CN115598233A - Gel adsorption film, gradient diffusion device and application of gel adsorption film and gradient diffusion device in neonicotinoid pesticide sampling - Google Patents

Gel adsorption film, gradient diffusion device and application of gel adsorption film and gradient diffusion device in neonicotinoid pesticide sampling Download PDF

Info

Publication number
CN115598233A
CN115598233A CN202211031786.4A CN202211031786A CN115598233A CN 115598233 A CN115598233 A CN 115598233A CN 202211031786 A CN202211031786 A CN 202211031786A CN 115598233 A CN115598233 A CN 115598233A
Authority
CN
China
Prior art keywords
film
gel
gel adsorption
adsorption film
environment
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.)
Pending
Application number
CN202211031786.4A
Other languages
Chinese (zh)
Inventor
陈伟
蒲昶
熊俊武
王康
方晶晶
廖媛
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.)
Hubei Geological Environment Station
Hubei Land Resources Vocational College
China University of Geosciences
Original Assignee
Hubei Geological Environment Station
Hubei Land Resources Vocational College
China University of Geosciences
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 Hubei Geological Environment Station, Hubei Land Resources Vocational College, China University of Geosciences filed Critical Hubei Geological Environment Station
Priority to CN202211031786.4A priority Critical patent/CN115598233A/en
Publication of CN115598233A publication Critical patent/CN115598233A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/10—Devices for withdrawing samples in the liquid or fluent state
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Immunology (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

The application discloses a gel adsorption film, a gradient diffusion device and application thereof in sampling of neonicotinoid pesticides. The gel adsorption film of the present application is prepared as follows: adding an adsorption resin filler into the agar solution to obtain a mixture system; cooling and forming the mixture system to form a gel adsorption film; the absorbent resin filler is at least one of HLB filler, PLS filler and WCX filler. The gel adsorption film can efficiently adsorb neonicotinoid pesticides in an environment to be detected. The gel adsorption film capable of efficiently adsorbing the neonicotinoid pesticides in the environment to be detected is filled in the gradient diffusion device, the neonicotinoid pesticides in the environment to be detected can be quantitatively enriched in situ, the time weighted average concentration of the neonicotinoid pesticides in the sampling time period is provided, and the sampling result is more representative; and the measurement result of the concentration of the neonicotinoid pesticides in the environment to be measured does not need to be calibrated, so that the concentration of the neonicotinoid pesticides in the environment to be measured can be estimated more accurately.

