CN102495016A - Method for detecting polychlorinated biphenyl (PCB) pollutants in soil - Google Patents

Method for detecting polychlorinated biphenyl (PCB) pollutants in soil Download PDF

Info

Publication number
CN102495016A
CN102495016A CN2011104144380A CN201110414438A CN102495016A CN 102495016 A CN102495016 A CN 102495016A CN 2011104144380 A CN2011104144380 A CN 2011104144380A CN 201110414438 A CN201110414438 A CN 201110414438A CN 102495016 A CN102495016 A CN 102495016A
Authority
CN
China
Prior art keywords
soil
pcbs
dot matrix
nano
cyclodextrin
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.)
Granted
Application number
CN2011104144380A
Other languages
Chinese (zh)
Other versions
CN102495016B (en
Inventor
朱贤方
孔令琦
占金华
来永超
张春婧
刘璟
王连洲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN 201110414438 priority Critical patent/CN102495016B/en
Publication of CN102495016A publication Critical patent/CN102495016A/en
Application granted granted Critical
Publication of CN102495016B publication Critical patent/CN102495016B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention relates to a method for detecting polychlorinated biphenyl (PCB) pollutants in soil, relating to a method for detecting soil pollutants. The method comprises the following steps of: cleaning a quartz plate, self-assembling centrifuged and properly-dispersed polystyrene nano-sphere sol on the cleaned quartz plate through a dispensing method, and obtaining a single-layer polystyrene nano-sphere hexagonal close-spaced structure after drying; depositing a metallic silver film by using a physical vaporous deposition method, obtaining a two-dimensional hexagonal-array triangular silver nano dot matrix by removing polystyrene spheres in an ultrasonic manner, then observing a large-area two-dimensional hexagonal-array silver nano dot matrix by using a scanning electron microscope, and measuring absorption spectrum of a test sample in an ultraviolet-visible-infrared spectrometer; modifying cyclodextrin at the position of the two-dimensional silver nano dot matrix, and then measuring the absorption spectrum; and modifying PCBs with different concentrations, wherein because the cyclodextrin is of a hollow cavity structure, the PCBs enter the hollow cavity of the cyclodextrin and are combined with each other with the help of action forces, such as Van der Waals force or hydrogen bond and the like, so that a supramolecular compound is formed; and measuring the absorption spectrum.

