CN115308334A - Method for evaluating ecotoxicity of imidacloprid - Google Patents
Method for evaluating ecotoxicity of imidacloprid Download PDFInfo
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- CN115308334A CN115308334A CN202211006454.0A CN202211006454A CN115308334A CN 115308334 A CN115308334 A CN 115308334A CN 202211006454 A CN202211006454 A CN 202211006454A CN 115308334 A CN115308334 A CN 115308334A
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- 239000005906 Imidacloprid Substances 0.000 title claims abstract description 102
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229940056881 imidacloprid Drugs 0.000 title claims abstract description 102
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- 238000010828 elution Methods 0.000 claims description 20
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- 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
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Abstract
A method for carrying out ecological toxicity assessment on imidacloprid, in particular to a method for carrying out ecological toxicity assessment on photodegraded imidacloprid in sewage, aiming at solving the problems that the imidacloprid in the sewage obtained by the traditional physical and chemical analysis method can not correctly assess the biological toxicity and is easy to cause biological poisoning, collecting the sewage containing the imidacloprid for photocatalytic degradation to obtain the sewage after photocatalytic degradation, wherein the sewage comprises water and degraded products; separating water and degraded products in the sewage by reverse phase chromatographic analysis; carrying out HPLC-HRMS analysis on the degraded product to obtain the specific structure of the product; obtaining a chemical structural formula of the product by using ACD/ChemSketch software according to the specific structure of the product; analyzing the chemical structural formula of the product by utilizing the quantitative structure-activity relationship to obtain the ecological toxicity ranking of the product; and calculating the ecological toxicity equivalent of the sewage according to the ecological toxicity ranking to finish the ecological toxicity evaluation. Belongs to the field of water quality evaluation.
Description
Technical Field
The invention relates to an ecological toxicity assessment method, in particular to a method for assessing ecological toxicity of photodegradable imidacloprid in sewage, and belongs to the field of water quality assessment.
Background
Imidacloprid is one of the most widely used insecticides, can be used as a neurotoxin, has high ecological toxicity to arthropods and aquatic organisms, and also has durability. Imidacloprid is reported to have a half-life in soil and water of about 30 days and is now found in surface and ground water worldwide. In order to prevent imidacloprid from entering the water body, the relevant personnel have been studying advanced treatment processes for many years, and the common characteristic of the treatment processes is that hydroxyl radicals are generated, which can be generated from water by ultraviolet irradiation, i.e. photocatalytic degradation, which has proven to be one of the most effective methods for degrading and eliminating the artificial micropollutants from water, so in order to generate hydroxyl radicals, the photocatalytic degradation is carried out with UVC radiation or UVA light and a suitable photocatalyst, such as titanium dioxide. Without reference standards, the evaluation of the ecotoxicity of the conversion products after photocatalytic degradation is still under investigation. The toxicity effect generated by the mixture system is a comprehensive result of antagonism, superposition, synergy or inhibition effects of pollutants of all components, and the concentration information of each component obtained by the traditional physical and chemical analysis method cannot completely reflect the potential influence of mixed pollution of the aquatic ecosystem. The biological toxicity directly affects the survival of aquatic organisms in the discharged water body, and the failure to correctly evaluate the biological toxicity of pollutants in the water can cause unqualified wastewater to be discharged into rivers, so that the toxic reaction of the organisms is caused, and the organisms are abnormal in behavior, disordered in physiological function, pathological changes of tissue cells and even death. Therefore, an analysis means with high efficiency, rapidness and abundant information content is urgently needed to be developed to evaluate the ecological toxicity of the conversion product after photocatalytic degradation.
Disclosure of Invention
The invention aims to solve the problem that the biotoxicity of imidacloprid in sewage can not be correctly evaluated and biotoxicity is easy to cause because the imidacloprid in the sewage obtained by the traditional physicochemical analysis method can not completely reflect the sewage, and further provides a method for evaluating the ecotoxicity of the imidacloprid.