Description

Gel adsorption film, gradient diffusion device and application of gel adsorption film and gradient diffusion device in neonicotinoid pesticide sampling
Technical Field
The application belongs to the technical field of environmental science, and in particular relates to a gel adsorption film, a gradient diffusion device and application of the gel adsorption film and the gradient diffusion device in neonicotinoid pesticide sampling.
Background
Neonicotinoids (NEOs) are a new class of chemical insecticides extracted from the natural toxin nicotine. Since the development and commercialization of the first NEOs (imidacloprid ) by bayer corporation in germany in the middle of the 80's of the 20 th century, NEOs have rapidly received attention from many companies both at home and abroad and have been registered in more than 120 countries throughout the world. To date, NEOs have been widely used worldwide due to their relatively high selective toxicity to arthropods and low toxicity to mammals, fish, and birds in 1990. However, studies have reported that NEOs adversely affect non-target organisms such as vertebrates, bees and aquatic organisms. Meanwhile, people are directly exposed to the NEOs after oral intake (diet and drinking), and potential risks are caused to human health. Since 2010, NEOs became the largest class of pesticides consumed, accounting for about one-fourth of the pesticide market. The production and export of NEOs in china are the first in the world, and the demand is further increasing in recent years. As of 2014, as NEOs registered in China, there are 10 kinds of insecticides such as imidacloprid (IMI), thiamethoxam (TMX), acetamiprid (ACE), thiacloprid (THI), clothianidin (CLO), nitenpyram (NIT), dinotefuran (DIN) and imidaclothiz (IMIT). The NEOs are generally used in seed coating agents and irrigation water, more than 80% of the NEOs will remain in water or soil in the plant growth process, so the NEOs widely exist in environmental media (agricultural and sideline products, water, soil and bottom mud), and pollute the external environment. Migration of NEOs to surface and subsurface runoff is promoted due to their high water solubility, high water phase partitioning, and low soil adsorption. In china, groundwater is still the most reliable public drinking water source in many areas, with most residents in urban areas using tap water (from surface water or deep groundwater treated by drinking water plants) as drinking water, and some residents in rural areas using untreated shallow well water (groundwater) as drinking water. Groundwater is cyclically refreshed for a long period of time and is difficult to recover in a short period of time once it is utilized or contaminated. Therefore, monitoring and studying the concentration and pollution level of the NEOs in the groundwater can provide data support for better understanding of local NEOs pollution conditions.
At present, the method for sampling NEOs in water mainly comprises active capture sampling and passive sampling by using a polar organic compound integration sampling technology (POCIS). The active grabbing sampling can only provide the instantaneous concentration of the target substance at a specific sampling time, and cannot reflect the fluctuation of the pollutant concentration along with the time, and the instantaneous concentration is not representative. However, the POCIS sampler must be calibrated in the field due to the difference between the field conditions and the laboratory calibration, and hydrodynamic conditions, such as flow rate, temperature and turbulence, may affect the sampling rate, resulting in uncertainty in the estimation of the concentration of the target in the water. The DGT technology is an efficient passive sampling technology based on Fick's first diffusion law, can quantitatively enrich pollutants to be detected in situ, and determines the Time Weighted Average (TWA) concentration of an object to be detected which penetrates through diffusion glue with a certain thickness in a sampling time period, so that the defect of active sampling is overcome.
At present, no DGT sampling method for neonicotinoid pesticides in water bodies is reported. Therefore, the DGT device capable of monitoring the concentration of the anabasine pesticide in the ground water body is developed, whether the anabasine pesticide can be accurately quantified in various water bodies including underground water or not is deeply explored, and the DGT device has important significance in more comprehensively monitoring the concentration of the anabasine pesticide in the water body by the DGT technology.
Disclosure of Invention
The application aims to overcome the defects of at least one aspect of the prior art and provide a gel adsorption film, a gradient diffusion device and application thereof in neonicotinoid pesticide sampling so as to solve the technical problems that the sampling concentration of the existing NEOs sampling method is not representative and the estimation of the concentration of the NEOs in a water body is inaccurate.
In order to achieve the above object, according to a first aspect of the present application, there is provided a gel-adsorption film, which is prepared by:
adding an adsorption resin filler into the agar solution to obtain a mixture system;
cooling and shaping the mixture system to form the gel adsorption film;
the adsorption resin filler is at least one of HLB filler, proElut PLS filler and WCX filler.
Further, the adsorption resin filler is subjected to cleaning and activation treatment by methanol and ultrapure water.
Further, the mass fraction of the agar in the agar solution is 1.4-1.6%.
Furthermore, in the mixture system, the mass of the adsorption resin filler added into each milliliter of the agar solution is 0.3 to 0.5g.
The second aspect of this application provides a gradient diffusion equipment, including above-mentioned any gel adsorption film, diffusion barrier, protection film and packaging shell, the protection film the diffusion barrier with gel adsorption film stacks gradually and sets up in the packaging shell, the protection film sets up packaging shell's opening end one side.
Further, the diffusion membrane is an agar gel membrane or a polyacrylamide gel membrane.
Further, the protective film is a hydrophilic polytetrafluoroethylene (wwPTFE) filter film.
