CN112266040B - Detection method for polybrominated diphenyl ethers in water body based on TpBD material solid phase microextraction - Google Patents
Detection method for polybrominated diphenyl ethers in water body based on TpBD material solid phase microextraction Download PDFInfo
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- UPNBETHEXPIWQX-UHFFFAOYSA-N 4-bromophenyl 2,4-dibromophenyl ether Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1Br UPNBETHEXPIWQX-UHFFFAOYSA-N 0.000 claims description 8
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
本发明提供了一种基于TpBD材料固相微萃取水体中多溴联苯醚的检测方法，包括以下步骤：S1：将Tp、BD分别溶解在混合溶剂中，高温处理得到橙红色沉淀，将橙红色沉淀进行索氏提取，得到TpBD粉末；S2：将处理后的钢丝插入处理溶液中，将钢丝一端在TpBD粉末中旋转，处理后得到TpBD涂覆的SPME材料；S3：将S2制备得到的TpBD涂覆的SPME材料置于水样中萃取，取出TpBD涂覆的SPME材料解吸，利用GC‑ECD检测解吸的气体。TpBD材料比表面积大，热稳定性好，结晶稳定，具有较高的富集效率，本发明将该材料制成固相微萃取涂层，用于检测水体中的多溴联苯醚，获得了比PDMS、PDMS/DVB商用针更好的萃取效果。
The present invention provides a method for detecting polybrominated diphenyl ethers in water based on solid-phase micro-extraction of TpBD materials, comprising the following steps: S1: dissolving Tp and BD in a mixed solvent respectively, treating at high temperature to obtain orange-red precipitate, and carrying out Soxhlet extraction to obtain TpBD powder; S2: Insert the treated steel wire into the treatment solution, rotate one end of the steel wire in the TpBD powder, and obtain the TpBD-coated SPME material after treatment; S3: The TpBD-coated material prepared in S2 The SPME material was extracted in a water sample, the TpBD-coated SPME material was taken out for desorption, and the desorbed gas was detected by GC‑ECD. The TpBD material has large specific surface area, good thermal stability, stable crystallization and high enrichment efficiency. In the present invention, the material is made into a solid-phase microextraction coating, which is used to detect polybrominated diphenyl ethers in water. PDMS/DVB commercial needles have better extraction results.
Description
Technical Field
The invention belongs to the technical field of material extraction, and particularly relates to a detection method for polybrominated diphenyl ethers in a solid-phase micro-extraction water body based on a TpBD material.
Background
Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants and are widely applied to materials such as building materials, electronic equipment, decoration materials, motor vehicles, textiles and the like. Since its addition is purely physical, its molecules are easily released into the environmental medium, exposing the human body. PBDEs have a major health risk to humans and can cause endocrine disrupting effects, neurodevelopmental toxicity, genotoxicity, tumors, and possibly carcinogenesis. The presence of PBDEs has been detected in water, sediments, fish, human blood, breast milk and other environmental media and biomass. The detection of PBDEs can be realized by gas chromatography, gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, high performance liquid chromatography and the like, wherein the gas chromatography is most commonly used at present, and the detection limit of an ECD detector is generally higher than that of an FID detector.
For the detection of PBDEs, the water body sample can adopt the following pretreatment technologies: liquid-liquid extraction (LLE), Soxhlet extraction, solid-phase extraction (SPE), solid-phase microextraction (SPME), and the like. Wherein, the liquid-liquid extraction method requires larger amount of samples and solvents and has poorer repeatability; the Soxhlet extraction method has long extraction time and large solvent consumption; the solid phase extraction method needs less solvent, but still needs more steps, and the enrichment efficiency of the sample is low.
The defects existing in the prior art are as follows: pretreatment: the liquid-liquid extraction method requires large amounts of samples and solvents; the Soxhlet extraction method has long extraction time and large solvent consumption; the solid phase extraction method needs less solvent, but still needs more steps, and the enrichment efficiency of the sample is low. ② the selective enrichment efficiency of commercial needle materials for PBDEs is relatively low. And thirdly, the detection limit of the existing method is not low enough, and PBDEs with very low concentration in the actual environment cannot be detected.
