CN109799291B - Method for determining perfluorinated compounds in sample - Google Patents
Method for determining perfluorinated compounds in sample Download PDFInfo
- Publication number
- CN109799291B CN109799291B CN201811609262.2A CN201811609262A CN109799291B CN 109799291 B CN109799291 B CN 109799291B CN 201811609262 A CN201811609262 A CN 201811609262A CN 109799291 B CN109799291 B CN 109799291B
- Authority
- CN
- China
- Prior art keywords
- mixture
- washing
- filter residue
- solution
- filtering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a method for determining perfluorinated compounds in a sample, which comprises the following steps: step A, weighing coconut shells, eggshell and walnut shells, and preparing a second mixture; step B, hydroxylating the second mixture to prepare a third mixture; step C, mixing the third mixture with hydroxyapatite powder for silanization reaction to prepare an adsorbent; step D, carrying out fermentation pretreatment on a sample to be detected, and filtering to separate solid from liquid; step E, extracting filter residues in the fermentation product to obtain a first extracting solution; step F, extracting the filtrate obtained from the fermentation product to obtain a second extracting solution; and G, combining the first extracting solution and the second extracting solution, and performing qualitative and quantitative analysis. The method has the advantages of greatly improving the extraction rate of the perfluorinated compounds in the sample by respectively extracting the fermented liquid and the fermented solid through fermentation pretreatment of the sample, along with high recovery rate, low detection limit, high sensitivity and strong matrix interference resistance.
Description
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to a method for measuring perfluorinated compounds in textile, coating, liquid and powder samples.
Background
Perfluoro compounds are a class of elemental organic compounds in which the hydrogen atom attached to a carbon atom in the organic compound molecule is replaced by fluorine. Fluorine is the element with the largest electronegativity, and the perfluorinated compounds have extremely stable chemical properties, can withstand high-temperature heating, illumination, chemical action, microbial action and metabolic action of higher vertebrates, and are mainly used in the fields of chemical industry, textiles, coatings, leather, synthetic detergents, cooker manufacturing (such as non-stick pans), paper food packaging materials and the like. In addition, perfluorinated compounds have hydrophobic and oleophobic properties and can be used as hydrophobic and oleophobic stain repellents (carpets, textiles, upholstery, leather, paper products, etc.), flame retardants (aerospace, fire protection), surfactants (fire fighting foams, alkaline cleaners), photoresists (semiconductor industry), plating antifogging agents, photographic paper antistatic agents, coating additives, etc.
Because of the wide range of applications of perfluorocompounds, the contamination it brings is also global. Many researchers around the world have found that perfluorinated compounds have had a wide and profound impact on the ecological environment. The most predominant perfluorinated contaminants in seawater are PFOA and PFOS, concentrations generally in the range of pg/L-ng/L, and atmospheric concentrations generally in pg/m3Within. For organisms, different concentrations of perfluorochemicals can be detected in almost all trophic organisms on the food chain in aquatic ecosystems.
As a new generation of Persistent Organic Pollutants (POPs), perfluorinated compounds have long-term residue, bioaccumulation, semi-volatility and high toxicity, and bring serious harm to human health. Therefore, there is a need for a high level of attention to the class of perfluorinated compounds.
In recent years, researchers at home and abroad increasingly perform qualitative and quantitative detection on perfluorinated compounds in living biological samples, the pretreatment of the samples is a key link of analysis and detection, as long as a detection instrument is stable, the repeatability and the accuracy of a detection result mainly depend on the pretreatment, and the sensitivity of the method has an important relationship with the sample treatment process. The method is characterized in that the content difference of perfluorinated compounds in biological samples such as textiles, coatings and the like is large, the perfluorinated compounds in the samples are tightly combined with other substances and are difficult to extract, and when the perfluorinated compounds in the samples are analyzed, the enrichment rate of the perfluorinated compounds is low, and the extraction rate of the perfluorinated compounds in the samples is low, so that the method is more critical to the pretreatment of the samples. The existing technology for measuring the perfluorinated compounds in the sample has the series problems of low extraction technology, low detection sensitivity and accuracy of the perfluorinated compounds, inaccurate detection, high detection limit and the like.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
It is still another object of the present invention to provide a method for detecting perfluorinated compounds in a sample, wherein the sample is pre-treated by fermentation, and the fermented liquid and solid are respectively extracted, thereby greatly increasing the extraction rate of perfluorinated compounds in the sample, and having the advantages of high recovery rate, low detection limit, high sensitivity and strong anti-matrix interference capability.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for determining a perfluorinated compound in a sample, comprising the steps of:
step A, respectively weighing 30-40 parts by weight of coconut shells, 12-15 parts by weight of eggshells and 1-3 parts by weight of walnut shells according to parts by weight, respectively cleaning, mixing, placing in a water bath at 80 ℃, boiling for 2h, filtering, washing with clear water, repeatedly boiling and washing for 2-4 times, placing in an oven at 100 ℃, taking out after 40-50 min, and crushing through a 20-40-mesh screen to obtain a first mixture; soaking the first mixture in 8-15% NaOH aqueous solution for 2-5 h, boiling for 40-70 nim, stopping heating, naturally cooling to room temperature, filtering, collecting first filter residue, washing the first filter residue to be neutral by using deionized water, then placing the first filter residue in an oven at 80-100 ℃, and taking out the first filter residue after 20-30 min to obtain a second mixture;