The third aspect of this application provides a gel adsorption film in neonicotinoid pesticide sampling's application, will the gel adsorption film is arranged in the environment that awaits measuring that contains neonicotinoid pesticide, makes the gel adsorption film adsorbs the neonicotinoid pesticide in the environment that awaits measuring.
The fourth aspect of the application provides an application of gradient diffusion equipment in neonicotinoid pesticide sampling, will the gradient diffusion equipment is arranged in the environment that awaits measuring that contains neonicotinoid pesticide, makes the gradient diffusion equipment adsorbs the neonicotinoid pesticide in the environment that awaits measuring.
Compared with the prior art, the method has the following technical effects:
the application discloses a gel adsorption film has excellent adsorptivity to neonicotinoid pesticide in the environment that awaits measuring, can high-efficiently adsorb neonicotinoid pesticide in the environment that awaits measuring.
The gel adsorption film capable of efficiently adsorbing the neonicotinoid pesticides in the environment to be detected is filled in the gradient diffusion device, the neonicotinoid pesticides in the environment to be detected can be quantitatively enriched in situ, the time-weighted average concentration of the neonicotinoid pesticides in a sampling time period is provided, and a sampling result is more representative; and the measurement result of the concentration of the neonicotinoid pesticides in the environment to be measured does not need to be calibrated, so that the concentration of the neonicotinoid pesticides in the environment to be measured can be estimated more accurately.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings used in the detailed description or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph of the adsorption capacity of HLB-DGT provided in example 3 of the present application;
FIG. 2 is a graph of mass (M, ng) versus time (days) of HLB-DGT adsorbed NEOs deployed in effluent from a wastewater treatment plant as provided in example 4 of the present application;
FIG. 3 is a graph of mass (M, ng) of NEOs adsorbed by HLB-DGT as deployed in a groundwater well as plotted against time (days) as provided in example 4 of the present application;
FIG. 4 is a graph of mean concentrations (ng/L) of NEOs detected by active grab sampling and HLB-DGT in shallow groundwater wells (a) and wastewater plants (b) as provided in example 4 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
Compared with an active sampling technology, the gradient diffusion thin film (DGT) technology can quantitatively enrich pollutants to be detected in situ, and the Time Weighted Average (TWA) concentration of the objects to be detected which penetrate through the diffusion film with a certain thickness in a sampling time period is measured, so that the defect of active sampling is overcome. And the DGT technology is generally thicker than the thickness of a Diffusion Boundary Layer (DBL) due to the thickness of the diffusion filmMaking it insensitive to hydrodynamic conditions and not requiring on-site calibration in a matrix-like solution. Concentration value (C) of object to be measured in water body DGT ) The calculation formula (1) is as follows:
C DGT ＝M(Δg+δ)/(D e At) (1)
in the formula (1), M is the amount (ng) of the substance to be detected accumulated in the gel adsorption film; t is the exposure time(s); de is the diffusion coefficient (cm) of the object to be measured in the diffusion film layer 2 S); a represents the sampling area (cm) of DGT 2 ) (ii) a Delta g is the thickness (cm) of the diffusion film layer which passes through the object to be detected before being absorbed by the binding phase; delta is the thickness (cm) of the DBL, when the water flow rate is sufficiently fast (>0.2 cm/s), δ is negligible.
In a first aspect, embodiments of the present application provide a gel adsorption film, which is prepared by the following method:
(1) Adding an adsorption resin filler into the agar solution to obtain a mixture system;
(2) And cooling and forming the mixture system to form the gel adsorption film.
In the step (1), the adsorbent resin filler is at least one of an HLB (hydrophilic lipophilic balance resin) filler, a proelst PLS (hydrophilic lipophilic balance resin) filler, and a WCX (mixed weak cation exchange resin) filler. Compared with PLS filler and WCX filler, the HLB filler has better adsorbability to neonicotinoid pesticides (NEOs) in a water sample, and the specific embodiment of the application takes the preparation of a gel adsorption film by the HLB filler as an example for illustration. In order to improve the adsorption performance of the adsorption resin filler on the NEOs, the adsorption resin filler in the embodiment of the application can be cleaned and activated by methanol and ultrapure water which are three times of the volume of the adsorption resin filler before being used.
The agar solution of the examples of the present application can be prepared by the following method: adding a certain amount of agar into ultrapure water, and heating the solution at 90 deg.C under stirring. In the examples of the present application, the mass fraction of agar in the agar solution may be selected from 1.4 to 1.6%, and may be 1.5%, for example.
In order to prepare gel adsorption films with good adsorption performance and film forming performance on NEOs, in the mixture system of the embodiment of the application, the mass of the adsorption resin filler added into each milliliter of agar solution is 0.3 to 0.5g, and specifically can be 0.4g.
The gel adsorption film of this application embodiment has excellent adsorptivity to neonicotinoid pesticide in the environment that awaits measuring, can high-efficiently adsorb neonicotinoid pesticide in the environment that awaits measuring. The environment to be measured can be water environment, sediment, sludge or soil and other environments.
In a second aspect of the embodiments of the present application, a gradient diffusion device is provided, which comprises the gel adsorption film, the diffusion film, the protection film and the package housing, wherein the protection film, the diffusion film and the gel adsorption film are sequentially stacked and arranged in the package housing, and the protection film is arranged on one side of an opening end of the package housing, namely, is in contact with an environment to be tested to allow one side of water sample infiltration in the environment to be tested.
