in the embodiment of the present invention, as an optional embodiment, the performing solid phase extraction on a water sample to be detected to obtain a concentrated solution includes:
a11, sequentially activating a solid phase extraction column by using 10ml of acetone, 10ml of dichloromethane, 10ml of methanol and 10ml of water;
in the embodiment of the invention, as an optional embodiment, the filler of the solid phase extraction column adopts styrene/divinylbenzene polymer or equivalent type, specification: 6ml/1000 mg. During the activation process, it should be ensured that the surface of the packing in the pillars does not expose the liquid level.
In the embodiment of the invention, the dosage of the acetone, the dichloromethane, the methanol and the water can be correspondingly adjusted according to the specification of the solid phase extraction column.
A12, weighing 500ml of water sample to be detected, adding 100 mul of substitute use solution, uniformly mixing, passing through the activated solid phase extraction column at the flow rate of 5.0ml/min, and blowing the solid phase extraction column to be nearly dry by using nitrogen after the sampling is finished;
in the embodiment of the present invention, as an alternative example, the substitute use solution is bisphenol a-d16, and the mass concentration is ρ 1 μ g/ml.
And A13, sequentially eluting the solid phase extraction column with 5.0ml of acetone and 15ml of dichloromethane at the flow rate of 1.0ml/min, collecting the eluent, adding a small amount of n-hexane into the eluent, dehydrating by using anhydrous sodium sulfate, and concentrating the dehydrated eluent to 0.5ml by using a concentrating device.
In the embodiment of the present invention, the amount of n-hexane added may be set in advance.
102, performing derivatization treatment on the concentrated solution to obtain a sample to be detected;
in the embodiment of the present invention, as an optional embodiment, performing derivatization treatment on the concentrated solution to obtain a sample to be tested, includes:
b11, transferring the concentrated solution into a 1ml volumetric flask, washing a concentration tube or a concentration bottle for containing the concentrated solution with a small amount of dichloromethane, and combining the washing solution into the volumetric flask;
in the embodiment of the invention, the amount of dichloromethane for washing is only required to ensure that a concentration tube or a concentration bottle is washed cleanly.
B12, sequentially adding 100 mul of internal standard substance use solution and 100 mul of derivative reagent, and performing constant volume to 1ml by using dichloromethane to obtain constant volume solution;
in the embodiment of the present invention, as an optional embodiment, the internal standard substance using solution includes: phenanthrene-d 10 and pyrene-d 10, rho 1 mug/ml; the derivatizing reagent comprises: n, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA).
In the embodiment of the invention, the liquid for internal standard substance is used for quantification, and the derivatization reagent is used for derivatization of target substances (4-branched nonyl phenol and bisphenol A).
And B13, derivatizing the constant volume solution at room temperature for 1h to obtain a sample to be measured.
103, performing gas chromatography-mass spectrometry on the sample to be detected based on the calibration curve by adopting the same gas chromatography reference condition and mass spectrometry reference condition as the calibration curve;
in the examples of the present invention, gas chromatography reference conditions were:
sample inlet temperature: no shunt sampling at 300 ℃;
temperature programming: keeping the column temperature at 50 deg.C for 2min, heating to 100 deg.C at 20 deg.C/min, heating to 200 deg.C at 10 deg.C/min, and heating to 300 deg.C at 20 deg.C/min for 5 min;
sample introduction amount: 1 mul;
mass spectrum reference conditions:
transmission line temperature: 280 ℃;
temperature of the quadrupole rods: 150 ℃;
ion source temperature: 230 ℃;
ionization energy: 70 eV;
the mass range is as follows: 35-400 amu;
the data acquisition mode is as follows: ion Scanning (SIM).
In the examples of the present invention, reference conditions such as the order of appearance of peaks, retention time, and quantitative ion of the target compound are shown in Table 1. Solvent delay time: and 4 min.