step B, adding the second mixture into a ferrous sulfate aqueous solution with the concentration of 0.15-0.8 mol/L, and uniformly stirring at the stirring speed of 500-1000 r/min to obtain a first suspension; h is to be2O2Dropwise adding the mixture into the first suspension, and stirring and reacting for 3-12 h at the temperature of 20-25 ℃ and the stirring speed of 500-1000 r/min to obtain a second suspension; to the secondAdding a hydrochloric acid aqueous solution with the mass fraction of 5-10% into the suspension, then filtering by using a G4 sand core funnel, washing the obtained second filter residue with distilled water until the pH of the filtrate is = 7-7.2, then placing the filtrate in a vacuum drying oven, and carrying out vacuum drying for 12-24 hours at the temperature of 50-70 ℃ and the vacuum degree of 0.01-0.03 MPa to obtain a third mixture;
wherein the mass ratio of the second mixture to the ferrous sulfate in the ferrous sulfate aqueous solution is 1: 1-5; h2O2The mass ratio of the volume of the dosage to the second mixture in the first suspension is 30-60 mL:1 g; the mass ratio of the volume of the dosage of the hydrochloric acid aqueous solution to the second mixture in the first suspension is 20-50 mL:1 g;
step C, uniformly dispersing the third mixture and the hydroxyapatite powder in N, N-dimethylformamide to obtain a third suspension, wherein the weight ratio of the third mixture to the hydroxyapatite powder is 1: 2; dissolving dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in N, N-dimethylformamide to obtain a mixed solution after complete dissolution, dropwise adding the mixed solution into a third suspension under the conditions of ice bath temperature of-6-0 ℃, stirring speed of 500-1000 r/min, nitrogen protection and light protection, reacting for 10-30 min, raising the temperature to 20-25 ℃, continuing to react for 1-3 h, raising the temperature to 38-42 ℃, continuing to react for 1-3 h, stopping the reaction, filtering the reaction solution while hot by using a G4 sand core funnel, filtering to collect a third filter residue, washing the third filter residue for 3-5 times by using N, N-dimethylformamide, then placing the washed third filter residue in a vacuum drying box, vacuum drying for 20-30 h under the conditions of temperature of 50-70 ℃ and vacuum degree of 0.01-0.03 MPa, then crushing by using a 80-100-mesh screen, obtaining the adsorbent;
wherein the volume ratio of the total mass of the third mixture and the hydroxyapatite powder in the third suspension to the N, N-dimethylformamide is 1g: 100-400 mL; the volume ratio of the mass of the dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride to the volume of the N, N-dimethylformamide in the mixed solution is 10g: 10-20 mL; the volume ratio of the mixed liquid to the third suspension liquid is 1: 3-6;
step D, washing a sample to be detected with clear water, saline water and ethanol in sequence, mixing the washed sample to be detected with microbial flora, sealing and standing at 20-25 ℃, taking out after 12-16 h, placing into a grinder for grinding, filtering to obtain fourth filter residue and second filtrate, washing the fourth filter residue with water for 2-4 times, and combining the second filtrate and multiple water washing solutions to obtain a crude extract;
step E, mixing the adsorbent obtained in the step C and the fourth filter residue according to the weight ratio of 2:1, placing the mixture into a centrifugal tube, adding alkaline artificial sweat into the centrifugal tube until the mixture of the adsorbent and the fourth filter residue is completely immersed, then placing the centrifugal tube into an ultrasonic oscillator for ultrasonic treatment for 30-40 min, collecting supernatant in the centrifugal tube, and repeatedly washing sediments in the centrifugal tube for 2-4 times by using the alkaline artificial sweat; mixing the supernatant with the washing solution of multiple alkaline artificial sweat to obtain a first extract;
step F, adding the adsorbent obtained in the step C into the crude extraction liquid according to the amount of 10mL/3g, standing for 30-40 min, filtering, and collecting filter residues to obtain fifth filter residues; repeatedly adding the adsorbent, filtering for 4-6 times, and combining the fifth filter residues obtained by filtering for multiple times to obtain a fourth mixture; immersing the fourth mixture in methanol, carrying out ultrasonic treatment for 120-130 min, then filtering and separating to obtain a third filtrate and a sixth filter residue, washing the sixth filter residue with methanol for 2-4 times, and combining the third filtrate and a methanol washing solution to obtain a second extracting solution;
and G, combining the first extracting solution and the second extracting solution, performing rotary evaporation and concentration until the first extracting solution and the second extracting solution are nearly dry, performing constant volume to 5mL by using methanol to obtain a solution to be detected, and performing qualitative and quantitative analysis on the solution to be detected by using a liquid chromatography-tandem mass spectrometer.
Preferably, the method for determining a perfluoro compound in a sample, step B, H2O2The dropping speed of (a) is 2-12 mL/min.
Preferably, in the method for measuring the perfluorinated compounds in the sample, the dropping speed of the mixed solution in the step C is 0.5-4 mL/min.
Preferably, in the method for determining the perfluorinated compounds in the sample, the ultrasonic treatment in the step E is performed under the condition of a water bath with the temperature of 40-50 ℃.
Preferably, in the method for determining the perfluorinated compounds in the sample, the ultrasonic treatment in the step F is carried out under the condition of a water bath with the temperature of 60-65 ℃.
Preferably, in the method for measuring the perfluorinated compounds in the sample, the liquid to be measured is filtered by a 0.22 mu m polytetrafluoroethylene filter membrane before measurement.
Preferably, in the method for determining the perfluorinated compounds in the sample, the microbial flora in the step D is a composition formed by one or more of Brevibacillus borstelensis, Paenibacillus, Bacillus subtilis, Bacillus amyloliquefaciens, Chromobacterium sulphuricum or Vibrio bacteriovorus.
