CN107632077B - Method for quantifying micro-plastic in landfill leachate - Google Patents
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Abstract
The invention discloses a method for quantifying micro-plastic in landfill leachate, which comprises the following steps: weighing a standard substance mixture of 7 kinds of micro-plastics as template molecules, adding functional monomers and the like, uniformly mixing, then dropwise adding the mixture into the mixed liquid of the magnetic fluid, heating to react to generate magnetic microspheres, and drying and washing the magnetic microspheres to prepare the magnetic selective adsorbent; sieving a landfill leachate sample, oxidizing organic matters on the surface of the landfill leachate sample, centrifuging to obtain sediments, adding an organic solvent, heating to dissolve the sediments, allowing the obtained sample to flow through a column which is filled with a magnetic selective adsorbent in advance, eluting with an acetone/dichloromethane mixed solution, collecting, and measuring the content of the micro-plastics in the final sample by using GC-MS. The method provided by the invention is based on the detection of the content of the characteristic plasticizer, and provides a convenient method for quantitative detection of the micro-plastic in the landfill leachate. The method is simple to operate, low in detection cost and mild in treatment condition, and provides a new idea for detection in the field of micro-plastic environmental pollution.
Description
Technical Field
The invention relates to a method for quantifying micro-plastic in landfill leachate.
Background
Plastics are widely used in daily life, but the recovery rate is not high due to high recovery cost. And the hard degradability of the compound makes the compound exist in the environment for a long time. The plastic in the environment is further decomposed into smaller plastic fragments or particles through physical and chemical actions, and the smaller plastic fragments or particles can be defined as micro plastic when the diameter of the plastic is less than 5 mm.
The use of plastic films, the dumping of marine garbage and the generation of household garbage in the production of pesticides all generate a certain amount of micro-plastics, the micro-plastics which are left in the environment for a long time can adsorb environmental pollutants (heavy metals, organic pollutants and the like), the micro-plastics with low density can migrate along with the ways of air, water flow, food chains and the like, and after animals ingest the polluted micro-plastics, the micro-plastics in the bodies can desorb to release the pollutants and even plastic additives, so that the change of biological forms and even death are caused. A slightly denser water body may be retained or settle. The migration of the contaminant-adsorbed micro-plastic may cause the contaminant to diffuse. In recent years, these small particles of plastics are susceptible to being eaten by marine organisms, and thus, micro-plastic pollution in the marine and coastal zones is receiving more and more attention.
However, for the separation and quantification of micro-plastics, a density separation method, such as soaking and separating sediment samples with a saturated sodium chloride solution, a sodium polytungstate solution, seawater, or the like, is widely used at present. However, the composition of substances in actual environmental samples is complex, the operation of the above method is complicated, and the separation efficiency still needs to be further improved.
201610030237.3 patent discloses a quantitative detection method for micro-plastics in aquatic organisms based on fluorescent tracing technology, but the method has large limitation and complex operation. The relevant European Union standards indicate that plastics for toys or child care products contain no more than 0.1% of 3-type phthalates (DEHP, DBP and BBP), DEHP being the most widely used plasticizer. The corresponding plasticizer content of each plastic is subject to certain standards, which will continue to be further specified in the future, which provides the possibility of micro-plastic quantification. Therefore, it is feasible and important to find an efficient and low cost method for the quantification of microplastics.
Disclosure of Invention
In order to overcome the defects of complex operation, low efficiency and the like in the conventional micro-plastic quantification technology, the invention aims to provide a method for quantifying micro-plastic in landfill leachate.
