CN113848190A - Rapid detection method and detection device for medium-long chain perfluorocarboxylic acid in water sample - Google Patents
Rapid detection method and detection device for medium-long chain perfluorocarboxylic acid in water sample Download PDFInfo
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- CN113848190A CN113848190A CN202111130635.XA CN202111130635A CN113848190A CN 113848190 A CN113848190 A CN 113848190A CN 202111130635 A CN202111130635 A CN 202111130635A CN 113848190 A CN113848190 A CN 113848190A
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- ZHZPKMZKYBQGKG-UHFFFAOYSA-N 6-methyl-2,4,6-tris(trifluoromethyl)oxane-2,4-diol Chemical compound FC(F)(F)C1(C)CC(O)(C(F)(F)F)CC(O)(C(F)(F)F)O1 ZHZPKMZKYBQGKG-UHFFFAOYSA-N 0.000 description 1
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- SIDINRCMMRKXGQ-UHFFFAOYSA-N perfluoroundecanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SIDINRCMMRKXGQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N21/3151—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths using two sources of radiation of different wavelengths
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
Abstract
The invention belongs to the field of rapid detection of water pollutants, and particularly relates to a rapid detection method and a rapid detection device for medium-long-chain perfluorocarboxylic acid in a water sample. The method for rapidly detecting the medium-long chain perfluorocarboxylic acid in the water sample comprises the following steps: preparing an Au @ PEI particle solution; obtaining a concentration-color standard colorimetric system; collecting a water sample, adding the water sample into the Au @ PEI particle solution, carrying out color comparison on the sample to be subjected to color comparison with a concentration-color standard colorimetric system, and judging the concentration content of the long-chain perfluorocarboxylic acid in the water sample. The detection method provided by the invention can realize the rapid detection of the medium-long chain perfluorocarboxylic acid in the water sample.
Description
Technical Field
The invention relates to the field of rapid detection of water pollutants, in particular to a rapid detection method and a rapid detection device for medium-long-chain perfluorocarboxylic acid in a water sample.
Background
Perfluoro compounds have gained wide attention in the environmental field as a new class of persistent organic pollutants. They have high chemical stability, thermal stability and good surface activity, and are widely applied in the fields of carpets, leather, textiles, food packaging bags, detergents, waterproofing agents, foam extinguishing agents and the like. However, in recent years, it has been found that environmental persistence, biodegradability, remote migration property, and bioaccumulation property of these substances are harmful to ecological environmental systems. In addition, animal experiments show that the compounds also have serious biological toxicity effects, can cause organ toxicity, neurotoxicity, immunity and endocrine toxicity, reproductive and developmental toxicity, carcinogenicity and the like, and the medium-long-chain perfluorinated compounds have stronger toxicity than the short-chain perfluorinated compounds and have great harm to human health.
The perfluorocarboxylic acid compound has good polarity and water solubility, and the water body is one of the main transmission media. The water-soluble organic fertilizer can enter various water environments along with the migration of water bodies, so that the water bodies are seriously polluted, and the safety of drinking water of people is threatened. Therefore, it is very necessary to establish an effective detection method to evaluate and investigate the risk of the perfluorocarboxylic acid pollution level in the environmental water sample in time. At present, the common detection methods for perfluorocarboxylic acid mainly comprise High Performance Liquid Chromatography (HPLC), high performance liquid chromatography-mass spectrometry (HPLC-MS) combination and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) technology. Although the chromatography has high sensitivity and accuracy, the method needs complicated pretreatment on a sample, uses expensive and precise instruments, has long detection period and cannot be used for on-site rapid detection. The prior art discloses a method for measuring perfluorooctane sulfonic acid by using a dual-wavelength ratio ultraviolet spectrometry, wherein perfluorooctane sulfonic acid and toluidine blue are subjected to electrostatic interaction under an acidic condition to form an ion association complex, the ion association complex has two characteristic peaks at 632nm and 502nm and is absorbed in a ratio, and the dual-wavelength ratio ultraviolet spectrometry for measuring perfluorooctane sulfonic acid is established according to the relationship between the concentration of a perfluorooctane sulfonic acid solution and an ultraviolet dual-wavelength absorption ratio value.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the existing method for rapidly detecting the long-chain perfluorocarboxylic acid in the water sample is limited in application condition and application range, so that the method and the device for rapidly detecting the long-chain perfluorocarboxylic acid in the water sample are provided.
A method for rapidly detecting medium-long chain perfluorocarboxylic acid in a water sample comprises the following steps:
s1, preparing an Au @ PEI particle solution;
s2, obtaining a concentration-color standard colorimetric system;
s3, collecting a water sample, adding the water sample into the Au @ PEI particle solution prepared in the step S1, mixing to obtain a sample to be colorimetric, carrying out colorimetric reaction on the sample to be colorimetric and a concentration-color standard colorimetric system, observing the color of the sample to be colorimetric, and judging the concentration content of the long-chain perfluorocarboxylic acid in the water sample.
According to the method, polyethyleneimine modified gold nanoparticles (Au @ PEI) are used as a signal probe, in the presence of medium-long-chain perfluorocarboxylic acid, amino groups with positive charges on the surface of the Au @ PEI can generate electrostatic interaction and hydrogen bond interaction with the medium-long-chain perfluorocarboxylic acid with negative charges, so that the dispersed Au @ PEI is aggregated, the color of a solution is changed from wine red to purple, the change of the color of the solution is observed visually, and the colorimetric method is established to quickly judge the pollution level of the long-chain perfluorocarboxylic acid in a water sample.
Further, the preparation of the Au @ PEI particle solution comprises the following steps: adding a polyethyleneimine solution into a chloroauric acid solution, stirring for a period of time, adding a sodium borohydride solution, and stirring to obtain an Au @ PEI particle solution, wherein the surface of the Au @ PEI has positive charges.
The nano gold prepared by the conventional method is negatively charged, generally, the nano gold is prepared by adopting a sodium citrate reduction method, at the moment, sodium citrate is a reducing agent and a protective agent, and the surface of the prepared nano gold contains citric acid molecules, so that the nano gold is negatively charged. In the preparation method of Au @ PEI, polyethyleneimine with positive charges is used as a protective agent, and sodium borohydride is used as a reducing agent, so that the surface of the prepared nanogold contains a large number of polyethyleneimine molecules, and the nanogold is enabled to have positive charges.
In the preparation method, the polyethyleneimine solution is added firstly when the Au @ PEI particle solution is prepared, the sodium borohydride solution is added, the polyethyleneimine is added firstly as a protective agent, the gold core of the chloroauric acid can be protected, the chloroauric acid can be quickly reduced into the nano gold particles after the sodium borohydride is added, and the polyethyleneimine is used as a protective agent to wrap the gold particles, so that the Au @ PEI particles are obtained. If the order of addition is reversed, no Au @ PEI particles are obtained.
The polyethyleneimine modified gold nanoparticle (Au @ PEI) signal probe is prepared at room temperature by adopting a one-step rapid reduction method, the preparation is simple and rapid, and the Au @ PEI with positive charges can be directly obtained through one-step reaction. Therefore, the amino with positive charges on the surface of the Au @ PEI can generate electrostatic interaction and hydrogen bonding interaction with the medium-long chain perfluorocarboxylic acid with negative charges, so that the dispersed Au @ PEI is aggregated, and the color change and the ultraviolet absorbance value change of the solution occur.
When preparing the nanogold with positive charges, different reaction conditions need to be examined, and the nanogold with amino groups with positive charges on the surface can be successfully obtained. In the invention, the molar ratio of chloroauric acid to polyethyleneimine is (18-22): 1; the molar ratio of the chloroauric acid to the sodium borohydride is 1 (1.8-2.3). Preferably, the molar ratio of chloroauric acid to polyethyleneimine is 20:1, the molar ratio of chloroauric acid to sodium borohydride is 1: 2.
the optimal molar ratio is determined by examining the addition of the three materials. The molar ratio of the chloroauric acid to the polyethyleneimine is (18-22): 1, and after the polyethyleneimine is added too much, Au @ PEI particles cannot be formed, and a large number of polyethyleneimine molecules can wrap chloroauric acid molecules and cannot be reduced into gold particles by sodium borohydride. When the amount of polyethyleneimine added is too small, the protection effect cannot be achieved, and after sodium borohydride is added, the solution becomes dark purple, so that a stable wine red Au @ PEI particle solution cannot be obtained, and therefore the molar ratio of the chloroauric acid to the polyethyleneimine is selected to be 20:1 as the optimal molar ratio. The molar ratio of the chloroauric acid to the sodium borohydride is 1 (1.8-2.3), when the addition amount of the sodium borohydride is too small, the chloroauric acid cannot be completely reduced to the gold nanoparticles, and when the addition amount of the sodium borohydride is too large, the solution can also become dark purple, a stable wine red Au @ PEI particle solution cannot be obtained, and the molar ratio of the chloroauric acid to the sodium borohydride is 1: 2 is the optimum molar ratio.
In the preparation process, the optimal dosage is obtained through optimization by adjusting and changing the adding amount of the materials, the ultraviolet absorption peak shape of the prepared Au @ PEI particle is narrow, and the particle has good dispersibility, uniformity and stability.
The concentration of the chloroauric acid solution is 0.5-2 mmol/L, the concentration of the polyethyleneimine solution is 0.5-1.5 mg/mL, and the concentration of the sodium borohydride solution is 25-30 mmol/L. Preferably, the concentration of the chloroauric acid solution is 0.5mmol/L, the concentration of the polyethyleneimine solution is 1mg/mL, and the concentration of the sodium borohydride solution is 25 mmol/L.
And adding a sodium borohydride solution, and stirring at room temperature for 1.5-2.5 h to obtain an Au @ PEI particle solution. According to the invention, sodium borohydride is used as a reducing agent, and the Au @ PEI particle solution can be prepared at room temperature without high-temperature heating, so that the operation is simple and rapid.
Further, the method for obtaining the concentration-color standard colorimetric system in step S2 includes the following steps:
s201, preparing a medium-long chain perfluorocarboxylic acid standard solution: dissolving medium-long-chain perfluorocarboxylic acid, preparing to obtain 3-5 mg/mL medium-long-chain perfluorocarboxylic acid standard stock solution, and then gradually diluting the stock solution into N parts of medium-long-chain perfluorocarboxylic acid standard solutions with different concentrations, wherein N is more than or equal to 3;
s202, respectively adding N parts of 40-60 mu L of medium-long chain perfluorocarboxylic acid standard solutions with different concentrations into N parts of 300-400 mu L of Au @ PEI particle solution, carrying out mixed reaction for 3-10 min to obtain N parts of perfluorocarboxylic acid standard for colorimetric detection, observing color, and establishing a concentration-color standard colorimetric system;
further, in S201, preparing a 4mg/mL medium-long chain perfluorocarboxylic acid standard stock solution, and then gradually diluting the stock solution into 8 parts of medium-long chain perfluorocarboxylic acid standard solutions with the concentrations of 0.2mg/mL, 0.4mg/mL, 0.6mg/mL, 0.8mg/mL, 1.2mg/mL, 1.6mg/mL, 2.0mg/mL and 2.4mg/mL in sequence;
in S202, 8 parts of medium-long chain perfluorocarboxylic acid standard solution with the volume of 50 mu L and the concentrations of 0.2mg/mL, 0.4mg/mL, 0.6mg/mL, 0.8mg/mL, 1.2mg/mL, 1.6mg/mL, 2.0mg/mL and 2.4mg/mL are respectively added into 8 parts of Au @ PEI particle solution with the volume of 350 mu L, and after mixing reaction is carried out for 5min, 8 parts of perfluorocarboxylic acid standard products with the final concentrations of 25 mu g/mL, 50 mu g/mL, 75 mu g/mL, 100 mu g/mL, 150 mu g/mL, 200 mu g/mL, 250 mu g/mL and 300 mu g/mL are obtained through colorimetric detection, the color is observed, and a concentration-color standard colorimetric system is established.
Further, collecting a water sample in step S3, adding 40-60 μ L of the water sample into 300-400 μ L of the Au @ PEI particle solution, mixing to obtain a sample to be colorimetric, carrying out color comparison on the sample to be colorimetric and a concentration-color standard colorimetric system, observing the color of the sample to be colorimetric, and judging the concentration content of the long-chain perfluorocarboxylic acid in the water sample.
As the concentration of perfluorocarboxylic acid increases, the color of the solution gradually changes from wine-red to purple-dark purple: when the color of the solution is wine red through visual observation, the water sample does not contain perfluorocarboxylic acid or the concentration of the perfluorocarboxylic acid is less than or equal to 75 mug/mL; when the color of the solution is purple red, the concentration of the perfluorocarboxylic acid in the water sample is between 75 mu g/mL and 150 mu g/mL; when the solution was dark purple in color, it was shown that the concentration of perfluorocarboxylic acid in the water sample was greater than 150. mu.g/mL.
Further, the method also comprises the following steps:
s4, determining the ultraviolet absorbance of the sample to be subjected to color comparison, and determining the concentration of the long-chain perfluorocarboxylic acid in the water sample according to a concentration-ultraviolet absorbance standard curve;
the concentration-ultraviolet absorbance standard curve is obtained by measuring the ultraviolet absorbance of a perfluorocarboxylic acid standard substance through colorimetric detection.
The dispersed Au @ PEI is aggregated, the ultraviolet absorbance of the system is increased, and the ultraviolet absorption wavelength is red-shifted. By further measuring the ultraviolet absorbance of the sample, the quantitative detection of the medium-long chain perfluorocarboxylic acid in the water sample can be realized based on the relation between the ultraviolet absorbance and the concentration of the perfluorocarboxylic acid.
After a water sample is collected, filtering the water sample, and then adding the water sample into the Au @ PEI particle solution. Preferably, a 0.22 μm filter membrane is used for filtering and purifying the environmental water sample.