The technical scheme adopted by the invention is as follows:
it comprises the following steps:
s1, collecting quantitative imidacloprid-containing sewage, and carrying out photocatalytic degradation on the sewage to obtain photocatalytic-degraded sewage, wherein the sewage comprises water and degraded products;
s2, separating water and degraded products in the sewage after photocatalytic degradation by utilizing reverse phase chromatographic analysis to obtain separated water and degraded products;
s3, carrying out HPLC-HRMS analysis on the degraded product to obtain the degraded product comprising a product generated by photocatalytic degradation of imidacloprid and undegraded imidacloprid and specific structures of the product and the imidacloprid;
s4, obtaining chemical structural formulas of the product and the imidacloprid by using ACD/ChemSketch software according to the specific structures of the product and the imidacloprid;
s5, analyzing chemical structural formulas of the product and the imidacloprid by utilizing a quantitative structure-activity relationship to obtain an ecotoxicity ranking of the product and the imidacloprid;
and S6, calculating the ecotoxicity equivalent of the sewage collected in the S1 according to the ecotoxicity ranking of the product, and finishing the evaluation of the ecotoxicity.
Further, collecting quantitative imidacloprid-containing sewage in the S1, and performing photocatalytic degradation on the sewage to obtain photocatalytic-degraded sewage, wherein the sewage comprises water and degraded products, and the specific process comprises the following steps:
pouring collected sewage containing imidacloprid and photocatalyst into a batch reactor in sequence, fixing the reaction temperature of the batch reactor to 22 +/-2 ℃ by using a thermometer, stirring the sewage by using a stirrer in the batch reactor for two minutes, simultaneously irradiating the sewage by using an ultraviolet lamp in the batch reactor for ten minutes, collecting 2mL of sewage from the batch reactor in the first five minutes Zhong Meige thirty seconds of irradiation, collecting 2mL of sewage from the batch reactor every five minutes, mixing all collected sewage, filtering, and storing the filtered sewage in a brown glass bottle to obtain the sewage after photocatalytic degradation, wherein the sewage comprises water and a degraded product.
Further, the photocatalyst is titanium dioxide, and the concentration of the titanium dioxide is 100mg/L; the rotational speed of the stirrer was 500rpm.
Further, the ultraviolet lamp is a medium-pressure mercury lamp or a low-pressure mercury lamp, the ultraviolet generated by the ultraviolet lamp comprises long-wave ultraviolet rays and short-wave ultraviolet rays, the medium-pressure mercury lamp emits the long-wave ultraviolet rays, the low-pressure mercury lamp emits the short-wave ultraviolet rays, and only one ultraviolet ray is adopted when the sewage is irradiated.
Further, the maximum intensity of ultraviolet rays of the long wave ultraviolet rays and the short wave ultraviolet rays are both at wavelengths of 313, 365, 405, 437, 547, 578 and 580 nm; the flux of long wave ultraviolet ray and short wave ultraviolet ray in the wavelength range of 200 nm-500 nm is measured with ferric oxalate photometer, and the flux of long wave ultraviolet ray is 3.50mmol min -1 L -1 Flux of short wave ultraviolet ray is 2.03mmol min -1 L -1 。
Further, in the step S2, water and degraded products in the photocatalytic-degraded sewage are separated by reverse phase chromatography analysis to obtain separated water and degraded products, and the specific process is as follows:
carrying out reversed phase chromatographic analysis on the sewage subjected to photocatalytic degradation by using an Eclipse Plus C18 chromatographic column; the elution time for the reverse phase chromatography was twenty minutes; the eluent for elution comprises ultrapure water and acetonitrile, wherein the ultrapure water and the acetonitrile are both acidified by 0.1% formic acid, and the ratio of the ultrapure water to the acetonitrile is 99; the sample size of the reverse phase liquid chromatography is 5 mu L; the reverse phase chromatography analysis showed that the ratio of ultrapure water to acetonitrile was 70 in 1 minute of elution, the ratio of ultrapure water to acetonitrile was 25 in 75 at 10 minutes of elution, the ratio of ultrapure water to acetonitrile was 1 in 99 at 11.1 minutes of elution, the ratio of ultrapure water to acetonitrile was 70 at 15 minutes of elution, the ratio of ultrapure water to acetonitrile was 25 in 16 minutes of elution, and the ratio was maintained for 4 minutes to obtain separated water and a degraded product.
Further, the column temperature in the reverse phase chromatography was 40 ℃ and the flow rate was 0.3mL/min.
Further, the chemical structural formulas of the product and the imidacloprid are analyzed by utilizing the quantitative structure-activity relationship in the S5, so as to obtain the ecological toxicity ranking of the product and the imidacloprid, and the specific process is as follows:
and (3) simultaneously inputting the product obtained in the step (S4) and the chemical structural formula of the imidacloprid into a quantitative structure-activity relationship tool box, outputting the ecological toxicity ranking of the product and the imidacloprid, and adopting an ecological structure-activity relationship model for the quantitative structure-activity relationship tool box.