TABLE 1
| Serial number | Name of Compound | CAS number | Quantitative ion | Qualitative ion | Corresponding internal standard |
| 1 | 4-branched nonyl phenol | 84852-15-3 | 207 | 221、193 | Pyrene-d 10 |
| 2 | Bisphenol A | 80-05-7 | 357 | 372 | Bisphenol A-d16 |
In the embodiment of the present invention, as an optional embodiment, the drawing a calibration curve includes:
d11, respectively removing predetermined amounts of the standard stock solution and the substitute stock solution, and placing the stock solutions in a series of 1ml volumetric flasks;
d12, respectively adding 100 μ l of internal standard substance using liquid and 100 μ l of derivative reagent into each volumetric flask, and fixing the volume to 1ml by using dichloromethane;
d13, preparing a calibration series with target concentration of 5.0. mu.g/L, 20.0. mu.g/L, 40.0. mu.g/L, 80.0. mu.g/L, 200. mu.g/L, 500. mu.g/L and 1000. mu.g/L respectively, deriving for 1h at room temperature, sequentially measuring from low concentration to high concentration according to gas chromatography reference conditions and mass spectrum reference conditions, and recording the retention time of each target compound and corresponding internal standard in the calibration series and the response value of quantitative ions.
In the embodiment of the invention, the gas chromatography-mass spectrometry analysis of the sample to be tested based on the calibration curve is carried out by adopting the gas chromatography reference condition and the mass spectrometry reference condition which are the same as those for drawing the calibration curve, and comprises the following steps:
taking a sample to be tested, and determining according to the gas chromatography reference condition and the mass spectrum reference condition which are the same as those for drawing a calibration curve;
in the measuring process, when the concentration of the sample to be measured exceeds the highest point of the calibration curve, a proper amount of the sample to be measured is diluted in the volumetric flask and then measured.
And 104, acquiring a mass concentration detection result of the target compound in the sample to be detected according to the mass concentration of the internal standard substance, the average relative response factor of the target compound, the response value of the target compound quantitative ion obtained by performing gas chromatography-mass spectrometry and the response value of the internal standard quantitative ion corresponding to the target compound.
In the embodiment of the invention, the mass concentration of the target compound in the sample to be detected is calculated according to the following formula:
in the formula:
ρxis the mass concentration of the target compound in the sample to be detected, mu g/L;
Axquantifying an ion response value for the target compound;
AISquantifying the response value of the ion for the internal standard corresponding to the target compound;
ρISthe mass concentration of the internal standard substance is shown as mu g/L;
d is the dilution factor.
In the embodiment of the invention, the sample to be tested is obtained after solid-phase extraction and derivatization, and the 4-branched-chain nonyl phenol and the bisphenol A in the sample to be tested are measured, so that the extraction efficiency is high, and the operation is simple; compared with non-derivatized bisphenol A and alkylphenol, the derivatized bisphenol A and alkylphenol have the advantages of lower polarity, lower boiling point and better stability, and because the non-derivatized bisphenol A and alkylphenol can cause serious tailing of peak shape and serious reduction of column efficiency in the analysis process, the analysis sensitivity can be seriously influenced when impurity interference exists in a sample to be detected. Although the derivatization method has relatively complex steps, the polarity and boiling point of the derivatized bisphenol A and alkylphenol are reduced, the volatility and stability are enhanced, the anti-interference capability is stronger during analysis, and the derivatized bisphenol A and alkylphenol can be stored for a longer time for retesting samples, so that the accuracy of analysis and determination can be ensured, the determination precision is high, the organic solvent dosage is small, and the method is environment-friendly.
The method of the present invention will be described in detail below with reference to a specific example, which is a gas chromatography-mass spectrometry detection of the content of 4-branched nonylphenol and bisphenol A in industrial wastewater.