A detection device used in a method for rapidly detecting medium-long chain perfluorocarboxylic acid in a water sample comprises a box body and a box cover, wherein a sampler, a filtering membrane, a colorimetric probe reagent tube and an ultraviolet spectrophotometer are arranged in the box body; and an Au @ PEI particle solution is arranged in the colorimetric probe reagent tube.
The specific detection process is as follows: the method comprises the following steps of (1) sucking a water sample by using a sampler (such as a sampling needle cylinder), connecting the sampler with a filtering membrane, taking a colorimetric probe reagent tube filled with Au @ PEI particle solution, filtering the water sample into the colorimetric probe reagent tube, uniformly mixing the mixed solution for a period of time to obtain a sample to be colorimetric, carrying out colorimetric reaction on the sample to be colorimetric and a concentration-color standard colorimetric system, and quickly judging whether the water sample contains medium-long-chain perfluorocarboxylic acid or perfluorocarboxylic acid in a concentration range; and measuring the ultraviolet absorbance of the sample by using an ultraviolet spectrophotometer, and determining the concentration of the long-chain perfluorocarboxylic acid in the water sample according to a concentration-ultraviolet absorbance standard curve.
Still be provided with reagent pipe support and cell pond in the box, the reagent pipe support is used for depositing unreacted colorimetric probe reagent pipe, and the cell pond is used for depositing the colorimetric probe solution after reacting with the water sample.
The ultraviolet spectrophotometer comprises an ultraviolet-visible light source, a sliding sample groove, a photoelectric converter, a darkroom and a darkroom cover; the ultraviolet-visible light source, the sliding sample groove and the photoelectric converter are arranged in the darkroom, the ultraviolet-visible light source is arranged corresponding to the photoelectric converter and is used for providing incident light to irradiate the sample to be colorimetric, the sliding sample groove is arranged between the ultraviolet-visible light source and the photoelectric converter, and the sample to be colorimetric is placed in the sliding sample groove; the photoelectric converter is used for receiving incident light which passes through a sample to be subjected to color comparison, and converting an optical signal into an electric signal to realize data acquisition and processing; the dark chamber cover is closed when the sample is detected, and a light-proof environment is provided for the detection process.
The ultraviolet spectrophotometer also comprises a data display screen, an operation key area and a waterproof wear-resistant surface layer. The data display screen can directly display the data processed by the photoelectric converter; the operation key area can control the switches of the detection program, the data converter and the display screen; the waterproof wear-resistant surface layer can protect devices in the box body and adapt to site environments.
The ultraviolet spectrophotometer also comprises a charging and data interface, and the charging and data interface can be connected with external equipment to charge the ultraviolet spectrophotometer and can directly lead out a data result.
The specific detection method for measuring the concentration of the medium-long chain perfluorocarboxylic acid in the sample to be colorimetric by using the ultraviolet spectrophotometer comprises the following steps: the method comprises the steps of putting a sample to be colorimetric into a sliding sample groove, closing a darkroom cover, opening an ultraviolet-visible light source through an operation key area to irradiate the sample to be colorimetric, determining the ultraviolet absorbance of the sample to be colorimetric, processing an optical signal through a photoelectric converter, reading the ultraviolet absorbance value on a data display screen, and then directly reading the concentration content of medium-long-chain perfluorocarboxylic acid in a water sample on the data display screen after converting data through the operation key area.
The established colorimetric method does not need expensive and precise instruments, is simple and convenient to operate, and can quickly judge whether the environmental water sample contains medium-long-chain perfluorocarboxylic acid or the concentration range of the perfluorocarboxylic acid through visual observation; the developed rapid detection device box is easy to carry, can realize rapid screening of batch samples, is used for monitoring the pollution level of long-chain perfluorocarboxylic acid in an environmental water body on site, and provides technical support for pollution early warning or rapid investigation of sudden water environment pollution events.
The technical scheme of the invention has the following advantages:
1. according to the method for rapidly detecting the medium-long-chain perfluorocarboxylic acid in the water sample, provided by the invention, polyethyleneimine modified gold nanoparticles (Au @ PEI) are used as a signal probe, in the presence of the medium-long-chain perfluorocarboxylic acid, the amino groups with positive charges on the surface of the Au @ PEI can generate electrostatic interaction and hydrogen bonding interaction with the medium-long-chain perfluorocarboxylic acid with negative charges, so that the dispersed Au @ PEI is aggregated, the color of the solution is changed from wine red to purple, the change of the color of the solution is observed visually, a colorimetric sensing method is established, the pollution level of the medium-long-chain perfluorocarboxylic acid in the water sample can be rapidly judged, the method is not limited by acid-base conditions, the measurement convenience is improved, and the application range of the detection method is expanded.