The diffusion membrane of the embodiment of the application can be selected as an agar gel membrane or a polyacrylamide gel membrane, and the adsorption rates of the agar gel membrane and the polyacrylamide gel membrane to NEOs in the environment to be tested are both lower and less than 10%, so that the agar gel membrane and the polyacrylamide gel membrane can be used as the diffusion membrane of the gradient diffusion device. The specific examples of the present application use agar gel membranes as diffusion membranes because of their ease of preparation.
The protection film of this application embodiment can be selected as wwPTFE filter membrane, namely hydrophilic polytetrafluoroethylene filter membrane. The wwPTFE filter membrane has extremely low adsorption rate to NEOs in the environment to be measured, and the wwPTFE filter membrane is used as a protective membrane, so that the influence of the gradient diffusion device on the measurement and calculation of the concentration of the NEOs in the environment to be measured can be reduced.
The packaging shell of the embodiment of the application can be made of common polyvinyl chloride plastics, and the adsorption rate of the packaging shell to NEOs in the environment to be tested is less than 5%.
The gel adsorption film capable of efficiently adsorbing the neonicotinoid pesticides in the environment to be detected is filled in the gradient diffusion device, the diffusion film and the protective film which have low adsorption rate to NEOs in the environment to be detected are used in a matched mode, the neonicotinoid pesticides in the environment to be detected can be quantitatively enriched in situ, the time-weighted average concentration of the neonicotinoid pesticides in the sampling time period is provided, and the sampling result is more representative; and the measurement result of the concentration of the neonicotinoid pesticides in the environment to be measured does not need to be calibrated, so that the concentration of the neonicotinoid pesticides in the environment to be measured can be estimated more accurately.
In a third aspect of the embodiments of the present application, an application of a gel adsorption film in neonicotinoid pesticide sampling is provided, and specifically, the gel adsorption film is placed in a water environment containing neonicotinoid pesticides, so that the gel adsorption film adsorbs the neonicotinoid pesticides in water.
In a fourth aspect of the embodiments of the present application, an application of a gradient diffusion device in neonicotinoid pesticide sampling is provided, specifically, the gradient diffusion device is placed in an environment to be tested containing neonicotinoid pesticide, so that the gradient diffusion device adsorbs the neonicotinoid pesticide in the environment to be tested.
The gel adsorption film, the gradient diffusion device and the application thereof in the sampling of neonicotinoid pesticides in the embodiments of the present application are illustrated by a plurality of specific examples.
Example 1
The embodiment 1 of the application provides a gel adsorption film, a gradient diffusion device and a preparation method of the gel adsorption film. The method specifically comprises the following steps:
(1) Preparation of agar gel membrane (diffusion membrane): agar with the mass ratio of 1.5 percent is added into ultrapure water, the solution is heated at 85 ℃ and continuously stirred, and simultaneously a glass mold is placed into an oven and heated to 75 ℃. When the agar was completely dissolved and no suspended particles were visible in the solution, the solution was poured into a glass mold with a spacer of 0.8mm thickness. The mold was naturally placed upright, after the solution cooled to room temperature and coagulated, the glass mold was opened, the gel was cut into disks of 2.5cm in diameter to give agar gel membranes, which were stored in 0.01M NaCl solution at 4 ℃.
(2) Preparing a gel adsorption film: selecting HLB filler with particle size of 45-60 μm, and adding into the mixture for 1mL min -1 Is washed and activated with three times its volume of methanol and ultrapure water. 4.0g of the washed and activated filler (wet weight) was added to 10mL of a hot clear agar solution (1.5%) and mixed well while hot. The above-mentionedAfter the solutions were mixed well, the solution was poured into a preheated (75 ℃ C.) glass plate mold with a 0.5mm thick PTFE gasket sandwiched between them. Cooling at room temperature to form a solidified gel-adsorbed film. The glass mold was opened, and the gel adsorption film was cut into disks having a diameter of 2.5cm to obtain an HLB gel adsorption film, which was stored in a 0.01M NaCl solution at 4 ℃. The PLS gel adsorption film and the WCX gel adsorption film can be obtained by the same preparation method.
(3) Assembly of gradient diffusion device (DGT device): the DGT housing base was placed horizontally on a table top and the HLB gel adsorption membrane, agar gel membrane, and wwPTFE filter membrane were laid flat on top of each other using clean forceps. And buckling the DGT shell cover to ensure that no bubbles exist between the films, and finishing the assembly of the DGT device.
Example 2
The diffusion coefficient of the neonicotinoid pesticide in the agar gel membrane prepared in example 1 of the present application was determined by the following steps:
measurement of diffusion coefficient (25 ℃,30 ℃): a1 mm thick agar gel membrane was placed on the disk window between the two clean diffusion cell compartments. The temperatures during the experiment were set at 25 ℃ and 30 ℃ respectively. The solutions in the two compartments were stirred with a magnetic stir bar at 350 rpm. Initially, 80mL of 0.01M NaCl solution was placed in each of the two compartments, no NEOs was added to the source chamber, the temperature of the solution in each compartment was measured continuously over the first few hours using a thermometer, and after the temperature had stabilized, the target was added to the source chamber (2000 mg L of NaCl was taken) -1 0.12mL of the NEOs solution, the final concentration of the source chamber NEOs was about 3mg L -1 ) While the other compartment was also filled with 0.12mL of 0.01M NaCl solution. pH =6.3 ± 0.2 before and after the experiment, and the diffusion cell was wrapped with aluminum foil. 0.5mL of sample was taken from both compartments at intervals. Samples were taken every 60 minutes for the first 3 hours, then every 30 minutes for the next 9 hours, and every 6 hours for the remaining 12 hours.