The invention at least comprises the following beneficial effects:
1. according to the invention, the sample is subjected to fermentation pretreatment, and the fermented liquid and solid are respectively extracted, so that the extraction rate of the perfluorinated compounds in the sample is greatly improved, and the method has the advantages of high recovery rate, low detection limit, high sensitivity and strong matrix interference resistance;
2. the coconut shells, the eggshells and the walnut shells are subjected to a series of pre-treatments such as washing, boiling and the like, impurities on the outer surfaces of the coconut shells, the eggshells and the walnut shells are removed, and the sizes of pores of the coconut shells, the eggshells and the walnut shells are increased; carrying out surface hydroxylation modification treatment on a second mixture obtained by mixing purified coconut shells, eggshells and walnut shells to finally obtain a third mixture with a large number of hydroxyl groups carried on the outer surface; hydroxyapatite powder is a porous material carrying hydroxyl, is mixed with a third mixture to be used as a substrate (a solid phase micro-extraction coating), is subjected to silanization reaction with silane agent dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride, is prepared in situ to obtain a compound which has high extraction rate, high stability and high selectivity and can adsorb perfluorinated compounds in a sample, coconut shells, eggshells and walnut shells are selected,
3. according to the literature report and review of the relevant patents, [ European Patent No.0522990A1 ]]Quaternary ammonium salt (R) was found4N+) The positive ion can react with the perfluoroacid compound (C)nFn+1COO-Or CnFn+1SO3-) The negative ions are subjected to ion pairing to form corresponding ionic bonds and can be desorbed in a methanol solution, so that the quaternary ammonium salt (R) is contained in the invention4N+) Cationic dimethyloctadecyl [ 3-trimethoxysilylpropyl ] radical]The ammonium chloride is used as a coating and is combined with a third mixture with a large number of hydroxyl groups on the surface and hydroxyapatite powder through a silanization reaction, so that the high-selectivity extraction and high-efficiency enrichment of the perfluorinated compounds in the sample are realized; the solid-phase microextraction technology is utilized to improve the selectivity of perfluorinated compounds in the sample treatment process, greatly reduce impurities in the on-machine sample, reduce the detection limit, prolong the service life of the chromatographic column and reduce the equipment maintenance cost;
4. the perfluorinated compounds have extremely strong stability and can resist the action of microorganisms, and the sample is subjected to fermentation pretreatment based on the characteristics of the perfluorinated compounds, and other substances in the sample are subjected to microbial fermentation decomposition, so that the perfluorinated compounds in the sample can be adsorbed and extracted more easily, and the enrichment rate of the perfluorinated compounds is further improved; the fermented sample is filtered, solid-liquid separation is carried out, and the solid and liquid of the fermentation product are respectively extracted, so that the pertinence is stronger, the adsorption efficiency is higher, and the extraction rate of the perfluorinated compounds is further improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
< example 1>
The invention provides a method for determining perfluorinated compounds in a sample, which comprises the following steps:
step A, respectively weighing 30 parts by weight of coconut shells, 12 parts by weight of eggshells and 1 part by weight of walnut shells according to parts by weight, respectively cleaning, mixing, placing in a water bath at 80 ℃, boiling for 2 hours, filtering, washing with clear water, repeatedly boiling and washing for 2 times, placing in an oven at 100 ℃, taking out after 40 minutes, and crushing through a 20-mesh screen to obtain a first mixture; soaking the first mixture in 8% NaOH aqueous solution for 2h, boiling for 40nim, stopping heating, naturally cooling to room temperature, filtering, collecting first filter residue, washing with deionized water to neutrality, placing in an oven at 80 deg.C, and taking out after 20min to obtain a second mixture;
step B, adding the second mixture into a ferrous sulfate aqueous solution with the concentration of 0.15mol/L, and uniformly stirring at the stirring speed of 500r/min to obtain a first suspension; h is to be2O2Dropwise adding the mixture into the first suspension at a dropwise adding speed of 2mL/min, and stirring and reacting for 3 hours at a temperature of 20 ℃ and a stirring speed of 500r/min to obtain a second suspension; adding a hydrochloric acid aqueous solution with the mass fraction of 5% into the second suspension, filtering by using a G4 sand core funnel, washing the obtained second filter residue with distilled water until the pH of the filtrate is =7, placing the filtrate in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 50 ℃ and the vacuum degree of 0.01MPa to obtain a third mixture;
wherein the mass ratio of the second mixture to the ferrous sulfate in the ferrous sulfate aqueous solution is 1: 1; h2O2The volume ratio of the dosage to the mass of the second mixture in the first suspension is 30mL:1 g; the mass ratio of the volume of the dosage of the hydrochloric acid aqueous solution to the second mixture in the first suspension is 20mL:1 g;
step C, uniformly dispersing the third mixture and the hydroxyapatite powder in N, N-dimethylformamide to obtain a third suspension, wherein the weight ratio of the third mixture to the hydroxyapatite powder is 1: 2; dissolving dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in N, N-dimethylformamide to obtain a mixed solution after complete dissolution, dropwise adding the mixed solution into the third suspension at a dropwise adding speed of 0.5mL/min under the conditions of ice bath temperature of-6 ℃, stirring speed of 500r/min, nitrogen protection and light protection, after 10min of reaction, raising the temperature to 20 ℃, continuing to react for 1h, raising the temperature to 38 ℃, continuing to react for 1h, stopping the reaction, filtering the reaction solution while the reaction solution is hot by using a G4 sand core funnel, filtering and collecting third filter residue, washing the third filter residue for 3 times by using N, N-dimethylformamide, then placing the washed third filter residue in a vacuum drying box, vacuum drying at 50 deg.C and 0.01MPa for 20 hr, pulverizing, and sieving with 80 mesh sieve to obtain adsorbent;
wherein the volume ratio of the total mass of the third mixture and the hydroxyapatite powder in the third suspension to the N, N-dimethylformamide is 1g:100 mL; the volume ratio of the mass of the dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride to the volume of the N, N-dimethylformamide in the mixed solution is 10g:10 mL; the volume ratio of the mixed solution to the third suspension is 1: 3;
step D, washing a sample to be detected with clear water, saline water and ethanol in sequence, mixing the washed sample to be detected with microbial flora, sealing and standing at 20 ℃, taking out the sample after 12 hours, placing the mixture into a grinder for grinding, filtering to obtain fourth filter residue and second filtrate, washing the fourth filter residue for 2 times with water, and combining the second filtrate and multiple water washing solutions to obtain a crude extraction solution; wherein the weight ratio of the microbial flora to the washed sample to be detected is 0.1:1, and the microbial flora is a composition formed by Brevibacillus borstelensis, Paenibacillus and Bacillus subtilis with the weight ratio of 1:1: 1;
step E, mixing the adsorbent obtained in the step C and the fourth filter residue according to the weight ratio of 2:1, placing the mixture into a centrifugal tube, adding alkaline artificial sweat into the centrifugal tube until the mixture of the adsorbent and the fourth filter residue is completely immersed, then placing the centrifugal tube into an ultrasonic oscillator to carry out ultrasonic treatment for 30min under the condition of water bath at 40 ℃, collecting supernatant in the centrifugal tube, and repeatedly washing sediments in the centrifugal tube for 2 times by using the alkaline artificial sweat; mixing the supernatant with the washing solution of multiple alkaline artificial sweat to obtain a first extract;
step F, adding the adsorbent obtained in the step C into the crude extraction liquid according to the amount of 10mL/3g, standing for 30min, filtering, and collecting filter residues to obtain fifth filter residues; repeatedly adding the adsorbent, filtering for 4 times, and combining the fifth filter residues obtained by filtering for multiple times to obtain a fourth mixture; immersing the fourth mixture in methanol, performing ultrasonic treatment for 120min under the condition of water bath at 60 ℃, filtering and separating to obtain a third filtrate and a sixth filter residue, washing the sixth filter residue with methanol for 2 times, and combining the third filtrate and a methanol washing solution to obtain a second extracting solution;
and G, combining the first extracting solution and the second extracting solution, performing rotary evaporation and concentration until the solution is nearly dry, performing constant volume to 5mL by using methanol, filtering by using a 0.22-micrometer polytetrafluoroethylene filter membrane to obtain a solution to be detected, and performing qualitative and quantitative analysis on the solution to be detected by using a liquid chromatography-tandem mass spectrometer.
