CN111192642B - Method for predicting biotoxicity of offshore organism heavy metal applicable to field - Google Patents

Method for predicting biotoxicity of offshore organism heavy metal applicable to field Download PDF

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CN111192642B
CN111192642B CN201911312901.3A CN201911312901A CN111192642B CN 111192642 B CN111192642 B CN 111192642B CN 201911312901 A CN201911312901 A CN 201911312901A CN 111192642 B CN111192642 B CN 111192642B
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李瑞利
于凌云
沈小雪
关淳雅
王茜
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Peking University Shenzhen Graduate School
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Abstract

The invention provides a method for predicting heavy metal biotoxicity of offshore organisms, which is suitable for the field. The method comprises the following steps: s01, acquiring the data of the heavy metal enrichment kinetics of the offshore organisms; s02, constructing a water body-organism heavy metal fitting model based on a two-phase distribution model; s03, obtaining parameters of a model for predicting the content of heavy metal in the offshore organism through linear fitting based on a double-box model fitting result; s04, correcting parameters of a prediction model of the heavy metal content in the offshore organism based on field data; s05, calculating a heavy metal eating safety threshold and an acute biotoxicity threshold based on an offshore biotoxicity prediction model suitable for the field. The offshore biological heavy metal content and biotoxicity prediction method provided by the invention can predict the content of different types of heavy metals of different types of organisms in the corresponding sea area only by monitoring the heavy metals in the sea water, can calculate the biotoxicity condition of the heavy metals, has the advantages of simplicity, convenience and rapidness, and can be applied on a large scale. The invention corrects the coefficients of the model through a plurality of groups of field verification data, can be more in line with the actual situation, and has practicability and certain accuracy.