2. According to the method for rapidly detecting the medium-long-chain perfluorocarboxylic acid in the water sample, the Au @ PEI particle solution is prepared by taking polyethyleneimine with positive charges as a protective agent and sodium borohydride as a reducing agent, so that the prepared nanogold contains a large number of polyethyleneimine molecules on the surface, and the nanogold is enabled to have positive charges. The polyethyleneimine modified gold nanoparticle (Au @ PEI) signal probe is prepared at room temperature by adopting a one-step rapid reduction method, the preparation is simple and rapid, and the Au @ PEI with positive charges can be directly obtained through one-step reaction.
3. According to the method for rapidly detecting the medium-long-chain perfluorocarboxylic acid in the water sample, provided by the invention, the optimal using amount is obtained by optimizing through adjusting and changing the adding amount of the materials, the ultraviolet absorption peak shape of the prepared Au @ PEI particle is narrow, and the particle has good dispersibility, uniformity and stability.
4. The invention not only establishes the Au @ PEI colorimetric method capable of detecting the medium-long chain perfluorocarboxylic acid, but also develops the rapid detection device based on the principle of the method, the detection device integrates the sample pretreatment and detection functions into a whole, is convenient to carry, and the device in the box body is stable, thereby being suitable for being used outdoors and realizing the rapid detection of batch samples on project sites.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph of the UV absorption spectra of Au @ PEI particle solutions in example 1 in the presence of different concentrations of perfluorooctanecarboxylic acid;
FIG. 2 is a linear plot of perfluorooctane carboxylic acid concentration versus UV absorbance for example 1;
FIG. 3 is a plan view of the rapid test device of embodiment 2;
fig. 4 is a perspective view of the rapid detection device of embodiment 2.
Reference numerals:
1-a box body; 2-box cover; 3-sampling syringe; 4-a filtration membrane; 5-reagent tube rack; 6-colorimetric probe reagent tube; 7-cuvette pool; 8-uv-vis light source; 9-sliding the sample tank; 10-a photoelectric converter; 11-a data display screen; 12-operation key area; 13-waterproof wear-resistant surface layer; 14-dark chamber lid; 15-charging and data interface.
Detailed Description
Example 1
In example 1, perfluorooctane carboxylic acid (PFOA) is selected as the medium-and long-chain perfluorocarboxylic acid, but the embodiment of the present invention is not limited to perfluorooctane carboxylic acid, and may be applied to medium-and long-chain perfluorocarboxylic acids such as perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorotetradecanoic acid.
A method for rapidly detecting medium-long chain perfluorocarboxylic acid in a water sample comprises the following steps:
s1, preparation of Au @ PEI particles: adding 1.5mL of 1mg/mL polyethyleneimine solution into 30mL of 0.5mmol/L chloroauric acid solution, wherein the average molecular weight of polyethyleneimine is 2000g/mol, stirring for 20 minutes, then continuously adding 1.2mL of 25mmol/L sodium borohydride solution, taking sodium borohydride as a reducing agent to rapidly reduce chloroauric acid into gold nanoparticles, and stirring the reaction solution at room temperature for 2 hours to obtain the Au @ PEI particle solution.
S2, obtaining a concentration-color standard colorimetric system:
s201, preparing a perfluorooctane carboxylic acid standard solution: after dissolving the perfluorooctane carboxylic acid, preparing 4mg/mL perfluorooctane carboxylic acid standard stock solution, and then gradually diluting the stock solution into 8 parts of perfluorooctane carboxylic acid standard solutions with the concentrations of 0.2, 0.4, 0.6, 0.8, 1.2, 1.6, 2.0 and 2.4mg/mL respectively.
S202, 8 parts of 350 mu L Au @ PEI solution are taken, and perfluorooctane carboxylic acid standard solutions prepared in 50 mu L S201 and having the concentrations of 0.2mg/mL, 0.4mg/mL, 0.6mg/mL, 0.8mg/mL, 1.2mg/mL, 1.6mg/mL, 2.0mg/mL and 2.4mg/mL respectively are added to the solution so that the final concentrations of perfluorooctane carboxylic acid in the reaction solution are 25 mu g/mL, 50 mu g/mL, 75 mu g/mL, 100 mu g/mL, 150 mu g/mL, 200 mu g/mL, 250 mu g/mL and 300 mu g/mL respectively. And (3) uniformly mixing and reacting for 5 minutes to obtain 8 parts of a standard substance for colorimetric detection of perfluorooctane carboxylic acid, observing the color change of a solution of the standard substance to obtain a concentration-color standard colorimetric system, and gradually changing the color of the solution from wine red to purple-deep purple with the increase of the concentration of the perfluorooctane carboxylic acid. When the color of the solution is wine red through visual observation, the water sample does not contain perfluorocarboxylic acid or the concentration of the perfluorocarboxylic acid is less than or equal to 75 mug/mL; when the color of the solution is purple red, the concentration of the perfluorocarboxylic acid in the water sample is between 75 mu g/mL and 150 mu g/mL; when the solution was dark purple in color, it was shown that the concentration of perfluorocarboxylic acid in the water sample was greater than 150. mu.g/mL.