Firstly, solid phase extraction:
the solid phase extraction column (the filler is styrene/divinylbenzene polymer or equivalent type) is activated by 10ml of acetone, 10ml of dichloromethane, 10ml of methanol and 10ml of water in sequence, and the surface of the filler in the small column is ensured not to expose the liquid level in the activation process. A500 ml water sample was accurately weighed, 100. mu.l of a substitute solution (bisphenol A-d16, p. mu.g/ml) was added thereto, the mixture was mixed, passed through a solid phase extraction column at a flow rate of 5.0ml/min, and after completion of the sample application, nitrogen gas was blown to near dryness. Eluting the small column with 5.0ml acetone and 15ml dichloromethane sequentially at flow rate of 1.0ml/min, collecting eluate, adding small amount of n-hexane into the eluate, dehydrating with anhydrous sodium sulfate, and concentrating to 0.5ml with a concentrating device.
II, derivation:
the concentrated sample was transferred to a 1ml volumetric flask, the tube or flask was washed with a small amount of dichloromethane and the washings were combined into the volumetric flask. 100. mu.l of an internal standard use solution (phenanthrene-d 10 and pyrene-d 10, ρ ═ 1. mu.g/ml) and 100. mu.l of a derivatization reagent (N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA)) were added in this order, and the volume was adjusted to 1ml with dichloromethane. And deriving for 1h at room temperature to obtain a sample to be detected.
Thirdly, gas chromatography-mass spectrometry detection:
and (3) taking a sample to be measured, measuring according to the same instrument analysis conditions as the calibration curve, when the concentration of the sample to be measured exceeds the highest point of the calibration curve, taking a proper amount of the sample to be measured, diluting the sample in the volumetric flask, then measuring, and recording the dilution times.
In the embodiment of the invention, the analysis conditions of the instrument comprise gas chromatography reference conditions and mass spectrum reference conditions, wherein,
gas chromatography reference conditions:
sample inlet temperature: and injecting samples at 300 ℃ without shunting. Temperature programming: keeping the column temperature at 50 deg.C for 2min, heating to 100 deg.C at 20 deg.C/min, heating to 200 deg.C at 10 deg.C/min, and heating to 300 deg.C at 20 deg.C/min for 5 min; sample introduction amount: 1 μ l.
Mass spectrum reference conditions:
transmission line temperature: 280 ℃. Temperature of the quadrupole rods: 150 ℃; ion source temperature: 230 ℃ to 230 ℃. Ionization energy: 70 eV. The mass range is as follows: 35-400 amu; the data acquisition mode is as follows: selective ion Scanning (SIM). Reference conditions for the order of appearance of peaks, retention time, and quantification of ions of the target compound are shown in Table 1. Solvent delay time: and 4 min.
Fourthly, drawing a calibration curve:
a certain amount of the standard stock solution and the substitute stock solution were removed and placed in a series of 1ml volumetric flasks, respectively. Then, 100. mu.l of the internal standard substance-use solution and 100. mu.l of the derivatizing agent were added thereto, and the volume was adjusted to 1ml with methylene chloride. Preparing target concentration calibration series of 5.0 mug/L, 20.0 mug/L, 40.0 mug/L, 80.0 mug/L, 200 mug/L, 500 mug/L and 1000 mug/L, deriving for 1h at room temperature, sequentially determining from low concentration to high concentration according to chromatographic reference conditions, and recording retention time and quantitative ion response values of the target compounds of the calibration series and corresponding internal standards.
And fifthly, measuring the sample to be measured:
and taking a sample to be tested, determining according to the same instrument analysis conditions as the calibration curve, and quantifying by retention time, fragment ion mass-to-charge ratio and different ion abundance ratios by an internal standard method.
Sixthly, calculating a result:
calculating the mass concentration of the target compound in the sample to be tested by using the following formula:
in the formula:
ρxis the mass concentration of the target compound in the sample to be detected, mu g/L;
Axquantifying an ion response value for the target compound;
AISquantifying the response value of the ion for the internal standard corresponding to the target compound;
ρISthe mass concentration of the internal standard substance is shown as mu g/L;
d is the dilution factor.