Description

A kind of method that detects pollution by polychlorinated biphenyles thing in the soil
Technical field
The present invention relates to the detection method of soil pollutant, especially relate to a kind of method that detects pollution by polychlorinated biphenyles thing in the soil.
Background technology
Polychlorinated biphenyl (PCBs) is the organism of one type of synthetic, is that the hydrogen atom on the biphenyl phenyl ring is replaced and one type of chloride of formation by the chlorine atom.As a kind of noxious material that is difficult to degrade, the PCBs in the environment has great harm to health and ecologic environment.PCBs being widely used in industry caused global environmental pollution (list of references: Nadine Lambert, Titan S.Fan; Jean-Francois Pilette; Analysis of PCBs in waste oil by enzymeimmunoassay, Science of the Total Environment Volume 196, Issue 1; 9March 1997, Pages57-61).Therefore, how can detect the residual of PCBs in the environment accurately and efficiently, and guarantee the repeatability of technology, become and realize above-mentioned potential key in application through cost method low, easy and simple to handle, and particularly important for eliminating its harm.Though bibliographical information solid phase disk extraction-gas chromatography-mass spectrography (list of references: Nadine Lambert, Titan S.Fan, Jean-Francois Pilette is arranged; Analysis of PCBs in waste oil by enzyme immunoassay, Science of the TotalEnvironment Volume 196, Issue 1; 9March 1997, Pages 57-61), but the extraction of the solid phase disk in this method is a kind of new special SPE; Do not have in the common laboratory, its maturity waits checking, and step is complicated; Experimental cost is high, and efficient is lower.
Summary of the invention
The object of the invention aims to provide and a kind ofly learns a skill through supermolecular, and quickness and high efficiency detects the method for pollution by polychlorinated biphenyles thing in the soil.
The present invention includes following steps:
1) self assembly: piezoid is cleaned, centrifugal, scattered pipe/polyhenylethylene nano ball colloidal sol is carried out self assembly through drop-coating on the piezoid after the cleaning, after the drying, obtain the pipe/polyhenylethylene nano ball hexagonal solid matter structure of individual layer;
2) plated metal: use physical vaporous deposition plated metal silverskin,, obtain two-dimentional hexagonal and arrange triangle silver nano-dot matrix then through the ultrasonic polystyrene spheres of removing;
3) two-dimentional silver nano-grain lattice structure: with step 2) the two-dimentional hexagonal of gained is arranged the silver-colored nano-dot matrix that triangle silver nano-dot matrix is arranged to large-area two-dimentional hexagonal with scanning electronic microscope observation, sample absorbance spectrum in ultraviolet-visible-infrared spectrometer then;
4) bio-modification and spectral measurement: earlier in the silver-colored nano-dot matrix of two dimension position modification cyclodextrin (CDs), absorbance spectrum; And then the PCBs of modification variable concentrations, because cyclodextrin is a cavity structure, PCBs gets into cyclodextrin cavity, relies on acting forces such as Van der Waals force or hydrogen bond to combine, and forms super molecular compound, absorbance spectrum then;
5) repeatability detects: after falling PCBs with the eccysis of methanol mixed solution, and absorbance spectrum, and then repeat to modify PCBs, measure its absorption spectrum again.
In step 1), said cleaning can be passed through H successively 2O 2/ H 2SO 4, reagent such as ethanol, acetone clean said H 2O 2/ H 2SO 4Volume ratio can be 1: 3, said H 2O 2Mass percent can be 30%; The temperature of said drying can be 50 ℃.
In step 2) in, vacuum pressure＜1 * 10 of said use physical vaporous deposition plated metal silverskin -4Pa; The thickness of said metal silverskin can be 150nm; Said ultrasonic can be in organic solvent for ultrasonic, said organic solvent can adopt ethanol etc., said ultrasonic power can be 150W, frequency can be 42kHz, the ultrasonic time can be 2min.
The present invention utilizes supermolecular to learn a skill, and the control experiment parameter constitutes super molecular compound with cyclodextrin and polychlorinated biphenyl, utilizes cyclodextrin (CDs) to combine with the specificity of PCBs, prepares super molecular compound and detects.Used CDs is with low cost in the experiment, and efficient is higher, and the least concentration that can detect PCBs reaches 10 -7G/ml, and can carry out duplicate detection to PCBs.In addition, the present invention has advantages such as simple to operate, with low cost.