< example 2>
The invention provides a method for determining perfluorinated compounds in a sample, which comprises the following steps:
step A, respectively weighing 40 parts by weight of coconut shells, 15 parts by weight of eggshells and 3 parts by weight of walnut shells according to parts by weight, respectively cleaning, mixing, placing in a water bath at 80 ℃, boiling for 2 hours, filtering, washing with clear water, repeatedly boiling and washing for 4 times, placing in an oven at 100 ℃, taking out after 50 minutes, and crushing through a 40-mesh screen to obtain a first mixture; soaking the first mixture in 8-15% NaOH aqueous solution for 5h, boiling for 70nim, stopping heating, naturally cooling to room temperature, filtering, collecting first filter residue, washing with deionized water to be neutral, placing in an oven at 100 ℃, and taking out after 30min to obtain a second mixture;
step B, adding the second mixture into a ferrous sulfate aqueous solution with the concentration of 0.8mol/L, and uniformly stirring at the stirring speed of 1000r/min to obtain a first suspension; h is to be2O2Dropwise adding the mixture into the first suspension at a dropping speed of 12mL/min, and stirring and reacting for 12 hours under the conditions that the temperature is 25 ℃ and the stirring speed is 1000r/min to obtain a second suspension; adding 10% hydrochloric acid aqueous solution by mass into the second suspension, filtering by using a G4 sand core funnel, washing the obtained second filter residue with distilled water until the pH of the filtrate is =7.2, placing in a vacuum drying oven, and vacuum-drying at 70 ℃ and 0.03MPa for 24h to obtain a third mixture;
wherein the mass ratio of the second mixture to the ferrous sulfate in the ferrous sulfate aqueous solution is 1: 5; h2O2The mass ratio of the volume of the dosage to the second mixture in the first suspension is 60mL:1 g; the mass ratio of the volume of the dosage of the hydrochloric acid aqueous solution to the second mixture in the first suspension is 50mL:1 g;
step C, uniformly dispersing the third mixture and the hydroxyapatite powder in N, N-dimethylformamide to obtain a third suspension, wherein the weight ratio of the third mixture to the hydroxyapatite powder is 1: 2; dissolving dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in N, N-dimethylformamide to obtain a mixed solution after complete dissolution, dropwise adding the mixed solution into the third suspension at a dropwise adding speed of 4mL/min under the conditions of ice bath temperature of 0 ℃, stirring speed of 1000r/min, nitrogen protection and light protection, after reacting for 30min, raising the temperature to 25 ℃, continuing to react for 1-3 h, raising the temperature to 42 ℃, continuing to react for 3h, stopping the reaction, filtering the reaction solution while the reaction solution is hot by using a G4 sand core funnel, filtering and collecting third filter residue, washing the third filter residue for 5 times by using N, N-dimethylformamide, then placing the washed third filter residue in a vacuum drying box, vacuum drying at 70 deg.C and 0.03MPa for 30 hr, pulverizing, and sieving with 100 mesh sieve to obtain adsorbent;
wherein the volume ratio of the total mass of the third mixture and the hydroxyapatite powder in the third suspension to the N, N-dimethylformamide is 1g:400 mL; the volume ratio of the mass of the dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride to the volume of the N, N-dimethylformamide in the mixed solution is 10g:20 mL; the volume ratio of the mixed solution to the third suspension is 1: 6;
step D, washing a sample to be detected with clear water, saline water and ethanol in sequence, mixing the washed sample to be detected with microbial flora, sealing and standing at 25 ℃, taking out the sample after 16 hours, placing the mixture into a grinder for grinding, filtering to obtain fourth filter residue and second filtrate, washing the fourth filter residue with water for 4 times, and combining the second filtrate and multiple water washing solutions to obtain a crude extraction solution; wherein the weight ratio of the microbial flora to the washed sample to be detected is 0.2:1, and the microbial flora is a composition formed by bacillus amyloliquefaciens, chromycinia sulphureus or bdellovibrio bacteriovorus with the weight ratio of 1:1: 1;
step E, mixing the adsorbent obtained in the step C and the fourth filter residue according to the weight ratio of 2:1, placing the mixture into a centrifugal tube, adding alkaline artificial sweat into the centrifugal tube until the mixture of the adsorbent and the fourth filter residue is completely immersed, then placing the centrifugal tube into an ultrasonic oscillator to perform ultrasonic treatment for 40min under the condition of a water bath with the temperature of 50 ℃, collecting supernatant in the centrifugal tube, and repeatedly washing sediments in the centrifugal tube for 4 times by using the alkaline artificial sweat; mixing the supernatant with the washing solution of multiple alkaline artificial sweat to obtain a first extract;
step F, adding the adsorbent obtained in the step C into the crude extraction liquid according to the amount of 10mL/3g, standing for 40min, filtering, and collecting filter residues to obtain fifth filter residues; repeatedly adding the adsorbent, filtering for 6 times, and combining the fifth filter residues obtained by filtering for multiple times to obtain a fourth mixture; immersing the fourth mixture in methanol, performing ultrasonic treatment for 130min under the water bath condition at the temperature of 65 ℃, filtering and separating to obtain a third filtrate and a sixth filter residue, washing the sixth filter residue with methanol for 4 times, and combining the third filtrate and a methanol washing solution to obtain a second extracting solution;
and G, combining the first extracting solution and the second extracting solution, performing rotary evaporation and concentration until the solution is nearly dry, performing constant volume to 5mL by using methanol, filtering by using a 0.22-micrometer polytetrafluoroethylene filter membrane to obtain a solution to be detected, and performing qualitative and quantitative analysis on the solution to be detected by using a liquid chromatography-tandem mass spectrometer.