FIG. 2 is a schematic structural diagram of an apparatus for measuring 4-branched nonyl phenol and bisphenol A in water according to the present invention. As shown in fig. 2, the apparatus includes:
the solid-phase extraction module 201 is used for performing solid-phase extraction on a water sample to be detected to obtain a concentrated solution;
in this embodiment of the present invention, as an optional embodiment, the solid phase extraction module 201 includes:
an activation unit (not shown in the figure) for activating the solid phase extraction column with 10ml of acetone, 10ml of dichloromethane, 10ml of methanol and 10ml of water in this order;
in the embodiment of the invention, the filler of the solid phase extraction column adopts styrene/divinylbenzene polymer.
The extraction unit is used for measuring 500ml of water sample to be detected, adding 100 mul of substitute using solution, uniformly mixing, passing through the activated solid phase extraction column at the flow rate of 5.0ml/min, and blowing the solid phase extraction column to be nearly dry by using nitrogen after the sampling is finished;
in the examples of the present invention, the substitute use solution was bisphenol a-d16, and the mass concentration was ρ 1 μ g/ml.
And the concentration unit is used for eluting the solid phase extraction column by using 5.0ml of acetone and 15ml of dichloromethane in sequence at the flow rate of 1.0ml/min, collecting eluent, adding a small amount of normal hexane into the eluent, dehydrating by using anhydrous sodium sulfate, and concentrating the dehydrated eluent to 0.5ml by using a concentration device.
The derivatization module 202 is configured to perform derivatization on the concentrated solution to obtain a sample to be tested, and includes: transferring the concentrated solution into a 1ml volumetric flask, washing a concentration tube or a concentration flask for containing the concentrated solution with a small amount of dichloromethane, and combining the washing solution into the volumetric flask; sequentially adding 100 mul of internal standard substance use solution and 100 mul of derivative reagent, and fixing the volume to 1ml by using dichloromethane to obtain a fixed volume solution; deriving the constant volume solution at room temperature for 1h to obtain a sample to be detected;
in the embodiment of the invention, the internal standard substance using liquid comprises: phenanthrene-d 10 and pyrene-d 10, rho 1 mug/ml; the derivatization reagent is N, O-bis (trimethylsilyl) trifluoroacetamide.
The analysis module 203 is used for performing gas chromatography-mass spectrometry analysis on the sample to be detected based on the calibration curve by adopting the same gas chromatography reference condition and mass spectrometry reference condition as the calibration curve;
in the embodiment of the invention, the gas chromatography reference conditions are as follows:
sample inlet temperature: no shunt sampling at 300 ℃;
temperature programming: keeping the column temperature at 50 deg.C for 2min, heating to 100 deg.C at 20 deg.C/min, heating to 200 deg.C at 10 deg.C/min, and heating to 300 deg.C at 20 deg.C/min for 5 min;
sample introduction amount: 1 mul;
the mass spectrum reference conditions are as follows:
transmission line temperature: 280 ℃; temperature of the quadrupole rods: 150 ℃;
ion source temperature: 230 ℃; ionization energy: 70 eV;
the mass range is as follows: 35-400 amu;
the data acquisition mode is as follows: and (4) scanning the ions.
Drawing a calibration curve comprising:
respectively transferring predetermined amounts of standard stock solution and substitute stock solution, and placing in a series of 1ml volumetric flasks;
respectively adding 100 mul of internal standard substance using liquid and 100 mul of derivative reagent into each volumetric flask, and using dichloromethane to fix the volume to 1 ml;
preparing calibration series with target concentration of 5.0. mu.g/L, 20.0. mu.g/L, 40.0. mu.g/L, 80.0. mu.g/L, 200. mu.g/L, 500. mu.g/L and 1000. mu.g/L respectively, deriving for 1h at room temperature, sequentially measuring from low concentration to high concentration according to gas chromatography reference condition and mass spectrum reference condition, and recording retention time and quantitative ion response value of each target compound and corresponding internal standard in the calibration series.
In this embodiment of the present invention, as an optional embodiment, the analysis module 203 is specifically configured to:
taking a sample to be tested, and determining according to the gas chromatography reference condition and the mass spectrum reference condition which are the same as those for drawing a calibration curve;
in the measuring process, when the concentration of the sample to be measured exceeds the highest point of the calibration curve, a proper amount of the sample to be measured is diluted in the volumetric flask and then measured.