Compared with the prior art, the SPME enrichment method has high enrichment efficiency, integrates extraction, concentration, desorption and sample injection, greatly simplifies the pretreatment process of the sample, improves the repeatability, selectivity and sensitivity of environmental analysis, and is a method for analyzing the PBDEs with great prospect, and the stationary phase coating is the core of the solid phase microextraction method.
Disclosure of Invention
Aiming at the problems, the invention provides a detection method for polybrominated diphenyl ethers in a solid-phase micro-extraction water body based on a TpBD material.
The technical scheme of the invention is as follows: a detection method for polybrominated diphenyl ethers in a solid phase microextraction water body based on TpBD materials mainly comprises the following steps:
s1: hydrothermal synthesis of TpBD
Respectively mixing 4.5mL of 1, 4-dioxane and 4.5mL of mesitylene to obtain a mixed solvent A, preparing a mixed solvent B according to the same proportion, dissolving 42mg of Tp in the mixed solvent A to obtain a mixed solution A, dissolving 55.2mg of BD in the mixed solvent B to obtain a mixed solution B, uniformly mixing the mixed solution A and the mixed solution B to obtain a mixed solution C,
dropwise adding 1mL of catalyst into the mixed solution C, uniformly stirring, transferring the mixed solution C into an autoclave, raising the temperature in the autoclave to 70-80 ℃, preheating for 3-5h, then raising the temperature in the autoclave to 110-120 ℃, keeping the temperature, standing for 70-75h to obtain an orange-red precipitate, performing Soxhlet extraction on the orange-red precipitate to remove impurities on the surface and among pores of the orange-red precipitate, and performing vacuum drying on the extracted powder at 60 ℃ for 10-12h to obtain TpBD powder;
s2: preparation of TpBD-coated SPME Material
Placing a steel wire in an ultrasonic cleaning container, adding 40% hydrofluoric acid with concentration over the steel wire into the ultrasonic cleaning container, performing ultrasonic treatment for 3-5min, taking out the steel wire, washing with deionized water, placing in the cleaned ultrasonic cleaning container, adding methanol with concentration over the steel wire into the ultrasonic cleaning container, performing ultrasonic treatment for 5-8min, taking out the steel wire, placing in the cleaned ultrasonic cleaning container, adding deionized water with concentration over the steel wire into the ultrasonic cleaning container, performing ultrasonic treatment for 3-5min to obtain a treated steel wire,
dissolving 0.5g of silicone adhesive in 1mL of toluene to obtain a treatment solution, inserting the treated steel wire into the treatment solution, taking out after inserting for 5S, wiping one end of the steel wire inserted into the treatment solution with filter paper, repeating the insertion-wiping step for 2-3 times, rotating one end of the steel wire inserted into the treatment solution in the TpBD powder obtained in S1 until the treated end of the steel wire is uniformly coated with the TpBD powder, drying the steel wire at 110 ℃ for 20-30min, and then carrying out aging treatment at 300 ℃ for 60min at 280 ℃ to obtain the SPME material coated with the TpBD;
s3: detection of polybrominated diphenyl ethers in water
And (2) adding 125 mu L of PBDEs mixed standard solution with the concentration of 125ppb into 30mL of deionized water to obtain a 50ppt water sample, extracting the TpBD coated SPME material prepared in the step (2) in the water sample for 1h at the temperature of 30 ℃, taking out the TpBD coated SPME material, desorbing at the temperature of 280 ℃ for 4min, and detecting desorbed gas by using GC-ECD.
Further, in S1, the catalyst is 9M acetic acid solution, and the catalyst can promote the rate of orange-red precipitate formation of the mixed solution C.
Further, in S1, the specific step of performing soxhlet extraction on the orange-red precipitate is: and filling the orange-red precipitate into a filter paper bag, putting the filter paper bag into an extraction bottle, adding acetone without the filter paper bag into the extraction bottle, performing constant-temperature water bath extraction at 68-70 ℃, wherein the extraction time is 22-26h, taking out the filter paper bag after the extraction is finished, placing the filter paper bag in a ventilation position, volatilizing residual acetone to obtain extraction powder, and removing impurities on the surface and among pores of the orange-red precipitate to avoid the impurities from influencing the subsequent extraction detection.
Further, in S2, the steel wire is a 0.15mm 304 stainless steel wire, and the 304 stainless steel wire has good workability and high toughness.