< example 3>
The invention provides a method for determining perfluorinated compounds in a sample, which comprises the following steps:
step A, respectively weighing 35 parts by weight of coconut shells, 14 parts by weight of eggshells and 2 parts by weight of walnut shells according to parts by weight, respectively cleaning, mixing, placing in a water bath at 80 ℃, boiling for 2 hours, filtering, washing with clear water, repeatedly boiling and washing for 3 times, placing in an oven at 100 ℃, taking out after 45 minutes, and crushing through a 30-mesh screen to obtain a first mixture; soaking the first mixture in a 12% NaOH aqueous solution for 4h, boiling for 55nim, stopping heating, naturally cooling to room temperature, filtering, collecting first filter residue, washing with deionized water to neutrality, placing in an oven at 90 deg.C, and taking out after 25min to obtain a second mixture;
step B, adding the second mixture into a ferrous sulfate aqueous solution with the concentration of 0.48mol/L, and uniformly stirring at the stirring speed of 750r/min to obtain a first suspension; h is to be2O2Dropwise adding the mixture into the first suspension at a dropwise adding speed of 7mL/min, and stirring and reacting for 8 hours at a temperature of 23 ℃ and a stirring speed of 500-1000 r/min to obtain a second suspension; adding a hydrochloric acid aqueous solution with the mass fraction of 8% into the second suspension, filtering by using a G4 sand core funnel, washing the obtained second filter residue with distilled water until the pH of the filtrate is =7.1, then placing the filtrate in a vacuum drying oven, and carrying out vacuum drying for 18h at the temperature of 60 ℃ and the vacuum degree of 0.02MPa to obtain a third mixture;
wherein the mass ratio of the second mixture to the ferrous sulfate in the ferrous sulfate aqueous solution is 1: 3; h2O2The mass ratio of the volume of the dosage to the second mixture in the first suspension is 45mL:1 g; the mass ratio of the volume of the dosage of the hydrochloric acid aqueous solution to the second mixture in the first suspension is 35mL:1 g;
step C, uniformly dispersing the third mixture and the hydroxyapatite powder in N, N-dimethylformamide to obtain a third suspension, wherein the weight ratio of the third mixture to the hydroxyapatite powder is 1: 2; dissolving dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in N, N-dimethylformamide to obtain a mixed solution after complete dissolution, dropwise adding the mixed solution into the third suspension at the dropwise adding speed of 2.3mL/min under the conditions of ice bath temperature of-3 ℃, stirring speed of 750r/min, nitrogen protection and light protection, after 20min of reaction, raising the temperature to 23 ℃, continuing to react for 2h, raising the temperature to 41 ℃, continuing to react for 2h, stopping the reaction, filtering the reaction solution while the reaction solution is hot by using a G4 sand core funnel, filtering and collecting third filter residue, washing the third filter residue for 4 times by using N, N-dimethylformamide, then placing the washed third filter residue in a vacuum drying box, vacuum drying at 60 deg.C and 0.01-0.03 MPa for 25 hr, pulverizing, and sieving with 90 mesh sieve to obtain adsorbent;
wherein the volume ratio of the total mass of the third mixture and the hydroxyapatite powder in the third suspension to the N, N-dimethylformamide is 1g:250 mL; the volume ratio of the mass of the dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride to the volume of the N, N-dimethylformamide in the mixed solution is 10g:15 mL; the volume ratio of the mixed solution to the third suspension is 1: 5;
step D, washing a sample to be detected with clear water, saline water and ethanol in sequence, mixing the washed sample to be detected with microbial flora, sealing and standing at 23 ℃, taking out the mixture after 14 hours, placing the mixture into a grinder for grinding, filtering to obtain fourth filter residue and second filtrate, washing the fourth filter residue 3 times with water, and combining the second filtrate and multiple water washing solutions to obtain a crude extract; wherein the weight ratio of the microbial flora to the washed sample to be detected is 0.15:1, and the microbial flora is a composition formed by Brevibacillus borstelensis, Paenibacillus and Bacillus amyloliquefaciens in the weight ratio of 1:1: 1;
step E, mixing the adsorbent obtained in the step C and the fourth filter residue according to the weight ratio of 2:1, placing the mixture into a centrifugal tube, adding alkaline artificial sweat into the centrifugal tube until the mixture of the adsorbent and the fourth filter residue is completely immersed, then placing the centrifugal tube into an ultrasonic oscillator, carrying out ultrasonic treatment for 35min under the condition of water bath at the temperature of 45 ℃, collecting supernatant in the centrifugal tube, and repeatedly washing sediments in the centrifugal tube for 3 times by using the alkaline artificial sweat; mixing the supernatant with the washing solution of multiple alkaline artificial sweat to obtain a first extract;
step F, adding the adsorbent obtained in the step C into the crude extraction liquid according to the amount of 10mL/3g, standing for 35min, filtering, and collecting filter residue to obtain fifth filter residue; repeatedly adding the adsorbent, filtering for 5 times, and combining the fifth filter residues obtained by filtering for multiple times to obtain a fourth mixture; immersing the fourth mixture in methanol, performing ultrasonic treatment for 125min under the water bath condition at the temperature of 63 ℃, filtering and separating to obtain a third filtrate and a sixth filter residue, washing the sixth filter residue with methanol for 3 times, and combining the third filtrate and a methanol washing solution to obtain a second extracting solution;
and G, combining the first extracting solution and the second extracting solution, performing rotary evaporation and concentration until the solution is nearly dry, performing constant volume to 5mL by using methanol, filtering by using a 0.22-micrometer polytetrafluoroethylene filter membrane to obtain a solution to be detected, and performing qualitative and quantitative analysis on the solution to be detected by using a liquid chromatography-tandem mass spectrometer.