The purpose of the invention is realized by the following technical scheme:
a method for quantifying micro-plastic in landfill leachate comprises the following steps:
(1) mixing nano Fe3O4Ultrasonically dispersing the mixture in water uniformly, then adding polyvinyl alcohol suspension to completely immerse the mixture, and heating and stirring the mixture uniformly to obtain magnetic fluid mixed solution; in the invention, the nano ferric oxide is used for providing magnetism, and the polyvinyl alcohol suspension is used for forming a film in a subsequent forming way;
(2) a standard mixture V of DEHP (dioctyl phthalate), DBP (dibutyl phthalate), BBP (butyl benzyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BPA (bisphenol A) and DNOP (di-n-octyl phthalate) was weighed1The mL is used as a template molecule, a functional monomer and a cosolvent are added, and ultrasonic mixing is carried out; adding a cross-linking agent and an initiator, and uniformly mixing by ultrasonic dispersion;
the functional monomer is preferably α -methacrylic acid (α -MAA) and styrene, and the dosage of the functional monomer is (0.02-0.10) V1mL, wherein the volume ratio of α -methacrylic acid (α -MAA) to styrene is 3: 5;
the cosolvent is preferably acetone or propylene glycol, and the dosage is preferably (3-4) V1mL；
The cross-linking agent is preferably one of dimethylamino propylamine, triethylene tetramine or diethylamino propylamine, and the using amount of the cross-linking agent is 1.1-1.5 times of the molar weight of the mixture of the 7 micro-plastic standard products;
the initiator is preferably one of azodiisobutyronitrile or dimethyl azodiisobutyrate, and the using amount of the initiator is 0.1-0.3 time of the molar amount of the 7 micro-plastic standard substance mixture;
(3) dropwise adding the mixed solution prepared in the step (2) into the magnetic fluid mixed solution prepared in the step (1), and then heating in a water bath to react to generate magnetic microspheres; sucking out the magnetic microspheres by using a magnet, drying the magnetic microspheres after washing, and eluting the dried magnetic microspheres by using acetone at 70-90 ℃ until template molecules cannot be detected to prepare the magnetic selective adsorbent; the amount (by volume) of the magnetic fluid mixed solution is larger than that (by volume) of the mixed solution in the step (2), and is about 1.1-1.2 times;
the water bath heating in the step (3) is preferably carried out for 6-8 h at the temperature of 45-50 ℃;
(4) passing the collected landfill leachate sample through a screen to remove impurities such as large particles, and using UV/H (ultraviolet/hydrogen) to obtain filtrate2O2Oxidizing organic matter on the surface by an advanced oxidation method, centrifuging for 2 times to obtain sediment, adding sodium hydroxide into the sediment to quench H2O2Then adding sulfuric acid to adjust the sediment to be neutral;
the sampling method is a large sample method, namely a sampling method which does not separate components on site but retains all samples;
the aperture of the screen is preferably 5 mm;
the reaction time of the advanced oxidation method in the step (4) is 1-2 h;
step (4) UV/H2O2The UV source in the advanced oxidation method adopts a 185-254 nm wave band ultraviolet source, and the light intensity reaches 5mw/cm2；
Centrifuging preferably at 2000-3000 r/min for 10min in the step (4);
the UV/H2O2Advanced oxidation methods are described in the prior art (Jiajimin. UV/H)2O2And UV/TiO2Study of degradation of typical PPCPs by advanced Oxidation [ D]Journal of Beijing university of construction, 2016.);
(5) adding an organic solvent into the sediment obtained in the step (4), heating in a water bath for dissolving, cooling the solution, filtering by using a glass sand core for removing impurities, allowing the obtained sample to flow through a column filled with a magnetic selective adsorbent in advance, and after the adsorption of the column is finished, freezing, vacuum drying and draining water; then eluting with acetone/dichloromethane mixed solution and collecting, concentrating the eluent to 1mL, blow-drying with a nitrogen blowing instrument, adding chromatographic grade methanol, transferring to a brown sample injection bottle, and fixing the volume to 1 mL;
the organic solvent in the step (5) is preferably one of dimethylformamide, hexafluoroisopropanol or cyclohexanone;
heating and dissolving in the water bath in the step (5), preferably heating in the water bath at 60-70 ℃ for 1-2 h;
the acetone/dichloromethane mixed solution in the step (5) adopts three different volume ratios in sequence, wherein the volume ratios of acetone to dichloromethane are respectively 3:7, 1:1 and 7: 3;
(6) measuring the contents of DEHP, DBP, BBP, DINP, DIDP, BPA and DNOP in the final sample obtained in the step (5) by using GC-MS to obtain the total content of a mg/L; calculating the content (Y mg/L) of the micro-plastics in the collected landfill leachate by the following formula;
The principle of the invention is as follows: centrifuging the sediments in the landfill leachate, oxidizing and removing organic matters on the surface by using an advanced oxidation technology, dissolving the sediments obtained by centrifuging by using an organic solvent, adsorbing by using a magnetic selective adsorbent, eluting and purifying by using the organic solvent, measuring the total content of 7 PAEs (phthalic acid esters), and representing the content of the micro-plastics by using the total content of the PAEs.