S3, collecting an environmental water sample around a fluorine chemical industry enterprise, filtering the water sample by using a 0.22-micron filter membrane, adding 50-micron water sample into 350-micron Au @ PEI particle solution, uniformly mixing, reacting for 5 minutes, and observing that the color of the solution is changed from wine red to purple, which indicates that the concentration of perfluorooctane carboxylic acid in the water sample is between 75-150-micron g/mL.
S4, measuring the ultraviolet absorbance of each perfluorooctane carboxylic acid standard solution by using an ultraviolet spectrophotometer, wherein as shown in figure 1, the ultraviolet absorbance value of the sample solution gradually increases along with the increase of the concentration of the perfluorooctane carboxylic acid; according to the relation between the ultraviolet absorbance and the concentration of the perfluorooctane carboxylic acid, the standard curve equation of detecting the perfluorooctane carboxylic acid is obtained, wherein y is 0.0005x +0.4638(R20.9801) linear in the range of 25 to 300 μ g/mL, as shown in figure 2.
And determining the ultraviolet absorbance of the sample to be subjected to color comparison, and determining the concentration of the perfluorooctane carboxylic acid in the environmental water sample to be 86 mu g/mL according to the relation between the ultraviolet absorbance and the concentration of the perfluorooctane carboxylic acid, which indicates that the pollution of the perfluorooctane carboxylic acid in the environmental water sample around the fluorine chemical industry enterprise is serious.
Example 2
A detection device for a method for rapidly detecting medium-long chain perfluorocarboxylic acid in a water sample comprises a box body 1 and a box cover 2, wherein the box body is internally provided with a sampling needle cylinder 3, a filtering membrane 4, a reagent pipe frame 5, a colorimetric probe reagent pipe 6, a cuvette pool 7, an ultraviolet-visible light source 8, a sliding sample groove 9, a photoelectric converter 10, a data display screen 11, an operation key area 12, a waterproof wear-resistant surface layer 13, a dark chamber cover 14 and a charging and data interface 15.
The sampling needle cylinder 3 is a 10mL plastic injector and is used for extracting an environmental water sample; the filtering membrane 4 is a cellulose microporous filtering membrane with the diameter of 0.22 mu m and is used for filtering and pretreating a water sample; the reagent tube rack 5 comprises 24 reagent tube holes for storing the colorimetric probe reagent tubes 6; the colorimetric probe reagent tube 6 is used for storing Au @ PEI particle solution; the cuvette pool 7 is used for storing a colorimetric probe solution obtained after reaction of Au @ PEI and a water sample; the ultraviolet-visible light source 8 is used for providing incident light to irradiate the sample to be colorimetric; the sliding sample groove 9 contains a groove for holding 5 cuvette pools 7, and 5 samples can be measured at one time through continuous sliding; the photoelectric converter 10 can convert the optical signal into an electrical signal to realize data acquisition and processing; the data display screen 11 can directly display the processed data; the operation key area 12 can control the detection program, data conversion and the switch of the display screen; the waterproof wear-resistant surface layer 13 can adapt to the field environment and protect a detection device in the box body; the dark chamber cover 14 can be closed during sample detection, so that a light-proof environment is provided for the detection process; the charging and data interface 15 can be connected with external equipment to charge the detection box body and can directly lead out data results.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A method for rapidly detecting medium-long chain perfluorocarboxylic acid in a water sample is characterized by comprising the following steps:
s1, preparing an Au @ PEI particle solution;
s2, obtaining a concentration-color standard colorimetric system;
s3, collecting a water sample, adding the water sample into the Au @ PEI particle solution prepared in the step S1, mixing to obtain a sample to be colorimetric, carrying out colorimetric reaction on the sample to be colorimetric and a concentration-color standard colorimetric system, observing the color of the sample to be colorimetric, and judging the concentration content of the long-chain perfluorocarboxylic acid in the water sample.
2. The method for rapidly detecting long-chain perfluorocarboxylic acid in a water sample as claimed in claim 1, wherein the preparation of the Au @ PEI particle solution comprises the following steps: and adding a polyethyleneimine solution into a chloroauric acid solution, stirring, then adding a sodium borohydride solution, and stirring again to obtain an Au @ PEI particle solution.