< example 4>
A method for measuring perfluorinated compounds in a sample is different from the method in the example 3 in that the step D is omitted, the sample to be measured is directly mixed with an adsorbent according to the weight ratio of 2:1, the operation of the step E is carried out, and the rest conditions and parameters are the same as the conditions and parameters in the example 3.
< example 5>
A method for determining perfluorinated compounds in a sample comprises the steps of directly processing the sample to be determined according to the step D in the embodiment 3, adding microbial flora, sealing, fermenting, crushing, adding alkaline artificial sweat into the crushed object, immersing, performing ultrasonic processing by adopting the ultrasonic oscillation processing method and conditions in the step F in the embodiment 3, washing, collecting supernatant and washing liquid of the alkaline artificial sweat, obtaining extracting solution, performing rotary evaporation and concentration to be near dry, performing constant volume to 5mL by using methanol to obtain a solution to be determined, and performing qualitative and quantitative analysis on the solution to be determined by using a liquid chromatography-tandem mass spectrometer.
< example 6>
A method for determining perfluorinated compounds in a sample comprises the steps of directly immersing the sample to be determined in alkaline artificial sweat, carrying out ultrasonic treatment and subsequent washing by adopting the ultrasonic oscillation treatment method and conditions in the step F in the embodiment 3, collecting supernatant and washing liquid of the alkaline artificial sweat to obtain extracting solution, carrying out rotary evaporation concentration until the extracting solution is nearly dry, carrying out constant volume to 5mL by using methanol to obtain liquid to be determined, and carrying out qualitative and quantitative analysis on the liquid to be determined by using a liquid chromatogram-tandem mass spectrometer.
< test example 1>
Determination of the recovery of Perfluorocompounds in samples
Selecting a known composition containing 0.489 μ g/m2PFOA of (1) and 0.512. mu.g/m2The textile of PFOA (Perfluorooctanoic acid) is used as a sample, the textile is measured according to the methods of the embodiments 1 to 6, the measurement results are counted and recorded, and the recovery rates of PFOA and PFOA are calculated, wherein the results are shown in the table 1:
as can be seen from Table 1, the recovery rate corresponding to the determination methods of examples 1 to 3 of the invention is higher than that corresponding to the determination methods of examples 4 to 6, especially the recovery rate of example 3 is as high as 100, and the perfluoro compounds in the sample can be enriched and extracted more thoroughly; example 4 differs from example 3 in that the sample was not subjected to a fermentation pretreatment in the assay method of example 4; example 5 differs from example 3 in that there is no solid-liquid separation after the fermentation pretreatment of the sample in the measurement method of example 5; example 6 differs from example 3 in that the sample was not subjected to fermentation pretreatment and was not extracted with an adsorbent in the measurement method of example 6; therefore, the product containing the perfluorinated compounds is subjected to fermentation pretreatment, the fermentation product is subjected to solid-liquid separation for targeted extraction, and the adsorbent provided by the invention is added in the extraction of the perfluorinated compounds, so that the enrichment extraction rate of the perfluorinated compounds can be greatly improved, and the interference of other matrixes on the detection of the perfluorinated compounds is reduced.
The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be apparent to those skilled in the art.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (7)
1. A method for determining perfluorochemicals in a sample, comprising the steps of:
step A, respectively weighing 30-40 parts by weight of coconut shells, 12-15 parts by weight of eggshells and 1-3 parts by weight of walnut shells according to parts by weight, respectively cleaning, mixing, placing in a water bath at 80 ℃, boiling for 2h, filtering, washing with clear water, repeatedly boiling and washing for 2-4 times, placing in an oven at 100 ℃, taking out after 40-50 min, and crushing through a 20-40-mesh screen to obtain a first mixture; soaking the first mixture in 8-15% NaOH aqueous solution for 2-5 h, boiling for 40-70 nim, stopping heating, naturally cooling to room temperature, filtering, collecting first filter residue, washing the first filter residue to be neutral by using deionized water, then placing the first filter residue in an oven at 80-100 ℃, and taking out the first filter residue after 20-30 min to obtain a second mixture;
step B, adding the second mixture into a ferrous sulfate aqueous solution with the concentration of 0.15-0.8 mol/L, and uniformly stirring at the stirring speed of 500-1000 r/min to obtain a first suspension; h is to be2O2Dropwise adding the mixture into the first suspension, and stirring and reacting for 3-12 h at the temperature of 20-25 ℃ and the stirring speed of 500-1000 r/min to obtain a second suspension; adding a hydrochloric acid aqueous solution with the mass fraction of 5-10% into the second suspension, then filtering by using a G4 sand core funnel, washing the obtained second filter residue with distilled water until the pH of the filtrate is = 7-7.2, then placing in a vacuum drying oven, and carrying out vacuum drying for 12-24 hours at the temperature of 50-70 ℃ and the vacuum degree of 0.01-0.03 MPa to obtain a third mixture;
wherein the mass ratio of the second mixture to the ferrous sulfate in the ferrous sulfate aqueous solution is 1: 1-5; h2O2The mass ratio of the volume of the dosage to the second mixture in the first suspension is 30-60 mL:1 g; the mass ratio of the volume of the dosage of the hydrochloric acid aqueous solution to the second mixture in the first suspension is 20-50 mL:1 g;