Description of drawings
Fig. 1 is that two-dimentional hexagonal is arranged triangle silver nano-dot matrix SEM picture.
Fig. 2 modifies CDs and variable concentrations PCBs front and back abosrption spectrogram for dot matrix.In Fig. 2, horizontal ordinate is wavelength (nm), and ordinate is absorption intensity (a.u.); Curve a is for modifying CD s+1 * 10 -7G/ml PCBs, summit are 519nm; Curve b is for modifying CD s+1 * 10 -4G/ml PCBs, summit are 523nm; Curve c is for modifying CD s, and summit is 502nm; Curve d is a unmodified, and summit is 472nm.
Fig. 3 modifies CDs and PCBs and eccysis for dot matrix and falls PCBs front and back abosrption spectrogram.In Fig. 3, horizontal ordinate is wavelength (nm), and ordinate is absorption intensity (a.u.); Curve a is for repeating to modify PCBs, and summit is 519nm; Curve b is that methanol is mixed eccysis, and summit is 522nm; Curve c is for modifying CD s+PCBs, and summit is 499nm; Curve d is CDs, and summit is 502nm; Curve e is a unmodified, and summit is 472nm.
Embodiment
Combine accompanying drawing that the present invention is described further through embodiment below.
Embodiment 1:
1) self assembly: piezoid is successively through volume ratio 1: 3H 2O 2(mass percent 30%)/H 2SO 4Reagent such as (mass percent 98%), ethanol, acetone clean, and in nitrogen atmosphere, dry then.Centrifugal, scattered 3% pipe/polyhenylethylene nano ball colloidal sol is carried out self assembly through drop-coating on the piezoid after the cleaning, and, obtain the pipe/polyhenylethylene nano ball hexagonal solid matter structure of individual layer in 50 ℃ of following freeze-day with constant temperature.
2) plated metal: the present invention uses method (vacuum pressure＜1 * 10 of physical vapour deposition (PVD) -4Pa), vertical deposition metal silverskin (the about 150nm of thickness) in resistance-type high vacuum coating appearance.Then through (power=150W, frequency=42kHz) 2min removes polystyrene spheres in organic solvent for ultrasonic such as ethanol.
3) two-dimentional silver nano-grain lattice structure: resulting structures is observed under scanning electron microscope, observed the silver-colored nano-dot matrix (as shown in Figure 1) that large-area two-dimentional hexagonal is arranged.Then sample is placed on absorbance spectrum in ultraviolet-visible-infrared spectrometer.
4) bio-modification and spectral measurement: modify CDs, absorbance spectrum in the two-dimentional silver-colored nano-dot matrix position of sample earlier; And then same position modification concentration is 1 * 10 on sample -4Behind the PCBs of g/ml, absorbance spectrum, the gained absorption spectrum is as shown in Figure 3.
Embodiment 2:
1) self assembly: piezoid is successively through volume ratio 1: 3H 2O 2(mass percent 30%)/H 2SO 4Reagent such as (mass percent 98%), ethanol, acetone clean, and in nitrogen atmosphere, dry then.Centrifugal, scattered 3% pipe/polyhenylethylene nano ball colloidal sol is carried out self assembly through drop-coating on the piezoid after the cleaning, and, obtain the pipe/polyhenylethylene nano ball hexagonal solid matter structure of individual layer in 50 ℃ of following freeze-day with constant temperature.
2) plated metal: the present invention uses method (vacuum pressure＜1 * 10 of physical vapour deposition (PVD) -4Pa), vertical deposition metal silverskin (the about 150nm of thickness) in resistance-type high vacuum coating appearance.Then through (power=150W, frequency=42kHz) 2min removes polystyrene spheres in organic solvent for ultrasonic such as ethanol.
3) two-dimentional silver nano-grain lattice structure: resulting structures is observed under scanning electron microscope, observed the silver-colored nano-dot matrix (as shown in Figure 1) that large-area two-dimentional hexagonal is arranged.Then sample is placed on absorbance spectrum in ultraviolet-visible-infrared spectrometer.
4) bio-modification and spectral measurement: modify CDs, absorbance spectrum in the two-dimentional silver-colored nano-dot matrix position of sample earlier; And then same position modification concentration is 1 * 10 on sample -7Behind the PCBs of g/ml, absorbance spectrum, the gained absorption spectrum is as shown in Figure 2.
5) repeatability detects: after falling PCBs with the eccysis of methanol mixed solution, and absorbance spectrum, and then repeat to modify PCBs, and measure its absorption spectrum again, it is as shown in Figure 3 to record spectrum.