3. The method for rapidly detecting the long-chain perfluorocarboxylic acid in the water sample as claimed in claim 2, wherein the molar ratio of the chloroauric acid to the polyethyleneimine is (18-22): 1; the molar ratio of the chloroauric acid to the sodium borohydride is 1 (1.8-2.3);
the concentration of the chloroauric acid solution is 0.5-2 mmol/L, the concentration of the polyethyleneimine solution is 0.5-1.5 mg/mL, and the concentration of the sodium borohydride solution is 25-30 mol/L.
4. The method for rapidly detecting the long-chain perfluorocarboxylic acid in the water sample as claimed in claim 2, wherein the solution of Au @ PEI is obtained by stirring at room temperature for 1.5-2.5 h after adding the solution of sodium borohydride.
5. The method for rapidly detecting the long-chain perfluorocarboxylic acid in the water sample as claimed in claim 1, wherein the method for obtaining the concentration-color standard colorimetric system in step S2 comprises the following steps:
s201, preparing a medium-long chain perfluorocarboxylic acid standard solution: dissolving medium-long-chain perfluorocarboxylic acid, preparing to obtain 3-5 mg/mL medium-long-chain perfluorocarboxylic acid standard stock solution, and then gradually diluting the stock solution into N parts of medium-long-chain perfluorocarboxylic acid standard solutions with different concentrations, wherein N is more than or equal to 3;
s202, respectively adding N parts of 40-60 mu L of medium-long chain perfluorocarboxylic acid standard solutions with different concentrations into N parts of 300-400 mu L of Au @ PEI particle solution, mixing and reacting for 3-10 min to obtain N parts of perfluorocarboxylic acid standard for colorimetric detection, and recording the color of each part of perfluorocarboxylic acid standard to obtain a concentration-color standard colorimetric system.
6. The method for rapidly detecting long-chain perfluorocarboxylic acid in a water sample according to claim 5, wherein in S201, a 4mg/mL standard stock solution of medium-and long-chain perfluorocarboxylic acid is prepared, and then the stock solution is gradually diluted into 8 parts of standard solution of medium-and long-chain perfluorocarboxylic acid, the concentration of which is 0.2mg/mL, 0.4mg/mL, 0.6mg/mL, 0.8mg/mL, 1.2mg/mL, 1.6mg/mL, 2.0mg/mL, and 2.4mg/mL in sequence;
in the S202, 8 parts of medium-long chain perfluorocarboxylic acid standard solution with the volume of 50 mu L and the concentrations of 0.2mg/mL, 0.4mg/mL, 0.6mg/mL, 0.8mg/mL, 1.2mg/mL, 1.6mg/mL, 2.0mg/mL and 2.4mg/mL in sequence are respectively added into 8 parts of Au @ PEI particle solution with the volume of 350 mu L, mixed and reacted for 3-10 min to obtain 8 parts of medium-long chain perfluorocarboxylic acid standard products with the final concentrations of 25 mu g/mL, 50 mu g/mL, 75 mu g/mL, 100 mu g/mL, 150 mu g/mL, 200 mu g/mL, 250 mu g/mL and 300 mu g/mL in sequence, and the color of each part of perfluorocarboxylic acid standard product is recorded to obtain the concentration-color standard colorimetric system.
7. The method for rapidly detecting the long-chain perfluorocarboxylic acid in the water sample according to claim 1, wherein the step S3 is to collect the water sample, add 40-60 μ L of the water sample into 300-400 μ L of Au @ PEI particle solution, mix the water sample and the Au @ PEI particle solution to obtain a sample to be colorimetric, compare the sample to be colorimetric with a concentration-color standard colorimetric system, observe the color of the sample to be colorimetric, and determine the concentration content of the long-chain perfluorocarboxylic acid in the water sample;
when the color of the sample to be colorimetric is wine red in the step S3, the water sample does not contain medium-long chain perfluorocarboxylic acid or the concentration of medium-long chain perfluorocarboxylic acid is less than or equal to 75 mug/mL; when the color of the sample to be colorimetric is purple red, the concentration of the long-chain perfluorocarboxylic acid in the water sample is between 75 mu g/mL and 150 mu g/mL; when the color of the sample to be colorimetric is dark purple, the concentration of the long-chain perfluorocarboxylic acid in the water sample is more than 150 mug/mL.
8. The method for rapidly detecting long-chain perfluorocarboxylic acid in a water sample as claimed in claim 1, further comprising:
s4, determining the ultraviolet absorbance of the sample to be subjected to color comparison, and determining the concentration of the long-chain perfluorocarboxylic acid in the water sample according to a concentration-ultraviolet absorbance standard curve;
the concentration-ultraviolet absorbance standard curve is obtained by measuring the ultraviolet absorbance of the colorimetric detection perfluorocarboxylic acid standard substance.