step C, uniformly dispersing the third mixture and the hydroxyapatite powder in N, N-dimethylformamide to obtain a third suspension, wherein the weight ratio of the third mixture to the hydroxyapatite powder is 1: 2; dissolving dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride in N, N-dimethylformamide to obtain a mixed solution after complete dissolution, dropwise adding the mixed solution into a third suspension under the conditions of ice bath temperature of-6-0 ℃, stirring speed of 500-1000 r/min, nitrogen protection and light protection, reacting for 10-30 min, raising the temperature to 20-25 ℃, continuing to react for 1-3 h, raising the temperature to 38-42 ℃, continuing to react for 1-3 h, stopping the reaction, filtering the reaction solution while hot by using a G4 sand core funnel, filtering to collect a third filter residue, washing the third filter residue for 3-5 times by using N, N-dimethylformamide, then placing the washed third filter residue in a vacuum drying box, vacuum drying for 20-30 h under the conditions of temperature of 50-70 ℃ and vacuum degree of 0.01-0.03 MPa, then crushing by using a 80-100-mesh screen, obtaining the adsorbent;
wherein the volume ratio of the total mass of the third mixture and the hydroxyapatite powder in the third suspension to the N, N-dimethylformamide is 1g: 100-400 mL; the volume ratio of the mass of the dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride to the volume of the N, N-dimethylformamide in the mixed solution is 10g: 10-20 mL; the volume ratio of the mixed liquid to the third suspension liquid is 1: 3-6;
step D, washing a sample to be detected with clear water, saline water and ethanol in sequence, mixing the washed sample to be detected with microbial flora, sealing and standing at 20-25 ℃, taking out after 12-16 h, placing into a grinder for grinding, filtering to obtain fourth filter residue and second filtrate, washing the fourth filter residue with water for 2-4 times, and combining the second filtrate and multiple water washing solutions to obtain a crude extract;
step E, mixing the adsorbent obtained in the step C and the fourth filter residue according to the weight ratio of 2:1, placing the mixture into a centrifugal tube, adding alkaline artificial sweat into the centrifugal tube until the mixture of the adsorbent and the fourth filter residue is completely immersed, then placing the centrifugal tube into an ultrasonic oscillator for ultrasonic treatment for 30-40 min, collecting supernatant in the centrifugal tube, and repeatedly washing sediments in the centrifugal tube for 2-4 times by using the alkaline artificial sweat; mixing the supernatant with the washing solution of multiple alkaline artificial sweat to obtain a first extract;
step F, adding the adsorbent obtained in the step C into the crude extraction liquid according to the amount of 10mL/3g, standing for 30-40 min, filtering, and collecting filter residues to obtain fifth filter residues; repeatedly adding the adsorbent, filtering for 4-6 times, and combining the fifth filter residues obtained by filtering for multiple times to obtain a fourth mixture; immersing the fourth mixture in methanol, carrying out ultrasonic treatment for 120-130 min, then filtering and separating to obtain a third filtrate and a sixth filter residue, washing the sixth filter residue with methanol for 2-4 times, and combining the third filtrate and a methanol washing solution to obtain a second extracting solution;
and G, combining the first extracting solution and the second extracting solution, performing rotary evaporation and concentration until the first extracting solution and the second extracting solution are nearly dry, performing constant volume to 5mL by using methanol to obtain a solution to be detected, and performing qualitative and quantitative analysis on the solution to be detected by using a liquid chromatography-tandem mass spectrometer.
2. The method for detecting a perfluoro compound in a sample according to claim 1 wherein in step B H2O2The dropping speed of (a) is 2-12 mL/min.
3. The method for detecting a perfluoro compound in a sample according to claim 2 wherein the dropping rate of the mixed solution in the step C is 0.5 to 4 mL/min.
4. The method for detecting perfluoro compounds in the sample according to claim 3 wherein the ultrasonication in step E is carried out in a water bath at a temperature of 40 to 50 ℃.
5. The method for detecting perfluoro compounds in the sample according to claim 4 wherein the ultrasonication in step F is carried out in a water bath at a temperature of 60 to 65 ℃.
6. The method for measuring a perfluoro compound in a sample according to claim 5, wherein the solution to be measured is filtered through a 0.22 μm polytetrafluoroethylene filter before measurement.
7. The method of claim 6, wherein the microbial population of step D is a composition of one or more of brevibacillus borstelensis, paenibacillus, bacillus subtilis, bacillus amyloliquefaciens, chromycotus sulphureus, or bdellovibrio bacteriovorus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811609262.2A CN109799291B (en) | 2018-12-27 | 2018-12-27 | Method for determining perfluorinated compounds in sample |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811609262.2A CN109799291B (en) | 2018-12-27 | 2018-12-27 | Method for determining perfluorinated compounds in sample |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109799291A CN109799291A (en) | 2019-05-24 |
| CN109799291B true CN109799291B (en) | 2021-06-01 |
Family
ID=66557629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811609262.2A Active CN109799291B (en) | 2018-12-27 | 2018-12-27 | Method for determining perfluorinated compounds in sample |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109799291B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485973A (en) * | 2009-01-07 | 2009-07-22 | 中国科学院生态环境研究中心 | Preparation and application of alginic acid polymer coated Fe3O4@C18 magnetic nano solid phase extractive agent |
| CN101685086A (en) * | 2008-09-25 | 2010-03-31 | 江苏省优联检测技术服务有限公司 | Method for rapidly detecting content of perfluor octyl sulfonic acid (PFOS) and perfluor octylic acid (PFOA) |
| CN102253138A (en) * | 2011-05-27 | 2011-11-23 | 国家皮革质量监督检验中心（浙江） | Method for detecting total amount of perfluorooctane sulphonates (PFOS) in textile and leather |
| CN104853841A (en) * | 2012-12-07 | 2015-08-19 | 大金工业株式会社 | Organic fluorine-based-compound adsorbent comprising cyclodextrin-supporting polymer |