Further, in S2, the specific steps of dissolving 0.5g of silicone gum in 1mL of toluene to obtain a treatment solution are: adding 1ml of toluene into a test tube, then weighing 0.5g of silicone adhesive, adding the test tube into the test tube, oscillating until the silicone adhesive is dissolved, placing the test tube into an ultrasonic generator, and starting the ultrasonic generator to carry out ultrasonic fluxing on the silicone adhesive and the toluene in the test tube with the power of 2.3-2.5W/cm2 so as to quickly and uniformly dissolve the silicone adhesive in the toluene.
Furthermore, in S3, the PBDEs mixed standard solution with the concentration of 125ppb is prepared from BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-138 in equal proportion.
Further, in S3, the detection conditions for the GC-ECD detection are: keeping at 80 deg.C for 1 min; heating to 280 deg.C at 20 deg.C/min, and maintaining for 5 min; heating to 300 deg.C at 2 deg.C/min, maintaining for 2min, and measuring at 310 deg.C.
The invention has the beneficial effects that: the detection method for polybrominated diphenyl ethers in water body based on TpBD material solid phase microextraction has the following advantages:
1. the PBDEs in the water body are efficiently, quickly and sensitively detected;
2. the enrichment efficiency is high, the extraction, concentration, desorption and sample injection are integrated, the pretreatment process of the sample is greatly simplified, and the repeatability, selectivity and sensitivity of environmental analysis are improved;
the COF coating is stable and durable, and has a good in-situ application prospect;
the TpBD material has the advantages of large specific surface area, good thermal stability, stable crystallization and higher enrichment efficiency, and the material is prepared into a solid-phase microextraction coating for detecting polybrominated diphenyl ethers (BDE-28, BDE-47, BDE-100, BDE-99, BDE-153 and BDE-138) in a water body, so that the extraction effect better than that of PDMS and PDMS/DVB materials is obtained.
Drawings
FIG. 1 is a 30 μm micrograph of one end of a steel wire treated with a treating solution inserted in S2 in example 3 of the present invention;
FIGS. 2, 3 and 4 are micrographs of a TpBD coated SPME material at S2 of example 3 of the present invention at 300 μm, 30 μm and 5 μm, respectively;
FIG. 5 is a graph showing the results of GC-ECD detection of BEDs of different structures of S3 in example 3 of the present invention;
FIG. 6 is a graph comparing the detection effects of TpBD, PDMS and PDMS/DVB in the experimental examples of the present invention.
Detailed Description
For the convenience of understanding the technical scheme of the present invention, the present invention is further explained with reference to the accompanying fig. 1 to 6 and the specific embodiments, which are not to be construed as limiting the scope of the present invention.
Example 1: a detection method for polybrominated diphenyl ethers in a solid phase microextraction water body based on TpBD materials mainly comprises the following steps:
s1: hydrothermal synthesis of TpBD
Respectively mixing 4.5mL of 1, 4-dioxane and 4.5mL of mesitylene to obtain a mixed solvent A, preparing a mixed solvent B according to the same proportion, dissolving 42mg of Tp in the mixed solvent A to obtain a mixed solution A, dissolving 55.2mg of BD in the mixed solvent B to obtain a mixed solution B, uniformly mixing the mixed solution A and the mixed solution B to obtain a mixed solution C,
dropwise adding 1mL of catalyst into the mixed solution C, uniformly stirring, wherein the catalyst is 9M acetic acid aqueous solution, transferring the mixed solution C into an autoclave, raising the temperature in the autoclave to 70 ℃, preheating for 3h, then raising the temperature in the autoclave to 110 ℃, keeping the temperature, standing for 70h to obtain orange-red precipitate, performing Soxhlet extraction on the orange-red precipitate to remove impurities on the surface and among pores of the orange-red precipitate, and performing vacuum drying on the extracted powder at 60 ℃ for 10h to obtain TpBD powder,
the specific steps of performing Soxhlet extraction on the orange-red precipitate are as follows: putting the orange-red precipitate into a filter paper bag, putting the filter paper bag into an extraction bottle, adding acetone without the filter paper bag into the extraction bottle, performing constant-temperature water bath extraction at 68 ℃ for 22h, taking out the filter paper bag after the extraction is finished, putting the filter paper bag in a ventilation position, and volatilizing residual acetone to obtain extracted powder;