The measurement result shows that: the diffusion coefficient of NEOs at 25 deg.C is 4.91 × 10 -6 –6.27×10 -6 cm 2 (s) diffusion coefficient of NEOs at 30 ℃ of 6.05X 10 -6 –7.54×10 -6 cm 2 S, and experimentally measured diffusion coefficient and theoryThe standard deviation of the theoretical diffusion coefficient is within 20%, and the result is acceptable.
Example 3
The HLB gel adsorption film and the HLB-DGT adsorption capacity of the gradient diffusion device prepared in the embodiment 1 are measured, and the specific process is as follows:
placing HLB gel adsorption membranes into brown bottles containing 10mL of NEOs solution with different concentrations, wherein the concentration of the NEOs solution is 50 μ g L -1 ，100μg L -1 ，200μg L -1 ，500μg L -1 ，1mg L -1 ，3mg L -1 ，6mg L -1 ，9mg L -1 ，12mg L -1 . IS (ionic strength) =0.01M. The brown bottle was shaken on an orbital shaker at 80rpm for 20h. A volume of the solution (before/after shaking) was taken out of the brown bottle, respectively, into the cell bottle, and the concentration was measured on the machine. The amount of NEOs adsorbed by the HLB-gel adsorption membrane was calculated from the difference in concentration of the solution before and after the experiment.
The results are shown in FIG. 1, DIN: dinotefuran; IMIT: a imidaclothiz; FLO: flonicamid; NIT: nitenpyram; CLO: clothianidin; IMI: imidacloprid; TMX: thiamethoxam; ACE: acetamiprid; THI: thiacloprid. Error bars represent one standard deviation.
As seen in fig. 1: the adsorption capacity of the dinotefuran is at least linearly increased to a solution concentration of about 1mg L -1 The remaining 8 NEOs increased at least linearly to a solution concentration of about 6mg L -1 . Taking dinotefuran as an example, if the HLB-DGT deployment time is 1 week, the DGT can determine that the maximum dinotefuran concentration in the solution is 55.4 mu g L according to the calculation of the formula (1) -1 (ii) a If the deployment time is 1 month (30 days), the DGT can measure the maximum concentration of the dinotefuran in the solution to be 12.9 mu g L -1 . In most cases, the concentration of NEOs in aqueous environments is less than 1 μ g L -1 . Thus, the capacity of the gradient diffusion device HLB-DGT implemented in the present application is sufficient to monitor NEOs in a contaminated environment.
Example 4
The HLB-DGT prepared by the gradient diffusion device in the embodiment 1 is applied to sampling of a field water environment, and the specific process is as follows:
an HLB-DGT device (up to 4 weeks) was deployed in sewage plants and underground water wells (shallow wells), and active samples 1L in sewage plants and underground water wells were collected in brown glass bottles that had been pre-washed, at the first deployment of the HLB-DGT and each retrieval of the HLB-DGT ( day 7, 10, 14, 21 and 28 retrieval), to verify the suitability of the HLB-DGT (linear changes in adsorption amount and deployment time), and the HLB-DGT concentration results were compared to the active samples. After the HLB-DGT is retrieved, the HLB-DGT shell is rinsed with deionized water and then sealed in a clean plastic bag for transport. In a laboratory, the HLB-DGT shell is disassembled, the gel adsorption film is extracted by acetonitrile, and 50ng of each of 4 internal standards (4 internal standards: clothianidin-d) are added before extraction 3 Thiamethoxam-d 3 Imidacloprid-d 4 And acetamiprid-d 3 ). And (4) after the active water sample is transported back to the laboratory, storing the active water sample in a dark room at 4 ℃ and treating the active water sample within 24 hours. The water samples were filtered through a pre-fabricated glass fiber filter (GF/F). Before extraction, 50ng of internal standard is added into the filtered sample, and the active water sample is subjected to solid-phase extraction. Before detection in a liquid chromatography tandem mass spectrometer (LC-MS/MS), 0.2mL of the active sample (0.3 mL of the HLB-DGT sample) was taken and nitrogen was blown dry in the inner liner tube and redissolved to 50. Mu.L.
The relationship graph of mass (M, ng) and time (day) of HLB-DGT adsorption NEOs (TMX: thiamethoxam; CLO: clothianidin; IMI: imidacloprid; ACE: acetamiprid) deployed in effluent of a sewage plant is shown in FIG. 2. The relationship between mass (M, ng) and time (day) of HLB-DGT adsorbing NEOs (IMI: imidacloprid; ACE: acetamiprid) deployed in an underground water well is shown in FIG. 3.
Average concentrations (ng/L) of NEOs (DIN: dinotefuran; FLO: flonicamid; CLO: clothianidin; IMI: imidacloprid; TMX: thiamethoxam; ACE: acetamiprid; THI: thiacloprid) detected by active grab sampling and HLB-DGT in shallow groundwater wells and sewage plants are shown in FIG. 4, where the error bars represent one standard deviation.
The experimental results show that: (1) After the HLB-DGT device is deployed in underground water wells and sewage plants for 28 days (figures 2-3), the adsorption capacity of most compounds slowly rises or tends to be stable after linear adsorption in the DGT for about 14 days, and the optimal deployment time is recommended to be about 10-14 days; (2) Compared with the average concentration measured by active sampling on the 1 st day and the 10 th day, the time-weighted average concentration measured by DGT passive sampling devices deployed for 10 days in an underground water well (a shallow well, figure 4 a) and a sewage treatment plant (figure 4 b), the neonicotinoid pesticides measured by active sampling and passive sampling are the same in type, and the concentration difference of most target objects is within one order of magnitude, which indicates that DGT can accurately monitor most neonicotinoid compounds in water.
The above examples only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent application shall be subject to the appended claims.

