CN112986418B - Method for constructing large complex exposure system with constant free concentration of hydrophobic organic matters - Google Patents
Method for constructing large complex exposure system with constant free concentration of hydrophobic organic matters Download PDFInfo
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- CN112986418B CN112986418B CN202110167839.4A CN202110167839A CN112986418B CN 112986418 B CN112986418 B CN 112986418B CN 202110167839 A CN202110167839 A CN 202110167839A CN 112986418 B CN112986418 B CN 112986418B
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Abstract
The invention relates to the technical field of organic pollutant determination, and discloses a method for constructing a large complex exposure system with constant concentration of free state of hydrophobic organic matters. According to the invention, HOCs are added into a water body containing a complex matrix by a passive labeling method to simulate a large complex exposure system, the loaded polymer film is used as a source of HOCs, partial hydrophobic organic compounds lost in the system are continuously supplemented, and the content of HOCs enriched on polydimethylsiloxane fibers is measured to find that the concentration of free HOCs in the large complex exposure system can be kept relatively stable, namely, the method can be used for constructing the large complex exposure system with constant concentration of free hydrophobic organic matters. The method has important application significance for accurately measuring the damage of the biological effectiveness HOCs to aquatic organisms.
Description
Technical Field
The invention relates to the technical field of organic pollutant determination, in particular to a method for constructing a large complex exposure system with constant concentration of free state of hydrophobic organic matters.
Background
Simulating biological exposure is a common research means in environmental science, and by simulating an aquatic organism exposure system, enrichment, migration and conversion processes of various pollutants in the environment in organisms can be researched, and harm of pollutant emission to the organisms can be estimated. The passive labeling method adopts a polymer with high adsorption performance as an adsorption carrier of pollutants, and is placed in an exposure system, so that the pollutants can be continuously released in an exposure solution, and the free concentration in an aqueous solution is kept constant, thereby more truly simulating the exposure condition of the pollutants in an actual water environment, and overcoming the defect of unstable concentration in the traditional exposure method. Currently, passive labeling methods have been applied to determine the equilibrium partition coefficient of Hydrophobic Organic Compounds (HOCs) (Li Huizhen, you Jing, pei Yuanyuan. A passive labeling method for HOCs and its use in effect-directed analysis. CN 106970171A) and effect-directed analysis (Li Huizhen, calm, keemun. A passive labeling method for HOCs and its use in effect-directed analysis. CN 106970171A). However, the prior art focuses on how to construct a hydrophobic organic compound exposure system and determine the total concentration of HOCs in the system, and the adopted small-volume simulation device is difficult to meet the growth requirements of test organisms (such as fish, etc.), so that the exposure system of the actual environment cannot be accurately simulated. More importantly, in the practical environment, the morphology of the presence of HOCs in water can be broadly divided into a free state, a soluble organic bound state, and a particle bound state. With the increasing depth of research into HOCs, it has been found that the damage of HOCs to the environment and organisms often does not depend on the total amount of organic contaminants, but on the concentration of the bioavailable species. It is currently generally accepted that only free HOCs can be bioavailable and are bioavailable. However, when complex substrates (e.g., microplastic, fish oil, etc.) are present in the exposed system, the complex substrates often combine with the HOCs to form bound HOCs, which can have a serious impact on the stability of the free HOCs concentration in the body of water, and therefore, how to more accurately simulate the free HOCs concentration in the body of water containing the complex substrate remains a challenge to be solved. Therefore, the construction of an exposure system with constant concentration of free HOCs and accurate concentration monitoring has important application significance.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the prior art and provide a method for constructing a large complex exposure system with constant concentration of free hydrophobic organic matters.
The above object of the present invention is achieved by the following technical solutions:
a method of constructing a large complex exposure system with a constant concentration of free hydrophobic organic species comprising the steps of: putting the polymer membrane loaded with HOCs into an exposed water body containing a complex matrix, adding polydimethylsiloxane fibers, aerating, stirring, and diffusing the HOCs from the polymer membrane to a system; and after the HOCs are diffused to reach equilibrium, adding the test organism, taking out the polydimethylsiloxane fiber at different time points, and measuring the HOCs content enriched on the polydimethylsiloxane fiber.