s2: preparation of TpBD-coated SPME Material
Placing a steel wire into an ultrasonic cleaning container, wherein the steel wire is a 0.15mm 304 stainless steel wire, adding 40% hydrofluoric acid with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 3min, taking out the steel wire, washing with deionized water, placing into the cleaned ultrasonic cleaning container after washing, adding methanol with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 5min, taking out the steel wire, placing into the cleaned ultrasonic cleaning container, adding deionized water with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 3min to obtain a treated steel wire,
dissolving 0.5g of silicone adhesive in 1mL of toluene to obtain a treatment solution, inserting the treated steel wire into the treatment solution, taking out after inserting for 5S, wiping one end of the steel wire inserted into the treatment solution with filter paper, repeating the insertion-wiping step for 2 times, rotating one end of the steel wire inserted into the treatment solution in the TpBD powder obtained in S1 until the treated end of the steel wire is uniformly coated with the TpBD powder, drying the steel wire at 100 ℃ for 20min, then performing aging treatment at 280 ℃ for 60min to obtain the TpBD coated SPME material,
the specific steps for dissolving 0.5g of silicone gum in 1mL of toluene to obtain a treatment solution are: adding 1ml toluene into test tube, weighing 0.5g silicone adhesive, adding into the test tube, oscillating until the silicone adhesive is dissolved, placing the test tube in ultrasonic generator, and turning on the ultrasonic generator to obtain the final product with 2.3W/cm2The power of the ultrasonic assisting device is used for carrying out ultrasonic assisting dissolution on the silicone adhesive and the methylbenzene in the test tube, so that the silicone adhesive is quickly and uniformly dissolved in the methylbenzene;
s3: detection of polybrominated diphenyl ethers in water
Preparing a PBDEs mixed standard solution with the concentration of 125ppb from BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-138 in equal proportion, adding 125 mu L of the PBDEs mixed standard solution with the concentration of 125ppb into 30mL of deionized water to obtain a water sample of 50ppt, placing the SPME material coated with TpBD prepared by S2 into the water sample at the temperature of 30 ℃ for extraction for 1h, taking out the SPME material coated with TpBD, desorbing the material at 280 ℃ for 4min, and detecting the desorbed gas by using GC-ECD, wherein the detection conditions of the GC-ECD detection are as follows: keeping at 80 deg.C for 1 min; heating to 280 deg.C at 20 deg.C/min, and maintaining for 5 min; heating to 300 deg.C at 2 deg.C/min, maintaining for 2min, and measuring at 310 deg.C.
Example 2: a detection method for polybrominated diphenyl ethers in a solid phase microextraction water body based on TpBD materials mainly comprises the following steps:
s1: hydrothermal synthesis of TpBD
Respectively mixing 4.5mL of 1, 4-dioxane and 4.5mL of mesitylene to obtain a mixed solvent A, preparing a mixed solvent B according to the same proportion, dissolving 42mg of Tp in the mixed solvent A to obtain a mixed solution A, dissolving 55.2mg of BD in the mixed solvent B to obtain a mixed solution B, uniformly mixing the mixed solution A and the mixed solution B to obtain a mixed solution C,
dropwise adding 1mL of catalyst into the mixed solution C, uniformly stirring, wherein the catalyst is 9M acetic acid aqueous solution, transferring the mixed solution C into an autoclave, raising the temperature in the autoclave to 75 ℃, preheating for 4h, then raising the temperature in the autoclave to 115 ℃, keeping the temperature, standing for 73h to obtain orange-red precipitate, performing Soxhlet extraction on the orange-red precipitate to remove impurities on the surface and among pores of the orange-red precipitate, and performing vacuum drying on the extracted powder at 60 ℃ for 11h to obtain TpBD powder,
the specific steps of performing Soxhlet extraction on the orange-red precipitate are as follows: putting the orange-red precipitate into a filter paper bag, putting the filter paper bag into an extraction bottle, adding acetone without the filter paper bag into the extraction bottle, performing constant-temperature water bath extraction at 69 ℃ for 24 hours, taking out the filter paper bag after the extraction is finished, putting the filter paper bag in a ventilation position, and volatilizing residual acetone to obtain extracted powder;