Claims (9)

1. The gel adsorption film is characterized by being prepared by the following method:
adding an adsorption resin filler into the agar solution to obtain a mixture system;
cooling and shaping the mixture system to form the gel adsorption film;
the adsorption resin filler is at least one of HLB filler, proElut PLS filler and WCX filler.
2. The gel adsorbent film according to claim 1, wherein said adsorbent resin filler is washed and activated with methanol and ultrapure water.
3. The gel adsorption membrane of claim 1, wherein the mass fraction of agar in the agar solution is 1.4-1.6%.
4. The gel adsorption film according to claim 3, wherein the mass of the adsorbent resin filler added to the agar solution per ml is 0.3-0.5 g.
5. A gradient diffusion device, comprising the gel adsorption film, the diffusion film, the protection film and the package housing of any one of claims 1 to 4, wherein the protection film, the diffusion film and the gel adsorption film are sequentially stacked in the package housing, and the protection film is arranged on one side of the open end of the package housing.
6. The gradient diffusion device of claim 5, wherein the diffusion membrane is an agar gel membrane or a polyacrylamide gel membrane.
7. The gradient diffusion device of claim 5, wherein the protective membrane is a hydrophilic polytetrafluoroethylene filter membrane.
8. The application of the gel adsorption film in neonicotinoid pesticide sampling according to any one of claims 1 to 4, wherein the gel adsorption film is placed in an environment to be tested containing neonicotinoid pesticides, so that the gel adsorption film adsorbs the neonicotinoid pesticides in the environment to be tested.
9. Use of a gradient diffusion device according to any one of claims 5 to 7 in neonicotinoid pesticide sampling, wherein the gradient diffusion device is placed in an environment to be tested containing neonicotinoid pesticides, such that the gradient diffusion device adsorbs neonicotinoid pesticides in the environment to be tested.
CN202211031786.4A 2022-08-26 2022-08-26 Gel adsorption film, gradient diffusion device and application of gel adsorption film and gradient diffusion device in neonicotinoid pesticide sampling Pending CN115598233A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211031786.4A CN115598233A (en) 2022-08-26 2022-08-26 Gel adsorption film, gradient diffusion device and application of gel adsorption film and gradient diffusion device in neonicotinoid pesticide sampling