Compared with the prior art, the invention has the following advantages and effects:
the method provided by the invention is based on the detection of the content of the characteristic plasticizer, and provides a relatively convenient method for quantitatively detecting the micro-plastic in the landfill leachate. The method disclosed by the invention is simple to operate, low in detection cost and mild in treatment conditions, and provides a new idea for detection in the field of micro-plastic environmental pollution.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Examples
A quantitative analysis method for micro-plastics in landfill leachate comprises the following steps:
(1) preparation of the magnetic selective adsorbent: 1.2g of nano Fe3O4Performing ultrasonic treatment in 30mL of water for 10min, adding 100mL of 0.03mol/L polyvinyl alcohol suspension, heating in water bath at 70 ℃, and stirring for 20min to obtain a magnetic fluid mixed solution for later use.
(2) Weighing 2.5mL (0.1mol/L) of a liquid standard mixture of DEHP, DBP, BBP, DINP, DIDP, BPA and DNOP as a template molecule, adding 0.1mL α -mixed solution of methacrylic acid (α -MAA) and styrene (α -MAA is 0.05mol/L, and the volume ratio of α -MAA to styrene is 3:5) as a functional monomer and 10mL acetone as a cosolvent, carrying out ultrasonic treatment for 10min to uniformly mix the mixture, then adding 1mL 0.3mol/L of dimethylaminopropylamine serving as a crosslinking agent, adding 0.5mL0.1mol/L of azobisisobutyronitrile (initiator), and continuing ultrasonic dispersion for 15 min.
(3) And slowly dripping the mixed liquid after the ultrasonic treatment into the spare magnetic fluid mixed liquid by using a dropper, and reacting for 7 hours under the heating of a water bath at 50 ℃ after the addition to synthesize the magnetic molecular microspheres. And (4) sucking out the magnetic microspheres by using a magnet, washing for 4-6 times until the washing liquid is clear, and drying the obtained microspheres. The dried microspheres were eluted with acetone at 80 ℃ until no template molecules could be detected. Finally drying to obtain 5g of magnetic selective adsorbent;
(4) collecting samples: collecting a certain landfill leachate sample by a large sample method which does not separate components on site but retains all samples, wherein the year of a landfill is 5 years, and the annual average temperature is 22.3 ℃;
(5) sample pretreatment: taking a 50mL landfill leachate sample, passing the landfill leachate sample through a screen with the aperture of 5mm, preliminarily removing impurities such as large particles and the like to obtain filtrate, and utilizing UV/H (ultraviolet/hydrogen) to remove impurities2O2Oxidizing by advanced oxidation method for 90min to oxidize organic matter on surface, centrifuging for 2 times (2500r/min for 10min) to obtain precipitate, adding sodium hydroxide to quench H2O2Adding sulfuric acid to adjust the neutrality;
(6) sample treatment: to the deposit 50mL of dimethylformamide was added and the solution was heated in a water bath at 65 ℃ for 90min, so that the microplastic was completely dissolved. After the solution is cooled, the solution is filtered by a glass sand core to remove impurities, the obtained sample passes through a magnetic selective adsorbent column which is purified in advance at a certain flow rate (the bed body is 25mL, and the flow rate is 25mL/min), and after the adsorption of the column is finished, water is drained by a freezing vacuum dryer. Then eluting with 100mL of 3 acetone/dichloromethane mixtures (volume ratio of 3:7, 1:1, 7:3 respectively) with different volume ratios, collecting, concentrating the eluate to 1mL at 40 deg.C by a rotary evaporator, blow-drying with a mild nitrogen blower, adding chromatographic grade methanol, transferring to a brown sample introduction bottle, and diluting to 1 mL.
(7) And (3) sample determination: measuring the contents of DEHP, DBP, BBP, DINP, DIDP and DNOP in a brown sample injection bottle by GC-MS, wherein the total content is 0.083mg/L (P < 0.05);
(8) characterization of the content of the micro-plastic: quantitative analysis of the micro-plastic was performed by means of total reflection Fourier transform micro-infrared spectroscopy to obtain a sample with a content of 118.22 mg/L.
By the formula
The content of the micro-plastic is calculated to obtain 115.66mg/L, and the error of the result obtained by the total reflection Fourier transform micro infrared spectrum is 2.2 percent.