9. The method for rapidly detecting the long-chain perfluorocarboxylic acid in the water sample according to claim 1, wherein after the water sample is collected in step S3, the water sample is filtered, and then the water sample is added to the Au @ PEI particle solution.
10. The detection device for the rapid detection method of the long-chain perfluorocarboxylic acid in the water sample according to any one of claims 1 to 9, which comprises a box body, wherein a sampler, a filter membrane, a colorimetric probe reagent tube, an ultraviolet spectrophotometer and a cuvette cell are arranged in the box body; an Au @ PEI particle solution is arranged in the colorimetric probe reagent tube; the cuvette pool is used for storing a colorimetric probe reagent after reaction with a water sample.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115825291A (en) * | 2023-02-08 | 2023-03-21 | 山东东岳高分子材料有限公司 | Method for determining content of trace perfluorocarboxylic acid compounds in fluorine-containing polymer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102435571A (en) * | 2011-09-16 | 2012-05-02 | 东华大学 | Method for detecting heparin content with polyethyleneimine-stabilized gold nanoparticle |
| CN103990811A (en) * | 2014-05-30 | 2014-08-20 | 吉林大学 | Electropositive fluorescent metal nanodot, preparation method and application of electropositive fluorescent metal nanodot in terms of cell fluorescence imaging |
| CN105060389A (en) * | 2015-07-16 | 2015-11-18 | 广西大学 | Method for photocatalytic degradation of PFOA (perfluorooctanoic acid) in water through noble-metal-doped gallium oxide |
| CN107778150A (en) * | 2016-08-24 | 2018-03-09 | 中昊晨光化工研究院有限公司 | A kind of method for preparing perfluoroisopropyl ethyl ketone |
| CN108780049A (en) * | 2016-01-27 | 2018-11-09 | 隐蔽色彩股份有限公司 | Devices, systems, and methods for detecting target substance |
| CN108956590A (en) * | 2018-05-23 | 2018-12-07 | 西北师范大学 | Purposes of the Au nano particle/polyethyleneimine composite material in detection mercury ion |
-
2021
- 2021-09-26 CN CN202111130635.XA patent/CN113848190A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102435571A (en) * | 2011-09-16 | 2012-05-02 | 东华大学 | Method for detecting heparin content with polyethyleneimine-stabilized gold nanoparticle |
| CN103990811A (en) * | 2014-05-30 | 2014-08-20 | 吉林大学 | Electropositive fluorescent metal nanodot, preparation method and application of electropositive fluorescent metal nanodot in terms of cell fluorescence imaging |
| CN105060389A (en) * | 2015-07-16 | 2015-11-18 | 广西大学 | Method for photocatalytic degradation of PFOA (perfluorooctanoic acid) in water through noble-metal-doped gallium oxide |
| CN108780049A (en) * | 2016-01-27 | 2018-11-09 | 隐蔽色彩股份有限公司 | Devices, systems, and methods for detecting target substance |
| CN107778150A (en) * | 2016-08-24 | 2018-03-09 | 中昊晨光化工研究院有限公司 | A kind of method for preparing perfluoroisopropyl ethyl ketone |
| CN108956590A (en) * | 2018-05-23 | 2018-12-07 | 西北师范大学 | Purposes of the Au nano particle/polyethyleneimine composite material in detection mercury ion |
Non-Patent Citations (6)
| Title |
|---|
| WANG, Q 等: "Occurrence and distribution of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in natural forest soils: A nationwide study in China", SCIENCE OF THE TOTAL ENVIRONMENT, vol. 645, pages 596 - 602, XP085475610, DOI: 10.1016/j.scitotenv.2018.07.151 * |
| 丛妍斌 等: "基于金纳米粒子比色法检测全氟辛烷磺酸", 光谱学与光谱分析, vol. 35, no. 01, pages 189 - 192 * |
| 吴建刚 等: "环境水样中全氟磺酸类和全氟羧酸类化合物分析方法研究进展", 环境化学, vol. 37, no. 08, pages 1851 - 1855 * |
| 胡聪 等: "超声靶向介导载CD-TK双自杀基因的微泡对肺癌的治疗作用", 重庆医科大学学报, vol. 44, no. 02, pages 157 - 162 * |
| 贺锦灿 等: "典型全氟有机酸类化合物的样品前处理与分析方法研究进展", 色谱, vol. 38, no. 01, pages 86 - 94 * |
| 马永存: "纺织厂污水污泥中全氟化合物分析检测体系构建及验证", 中国优秀硕士学位论文全文数据库工程科技Ⅰ辑, no. 8, pages 027 - 661 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115825291A (en) * | 2023-02-08 | 2023-03-21 | 山东东岳高分子材料有限公司 | Method for determining content of trace perfluorocarboxylic acid compounds in fluorine-containing polymer |
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