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211031786.4A CN115598233A (en) 2022-08-26 2022-08-26 Gel adsorption film, gradient diffusion device and application of gel adsorption film and gradient diffusion device in neonicotinoid pesticide sampling

Publications (1)

Publication Number Publication Date
CN115598233A true CN115598233A (en) 2023-01-13

Family

ID=84842400

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211031786.4A Pending CN115598233A (en) 2022-08-26 2022-08-26 Gel adsorption film, gradient diffusion device and application of gel adsorption film and gradient diffusion device in neonicotinoid pesticide sampling

Country Status (1)

Country Link
CN (1) CN115598233A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437275A (en) * 2020-11-05 2022-05-06 万华化学集团股份有限公司 High-specific-surface-area adsorption resin and application thereof in removing dinotefuran residues

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104492376A (en) * 2014-12-19 2015-04-08 南京大学 Preparation method of activated carbon adsorption film and method for measuring bisphenol substances in wetland soil or sediment based on thin-film diffusion gradient technique
CN110423113A (en) * 2019-07-15 2019-11-08 大连理工大学 A kind of preparation method and application preparing ceramic membrane diffusion layer using yttrium stable zirconium oxide material
CN110702802A (en) * 2019-10-24 2020-01-17 上海海洋大学 Method for passively monitoring antibiotic content in aquaculture water in situ
CN111659358A (en) * 2020-06-11 2020-09-15 南京大学 DGT adsorption membrane, preparation method thereof and method for monitoring perfluoro and polyfluoro compounds based on DGT technology
CN113231034A (en) * 2021-04-21 2021-08-10 华南师范大学 DGT binding phase and preparation method and application thereof
CN113426420A (en) * 2021-06-29 2021-09-24 南京大学 DGT adsorption film and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104492376A (en) * 2014-12-19 2015-04-08 南京大学 Preparation method of activated carbon adsorption film and method for measuring bisphenol substances in wetland soil or sediment based on thin-film diffusion gradient technique
CN110423113A (en) * 2019-07-15 2019-11-08 大连理工大学 A kind of preparation method and application preparing ceramic membrane diffusion layer using yttrium stable zirconium oxide material
CN110702802A (en) * 2019-10-24 2020-01-17 上海海洋大学 Method for passively monitoring antibiotic content in aquaculture water in situ
CN111659358A (en) * 2020-06-11 2020-09-15 南京大学 DGT adsorption membrane, preparation method thereof and method for monitoring perfluoro and polyfluoro compounds based on DGT technology
CN113231034A (en) * 2021-04-21 2021-08-10 华南师范大学 DGT binding phase and preparation method and application thereof
CN113426420A (en) * 2021-06-29 2021-09-24 南京大学 DGT adsorption film and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ROBIN GUIBAL ET AL.: "Passive sampling of anionic pesticides using the Diffusive Gradients in Thin films technique (DGT)" *
ROBIN GUIBAL ET AL.: "Passive sampling of anionic pesticides using the Diffusive Gradients in Thin films technique (DGT)", ANALYTICA CHIMICA ACTA *
SISI LIU ET AL.: "Development and application of diffusive gradients in thin-films for in situ sampling of the bitterest chemical – denatonium benzoate in waters", JOURNAL OFHAZARDOUSMATERIALS *
李财;任明漪;石丹;王燕;杨丽原;丁士明;: "薄膜扩散梯度(DGT)――技术进展及展望" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437275A (en) * 2020-11-05 2022-05-06 万华化学集团股份有限公司 High-specific-surface-area adsorption resin and application thereof in removing dinotefuran residues
CN114437275B (en) * 2020-11-05 2023-10-20 万华化学集团股份有限公司 High specific surface area adsorption resin and application thereof in removing dinotefuran residues