Claims (8)

1. method that detects pollution by polychlorinated biphenyles thing in the soil is characterized in that may further comprise the steps:
1) self assembly: piezoid is cleaned, centrifugal, scattered pipe/polyhenylethylene nano ball colloidal sol is carried out self assembly through drop-coating on the piezoid after the cleaning, after the drying, obtain the pipe/polyhenylethylene nano ball hexagonal solid matter structure of individual layer;
2) plated metal: use physical vaporous deposition plated metal silverskin,, obtain two-dimentional hexagonal and arrange triangle silver nano-dot matrix then through the ultrasonic polystyrene spheres of removing;
3) two-dimentional silver nano-grain lattice structure: with step 2) the two-dimentional hexagonal of gained is arranged the silver-colored nano-dot matrix that triangle silver nano-dot matrix is arranged to large-area two-dimentional hexagonal with scanning electronic microscope observation, sample absorbance spectrum in ultraviolet-visible-infrared spectrometer then;
4) bio-modification and spectral measurement: elder generation is modification cyclodextrin in the silver-colored nano-dot matrix of two dimension position, absorbance spectrum; And then the PCBs of modification variable concentrations, because cyclodextrin is a cavity structure, PCBs gets into cyclodextrin cavity, relies on acting forces such as Van der Waals force or hydrogen bond to combine, and forms super molecular compound, absorbance spectrum then;
5) repeatability detects: after falling PCBs with the eccysis of methanol mixed solution, and absorbance spectrum, and then repeat to modify PCBs, measure its absorption spectrum again.
2. a kind of method that detects pollution by polychlorinated biphenyles thing in the soil as claimed in claim 1 is characterized in that in step 1) said cleaning is to pass through H successively 2O 2/ H 2SO 4, ethanol, acetone reagent cleans.
3. a kind of method that detects pollution by polychlorinated biphenyles thing in the soil as claimed in claim 2 is characterized in that said H 2O 2/ H 2SO 4Volume ratio be 1: 3, said H 2O 2Mass percent be 30%.
4. a kind of method that detects pollution by polychlorinated biphenyles thing in the soil as claimed in claim 1 is characterized in that in step 1) the temperature of said drying is 50 ℃.
5. a kind of method that detects pollution by polychlorinated biphenyles thing in the soil as claimed in claim 1 is characterized in that in step 2) in, vacuum pressure＜1 * 10 of said use physical vaporous deposition plated metal silverskin -4Pa.
6. like claim 1 or 5 described a kind of methods that detect pollution by polychlorinated biphenyles thing in the soil, the thickness that it is characterized in that said metal silverskin is 150nm.
7. a kind of method that detects pollution by polychlorinated biphenyles thing in the soil as claimed in claim 1 is characterized in that in step 2) in, said ultrasonic be in organic solvent for ultrasonic, said organic solvent adopts ethanol.
8. like claim 1 or 7 described a kind of methods that detect pollution by polychlorinated biphenyles thing in the soil, it is characterized in that in step 2) in, said ultrasonic power is 150W, and frequency is 42kHz, and the ultrasonic time is 2min.
CN 201110414438 2011-12-12 2011-12-12 Method for detecting polychlorinated biphenyl (PCB) pollutants in soil Expired - Fee Related CN102495016B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110414438 CN102495016B (en) 2011-12-12 2011-12-12 Method for detecting polychlorinated biphenyl (PCB) pollutants in soil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110414438 CN102495016B (en) 2011-12-12 2011-12-12 Method for detecting polychlorinated biphenyl (PCB) pollutants in soil

Publications (2)

Publication Number Publication Date
CN102495016A true CN102495016A (en) 2012-06-13
CN102495016B CN102495016B (en) 2013-03-27

Family

ID=46186858

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110414438 Expired - Fee Related CN102495016B (en) 2011-12-12 2011-12-12 Method for detecting polychlorinated biphenyl (PCB) pollutants in soil

Country Status (1)

Country Link
CN (1) CN102495016B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103837519A (en) * 2014-04-10 2014-06-04 中国科学院合肥物质科学研究院 A method of measuring a plurality of polychlorinated biphenyls by surface enhanced Raman spectroscopy
CN111426675A (en) * 2020-03-31 2020-07-17 江苏海尔森检测技术服务有限公司 Detection method of dioxin compound

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4726905A (en) * 1986-04-30 1988-02-23 American Maize-Products Company Method for removing polychlorinated biphenyl compounds from water
WO1991001721A1 (en) * 1989-08-11 1991-02-21 Edward Vanzo Cyclodextrin polymer beads
CN1341855A (en) * 2001-08-23 2002-03-27 中国科学院南京土壤研究所 Determination method of trace organic chlorine pesticide and polychlorobiphenyl residual amount
CN101474630A (en) * 2008-01-02 2009-07-08 北京师范大学 Cyclodextrin eluting/Fenton oxidation degradation method for polychlorinated biphenyl in soil
WO2009140264A2 (en) * 2008-05-12 2009-11-19 Enchem Engineering, Inc. Chemical oxidation method and compounds
CN102211795A (en) * 2011-04-20 2011-10-12 华中科技大学 Method for regenerating eluant in organic polluted soil eluent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4726905A (en) * 1986-04-30 1988-02-23 American Maize-Products Company Method for removing polychlorinated biphenyl compounds from water
WO1991001721A1 (en) * 1989-08-11 1991-02-21 Edward Vanzo Cyclodextrin polymer beads
CN1341855A (en) * 2001-08-23 2002-03-27 中国科学院南京土壤研究所 Determination method of trace organic chlorine pesticide and polychlorobiphenyl residual amount
CN101474630A (en) * 2008-01-02 2009-07-08 北京师范大学 Cyclodextrin eluting/Fenton oxidation degradation method for polychlorinated biphenyl in soil
WO2009140264A2 (en) * 2008-05-12 2009-11-19 Enchem Engineering, Inc. Chemical oxidation method and compounds
CN102211795A (en) * 2011-04-20 2011-10-12 华中科技大学 Method for regenerating eluant in organic polluted soil eluent