s2: preparation of TpBD-coated SPME Material
Placing a steel wire into an ultrasonic cleaning container, wherein the steel wire is a 0.15mm 304 stainless steel wire, adding 40% hydrofluoric acid with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 4min, taking out the steel wire, washing with deionized water, placing into the cleaned ultrasonic cleaning container after washing, adding methanol with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 6min, taking out the steel wire, placing into the cleaned ultrasonic cleaning container, adding deionized water with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 4min to obtain a treated steel wire,
dissolving 0.5g of silicone adhesive in 1mL of toluene to obtain a treatment solution, inserting the treated steel wire into the treatment solution, taking out after inserting for 5S, wiping one end of the steel wire inserted into the treatment solution with filter paper, repeating the insertion-wiping step for 3 times, rotating one end of the steel wire inserted into the treatment solution in the TpBD powder obtained in S1 until the treated end of the steel wire is uniformly coated with the TpBD powder, drying the steel wire at 105 ℃ for 25min, then performing aging treatment at 290 ℃ for 60min to obtain the TpBD coated SPME material,
the specific steps for dissolving 0.5g of silicone gum in 1mL of toluene to obtain a treatment solution are: adding 1ml toluene into test tube, weighing 0.5g silicone adhesive, adding into the test tube, oscillating until the silicone adhesive is dissolved, placing the test tube in ultrasonic generator, and turning on the ultrasonic generator to obtain the final product with 2.4W/cm2The power of the ultrasonic assisting device is used for carrying out ultrasonic assisting dissolution on the silicone adhesive and the methylbenzene in the test tube, so that the silicone adhesive is quickly and uniformly dissolved in the methylbenzene;
s3: detection of polybrominated diphenyl ethers in water
Preparing a PBDEs mixed standard solution with the concentration of 125ppb from BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-138 in equal proportion, adding 125 mu L of the PBDEs mixed standard solution with the concentration of 125ppb into 30mL of deionized water to obtain a water sample of 50ppt, placing the SPME material coated with TpBD prepared by S2 into the water sample at the temperature of 30 ℃ for extraction for 1h, taking out the SPME material coated with TpBD, desorbing the material at 280 ℃ for 4min, and detecting the desorbed gas by using GC-ECD, wherein the detection conditions of the GC-ECD detection are as follows: keeping at 80 deg.C for 1 min; heating to 280 deg.C at 20 deg.C/min, and maintaining for 5 min; heating to 300 deg.C at 2 deg.C/min, maintaining for 2min, and measuring at 310 deg.C.
Example 3: a detection method for polybrominated diphenyl ethers in a solid phase microextraction water body based on TpBD materials mainly comprises the following steps:
s1: hydrothermal synthesis of TpBD
Respectively mixing 4.5mL of 1, 4-dioxane and 4.5mL of mesitylene to obtain a mixed solvent A, preparing a mixed solvent B according to the same proportion, dissolving 42mg of Tp in the mixed solvent A to obtain a mixed solution A, dissolving 55.2mg of BD in the mixed solvent B to obtain a mixed solution B, uniformly mixing the mixed solution A and the mixed solution B to obtain a mixed solution C,
dropwise adding 1mL of catalyst into the mixed solution C, uniformly stirring, wherein the catalyst is 9M acetic acid aqueous solution, transferring the mixed solution C into an autoclave, raising the temperature in the autoclave to 80 ℃, preheating for 5h, then raising the temperature in the autoclave to 120 ℃, keeping the temperature, standing for 75h to obtain orange-red precipitate, performing Soxhlet extraction on the orange-red precipitate to remove impurities on the surface and among pores of the orange-red precipitate, and performing vacuum drying on the extracted powder at 60 ℃ for 12h to obtain TpBD powder,