Similar Documents

Publication Publication Date Title
Namieśnik et al. Passive sampling and/or extraction techniques in environmental analysis: a review
Alvarez et al. Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments
Peijnenburg et al. Passive sampling methods for contaminated sediments: State of the science for metals
US7059206B1 (en) Aquatic passive sampling device and methods for its use
Mari Carbon content and C: N ratio of transparent exopolymeric particles (TEP) produced by bubbling exudates of diatoms
Lissalde et al. Overview of the Chemcatcher® for the passive sampling of various pollutants in aquatic environments Part B: Field handling and environmental applications for the monitoring of pollutants and their biological effects
Qiu et al. Effects of oxygen concentration on phosphorus release from reflooded air-dried wetland sediments
JPH09504097A (en) Device for concentrating trace constituents in liquids
Quigley et al. Sorption irreversibility and coagulation behavior of 234Th with marine organic matter
CN115598233A (en) Gel adsorption film, gradient diffusion device and application of gel adsorption film and gradient diffusion device in neonicotinoid pesticide sampling
Bao et al. Development of a low‐density polyethylene‐containing passive sampler for measuring dissolved hydrophobic organic compounds in open waters
Barceló et al. Sampling of polar pesticides from water matrices
Larner et al. Evaluation of paper-based diffusive gradients in thin film samplers for trace metal sampling
Brownawell The role of colloidal organic matter in the marine geochemistry of PCB's
Peterson et al. Passive sampler for chlorinated pesticides in estuarine waters
Doig et al. Dialysis minipeeper for measuring pore‐water metal concentrations in laboratory sediment toxicity and bioavailability tests
Schneider et al. Retention of the Gram-negative bacterium SW8 on surfaces under conditions relevant to the subsurface environment: effects of conditioning films and substratum nature
Öhlander et al. Fractionation of trace metals in a contaminated freshwater stream using membrane filtration, ultrafiltration, DGT and transplanted aquatic moss
Smith et al. Concentrations and partitioning of polychlorinated biphenyls in the surface waters of the southern Baltic Sea—seasonal effects
KR20160120568A (en) THIN FILM FOR PASSIVE SAMPLER, PASSIVE SAMPER FOR MEASUREMENT OF BIOAVAILABLE PAHs, AND METHOD OF MANUFACTURING THEREOF
Amdurer et al. Studies of the chemical forms of trace elements in sea water using radiotracers
Ottosen et al. Denitrification in exposed intertidal mud-flats, measured with a new 15N-ammonium spray technique
CN115254063B (en) Gel adsorption film, gradient diffusion device and application thereof in artificial sweetener sampling
Sharifan Mechanistic insight on transfer rate of the polar organic compounds through the polyethersulfone membrane
Means et al. Fate and transport of selected herbicides in an estuarine environment

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20230113

RJ01 Rejection of invention patent application after publication