Further, the ecosystem-activity relationship model expresses chronic toxicity as a chronic value and acute toxicity as a median lethal concentration and a median effective concentration.
Further, in the step S6, the ecotoxicity equivalent of the sewage collected in the step S1 is calculated according to the ecotoxicity ranking of the product, and the ecotoxicity evaluation is completed, specifically including the steps of:
wherein ETE (t) represents the ecotoxicity equivalent of the wastewater for a certain irradiation time;
t represents an irradiation time;
n represents the number of identified products;
EQ represents ecotoxicity ranking value;
ETE (t = 0) represents a quantitative structure-activity relationship value of imidacloprid;
PeakArea A the mass spectral peak area corresponding to each product is indicated.
Has the beneficial effects that:
firstly, collecting a certain amount of sewage containing imidacloprid, wherein the concentration of the imidacloprid is not limited, carrying out photocatalytic degradation on the collected sewage by using an intermittent reactor, and degrading the imidacloprid which is difficult to degrade in the sewage into a plurality of inorganic products with different chemical structures in the presence of light and a photocatalyst by using the photocatalytic degradation to obtain the sewage after the photocatalytic degradation, wherein the sewage comprises water and the degraded products, and the pretreatment process of the sewage is simple and easy to operate; separating the products after photocatalytic degradation by reverse phase chromatographic analysis; performing HPLC-HRMS analysis on the degraded product to obtain the degraded product comprising a product generated after the imidacloprid is subjected to photocatalytic degradation and undegraded imidacloprid and simultaneously obtain the specific structures of the product and the imidacloprid, wherein the HPLC-HRMS is combined by high performance liquid chromatography and high resolution mass spectrometry, and can determine which products are specifically included in the degraded product and also monitor the products generated after the imidacloprid and the imidacloprid are subjected to photocatalytic degradation, and the combination of the HPLC and the HRMS is used as a detector to obtain more accurate product structure information and further used for ecological toxicity prediction of quantitative structure-activity relationship, and the HRMS can also easily monitor all the products; obtaining a chemical structural formula corresponding to the degraded product by using ACD/ChemSketch software according to the specific structure of the degraded product; analyzing the chemical structural formulas of the product and the imidacloprid by utilizing the quantitative structure-activity relationship to obtain the ecological toxicity ranking of the product and the imidacloprid; and calculating the ecotoxicity equivalent of the collected sewage according to the ecotoxicity ranking of the product, completing the ecotoxicity evaluation, and evaluating the ecotoxicity of the sewage at different times by introducing the ecotoxicity equivalent, so that the ETE depending on time can help the sewage to better estimate and eliminate the toxicity of the imidacloprid.
According to the method, the sewage after photocatalytic degradation is subjected to reversed-phase chromatographic analysis to separate pollutants (products), specific structures of the products in the sewage are accurately determined and obtained by HPLC-HRMS analysis aiming at the products obtained by separation to obtain accurate products, and the specific structures of the products are converted into chemical structural formulas by ACD/ChemSketch software, so that the ecological toxicity ranking of the products is conveniently carried out on the chemical structural formulas of the products by using a quantitative structure-activity relationship, the toxicity of each product is obtained, the ecological toxicity equivalent of the sewage is calculated, and the total risk potential of the sewage is evaluated.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a view showing the structure of a batch reactor for photocatalytic degradation;
FIG. 3 is a ranking chart of the ecotoxicity of the examples;
FIG. 4 is a graph of the ecotoxicity equivalents versus photocatalytic degradation time for the examples;
Detailed Description
The first embodiment is as follows: the embodiment is described with reference to fig. 1 to 4, and the method for evaluating the ecotoxicity of imidacloprid in the embodiment comprises the following steps:
s1, collecting quantitative imidacloprid-containing sewage, and carrying out photocatalytic degradation on the sewage to obtain photocatalytic-degraded sewage, wherein the sewage comprises water and degraded products, and the specific process comprises the following steps:
the quantitative amount is not particularly limited in capacity, and is determined by the volume of the batch reactor for photocatalytic degradation. The concentration of imidacloprid in the sewage is not limited, and the imidacloprid concentration adopted by the invention is 20mg/L (78 mu mol/L).