the specific steps of performing Soxhlet extraction on the orange-red precipitate are as follows: putting the orange-red precipitate into a filter paper bag, putting the filter paper bag into an extraction bottle, adding acetone without the filter paper bag into the extraction bottle, performing constant-temperature water bath extraction at 70 ℃ for 26h, taking out the filter paper bag after extraction is finished, putting the filter paper bag in a ventilation position, and volatilizing residual acetone to obtain extracted powder;
s2: preparation of TpBD-coated SPME Material
Placing a steel wire into an ultrasonic cleaning container, wherein the steel wire is a 0.15mm 304 stainless steel wire, adding 40% hydrofluoric acid with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 5min, taking out the steel wire, washing with deionized water, placing into the cleaned ultrasonic cleaning container after washing, adding methanol with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 8min, taking out the steel wire, placing into the cleaned ultrasonic cleaning container, adding deionized water with concentration over the steel wire into the ultrasonic cleaning container, carrying out ultrasonic treatment for 5min to obtain a treated steel wire,
dissolving 0.5g of silicone gum in 1mL of toluene to obtain a treatment solution, inserting the treated steel wire into the treatment solution, inserting for 5S, taking out, wiping one end of the steel wire inserted into the treatment solution with filter paper, repeating the insertion-wiping step 3 times, wherein a 30 μm micrograph of one end of the steel wire treated with the insertion treatment solution is shown in FIG. 1, rotating one end of the steel wire treated with the insertion treatment solution in the TpBD powder obtained in S1 until the treated end of the steel wire is uniformly coated with the TpBD powder, drying the steel wire at 110 ℃ for 30min, then aging at 300 ℃ for 60min to obtain a TpBD coated SPME material, wherein 300 μm, 30 μm and 5 μm micrographs of the TpBD coated SPME material are shown in FIGS. 2, 3 and 4,
the specific steps for dissolving 0.5g of silicone gum in 1mL of toluene to obtain a treatment solution are: adding 1ml toluene into test tube, weighing 0.5g silicone adhesive, adding into the test tube, oscillating until the silicone adhesive is dissolved, placing the test tube in ultrasonic generator, and turning on the ultrasonic generator to obtain the final product with 2.5W/cm2The power of the ultrasonic assisting device is used for carrying out ultrasonic assisting dissolution on the silicone adhesive and the methylbenzene in the test tube, so that the silicone adhesive is quickly and uniformly dissolved in the methylbenzene;
s3: detection of polybrominated diphenyl ethers in water
Preparing a PBDEs mixed standard solution with the concentration of 125ppb from BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-138 in equal proportion, adding 125 mu L of the PBDEs mixed standard solution with the concentration of 125ppb into 30mL of deionized water to obtain a water sample of 50ppt, placing the SPME material coated with TpBD prepared by S2 into the water sample at the temperature of 30 ℃ for extraction for 1h, taking out the SPME material coated with TpBD, desorbing the material at 280 ℃ for 4min, and detecting the desorbed gas by using GC-ECD, wherein the detection conditions of the GC-ECD detection are as follows: keeping at 80 deg.C for 1 min; heating to 280 deg.C at 20 deg.C/min, and maintaining for 5 min; the temperature is raised to 300 ℃ at the rate of 2 ℃/min and kept for 2min, the temperature of the detector is 310 ℃, and the detection result is shown in figure 5.
Experimental example: comparative example 3 extraction of TpBD coated SPME Material with PDMS, PDMS/DVB Material
Experimental materials: in example 3, PBDEs mixed standard solution with the concentration of 125ppb is prepared from BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-138 in equal proportion; the TpBD coated SPME material was obtained in example 3; a PDMS material; PDMS/DVB material.
The experimental conditions are as follows: the mixed standard solutions of PBDEs prepared from BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-138 in example 3 in equal proportions and having a concentration of 125ppb were divided into 3 parts on average, and the TpBD-coated SPME material obtained in example 3 was extracted with PDMS and PDMS/DVB respectively, and the extraction results are shown in FIG. 6.
And (4) conclusion: as can be seen from the comparison of fig. 6, the extraction effect of the SPME material coated with TpBD obtained in example 3 is significantly better than that of the PDMS material and the PDMS/DVB material.
