CN102495016B - Method for detecting polychlorinated biphenyl (PCB) pollutants in soil - Google Patents

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

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CN102495016B
CN102495016B CN 201110414438 CN201110414438A CN102495016B CN 102495016 B CN102495016 B CN 102495016B CN 201110414438 CN201110414438 CN 201110414438 CN 201110414438 A CN201110414438 A CN 201110414438A CN 102495016 B CN102495016 B CN 102495016B
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pcbs
detects
dot matrix
cyclodextrin
soil pollutant
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CN102495016A (en
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朱贤方
孔令琦
占金华
来永超
张春婧
刘璟
王连洲
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Xiamen University
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Xiamen University
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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 the PCBs in Soil pollutant
Technical field
The present invention relates to the detection method of soil pollutant, especially relate to a kind of method that detects the PCBs in Soil pollutant.
Background technology
Polychlorinated biphenyl (PCBs) is manually synthetic organism of a class, is that hydrogen atom on the biphenyl phenyl ring is replaced by the chlorine atom and the class chloride that forms.As a kind of noxious material of hard degradation, the PCBs in the environment has great harm to health and ecologic environment.PCBs is in industrial being widely used, 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 accurately and efficiently the residual of PCBs in the environment by cost method low, easy and simple to handle, and guarantee the repeatability of technique, become the key that realizes above-mentioned potential application, and particularly important for eliminating its harm.Though bibliographical information solid phase disk extraction-gas chromatography-mass spectrography (list of references: Nadine Lambert is arranged, Titan S.Fan, Jean-Francois Pilette, Analysis of PCBs in waste oil by enzyme immunoassay, Science of the TotalEnvironment Volume 196, Issue 1,9March 1997, but the solid phase disk in the method extraction is a kind of new special Solid-Phase Extraction, does not have in the common laboratory Pages 57-61),, its maturity waits checking, and step is complicated, and experimental cost is high, and efficient is lower.
Summary of the invention
Purpose of the present invention aims to provide and a kind ofly learns a skill by supermolecular, and quickness and high efficiency detects the method for PCBs in Soil pollutant.
The present invention includes following steps:
1) self assembly: piezoid is cleaned, centrifugal, scattered polystyrene nanospheres colloidal sol is carried out self assembly by the piezoid of drop-coating after cleaning, after the drying, obtain the polystyrene nanospheres Hexagonal Close-packed structure of individual layer;
2) plated metal: use physical vaporous deposition plated metal silverskin, then by the ultrasonic polystyrene spheres of removing, obtain two-dimentional hexagonal and arrange the Triangular Silver nano-dot matrix;
3) two-dimentional silver nano-grain lattice structure: with step 2) the two-dimentional hexagonal of gained is arranged the silver nanoparticle dot matrix that the Triangular Silver nano-dot matrix is arranged to large-area two-dimentional hexagonal with scanning electronic microscope observation, then sample absorbance spectrum in ultraviolet-visible-infrared spectrometer;
4) bio-modification and spectral measurement: first in two-dimentional silver nanoparticle lattice position modification cyclodextrin (CDs), absorbance spectrum; And then the PCBs of modification variable concentrations, because cyclodextrin is cavity structure, PCBs enters cyclodextrin cavity, relies on the acting forces such as Van der Waals force or hydrogen bond to combine, and forms super molecular compound, then absorbance spectrum;
5) repeatability detects: after falling PCBs with the eccysis of methanol/ethanol mixed solution, and absorbance spectrum, and then repeat to modify PCBs, measure again its absorption spectrum.
In step 1) in, described cleaning can be passed through H successively 2O 2/ H 2SO 4, the reagent such as ethanol, acetone clean described H 2O 2/ H 2SO 4Volume ratio can be 1: 3, described H 2O 2Mass percent can be 30%; The temperature of described drying can be 50 ℃.
In step 2) in, the vacuum pressure of described use physical vaporous deposition plated metal silverskin＜1 * 10 -4Pa; The thickness of described metal silverskin can be 150nm; Described ultrasonic can be in organic solvent for ultrasonic, described organic solvent can adopt ethanol etc., described 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 consists of super molecular compound with cyclodextrin and polychlorinated biphenyl, utilizes the specific binding of cyclodextrin (CDs) and 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 the advantages such as simple to operate, with low cost.
Description of drawings
Fig. 1 is that two-dimentional hexagonal is arranged Triangular Silver nano-dot matrix SEM picture.
Fig. 2 is that dot matrix is modified CDs and variable concentrations PCBs front and back abosrption spectrogram.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 unmodified, and summit is 472nm.
Fig. 3 is that dot matrix is modified CDs and PCBs and eccysis and fallen abosrption spectrogram before and after the PCBs.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/ethanol 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 unmodified, and summit is 472nm.
Embodiment
The invention will be further described by reference to the accompanying drawings below by embodiment.
Embodiment 1:
1) self assembly: piezoid is successively by volume ratio 1: 3H 2O 2(mass percent 30%)/H 2SO 4The reagent such as (mass percent 98%), ethanol, acetone clean, and then dry in nitrogen atmosphere.Centrifugal, scattered 3% polystyrene nanospheres colloidal sol is carried out self assembly by the piezoid of drop-coating after cleaning, and in 50 ℃ of lower freeze-day with constant temperature, obtain the polystyrene nanospheres Hexagonal Close-packed structure of individual layer.
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 instrument.Then by (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 nanoparticle 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 nanoparticle lattice position of sample first; 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 by volume ratio 1: 3H 2O 2(mass percent 30%)/H 2SO 4The reagent such as (mass percent 98%), ethanol, acetone clean, and then dry in nitrogen atmosphere.Centrifugal, scattered 3% polystyrene nanospheres colloidal sol is carried out self assembly by the piezoid of drop-coating after cleaning, and in 50 ℃ of lower freeze-day with constant temperature, obtain the polystyrene nanospheres Hexagonal Close-packed structure of individual layer.
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 instrument.Then by (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 nanoparticle 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 nanoparticle lattice position of sample first; 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/ethanol mixed solution, and absorbance spectrum, and then repeat to modify PCBs, and measure again its absorption spectrum, record spectrum as shown in Figure 3.