The invention relates to the technical field of organic pollutant determination, and discloses a method for constructing a large complex exposure system with constant concentration of free state of hydrophobic organic matters. According to the invention, the HOCs are added into the water body containing the complex matrix by a passive labeling method to simulate a large complex exposure system, the loaded polymer film is used as a source of the HOCs, partial hydrophobic organic compounds lost in the system are continuously supplemented, and the content of the HOCs enriched on the polydimethylsiloxane fibers is measured to find that the concentration of free HOCs in the large complex exposure system can be kept relatively stable, namely, the method can be used for constructing the large complex exposure system with constant concentration of free hydrophobic organic matters.
Preferably, the specific method comprises the following steps:
s1, preparing a polymer film loaded with HOCs: volatilizing an organic solvent in the HOCs mother liquor to dryness, adding methanol, fully shaking uniformly, adding a polymer membrane, oscillating, adding 5-10 mL of ultrapure water every 6-10 h during the shaking, and promoting the diffusion of HOCs molecules to the polymer membrane to obtain the polymer membrane loaded with HOCs;
s2, simulating a complex exposure system: placing the polymer membrane loaded with HOCs into an exposed water body containing a complex matrix, adding polydimethylsiloxane fibers and fixing the polymer membrane at any position in a system; then communicating the aeration pipeline, and sealing the periphery of the aeration pipe orifice to enable the whole water tank to be in a closed state; aerating and stirring until HOCs reach diffusion balance to obtain a complex exposure system;
s3, monitoring the concentration of free HOCs: and S2, adding test organisms into the complex exposure system, taking out the polydimethylsiloxane fibers at different time points, measuring the content of the HOCs enriched on the polydimethylsiloxane fibers, and evaluating the influence of the complex matrix on the concentration stability of the free HOCs in the exposure system.
Preferably, the polymer film in the step S1 is a polydimethylsiloxane film.
Preferably, the organic matters contained in the HOCs mother liquor in the step S1 include any one or more of polychlorinated biphenyl and polycyclic aromatic hydrocarbon.
More preferably, the organic matter contained in the HOCs mother liquor includes any one or more of PCB-18, PCB-52, and PCB-118.
Preferably, the shaking time in the step S1 is 4-6 days.
Preferably, the oscillating rotation speed in step S1 is 200-300 rpm.
Preferably, the volume of the system described in step S2 is 8-10L.
Preferably, the number of the polydimethylsiloxane fibers in the step S2 is 15-21.
Preferably, the diameter of the polydimethylsiloxane fiber in the step S2 is 42-46 μm.
Preferably, the length of the polydimethylsiloxane fiber in the step S2 is 3-4 cm.
Preferably, the polydimethylsiloxane fibers of step S2 should be completely immersed in the exposed system.
Preferably, the complex matrix in step S3 is any one or more of polystyrene, humic acid, and soluble organic carbon.
Preferably, the mass volume concentration of the complex matrix in the step S3 is 0-5 mg/L.
Preferably, the test organism in step S3 is trained in aerated tap water for two weeks before being added to the exposure system.
Preferably, the method for determining the content of the enriched HOCs on the polydimethylsiloxane fiber in the step S3 is as follows: 150-200 mu L of n-hexane is added into each polydimethylsiloxane fiber, the mixture is subjected to oscillation extraction for 2-4 days, and then quantitative analysis is carried out on the target compound through a gas chromatography mass spectrometer.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to the technical field of organic pollutant determination, and discloses a method for constructing a large complex exposure system with constant concentration of free state of hydrophobic organic matters. According to the invention, the HOCs are added into the water body containing the complex matrix by a passive labeling method to simulate a large complex exposure system, the loaded polymer film is used as a source of the HOCs, partial hydrophobic organic compounds lost in the system are continuously supplemented, and the content of the HOCs enriched on the polydimethylsiloxane fibers is measured to find that the concentration of free HOCs in the large complex exposure system can be kept relatively stable, namely, the method can be used for constructing the large complex exposure system with constant concentration of free hydrophobic organic matters. The establishment of the method has important application significance for determining the damage of the biological effectiveness HOCs to the aquatic organisms.
Drawings
FIG. 1 is a schematic diagram of a passive labeling method for constructing an exposure system.
FIG. 2 shows total PCBs concentrations in the system measured at different times in the experimental group and the control group.
FIG. 3 shows PCB-18 content enriched on PDMS fibers measured at different times.