And the mass concentration determination module 204 is configured to obtain a mass concentration detection result of the target compound in the sample to be detected according to the mass concentration of the internal standard substance, the average relative response factor of the target compound, a response value of the target compound quantitative ion obtained by performing gas chromatography-mass spectrometry, and a response value of the internal standard quantitative ion corresponding to the target compound.
As shown in fig. 3, an embodiment of the present application provides a computer apparatus 300 for executing the method for measuring 4-branched nonyl phenol and bisphenol a in water in fig. 1, the apparatus includes a memory 301, a processor 302, and a computer program stored in the memory 301 and operable on the processor 302, wherein the processor 302 implements the steps of the method for measuring 4-branched nonyl phenol and bisphenol a in water when executing the computer program.
Specifically, the memory 301 and the processor 302 can be general-purpose memories and processors, and are not specifically limited herein, and the processor 302 can execute the above-described method for measuring 4-branched nonyl phenol and bisphenol a in water when executing the computer program stored in the memory 301.
Corresponding to the method for measuring 4-branched nonyl phenol and bisphenol A in water in FIG. 1, the embodiment of the application also provides a computer readable storage medium, on which a computer program is stored, which when executed by a processor performs the steps of the method for measuring 4-branched nonyl phenol and bisphenol A in water.
Specifically, the storage medium can be a general-purpose storage medium such as a portable magnetic disk, a hard disk, or the like, and the computer program on the storage medium can be executed to perform the above-described method for measuring 4-branched nonylphenol and bisphenol a in water.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for determining 4-branched nonyl phenol and bisphenol A in an aqueous medium, comprising:
performing solid phase extraction on a water sample to be detected to obtain a concentrated solution;
performing derivatization treatment on the concentrated solution to obtain a sample to be detected, wherein the derivatization treatment comprises the following steps: transferring the concentrated solution into a 1ml volumetric flask, washing a concentration tube or a concentration flask for containing the concentrated solution with a small amount of dichloromethane, and combining the washing solution into the volumetric flask; sequentially adding 100 mul of internal standard substance use solution and 100 mul of derivative reagent, and fixing the volume to 1ml by using dichloromethane to obtain a fixed volume solution; deriving the constant volume solution at room temperature for 1h to obtain a sample to be detected;
performing gas chromatography-mass spectrometry on a sample to be detected based on the calibration curve by adopting gas chromatography reference conditions and mass spectrometry reference conditions which are the same as those for drawing the calibration curve;
and acquiring a mass concentration detection result of the target compound in the sample to be detected according to the mass concentration of the internal standard substance, the average relative response factor of the target compound, the response value of the quantitative ions of the target compound obtained by gas chromatography-mass spectrometry and the response value of the internal standard quantitative ions corresponding to the target compound.
2. The method according to claim 1, wherein the step of performing solid phase extraction on the water sample to be detected to obtain a concentrated solution comprises:
activating the solid phase extraction column by using 10ml of acetone, 10ml of dichloromethane, 10ml of methanol and 10ml of water in sequence;
weighing 500ml of water sample to be detected, adding 100 mul of substitute using solution, uniformly mixing, passing through the activated solid phase extraction column at the flow rate of 5.0ml/min, and blowing the solid phase extraction column to be nearly dry by using nitrogen after the sampling is finished;
eluting the solid phase extraction column with 5.0ml acetone and 15ml dichloromethane in sequence at a flow rate of 1.0ml/min, collecting the eluate, adding a small amount of n-hexane into the eluate, dehydrating with anhydrous sodium sulfate, and concentrating the dehydrated eluate to 0.5ml with a concentrating device.
3. The method of claim 1, wherein the solid phase extraction column is packed with styrene/divinylbenzene polymer.
4. The method according to claim 1, wherein the substitute use solution is bisphenol a-d16, and the mass concentration is rho-1 μ g/ml.