The collected imidacloprid-containing sewage and the photocatalyst are poured into a batch reactor in sequence, the reaction temperature of the batch reactor is fixed to be 22 +/-2 ℃ from the beginning to the end of photocatalytic degradation by a thermometer, and the sewage is stirred by a magnetic stirrer 4 in the batch reactor for two minutes to ensure that the collected imidacloprid-containing sewage and the photocatalyst are fully mixed in the reactor. Simultaneously irradiating the sewage by using an ultraviolet lamp 3 in the batch reactor for ten minutes, collecting 2mL of sewage from the batch reactor every first five minutes Zhong Meige thirty seconds of irradiation, collecting 2mL of sewage from the batch reactor every other one minute in the last five minutes, mixing all the collected sewage, filtering to remove the photocatalyst from the sewage, and filling the filtered sewage into a brown glass bottle for storage, so that no further photoreaction occurs. Obtaining the sewage after photocatalytic degradation, wherein the sewage comprises water and degraded products.
As shown in fig. 2. The intermittent type formula reactor includes casing 1, cooling system 2, ultraviolet lamp 3, magnetic stirrers 4, base 5, support 6, quartz capsule 7, stand 8, base 5 is the circular plate body, stand 8 fixed mounting is on the central line one side of the upper surface of base 5, magnetic stirrers 4 installs on the upper surface of base 5, magnetic stirrers 4 is circular structure, the axis of magnetic stirrers 4 and the coincidence of the axis of base 5, casing 1 is the cylinder casing, the diameter of casing 1 and the diameter of magnetic stirrers 4 equal, casing 1 installs at the upper surface outer fringe department of magnetic stirrers 4, the axis of casing 1 and the coincidence of the axis of magnetic stirrers 4, the quantity of quartz capsule 7 is a plurality of, a plurality of quartz capsules 7 are all installed perpendicularly on the upper surface of magnetic stirrers 4, the center department of the upper surface of magnetic stirrers 4 is installed perpendicularly to cooling system 2 lower extreme, ultraviolet lamp 3 is installed in cooling system 2's inside from cooling system's 2 lower extreme parallel, a plurality of quartz capsules 7 distribute around cooling system 2, support 6 installs on the well upper portion of stand 8, support 6 is perpendicular with stand 8, support 6 and 5 are installed on the perpendicular upper end of cooling system 6.
The photocatalyst is titanium dioxide, and the concentration of the titanium dioxide is 100mg/L.
The rotation speed of the magnetic stirrer is 500rpm.
The ultraviolet lamp is a medium-pressure mercury lamp or a low-pressure mercury lamp, ultraviolet rays generated by the ultraviolet lamp comprise long-wave ultraviolet rays (UVA) and short-wave ultraviolet rays (UVC), the medium-pressure mercury lamp emits the long-wave ultraviolet rays (UVA), the medium-pressure mercury lamp runs in the intermittent reactor by using a cooling water system and is preheated to reach the working temperature within 2 minutes, the low-pressure mercury lamp emits the short-wave ultraviolet rays (UVC), the low-pressure mercury lamp does not run in the intermittent reactor by using the cooling water system, and the low-pressure mercury lamp does not need to be preheated. Only one of the ultraviolet rays is used when the sewage is irradiated.
The maximum ultraviolet intensity of the long-wave Ultraviolet (UVA) and short-wave Ultraviolet (UVC) is 313, 365, 405, 437, 547, 578 and 580nm, and the maximum ultraviolet intensity of the short-wave Ultraviolet (UVC) emits 185 and 254 nm.
The flux of long wave Ultraviolet (UVA) and short wave Ultraviolet (UVC) in the wavelength range of 200nm to 500nm is measured with ferric oxalate photometer, and the flux of long wave Ultraviolet (UVA) is 3.50mmol min -1 L -1 Flux of short wave Ultraviolet (UVC) 2.03mmol min -1 L -1 。
Photocatalytic degradation can degrade difficult-to-degrade imidacloprid into a plurality of inorganic products with different chemical structures in the presence of light and photocatalyst.
S2, separating water and degraded products in the sewage after photocatalytic degradation by utilizing reverse phase chromatographic analysis to obtain separated water and degraded products, wherein the specific process comprises the following steps:
carrying out reversed phase chromatographic analysis on the sewage subjected to photocatalytic degradation by using an Eclipse Plus C18 chromatographic column, wherein the elution time of the reversed phase chromatographic analysis is twenty minutes; the eluent (mobile phase) eluted comprises ultrapure water and acetonitrile, both acidified with 0.1% formic acid, inhibiting ionization of weakly acidic analytes, resulting in better retention of ultrapure water and acetonitrile. The ratio of the ultrapure water to the acetonitrile is 99; the sample size of the reverse phase liquid chromatography is 5 mu L; reverse phase chromatography analysis the ratio of ultrapure water to acetonitrile at 1 minute of elution was 70, the ratio of ultrapure water to acetonitrile at 10 minutes of elution was 25.
The column temperature during the reverse phase chromatographic analysis was 40 ℃ and the flow rate was 0.3mL/min.
And S3, carrying out HPLC-HRMS analysis on the degraded product to obtain the degraded product comprising a product generated by photocatalytic degradation of imidacloprid and undegraded imidacloprid, and simultaneously obtaining the specific structures of the product and the imidacloprid.
The HPLC-HRMS is used by combining high performance liquid chromatography and high resolution mass spectrometry, can determine which products are specifically included in the degraded products, and can identify and monitor the products generated by the imidacloprid and the imidacloprid after photocatalytic degradation to obtain specific structures of the imidacloprid and the products generated by the imidacloprid after photocatalytic degradation.
And S4, obtaining chemical structural formulas of the product and the imidacloprid by using ACD/ChemSketch software according to the specific structures of the product and the imidacloprid.
And drawing the chemical structural formulas of the product and the imidacloprid by using ACD/ChemSketch software of 2016.1.1 edition according to the specific structures of the product and the imidacloprid.
S5, analyzing the chemical structural formulas of the product and the imidacloprid by utilizing the quantitative structure-activity relationship to obtain the ecological toxicity ranking of the product and the imidacloprid, wherein the specific process is as follows:
and (3) simultaneously inputting the chemical structural formulas of the product obtained in the S4 and the imidacloprid into a quantitative structure-activity relationship (QSAR) tool box, outputting the ecological toxicity ranking of the product and the imidacloprid, wherein the quantitative structure-activity relationship (QSAR) tool box adopts an ecological structure-activity relationship (ECOSAR) model.
Quantitative structure-activity relationship (QSAR) analysis is a computer-based method for rapidly evaluating ecological toxicology, and a quantitative structure-activity relationship (QSAR) tool box is existing software. The invention adopts a quantitative structure-activity relationship (QSAR) tool box of version 4.3.1 to evaluate the ecological toxicity of the degraded product. The quantitative structure-activity relationship kit uses the ECOSAR model to express chronic toxicity as a chronic value (CHV) and acute toxicity as a half lethal concentration (LC 50) and a half effective concentration (EC 50). And (4) analyzing according to the quantitative structure-activity relationship to obtain the predicted ecotoxicity of the degraded product, and ranking according to the ecotoxicity value from large to small or from small to small.
S6, calculating the ecotoxicity equivalent of the sewage collected in the S1 according to the ecotoxicity ranking of the product, and finishing the evaluation of the ecotoxicity, wherein the specific process is as follows:
wherein ETE (t) represents the ecotoxicity equivalent of a certain irradiation time of the wastewater;
t represents the irradiation time;
n represents the number of identified products;
EQ represents ecotoxicity ranking value;
ETE (t = 0) represents a quantitative structure-activity relationship value of imidacloprid;
PeakArea A the mass spectral peak area corresponding to each product is indicated.
The invention introduces ecotoxicity equivalent (ETE), and the quantitative structure-activity relationship value of a certain product is the multiplication of an ecotoxicity sequencing value and an MS peak area (mass spectrogram). The quantitative structure-activity relationship values of all products found at a certain moment are summed (namely, the area of each small peak in a mass spectrogram can obtain a mass spectrogram at each moment, and the mass spectrograms are different, so that the corresponding peak areas are different from each other when the sums are added), and the summed values are standardized and called the ecological toxicity equivalent of the sewage. Allows to rank the ecotoxicity values of the products and to evaluate the overall risk potential ETE (t) of the effluents at a given moment. The method has the advantages of simple operation, high sensitivity, rapidness, high efficiency and the like.
Examples
Collecting quantitative sewage containing imidacloprid with the concentration of 20mg/L (78 mu mol/L), carrying out photocatalytic degradation on the sewage, and pouring the sewage and a photocatalyst into an intermittent reactor, wherein the photocatalyst is titanium dioxide with the concentration of 100mg/L. The reaction temperature of the batch reactor is fixed to be 22 +/-2 ℃ from the beginning to the end of the photocatalytic degradation by a thermometer, and the collected imidacloprid-containing sewage and the photocatalyst are fully mixed in the reactor by stirring the sewage for two minutes by a magnetic stirrer 4 in the batch reactor at the rotating speed of 500rpm. And simultaneously irradiating the sewage by using an ultraviolet lamp 3 in the intermittent reactor for ten minutes, wherein the ultraviolet lamp is a medium-pressure mercury lamp or a low-pressure mercury lamp, ultraviolet rays generated by the ultraviolet lamp comprise long-wave ultraviolet rays (UVA) and short-wave ultraviolet rays (UVC), the medium-pressure mercury lamp emits the long-wave ultraviolet rays (UVA), the medium-pressure mercury lamp runs in the intermittent reactor by using a cooling water system, the medium-pressure mercury lamp reaches the working temperature within 2 minutes of preheating, the low-pressure mercury lamp emits the short-wave ultraviolet rays (UVC), the low-pressure mercury lamp runs in the intermittent reactor without using the cooling water system, and the low-pressure mercury lamp does not need preheating. Only one of the above ultraviolet rays is used when the sewage is irradiated. 2mL of wastewater was collected from the batch reactor at the first five minutes Zhong Meige thirty seconds of irradiation, 2mL of wastewater was collected from the batch reactor every other minute for the last five minutes, and the collected wastewater was filtered to remove the photocatalyst from the sample and loaded into a brown glass bottle so that no further photoreaction occurred. Obtaining the sewage after photocatalytic degradation, wherein the sewage comprises water and degraded products.
The maximum intensities (longest wavelengths) of the long wavelength ultraviolet rays (UVA) and the short wavelength ultraviolet rays (UVC) are both 313, 365, 405, 437, 547, 578, and 580nm, and the short wavelength ultraviolet rays (UVC) also emit 185nm and 254 nm. The flux of long-wave Ultraviolet (UVA) light in the wavelength range of 200nm to 500nm is measured with ferric oxalate photometer and the flux is 3.50mmol min -1 L -1 (ii) a The flux of short wave Ultraviolet (UVC) in 200-500 nm wavelength is measured with ferric oxalate photometer and is 2.03mmol min -1 L -1 。
Reversed phase chromatography analysis was performed on the photocatalytic-degraded wastewater using an Eclipse Plus C18 column at a column temperature of 40 ℃ and a flow rate of 0.3mL/min. The elution time for reverse phase chromatography was twenty minutes; the eluent (mobile phase) eluted comprises ultrapure water and acetonitrile, both acidified with 0.1% formic acid, inhibiting ionization of weakly acidic analytes, resulting in better retention of ultrapure water and acetonitrile. The ratio of ultrapure water to acetonitrile is 99; the sample size of the reverse phase liquid chromatography is 5 mu L; reverse phase chromatography analysis the ratio of ultrapure water to acetonitrile at 1 minute of elution was 70, the ratio of ultrapure water to acetonitrile at 10 minutes of elution was 25.
And performing HPLC-HRMS analysis on the degraded product, wherein the HPLC-HRMS is the combination of high performance liquid chromatography and high resolution mass spectrometry, and can determine which products are specifically included in the degraded product, obtain the degraded product comprising a product generated after the imidacloprid is subjected to photocatalytic degradation and undegraded imidacloprid, identify and monitor the products generated after the imidacloprid and the imidacloprid are subjected to photocatalytic degradation, and obtain the specific structures of the product and the imidacloprid. Retention times Rt for imidacloprid and degradation products and the observed higher order MS fragmentation are shown in table 1.
Table 1:
and drawing the chemical structural formulas of the product and the imidacloprid by using ACD/ChemSketch software of 2016.1.1 edition according to the specific structures of the product and the imidacloprid.
And (3) simultaneously inputting the chemical structural formulas of the product obtained in the S4 and the imidacloprid into a quantitative structure-activity relationship (QSAR) toolbox of version 4.3.1 to evaluate the ecological toxicity of the degraded product, wherein the quantitative structure-activity relationship (QSAR) analysis is a method for quickly evaluating the ecological toxicology based on a computer, and the quantitative structure-activity relationship (QSAR) toolbox is the existing software. Quantitative structure-activity relationship (QSAR) kits output product and imidacloprid ecotoxicity rankings, which employ an ecostructure-activity relationship (ECOSAR) model that represents chronic toxicity as a chronic value (CHV) and acute toxicity as a half-lethal concentration (LC 50) and a half-effective concentration (EC 50). And (4) analyzing according to the quantitative structure-activity relationship to obtain the predicted ecotoxicity of the degraded product, and ranking according to the ecotoxicity value from large to small or from small to large. The ordering of the structures determined during photodegradation is shown in fig. 2.
QSAR analysis of imidacloprid and degradation products with daphnia, fish and green algae selected as organisms is shown in table 2.
Table 2:
the mortality rate; n.p = no prediction
The ecotoxicity equivalent of the collected wastewater was calculated according to the ecotoxicity ranking of the product, and the time-dependent ecotoxicity equivalent of imidacloprid is shown in fig. 3. And (3) completing the ecological toxicity evaluation, and specifically comprising the following steps:
wherein ETE (t) represents the ecotoxicity equivalent of a certain irradiation time of the wastewater;
t represents the irradiation time;
n represents the number of identified products;
EQ represents ecotoxicity ranking value;
ETE (t = 0) represents a quantitative structure-activity relationship value of imidacloprid;
PeakArea A the mass spectral peak area corresponding to each product is indicated.
The invention introduces ecotoxicity equivalent (ETE), and the quantitative structure-activity relationship value of a certain product is the multiplication of an ecotoxicity ranking value and an MS peak area (mass spectrogram). The quantitative structure-activity relationship values of all products found at a certain moment are summed (namely, the area of each small peak in a mass spectrogram can obtain a mass spectrogram at each moment, and the mass spectrograms are different, so that the corresponding peak areas are different from each other when the sums are added), and the summed values are standardized and called the ecological toxicity equivalent of the sewage. The ecotoxicity values of the products were allowed to be ranked and the overall hazard potential ETE (t) of the wastewater was evaluated at a given time. The method has the advantages of simple operation, high sensitivity, rapidness, high efficiency and the like.
Claims (10)
1. A method for carrying out ecotoxicity evaluation on imidacloprid is characterized by comprising the following steps: it comprises the following steps:
s1, collecting quantitative imidacloprid-containing sewage, and carrying out photocatalytic degradation on the sewage to obtain photocatalytic-degraded sewage, wherein the sewage comprises water and degraded products;
s2, separating water and degraded products in the sewage after photocatalytic degradation by utilizing reverse phase chromatographic analysis to obtain separated water and degraded products;
s3, carrying out HPLC-HRMS analysis on the degraded product to obtain the degraded product comprising a product generated by photocatalytic degradation of imidacloprid and undegraded imidacloprid and specific structures of the product and the imidacloprid;
s4, obtaining chemical structural formulas of the product and the imidacloprid by using ACD/ChemSketch software according to the specific structures of the product and the imidacloprid;
s5, analyzing the chemical structural formulas of the product and the imidacloprid by utilizing the quantitative structure-activity relationship to obtain the ecological toxicity ranking of the product and the imidacloprid;
and S6, calculating the ecotoxicity equivalent of the sewage collected in the S1 according to the ecotoxicity ranking of the product, and finishing the evaluation of the ecotoxicity.
2. The method for ecotoxicity assessment of imidacloprid as claimed in claim 1, characterized in that: collecting quantitative imidacloprid-containing sewage in the S1, and carrying out photocatalytic degradation on the sewage to obtain photocatalytic-degraded sewage, wherein the sewage comprises water and degraded products, and the specific process comprises the following steps:
pouring collected sewage containing imidacloprid and photocatalyst into a batch reactor in sequence, fixing the reaction temperature of the batch reactor to 22 +/-2 ℃ by using a thermometer, stirring the sewage by using a stirrer in the batch reactor for two minutes, simultaneously irradiating the sewage by using an ultraviolet lamp in the batch reactor for ten minutes, collecting 2mL of sewage from the batch reactor in the first five minutes Zhong Meige thirty seconds of irradiation, collecting 2mL of sewage from the batch reactor every five minutes, mixing all collected sewage, filtering, and storing the filtered sewage in a brown glass bottle to obtain the sewage after photocatalytic degradation, wherein the sewage comprises water and a degraded product.
3. The method for ecotoxicity assessment of imidacloprid as claimed in claim 2, characterized in that:
the photocatalyst is titanium dioxide, and the concentration of the titanium dioxide is 100mg/L;
the rotational speed of the stirrer was 500rpm.
4. The method for the ecotoxicity assessment of imidacloprid as claimed in claim 3, characterized in that: the ultraviolet lamp is a medium-pressure mercury lamp or a low-pressure mercury lamp, ultraviolet rays generated by the ultraviolet lamp comprise long-wave ultraviolet rays and short-wave ultraviolet rays, the medium-pressure mercury lamp emits the long-wave ultraviolet rays, the low-pressure mercury lamp emits the short-wave ultraviolet rays, and only one ultraviolet ray is adopted when the sewage is irradiated.
5. The method for the ecotoxicity assessment of imidacloprid as claimed in claim 4, characterized in that: the maximum ultraviolet intensity of the long wave ultraviolet rays and the short wave ultraviolet rays is 313 nm, 365 nm, 405 nm, 437 nm, 547 nm, 578 nm and 580 nm;
the fluxes of the long-wave ultraviolet ray and the short-wave ultraviolet ray in the wavelength range of 200nm to 500nm are measured by an iron oxalate photometer, and the flux of the long-wave ultraviolet ray is 3.50mmol min -1 L -1 The flux of short-wave ultraviolet ray is 2.03mmol min -1 L -1 。
6. The method for ecotoxicity assessment of imidacloprid as claimed in claim 5, characterized in that: and in the S2, water in the sewage after photocatalytic degradation and the degraded product are separated by utilizing reverse phase chromatographic analysis to obtain the separated water and the degraded product, and the specific process comprises the following steps:
carrying out reversed phase chromatographic analysis on the sewage subjected to photocatalytic degradation by using an Eclipse Plus C18 chromatographic column; the elution time for reverse phase chromatography was twenty minutes; the eluent for elution comprises ultrapure water and acetonitrile, wherein the ultrapure water and the acetonitrile are both acidified by 0.1% formic acid, and the ratio of the ultrapure water to the acetonitrile is 99; the sample size of the reverse phase liquid chromatography is 5 mu L; the reverse phase chromatography analysis showed that the ratio of ultrapure water to acetonitrile was 70 in 1 minute of elution, the ratio of ultrapure water to acetonitrile was 25 in 75 at 10 minutes of elution, the ratio of ultrapure water to acetonitrile was 1 in 99 at 11.1 minutes of elution, the ratio of ultrapure water to acetonitrile was 70 at 15 minutes of elution, the ratio of ultrapure water to acetonitrile was 25 in 16 minutes of elution, and the ratio was maintained for 4 minutes to obtain separated water and a degraded product.
7. The method for the ecotoxicity assessment of imidacloprid as claimed in claim 6, characterized in that: the column temperature in the reverse phase chromatography was 40 ℃ and the flow rate was 0.3mL/min.
8. The method for the ecotoxicity assessment of imidacloprid as claimed in claim 7, characterized in that: and in the S5, the chemical structural formulas of the product and the imidacloprid are analyzed by utilizing the quantitative structure-activity relationship to obtain the ecological toxicity ranking of the product and the imidacloprid, and the specific process is as follows:
and (5) simultaneously inputting the product obtained in the S4 and the chemical structural formula of the imidacloprid into a quantitative structure-activity relationship toolbox, outputting the ecological toxicity ranking of the product and the imidacloprid, and adopting an ecological structure-activity relationship model for the quantitative structure-activity relationship toolbox.
9. The method for ecotoxicity assessment of imidacloprid as claimed in claim 8, characterized in that: the ecosystem-activity relationship model expresses chronic toxicity as a chronic value and acute toxicity as a median lethal concentration and a median effective concentration.
10. The method for ecotoxicity assessment of imidacloprid as claimed in claim 9, characterized in that: and in the S6, calculating the ecotoxicity equivalent of the sewage collected in the S1 according to the ecotoxicity ranking of the product to complete the evaluation of the ecotoxicity, wherein the specific process is as follows:
wherein ETE (t) represents the ecotoxicity equivalent of a certain irradiation time of the wastewater;
t represents an irradiation time;
n represents the number of identified products;
EQ represents ecotoxicity ranking value;
ETE (t = 0) represents a quantitative structure-activity relationship value of imidacloprid;
PeakArea A the mass spectral peak area corresponding to each product is indicated.
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