Claims (2)
1. A detection method for polybrominated diphenyl ethers in a solid-phase microextraction water body based on TpBD materials is characterized by mainly comprising the following steps:
s1: hydrothermal synthesis of TpBD
Respectively mixing 4.5mL of 1, 4-dioxane and 4.5mL of mesitylene to obtain a mixed solvent A, preparing a mixed solvent B according to the same proportion, dissolving 42mg of Tp in the mixed solvent A to obtain a mixed solution A, dissolving 55.2mg of BD in the mixed solvent B to obtain a mixed solution B, uniformly mixing the mixed solution A and the mixed solution B to obtain a mixed solution C,
dropwise adding 1mL of catalyst into the mixed solution C, uniformly stirring, transferring the mixed solution C into an autoclave, raising the temperature in the autoclave to 70-80 ℃, preheating for 3-5h, then raising the temperature in the autoclave to 110-120 ℃, keeping the temperature, standing for 70-75h to obtain an orange-red precipitate, performing Soxhlet extraction on the orange-red precipitate to remove impurities on the surface and among pores of the orange-red precipitate, and performing vacuum drying on the extracted powder at 60 ℃ for 10-12h to obtain TpBD powder;
s2: preparation of TpBD-coated SPME Material
Placing a steel wire in an ultrasonic cleaning container, adding 40% hydrofluoric acid with concentration over the steel wire into the ultrasonic cleaning container, performing ultrasonic treatment for 3-5min, taking out the steel wire, washing with deionized water, placing in the cleaned ultrasonic cleaning container, adding methanol with concentration over the steel wire into the ultrasonic cleaning container, performing ultrasonic treatment for 5-8min, taking out the steel wire, placing in the cleaned ultrasonic cleaning container, adding deionized water with concentration over the steel wire into the ultrasonic cleaning container, performing ultrasonic treatment for 3-5min to obtain a treated steel wire,
dissolving 0.5g of silicone adhesive in 1mL of toluene to obtain a treatment solution, inserting the treated steel wire into the treatment solution, taking out after inserting for 5S, wiping one end of the steel wire inserted into the treatment solution with filter paper, repeating the insertion-wiping step for 2-3 times, rotating one end of the steel wire inserted into the treatment solution in the TpBD powder obtained in S1 until the treated end of the steel wire is uniformly coated with the TpBD powder, drying the steel wire at 110 ℃ for 20-30min, and then carrying out aging treatment at 300 ℃ for 60min at 280 ℃ to obtain the SPME material coated with the TpBD;
s3: detection of polybrominated diphenyl ethers in water
Adding 125 mu L of PBDEs mixed standard solution with the concentration of 125ppb into 30mL of deionized water to obtain a 50ppt water sample, placing the TpBD coated SPME material prepared in S2 into the water sample at the temperature of 30 ℃ for extraction for 1h, taking out the TpBD coated SPME material, desorbing at 280 ℃ for 4min, and detecting desorbed gas by using GC-ECD;
in the S1, the catalyst is 9M acetic acid aqueous solution;
in the step S1, the specific steps of performing soxhlet extraction on the orange-red precipitate are as follows: putting the orange-red precipitate into a filter paper bag, putting the filter paper bag into an extraction bottle, adding acetone without the filter paper bag into the extraction bottle, performing constant-temperature water bath extraction at 68-70 ℃, wherein the extraction time is 22-26h, taking out the filter paper bag after the extraction is finished, and placing the filter paper bag in a ventilation place to volatilize residual acetone to obtain extracted powder;
in the step S2, the steel wire is a 0.15mm 304 stainless steel wire;
in the S3, the PBDEs mixed standard solution with the concentration of 125ppb is prepared from BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-138 in equal proportion;
in S2, the specific steps of dissolving 0.5g of silicone gum in 1mL of toluene to obtain a treatment solution are: adding 1ml of toluene into a test tube, then weighing 0.5g of silicone adhesive, adding the test tube into the test tube, oscillating until the silicone adhesive is dissolved, placing the test tube into an ultrasonic generator, and starting the ultrasonic generator to carry out ultrasonic fluxing on the silicone adhesive and the toluene in the test tube with the power of 2.3-2.5W/cm2 so as to quickly and uniformly dissolve the silicone adhesive in the toluene.
2. The method for detecting polybrominated diphenyl ethers in a solid-phase microextraction water body based on the TpBD material according to claim 1, wherein in S3, the detection conditions of the GC-ECD detection are as follows: keeping at 80 deg.C for 1 min; heating to 280 deg.C at 20 deg.C/min, and maintaining for 5 min; heating to 300 deg.C at 2 deg.C/min, maintaining for 2min, and measuring at 310 deg.C.
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