FIG. 4 shows PCB-52 content enriched on PDMS fiber measured at different times.
FIG. 5 shows PCB-118 content enriched on PDMS fibers measured at different times.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
According to the embodiment of the invention, a large-scale complex exposure system is simulated by adding polychlorinated biphenyl and microplastic into a water body, wherein the polychlorinated biphenyl is selected from PCB-18, PCB-52 and PCB-118, and solid standard samples are purchased from the technical company of carbofuran and then are dissolved in dichloromethane to prepare liquid standard samples with required concentration; the microplastic was a Polystyrene (PS) microsphere, purchased from alaa Ding Gongsi; PDMS film A silicone film having a thickness of 0.5mm was produced by ordinary commercial company. PDMS film pretreatment: firstly cutting the membrane into slices with the size of 10cm multiplied by 2.5cm, removing impurities by using methanol for 2 times of ultrasonic treatment, carrying out ultrasonic treatment for 5 minutes each time, soaking the membrane in ultrapure water for ultrasonic treatment to remove the methanol, and naturally airing in a fume hood to obtain the required PDMS membrane, wherein the mass of the membrane is about 1.5 g/slice.
Example 1
S1, preparing a polymer membrane carrying PCBs: HOCs mother liquor was simulated with a mixed solution of PCB-18, PCB-52 and PCB-118. PCB-18, PCB-52 and PCB-118 are dissolved in methylene dichloride respectively to prepare PCB-18 mother liquor with concentration of 2500mg/L, PCB-52 mother liquor with concentration of 2000mg/L and PCB-118 mother liquor with concentration of 1000 mg/L. Mixing 1.2mL of PCB-18 mother liquor, 2mL of PCB-52 mother liquor and 2mL of PCB-118 mother liquor to obtain PCBs solution, placing the PCBs solution in a fume hood, shaking until the PCBs solution is nearly dry, adding 5mL of methanol as a cosolvent, shaking uniformly, adding 12 pieces of cut PDMS film, shaking at 200rpm for four days at room temperature, and adding 10mL of ultrapure water into a conical flask every 8 hours to promote the diffusion of PCBs molecules into the PDMS film.
S2, simulating a complex exposure system: firstly, preparing 8L of exposure solution containing PS microplastic with the concentration of 2mg/L as an experimental group, and taking exposure solution without the microplastic as a control group; placing the PDMS film carrying PCBs into an exposure solution, wherein 12 pieces of PDMS film carrying PCBs are added into the microplastic-containing solution, and 10 pieces of PDMS film carrying PCBs are added into a control group; meanwhile, 15 PDMS fibers with the length of 4cm and the diameter of 45 mu m are added into the experimental group and the control group for monitoring the free concentration change of PCBs; and then covering the perforated acrylic plate above the exposed solution to achieve a closed state, aerating, and continuously stirring the system to promote the PCBs on the PDMS film to diffuse into water, wherein the release of the PCBs in the system achieves dynamic balance after 7 days.
S3, monitoring the concentration of free HOCs: respectively putting 18 tilapia mossambica which have been domesticated for two weeks in aeration tap water into the two exposure systems, wherein the wet weight of each tilapia mossambica is 4-5 g, the average body length is 6cm, the time is recorded as 0h, and the time for starting the exposure experiment is calculated. 3 PDMS fibers are taken down in the next 18, 36, 60 and 108 hours respectively, each fiber is independently placed in a 2mL brown sample injection bottle, 200 mu L of n-hexane is added for oscillation extraction for 2 days, and then quantitative analysis is carried out on PCB-18, PCB-52 and PCB-118 through a gas chromatography mass spectrometer to obtain the enrichment amount of the target compound.
The specific steps of quantitatively analyzing the PCB-18, the PCB-52 and the PCB-118 by using a gas chromatograph-mass spectrometer are as follows:
taking 1 mu L of n-hexane extract to be put on a machine, and entering a GC chromatographic column along with carrier gas to be separated, wherein the temperature of the GC chromatographic column is programmed: the initial temperature is gradually increased to 200 ℃ at a heating rate of 20 ℃/min and maintained for 6min; then gradually increasing to 250 ℃ at a rate of 20 ℃/min, and keeping at 250 ℃ for 5.5min; the total GC run time was 20min; (the GC chromatographic column adopts DB-5MS capillary column to make chromatographic separation, 30m×0.25mm,0.25 μm; using 99.99% high-purity helium gas as carrier gas, and maintaining at constant flow rate of 1 mL/min) to obtain the chromatograms of three PCB components and their corresponding peak areas; correction was made with the peak area of the added internal standard and the peak area of the recovery indicator and the concentrations of PCB-18, PCB-52 and PCB-118 were obtained.