5. The method according to claim 1, wherein the internal standard substance using solution comprises: phenanthrene-d 10 and pyrene-d 10, rho 1 mug/ml; the derivatization reagent is N, O-bis (trimethylsilyl) trifluoroacetamide.
6. The method according to any one of claims 1 to 5, wherein the gas chromatography reference conditions are:
sample inlet temperature: no shunt sampling at 300 ℃;
temperature programming: keeping the column temperature at 50 deg.C for 2min, heating to 100 deg.C at 20 deg.C/min, heating to 200 deg.C at 10 deg.C/min, and heating to 300 deg.C at 20 deg.C/min for 5 min;
sample introduction amount: 1 mul;
the mass spectrum reference conditions are as follows:
transmission line temperature: 280 ℃;
temperature of the quadrupole rods: 150 ℃;
ion source temperature: 230 ℃;
ionization energy: 70 eV;
the mass range is as follows: 35-400 amu;
the data acquisition mode is as follows: and (4) scanning the ions.
7. The method of any one of claims 1 to 6, wherein said plotting a calibration curve comprises:
respectively transferring predetermined amounts of standard stock solution and substitute stock solution, and placing in a series of 1ml volumetric flasks;
respectively adding 100 mul of internal standard substance using liquid and 100 mul of derivative reagent into each volumetric flask, and using dichloromethane to fix the volume to 1 ml;
preparing calibration series with target concentration of 5.0. mu.g/L, 20.0. mu.g/L, 40.0. mu.g/L, 80.0. mu.g/L, 200. mu.g/L, 500. mu.g/L and 1000. mu.g/L respectively, deriving for 1h at room temperature, sequentially measuring from low concentration to high concentration according to gas chromatography reference condition and mass spectrum reference condition, and recording retention time and quantitative ion response value of each target compound and corresponding internal standard in the calibration series.
8. The method according to any one of claims 1 to 6, wherein the performing of the GC-MS analysis on the sample to be tested based on the calibration curve using the same GC reference condition and MS reference condition as the calibration curve comprises:
taking a sample to be tested, and determining according to the gas chromatography reference condition and the mass spectrum reference condition which are the same as those for drawing a calibration curve;
in the measuring process, when the concentration of the sample to be measured exceeds the highest point of the calibration curve, a proper amount of the sample to be measured is diluted in the volumetric flask and then measured.
9. An apparatus for measuring 4-branched nonyl phenol and bisphenol A in water, comprising:
the solid phase extraction module is used for performing solid phase extraction on a water sample to be detected to obtain a concentrated solution;
the derivatization module is used for performing derivatization treatment on the concentrated solution to obtain a sample to be tested, and comprises: transferring the concentrated solution into a 1ml volumetric flask, washing a concentration tube or a concentration flask for containing the concentrated solution with a small amount of dichloromethane, and combining the washing solution into the volumetric flask; sequentially adding 100 mul of internal standard substance use solution and 100 mul of derivative reagent, and fixing the volume to 1ml by using dichloromethane to obtain a fixed volume solution; deriving the constant volume solution at room temperature for 1h to obtain a sample to be detected;
the analysis module is used for performing gas chromatography-mass spectrometry analysis on the sample to be detected based on the calibration curve by adopting the same gas chromatography reference condition and mass spectrometry reference condition as the calibration curve;
and the mass concentration determination module is used for obtaining a mass concentration detection result of the target compound in the sample to be detected according to the mass concentration of the internal standard substance, the average relative response factor of the target compound, the response value of the target compound quantitative ion obtained by performing gas chromatography-mass spectrometry and the response value of the internal standard quantitative ion corresponding to the target compound.
10. A computer device, comprising: a processor, a memory and a bus, the memory storing machine readable instructions executable by the processor, the processor and the memory communicating over the bus when a computer device is run, the machine readable instructions when executed by the processor performing the steps of the method of determining 4-branched nonyl phenol and bisphenol a in water quality as recited in claims 1 to 8.
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