Claims (8)

1. method that detects the PCBs in Soil pollutant is characterized in that may further comprise the steps:
1) self assembly: piezoid is cleaned, centrifugal, scattered polystyrene nanospheres colloidal sol is carried out self assembly by the piezoid of drop-coating after cleaning, after the drying, obtain the polystyrene nanospheres Hexagonal Close-packed structure of individual layer;
2) plated metal: use physical vaporous deposition plated metal silverskin, then by the ultrasonic polystyrene nanospheres of removing, obtain two-dimentional hexagonal and arrange the Triangular Silver nano-dot matrix;
3) two-dimentional silver nano-grain lattice structure: with step 2) the two-dimentional hexagonal of gained is arranged the silver nanoparticle dot matrix that the Triangular Silver nano-dot matrix is arranged to large-area two-dimentional hexagonal with scanning electronic microscope observation, then sample absorbance spectrum in ultraviolet-visible-infrared spectrometer;
4) bio-modification and spectral measurement: first in two-dimentional silver nanoparticle lattice position modification cyclodextrin, absorbance spectrum; And then the PCBs of modification variable concentrations, because cyclodextrin is cavity structure, PCBs enters cyclodextrin cavity, relies on Van der Waals force or Hyarogen-bonding to combine, and forms super molecular compound, then absorbance spectrum;
5) repeatability detects: after falling PCBs with the eccysis of methanol/ethanol mixed solution, and absorbance spectrum, and then repeat to modify PCBs, measure again its absorption spectrum.
2. a kind of method that detects the PCBs in Soil pollutant as claimed in claim 1 is characterized in that in step 1), and described cleaning is to pass through successively H 2O 2/ H 2SO 4, ethanol, acetone reagent cleans.
3. a kind of method that detects the PCBs in Soil pollutant as claimed in claim 2 is characterized in that described H 2O 2/ H 2SO 4Volume ratio be 1: 3, H 2O 2The quality of solute accounts for H 2O 2The mass percent of solution is 30%.
4. a kind of method that detects the PCBs in Soil pollutant as claimed in claim 1 is characterized in that in step 1), and the temperature of described drying is 50 ℃.
5. a kind of method that detects the PCBs in Soil pollutant as claimed in claim 1 is characterized in that in step 2) in, the vacuum pressure of described use physical vaporous deposition plated metal silverskin＜1 * 10 -4Pa.
6. such as claim 1 or 5 described a kind of methods that detect the PCBs in Soil pollutant, the thickness that it is characterized in that described metal silverskin is 150nm.
7. a kind of method that detects the PCBs in Soil pollutant as claimed in claim 1 is characterized in that in step 2) in, described ultrasonic be in organic solvent for ultrasonic, described organic solvent adopts ethanol.
8. such as claim 1 or 7 described a kind of methods that detect the PCBs in Soil pollutant, it is characterized in that in step 2) in, described 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)

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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

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

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