Analysis of results: the schematic diagram of the construction of a large complex exposure system by the passive labeling method is shown in figure 1. The total concentration of PCBs in the experimental group and the control group system is shown in figure 2, and at the same time point, the concentrations of PCB-18, PCB-52 and PCB-118 in the control group and the experimental group system are different, but the change trend of the total concentration of PCBs in the experimental group and the control group is basically consistent within 0-108 hours. The PCB-18, PCB-52 and PCB-118 contents enriched on PDMS fibers at different time points are shown in FIGS. 3, 4 and 5, respectively. In the comparison of the PCB-18 between the two groups, two independent samples in non-parametric test are adopted for Mann-Whitney U (Mann-Whitney U) test, and the obtained probability p value is 0.686>0.05, namely the dissolved state concentration of the PCB-18 of the two groups has no significant difference; similarly, in the comparison of PCB-52 between the two groups, the probability p value obtained is 0.343>0.05, i.e. there is no significant difference in the dissolved concentration of PCB-52 of the two groups; in the comparison of PCB-118 between the two groups, the probability p-value obtained was 0.886>0.05, i.e., there was no significant difference in the dissolved concentration of PCB-118 of the two groups. Meanwhile, the existence of the complex matrix (PS microplastic) can cause the difference between the total concentration of PCBs and the concentration of free PCBs in the system, but the variation trend of the total concentration of PCBs and the concentration of free PCBs in the experimental group is basically the same as that of the control group (no complex matrix exists), namely, the concentration of PCBs in a large complex exposure system constructed by the method can be kept stable under the condition of the existence of the complex matrix. The experimental result also shows that the measurement of the HOCs content enriched on the PDMS fiber can accurately reflect the concentration of free HOCs in the system, and the measured data has more practical reference significance.
Claims (4)
1. A method for constructing a large complex exposure system with constant concentration of free state of hydrophobic organic matter HOCs, comprising the steps of:
s1, preparation of HOCs-loaded polydimethylsiloxane membrane: volatilizing an organic solvent in the HOCs mother liquor to dryness, adding methanol, fully shaking uniformly, adding a polydimethylsiloxane membrane, continuously oscillating, adding 5-10 mL ultrapure water every 6-10 h during the period, and promoting the diffusion of HOCs molecules to the polydimethylsiloxane membrane to obtain the HOCs-loaded polydimethylsiloxane membrane;
s2, simulation of a complex exposure system: placing the HOCs-loaded polydimethylsiloxane membrane into an exposed water body containing polystyrene microspheres, adding polydimethylsiloxane fibers and fixing the polydimethylsiloxane fibers at any position in a system; then communicating the aeration pipeline, and sealing the periphery of the aeration pipe orifice to enable the whole water tank to be in a closed state; aerating and stirring until HOCs reach diffusion balance to obtain a complex exposure system;
s3, monitoring the concentration stability of free HOCs: adding tilapia mossambica into the complex exposure system in the step S2, taking out the polydimethylsiloxane fiber at different time points, measuring the content of HOCs enriched on the polydimethylsiloxane fiber, and evaluating the influence of the polystyrene microsphere on the concentration stability of free HOCs in the exposure system;
the HOCs mother liquor in the step S1 is a mixed solution of PCB-18, PCB-52 and PCB-118;
the volume of the system in the step S2 is 8-10L;
and step S3, the mass volume concentration of the polystyrene microsphere is 0-5 mg/L.
2. The method according to claim 1, wherein the time of the shaking in step S1 is 4 to 6 days.
3. The method according to claim 1, wherein the number of the polydimethylsiloxane fibers in the step S2 is 15 to 21.
4. The method according to claim 1, wherein the method for determining the content of enriched HOCs on the polydimethylsiloxane fiber in step S3 comprises: 150-200 mu L of n-hexane is added into each polydimethylsiloxane fiber, the mixture is subjected to oscillation extraction for 2-4 days, and then quantitative analysis is carried out on the target compound through a gas chromatography mass spectrometer.
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