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103837519A (en) * 2014-04-10 2014-06-04 中国科学院合肥物质科学研究院 A method of measuring a plurality of polychlorinated biphenyls by surface enhanced Raman spectroscopy
CN103837519B (en) * 2014-04-10 2016-11-16 中国科学院合肥物质科学研究院 Surface enhanced raman spectroscopy measures the method for Polychlorinated Biphenyls
CN111426675A (en) * 2020-03-31 2020-07-17 江苏海尔森检测技术服务有限公司 Detection method of dioxin compound

Also Published As

Publication number Publication date
CN102495016B (en) 2013-03-27

Similar Documents

Publication Publication Date Title
Jiang et al. Surface-enhanced Raman scattering detection of pesticide residues using transparent adhesive tapes and coated silver nanorods
Song et al. Molecular characterization of water-soluble humic like substances in smoke particles emitted from combustion of biomass materials and coal using ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry
Tao et al. Molecular characterization of organosulfates in organic aerosols from Shanghai and Los Angeles urban areas by nanospray-desorption electrospray ionization high-resolution mass spectrometry
Liu et al. Significant production of secondary organic aerosol from emissions of heated cooking oils
Funck et al. Identification of microplastics in wastewater after cascade filtration using Pyrolysis-GC–MS
Wang et al. Flexible gas sensors with assembled carbon nanotube thin films for DMMP vapor detection
Lam et al. Chemical composition of surface films on glass windows and implications for atmospheric chemistry
Zereini et al. Concentration and distribution of heavy metals in urban airborne particulate matter in Frankfurt am Main, Germany
Zdráhal et al. Improved method for quantifying levoglucosan and related monosaccharide anhydrides in atmospheric aerosols and application to samples from urban and tropical locations
Schauer et al. Polycyclic aromatic hydrocarbons in urban air particulate matter: decadal and seasonal trends, chemical degradation, and sampling artifacts
CN102004096B (en) Surface enhanced Raman detection method for polycyclic aromatic hydrocarbon and substitute thereof
Rajput et al. Atmospheric particulate matter (PM2. 5), EC, OC, WSOC and PAHs from NE–Himalaya: abundances and chemical characteristics
Waterman et al. Quantification of polycyclic aromatic hydrocarbons in the NIST standard reference material (SRM1649A) urban dust using thermal desorption GC/MS
McRae et al. Use of compound-specific stable isotope analysis to source anthropogenic natural gas-derived polycyclic aromatic hydrocarbons in a lagoon sediment
McNicholas et al. Sensitive detection of elemental mercury vapor by gold-nanoparticle-decorated carbon nanotube sensors
Alizadeh et al. A new chemiresistor sensor based on a blend of carbon nanotube, nano-sized molecularly imprinted polymer and poly methyl methacrylate for the selective and sensitive determination of ethanol vapor
Kondratyuk et al. Observation of a one-dimensional adsorption site on carbon nanotubes: adsorption of alkanes of different molecular lengths
Zhou et al. Rapid recognition of isomers of monochlorobiphenyls at trace levels by surface-enhanced Raman scattering using Ag nanorods as a substrate
Ro et al. An expert system for chemical speciation of individual particles using low-Z particle electron probe X-ray microanalysis data
Choi et al. Influence of biogenic organics on the chemical composition of Arctic aerosols
Bisiaux et al. Stormwater and fire as sources of black carbon nanoparticles to Lake Tahoe
Yin et al. Sensitive and rapid detection of trace microplastics concentrated through Au-nanoparticle-decorated sponge on the basis of surface-enhanced Raman spectroscopy
Favez et al. Significant formation of water‐insoluble secondary organic aerosols in semi‐arid urban environment
Wang et al. Application of parallel factor analysis model to decompose excitation-emission matrix fluorescence spectra for characterizing sources of water-soluble brown carbon in PM2. 5
Shen et al. Satellite remote sensing of air quality in the energy golden triangle in Northwest China

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130327

Termination date: 20151212

EXPY Termination of patent right or utility model