| CN105195100A (en) * | 2015-09-21 | 2015-12-30 | 济南大学 | Preparation method of beta-cyclodextrin modified loofah sponge adsorbent |
| CN105329976A (en) * | 2015-11-27 | 2016-02-17 | 清华大学 | Method for adsorbing and degrading perfluorinated compounds in water |
| CN105664847A (en) * | 2016-01-13 | 2016-06-15 | 南昌航空大学 | Method for preparing high-specific surface area porous carbon material based on oil tea seed husk and application thereof |
| CN105974041A (en) * | 2016-06-28 | 2016-09-28 | 广州纤维产品检测研究院 | Method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6841333B2 (en) * | 2002-11-01 | 2005-01-11 | 3M Innovative Properties Company | Ionic photoacid generators with segmented hydrocarbon-fluorocarbon sulfonate anions |
-
2018
- 2018-12-27 CN CN201811609262.2A patent/CN109799291B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101685086A (en) * | 2008-09-25 | 2010-03-31 | 江苏省优联检测技术服务有限公司 | Method for rapidly detecting content of perfluor octyl sulfonic acid (PFOS) and perfluor octylic acid (PFOA) |
| CN101485973A (en) * | 2009-01-07 | 2009-07-22 | 中国科学院生态环境研究中心 | Preparation and application of alginic acid polymer coated Fe3O4@C18 magnetic nano solid phase extractive agent |
| CN102253138A (en) * | 2011-05-27 | 2011-11-23 | 国家皮革质量监督检验中心（浙江） | Method for detecting total amount of perfluorooctane sulphonates (PFOS) in textile and leather |
| CN104853841A (en) * | 2012-12-07 | 2015-08-19 | 大金工业株式会社 | Organic fluorine-based-compound adsorbent comprising cyclodextrin-supporting polymer |
| CN105195100A (en) * | 2015-09-21 | 2015-12-30 | 济南大学 | Preparation method of beta-cyclodextrin modified loofah sponge adsorbent |
| CN105329976A (en) * | 2015-11-27 | 2016-02-17 | 清华大学 | Method for adsorbing and degrading perfluorinated compounds in water |
| CN105664847A (en) * | 2016-01-13 | 2016-06-15 | 南昌航空大学 | Method for preparing high-specific surface area porous carbon material based on oil tea seed husk and application thereof |
| CN105974041A (en) * | 2016-06-28 | 2016-09-28 | 广州纤维产品检测研究院 | Method for detecting perfluorinated compounds by using solid phase microextraction with liquid phase chromatography-tandem mass spectrum |
Non-Patent Citations (3)
| Title |
|---|
| Degradation of PFOA by hydrogen peroxide and persulfate activated by iron-modified diatomite;Celyna K.O. da Silva-Rackov et al;《Applied Catalysis B: Environmental》;20160331;253–259 * |
| Efficient adsorption of PFOS and F53B from chrome plating wastewater and their subsequent degradation in the regeneration process;Ziwen Du et al;《Chemi cal Engin eering Journal》;20160204;405–413 * |
| 改性活性炭对水中PFOS的吸附去除研究;童锡臻 等;《环境科学》;20120930;第33卷(第9期);3132-3138 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109799291A (en) | 2019-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108499549B (en) | Solid phase micro-extraction head for enriching perfluoro compounds and preparation method thereof | |
| Zhang et al. | Eggshell membrane-based solid-phase extraction combined with hydride generation atomic fluorescence spectrometry for trace arsenic (V) in environmental water samples | |
| CN108543527B (en) | Covalent organic framework compound solid phase micro-extraction fiber head and preparation method thereof | |
| CN108579689A (en) | A kind of beta cyclo dextrin polymer and preparation and the method for handling anionic dye waste water using it | |
| CN111777730A (en) | Reticular covalent organic framework material and preparation method and application thereof | |
| CN107376849A (en) | A kind of application of ethylenediamine tetraacetic acid modified diatomite adsorbant and preparation method thereof and processing heavy metal ions in wastewater | |
| CN112029106B (en) | Preparation method and application of modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane | |
| Huang et al. | Determination of aliphatic amines in food by on-fiber derivatization solid-phase microextraction with a novel zeolitic imidazolate framework 8-coated stainless steel fiber | |
| CN109400903A (en) | A kind of cage modle polysilsesquioxane/metal -2- amino terephthalic acid (TPA) metal-organic framework hybrid material and preparation method thereof | |
| CN109799291B (en) | Method for determining perfluorinated compounds in sample | |
| CN105688828B (en) | A method of extraction of uranium from seawater plant-inorganic compounding adsorbent is prepared using phosphoric acid modification folium cycas | |
| CN112111060B (en) | Porous organic framework material, preparation method thereof and application thereof in selective separation of perrhenate | |
| CN111413432B (en) | Method for detecting trace PFOA (perfluorooctanoic acid) in fluorine-containing polymer emulsion product | |
| CN113351167A (en) | Ion type skeleton structure porous adsorption material and preparation method and application thereof | |
| CN102861559A (en) | Production method of polyacrylonitrile chelating resin metal adsorbent | |
| CN108586648A (en) | A kind of chelating resin and its preparation method and application | |
| CN110156108A (en) | A kind of utilize is based on MIL-101 (Cr3+) metal-organic framework materials absorption water in organic dyestuff method | |
| CN115414919B (en) | Functionalized covalent organic framework material and preparation method and application thereof | |
| CN108414637B (en) | Method for detecting volatile disinfection byproducts in water by utilizing solid phase microextraction-gas chromatography-mass spectrometry combined technology | |
| CN110065989A (en) | A method of utilizing organic dyestuff in the metal organic framework material UIO-67 derivative absorption water of microcellular structure | |
| CN114015045B (en) | Fluorescent polymer and Fe 3+ Test paper and preparation method and application thereof | |
| CN110420622A (en) | The preparation method of the graphene oxide hybridized film of copper ion in a kind of removing water | |
| CN105536738B (en) | A kind of MAR and MIL 53（Al）Composite adsorbing material of combination and preparation method thereof | |
| CN109647356A (en) | A kind of preparation method and its application in removal waste water in anions and canons dyestuff at the same time of both sexes adsorbent material | |
| CN115541549A (en) | Rapid screening method for perfluorooctane sulfonate in water body based on zirconium-based fluorescent MOF |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |