CN109187517B - Prediction method for degradation rate of chloramide pesticides in biogas residue returning soil - Google Patents

Prediction method for degradation rate of chloramide pesticides in biogas residue returning soil Download PDF

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CN109187517B
CN109187517B CN201810838473.7A CN201810838473A CN109187517B CN 109187517 B CN109187517 B CN 109187517B CN 201810838473 A CN201810838473 A CN 201810838473A CN 109187517 B CN109187517 B CN 109187517B
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soil
pesticides
degradation
pesticide
chloramide
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蔡喜运
景旭东
李茜
牛丽丽
乔显亮
陈景文
汪国刚
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Dalian University of Technology
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Abstract

The invention belongs to the technical field of pesticide environment evaluation, and provides a prediction method of degradation rate of chloramide pesticides in biogas residue returning soil. Aiming at the problem of influence of biogas residue returning on degradation rate of chloramide pesticides, the invention develops adsorption degradation experiments of chloramide pesticides under different biogas residue dosage proportions by considering the influence of biogas residue returning on free dissolution state of pesticides in soil, activity of soil dehydrogenase, degradation time and the like, adopts a regression analysis method to construct a prediction model of degradation rate of chloramide pesticides in soil under the effect of biogas residue returning, verifies the model, proves that the model has better prediction capability, and has certain guiding significance on prediction of degradation rate of pesticides in soil with biogas residue returning.

Description

Prediction method for degradation rate of chloramide pesticides in biogas residue returning soil
Technical Field
The invention belongs to the technical field of pesticide environment evaluation, and particularly relates to a model and a method for predicting the degradation rate of chloramide pesticides in biogas residue returning soil.
Background
The biogas residue is a solid residue generated after anaerobic fermentation of agricultural and forestry wastes such as human and animal excreta, straws and the like, contains a large amount of nutrients required by plant growth, contains 36.0-50.0% of organic matters, 0.78-1.61% of total nitrogen, 0.4-0.6% of total phosphorus, 0.61-1.30% of total potassium, other trace elements and the like, can be used as a high-quality base fertilizer, improves the organic matter content of soil, improves the microbial activity of the soil, and simultaneously releases a plurality of beneficial trace nutrient elements. Patent CN 107673873A discloses a method for preparing ecological biogas residue fertilizer from biogas residue, which shows that the biogas fertilizer has two functions of quick effect and delayed effect and can be used as base fertilizer and additional fertilizer; patent CN 107954781A discloses a method for preparing a slow-release compound fertilizer from biogas residues, wherein a citrus compound fertilizer with a slow-release function is prepared by compounding biogas residues and an inorganic fertilizer, and the utilization rate of the fertilizer can be improved. The biogas residue can be used as a good fertilizer resource to be popularized and used in a large area in the fertilizer field.
The application of pesticides can be accompanied in the process of returning biogas residues to the field, the pesticides are an important guarantee for maintaining the grain yield increase, the amide herbicides are one of the indispensable pesticides for crop yield increase at present, the amide herbicides are widely used in the world agricultural production at present, the herbicides can be degraded by microorganisms in soil, and can also perform adsorption-desorption effects with organic matters in the soil, so that the bioavailability process of the pesticides in the soil is influenced, and further the biodegradation rate of the pesticides is influenced. The biogas residues are used as a biomass resource, contain loose and porous organic matters, and can influence the adsorption mass transfer and biodegradation processes of pesticides in soil after returning to the field. Researches show that the biogas residues can adsorb pesticides in soil after returning to the field, and the mass transfer and morphological distribution of the pesticides in the soil are influenced; and the biogas residues can also improve the micro-ecological environment of the soil, improve the microbial activity of the soil and strengthen the biodegradation of the pesticide after returning to the field. At present, a prediction model related to biodegradation of pesticides in soil by returning biogas residues to the field is lacked, and the prediction model of degradation rate of chloramide pesticides in the soil by returning biogas residues to the field is constructed according to experimental data to guide the returning of biogas residues to the field and the use of pesticides.
Disclosure of Invention
The invention constructs a model and a method for predicting the degradation rate of chloramide pesticides aiming at the influence of biogas residue returning on the degradation rate of chloramide pesticides. The method comprehensively considers various factors such as pesticide free dissolution state, soil dehydrogenase activity, pesticide degradation time and the like, and verifies a prediction model. The free dissolved state of the pesticide reflects the content of the effective state of the pesticide, which has certain guiding significance for evaluating the biological effectiveness of the pesticide.
The technical scheme of the invention is as follows:
a prediction method of degradation rate of chloramide pesticides in biogas residue returning soil comprises the following steps:
(1) determination of dehydrogenase activity in soil under effect of returning biogas residues to field
Measuring the activity of dehydrogenase in soil by adopting a formazan colorimetric method;
(2) determination of degradation rate and free dissolution state of chloramide pesticides in biogas residue returning soil
By the indoor constant-temperature culture method, the biogas residues and the soil are mixed, the dosage of the biogas residues accounts for 0-5% of the mass of the soil, and the influence of the dosage proportion of the biogas residues on the degradation rate of the pesticide is considered. The water content of the soil is maintained to be 60% of the maximum water content of the soil; respectively adding chloramide pesticides into the pre-cultured soil, wherein the concentration of each pesticide is 5mg/kg, uniformly mixing, subpackaging, and culturing in an artificial climate box, wherein the culturing temperature is maintained at 25 ℃, the humidity is 60%, and no illumination is provided; the chloramide pesticides are alachlor, acetochlor, metolachlor, butachlor and metalaxyl; sampling and analyzing on time, and obtaining the degradation rate of the pesticide according to the formula (1):
Crate of degradation=(CInitial concentration–CMeasured concentration)/CInitial concentration(1)
The adsorption of the chloramide pesticides to the soil adopts an oscillation balance method; the initial concentrations of the chloramide pesticides were set as follows: 20mg/L of alachlor, 20mg/L of acetochlor, 20mg/L of metolachlor, 10mg/L of butachlor and 10mg/L of metalaxyl; taking soil in a glass centrifuge tube, and mixing according to the mass ratio of soil to water: the ratio of the alachlor to the acetochlor to the metolachlor is 1:5, the ratio of the butachlor to the metalaxyl is 1:25, and the chloramide pesticide contains 10mmol/L of CaCl2A solution; oscillating for 24h at 25 ℃ and 180r/min, standing for 2h, transferring supernatant, filtering with 0.45 μm water system membrane, and measuring the residual amount of chloramide pesticide in filtrate by high performance liquid chromatography; establishing an adsorption isotherm Freu from the adsorption dataThe ndlich equation, which is shown in equation (2):
Figure BDA0001745031320000031
wherein Q is the adsorption amount of the pesticide in soil mg/kg-1;CeConcentration mg.L of pesticide in water phase for adsorption equilibrium-1;KfAnd 1/n is a constant related to temperature;
according to the degradation experiment and the adsorption experiment of the chloramide pesticides, the free soluble state of the chloramide pesticides is obtained by the formula (3):
fin the free dissolved state=(CeV/Ctm) (3)
In the formula, CtThe instantaneous concentration of the pesticide in the soil; ceIs the concentration of liquid phase when the pesticide is adsorbed and balanced in the soil, V is the water content in the soil, m is the dry weight of the soil, CeFrom formula Ct=kfCe 1/n+V CeK is obtained byfAnd 1/n is a constant related to temperature in a pesticide adsorption isotherm model Freundlich equation;
(3) construction of prediction model for degradation rate of chloramide pesticides
Performing regression analysis by taking the degradation rate of the chloramide pesticides as a dependent variable and taking the free dissolution state of the pesticides, the activity of soil dehydrogenase and the degradation time of the pesticides as independent variables to obtain an optimal model, calculating the degradation rate of the pesticides according to the regression analysis result, and analyzing the linear fitting result of the measured value and the predicted value;
degradation prediction model:
logCrate of degradation=0.010logfIn the free dissolved state+0.158logADehydrogenase activity+0.436logtTime of day-0.489(R2=0.830)
Wherein, CRate of degradationThe degradation rate of the pesticide; f. ofIn the free dissolved stateIs in a pesticide free-soluble state; a. theDehydrogenase activityIs soil dehydrogenase activity; t is tTime of dayThe time for degradation of the pesticide.
The invention has the beneficial effects that: according to the invention, under the condition of considering factors such as free dissolution state of pesticide, soil dehydrogenase activity, pesticide degradation time and biogas residue dosage ratio, the prediction model of degradation rate of chloramide pesticides changing along with time under the condition of returning biogas residue to field is constructed by using SPSS software regression analysis, and the model has the characteristics of good prediction and strong practicability.
Drawings
FIG. 1 is a graph comparing experimental values and predicted values of a model.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1 construction of model for predicting degradation rate of acetochlor under effect of biogas residues
Taking the free dissolution state of the pesticide, the activity of the soil dehydrogenase and the degradation time as independent variables, taking the degradation rate of the pesticide as dependent variables, constructing a regression model by adopting an input method after taking log values of all factors respectively, and verifying the model.
An input method comprises the following steps:
taking log value
logCRate of degradation=-0.068logfIn the free dissolved state+0.244logADehydrogenase activity+0.490logtTime of day-0.468(R20.852) not taking log value
CRate of degradation=-2.854fIn the free dissolved state-0.673ADehydrogenase activity+0.017tTime of day+0.882(R20.776) finally selecting an acetochlor degradation prediction model constructed by taking log values:
logCrate of degradation=-0.068logfIn the free dissolved state+0.244logADehydrogenase activity+0.490logtTime of day-0.468(R20.852) construction of model for predicting degradation rate of metolachlor under action of biogas residue in example 2
Taking the free dissolution state of the pesticide, the activity of the soil dehydrogenase and the degradation time as independent variables, taking the degradation rate of the pesticide as dependent variables, constructing a regression model by adopting an input method after taking log values of all factors respectively, and verifying the model.
An input method comprises the following steps:
taking log value
logCRate of degradation=-0.090logfIn the free dissolved state+0.041logADehydrogenase activity+0.429logtTime of day-0.801(R2=0.965)
Not taking log value
CRate of degradation=-3.369fFree soluble state-0.644ADehydrogenase activity+0.012tTime of day+0.707(R2=0.890)
Finally, selecting a metolachlor degradation rate prediction model constructed by taking a log value:
logCrate of degradation=-0.090logfIn the free dissolved state+0.041logADehydrogenase activity+0.429logtTime of day-0.801(R2=0.965)
Example 3 construction of a model for predicting degradation rate of butachlor under action of biogas residues
Taking the free dissolution state of the pesticide, the activity of the soil dehydrogenase and the degradation time as independent variables, taking the degradation rate of the pesticide as dependent variables, constructing a regression model by adopting an input method after taking log values of all factors respectively, and verifying the model.
An input method comprises the following steps:
taking log value
logCRate of degradation=0.016logfIn the free dissolved state+0.132logADehydrogenase activity+0.445logtTime of day-0.458(R2=0.943)
Not taking log value
CRate of degradation=-1.379fIn the free dissolved state-0.125ADehydrogenase activity+0.025tTime of day+0.484(R2=0.890)
Finally, selecting a butachlor degradation rate prediction model constructed by taking a log value:
logCrate of degradation=0.016logfIn the free dissolved state+0.132logADehydrogenase activity+0.445logtTime of day-0.458(R2=0.965)。

Claims (1)

1. A prediction method for degradation rate of chloramide pesticides in biogas residue returning soil is characterized by comprising the following steps:
(1) determination of dehydrogenase activity in soil under effect of returning biogas residues to field
Measuring the activity of dehydrogenase in soil by adopting a formazan colorimetric method;
(2) determination of degradation rate and free dissolution state of chloramide pesticides in biogas residue returning soil
Mixing biogas residues and soil by an indoor constant-temperature culture method, wherein the biogas residues account for 0-5% of the mass of the soil, and the water content of the soil is maintained at 60% of the maximum water content of the soil; respectively adding amide pesticides into the pre-cultured soil, wherein the concentration of each pesticide is 5mg/kg, uniformly mixing, subpackaging, and culturing in a climatic chamber, wherein the culturing temperature is maintained at 25 ℃, the humidity is 60%, and no illumination is provided; the chloramide pesticides are alachlor, acetochlor, metolachlor, butachlor and metalaxyl; sampling and analyzing on time, and obtaining the degradation rate of the pesticide according to the formula (1):
Crate of degradation=(CInitial concentration–CMeasured concentration)/CInitial concentration(1)
The adsorption of the chloramide pesticides to the soil adopts an oscillation balance method; initial concentrations of the pesticides were set as follows: 20mg/L of alachlor, 20mg/L of acetochlor, 20mg/L of metolachlor, 10mg/L of butachlor and 10mg/L of metalaxyl; taking soil in a glass centrifuge tube, and mixing according to the mass ratio of soil to water: the ratio of the alachlor to the acetochlor to the metolachlor is 1:5, the ratio of the butachlor to the metalaxyl is 1:25, and the chloramide pesticide contains 10mmol/L of CaCl2A solution; oscillating for 24h at 25 ℃ and 180r/min, standing for 2h, transferring supernatant, filtering with 0.45 μm water system membrane, and measuring pesticide residue in filtrate by high performance liquid chromatography; establishing an adsorption isotherm Freundlich equation according to the adsorption data, wherein the equation is shown in formula (2):
Figure FDA0002616146340000011
wherein Q is the adsorption amount of the pesticide in soil mg/kg-1;CeFor agricultureConcentration of liquid phase mg.L in adsorption equilibrium of medicine in soil-1;KfAnd 1/n is a constant related to temperature;
according to the degradation experiment and the adsorption experiment of the chloramide pesticides, the free soluble state of the chloramide pesticides is obtained by the formula (3):
fin the free dissolved state=(CeV/C1m) (3)
In the formula, CtThe instantaneous concentration of the pesticide in the soil; ceThe concentration of a liquid phase when the pesticide is adsorbed and balanced in the soil, V the water content of the soil, m is the dry weight of the soil, CeFrom formula Ct=kfCe 1/n+V CeK is obtained byfAnd 1/n is a constant related to temperature in a pesticide adsorption isotherm model Freundlich equation;
(3) construction of prediction model for degradation rate of amide pesticides
Performing regression analysis by taking the degradation rate of the amide pesticides as a dependent variable and taking the free dissolution state of the pesticides, the activity of the soil dehydrogenase and the degradation time as independent variables to obtain an optimal model, calculating the degradation rate of the pesticides according to the regression analysis result, and analyzing the linear fitting result of the measured value and the predicted value;
degradation prediction model:
logCrate of degradation=0.010logfIn the free dissolved state+0.158logADehydrogenase activity+0.436logtTime of day-0.489 , R2=0.830
Wherein, CRate of degradationThe degradation rate of the pesticide; f. ofIn the free dissolved stateIs in a pesticide free-soluble state; a. theDehydrogenase activityIs soil dehydrogenase activity; t is tTime of dayThe time for degradation of the pesticide.
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