The quantitative analysis method of the micro-plastic has the advantages of small error, simple operation and wide application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A method for quantifying micro-plastic in landfill leachate is characterized by comprising the following steps:
(1) mixing nano Fe3O4Ultrasonically dispersing the mixture in water uniformly, then adding polyvinyl alcohol suspension to completely immerse the mixture, and heating and stirring the mixture uniformly to obtain magnetic fluid mixed solution;
(2) weighing a standard mixture V of DEHP, DBP, BBP, DINP, DIDP, BPA and DNOP1The mL is used as a template molecule, a functional monomer and a cosolvent are added, and ultrasonic mixing is carried out; adding a cross-linking agent and an initiator, and uniformly mixing by ultrasonic dispersion;
the functional monomers are α -methacrylic acid and styrene, and the dosage is (0.02-0.10) V1mL；
(3) Dropwise adding the mixed solution prepared in the step (2) into the magnetic fluid mixed solution prepared in the step (1), and then heating in a water bath to react to generate magnetic microspheres; sucking out the magnetic microspheres by using a magnet, drying the magnetic microspheres after washing, and eluting the dried magnetic microspheres by using acetone at 80 ℃ until template molecules cannot be detected to prepare the magnetic selective adsorbent;
(4) screening the collected landfill leachate sample through a screen to remove large particles and impurities, and utilizing UV/H (ultraviolet/hydrogen) to obtain filtrate2O2Oxidizing organic matters on the surface by an advanced oxidation method, centrifuging to obtain sediments, adding sodium hydroxide into the sediments to quench H2O2Then adding sulfuric acid to adjust the sediment to be neutral;
(5) adding an organic solvent into the sediment obtained in the step (4), heating in a water bath for dissolving, cooling the solution, filtering by using a glass sand core for removing impurities, allowing the obtained sample to flow through a column filled with a magnetic selective adsorbent in advance, and after the adsorption of the column is finished, freezing, vacuum drying and draining water; then eluting with acetone/dichloromethane mixed solution and collecting, concentrating the eluent to 1mL, blow-drying with a nitrogen blowing instrument, adding chromatographic grade methanol, transferring to a brown sample injection bottle, and fixing the volume to 1 mL;
(6) measuring the contents of DEHP, DBP, BBP, DINP, DIDP, BPA and DNOP in the final sample obtained in the step (5) by using GC-MS to obtain the total content of a mg/L; then the content of the micro-plastic in the collected landfill leachate is calculated by the following formula to be Ymg/L;
the cross-linking agent in the step (2) is one of dimethylamino propylamine, triethylene tetramine or diethylamino propylamine;
the initiator in the step (2) is azobisisobutyronitrile or dimethyl azobisisobutyrate;
the acetone/dichloromethane mixed solution in the step (5) adopts three different volume ratios in sequence, wherein the volume ratios of acetone to dichloromethane are respectively 3:7, 1:1 and 7: 3.
2. The method of claim 1, wherein: the cosolvent in the step (2) is acetone or propylene glycol, and the dosage of the cosolvent is (3-4) V1mL。
3. The method of claim 1, wherein: the dosage of the cross-linking agent in the step (2) is 1.1-1.5 times of the molar weight of the mixture of the 7 kinds of micro-plastic standard products.
4. The method of claim 1, wherein: the dosage of the initiator in the step (2) is 0.1-0.3 time of the molar weight of the mixture of the 7 kinds of micro-plastic standard products.
5. The method of claim 1, wherein: and (4) centrifuging for 10min at 2000-3000 r/min.
6. The method of claim 1, wherein: the organic solvent in the step (5) is one of dimethylformamide, hexafluoroisopropanol or cyclohexanone.
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| CN110006723B (en) * | 2018-07-18 | 2022-11-04 | 广东海洋大学 | Fluorescent dyeing method for quantifying micro plastic based on expansion with heat and contraction with cold characteristics |
| CN109553798A (en) * | 2018-11-28 | 2019-04-02 | 南通市产品质量监督检验所 | A kind of preparation method of diisononyl phthalate molecular engram microsphere |
| CN110237821A (en) * | 2019-06-21 | 2019-09-17 | 中国科学院烟台海岸带研究所 | A kind of ferromagnetism nanometer particle preparation and its application in the extraction of micro- plastics and removal |
| CN111504741B (en) * | 2020-04-22 | 2023-04-18 | 山东师范大学 | Method for detecting micro-plastics in fish body |
| CN113933261A (en) * | 2021-11-15 | 2022-01-14 | 中国计量科学研究院 | Method for detecting micro-plastic in sediment based on solubility parameter calculation |
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