Description

Method for predicting biotoxicity of offshore organism heavy metal applicable to field
Technical Field
The invention belongs to the technical field of ecological environment protection, and particularly relates to a method for predicting the biotoxicity of offshore organisms in the open air.
Background
In recent years, with rapid development of coastal city and industrialization, offshore marine environments are severely damaged, heavy metal pollution in water areas in China is becoming serious, and living environments of aquatic organisms are seriously affected. Heavy metals such as Pb, as, hg, cd have become potentially harmful and important contaminants in marine environments due to their particular chemical properties and toxicity, and have attracted worldwide attention.
Shellfish is an important offshore economic organism, common shellfish comprises oyster, clam, perna viridis, philippine clam, single tooth snail, sinonovacula constricta lamarck, margaritifera, etc., and has high heavy metal enrichment capability due to the living characteristics of filter feeding, poor activity, etc. Different shellfish can influence the enrichment and release degree of pollutants in organisms due to the differences of physiological structures, life habits and the like. At present, some scholars at home and abroad research on stress effect and death effect of different kinds of shellfish on different heavy metals and enrichment capability of the heavy metals, and perform health risk evaluation on human edibility. However, the research on the relationship between the concentration of the heavy metal in the seawater and the concentration of the heavy metal in the shellfish is limited at present; in addition, the research on an offshore heavy metal biotoxicity prediction model through field verification is also relatively lacking.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for predicting the biotoxicity of the offshore organism heavy metal, which is suitable for the field and has wide application scene. The method comprises the following steps:
s01, acquiring the data of the heavy metal enrichment kinetics of the offshore organisms;
s02, constructing a water body-organism heavy metal fitting model based on a two-phase distribution model;
s03, obtaining parameters of a model for predicting the content of heavy metal in the offshore organism through linear fitting based on a double-box model fitting result;
s04, correcting parameters of a prediction model of the heavy metal content in the offshore organism based on field data;
s05, calculating a heavy metal eating safety threshold and an acute biotoxicity threshold based on an offshore biotoxicity prediction model suitable for the field;
as a further explanation of the method for predicting the biotoxicity of the off-shore organisms suitable for the field, the invention: in the step S01, heavy metal enrichment kinetic data related to heavy metals and offshore organisms are obtained mainly based on literature investigation or control experiments. The main research object is heavy metal enrichment kinetics of soft tissue;
as a further explanation of the method for predicting the biotoxicity of the off-shore organisms suitable for the field, the invention: in the step S02, the action process between the water body and the offshore organisms is described by a two-phase distribution model, and a good result is obtained; generally, assuming that the biological enrichment of heavy metals in organisms can be approximately regarded as a two-phase distribution process of heavy metals between an aqueous phase and the organisms, the adsorption and desorption processes can be described by a first-order kinetic process; neglecting the volatilization of heavy metals in a water body, the concentration of heavy metals in an organism can be expressed by the following formula (0 < t), wherein t is the number of days (d) at the end of the accumulation phase):
wherein k1 and k2 are respectively an enrichment rate constant and a biological discharge rate constant of organisms on a certain heavy metal;
enrichment factor (BCF), the ratio of the equilibrium concentration of a contaminant in an organism to the concentration of that contaminant in its environment of living, is an important indicator describing the tendency of a chemical to accumulate in an organism. BCF can be found by the following formula:
when enrichment reaches equilibrium, the metal content C in the organism Amax Expressed by the formula:
C Amax =BCF×C w
treating C with the corresponding heavy metal concentration w And the corresponding in-vivo C obtained by calculation Amax And drawing and modeling to obtain the offshore heavy metal biotoxicity prediction model, and carrying out model reliability inspection according to field research. Thereby achieving the purpose of measuring the heavy metal content of the seawater; a target for predicting heavy metal content in an organism and evaluating biotoxicity;
as a further explanation of the method for predicting the biotoxicity of the off-shore organisms suitable for the field, the invention: the steps are as followsIn S03, according to C obtained in S02 w And C Amax The value of the obtained solution can obtain the corresponding heavy metal treatment concentration C w And the corresponding in-vivo C obtained by calculation Amax Is a relationship diagram of (1);
the formula applies: c (C) Amax =22.03θkC w Performing linear fitting on the obtained product; k represents the enrichment capability of organisms on specific heavy metals, and the k value of cadmium can be obtained through calculation; the parameter theta represents a species difference index and represents the capability of enriching the heavy metals in the seawater by different organisms, and the theta value of the different organisms can be obtained through calculation;
as a further explanation of the method for predicting the biotoxicity of the off-shore organisms suitable for the field, the invention: in step S04, the model is constructed based on a double-box model, so that the model is suitable for laboratory culture experiments, and under laboratory conditions, because the concentration of added heavy metal is often about 100-10000 times of that of the wild, the influence of other heavy metals except the exchange between seawater and organisms is negligible. However, the accumulation and transformation of heavy metals in the field are complex and are not a two-box model environment, and since the concentration of seawater in the field is low, the concentration of heavy metals in the living body can not be ignored because of other sources such as surrounding sediments, and in this case, if the concentration of heavy metals in the seawater is considered only to estimate the heavy metal concentration in the living body, the accumulated heavy metal amount in the living body is likely to be misestimated. Correcting a coefficient sigma in the formula, acquiring field data through a literature retrieval method or field investigation, and fitting based on field experimental data; dividing the slope value in the fitting result by the corresponding slope value in the step S03 to obtain a coefficient sigma value; the corrected prediction model is: c (C) Amax =22.03σθkC w The method comprises the steps of carrying out a first treatment on the surface of the In the formula, C Amax Is the content of heavy metals in the offshore organisms to be predicted; c (C) w The concentration value of heavy metals in the sea water obtained by measurement; the coefficient σ is a correction coefficient between acquisition of field data by a literature search method and field investigation.
As a further explanation of the method for predicting the biotoxicity of the off-shore organisms suitable for the field, the invention: in the step S05, a heavy metal eating safety threshold and an acute biotoxicity threshold are calculated, specifically: (1) edible safety threshold: the upper limit of the content of various heavy metals in the mariculture water is regulated according to the pollution-free food mariculture water quality (NY 5052-2001) of the department of agriculture in China, and the edible safety threshold is obtained. If the safety threshold is exceeded, the sea area is considered to have edible safety risk corresponding to the offshore biological variety; (2) acute biotoxicity threshold: and predicting the content of heavy metals in the offshore organism based on a field model according to water heavy metal concentration data corresponding to 48h half-mortality of the offshore organism, namely, the acute biotoxicity threshold of the heavy metals in the soft tissue.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a double-box model fitting of an offshore shellfish to cadmium-containing seawater in an example;
FIG. 3 is a fitting result of a cadmium concentration prediction model in an offshore shellfish prior to field verification in an embodiment;
FIG. 4 is a graph showing the fit of the model for predicting the cadmium concentration in the offshore shellfish after field verification in the example.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specific example 1: and (3) constructing a prediction model of the content of heavy metal cadmium (Cd) and the biotoxicity in the offshore shellfish crassostrea gigas (Crassostrea rivularis), crassostrea gigas (Crassostrea gigas) and crassostrea gigas (Alectryonela plicatula).
S01, acquiring the data of the heavy metal enrichment kinetics of the offshore organisms. And acquiring heavy metal enrichment kinetic data related to heavy metal Cd and oyster mainly based on literature investigation or control experiments. The main study object is heavy metal enrichment kinetics of soft tissue.
S02, constructing a water body-organism heavy metal fitting model based on a two-phase distribution model. The action process between the water body and the three oysters is described by a two-phase distribution model, and good results are obtained. In general, assuming that the biological enrichment of heavy metals in organisms can be approximately regarded as a two-phase distribution process of heavy metals between an aqueous phase and oysters, the adsorption and desorption processes can be described by a first-order kinetic process. Neglecting the volatilization of heavy metals in the water body, the concentration of heavy metals in oyster bodies can be expressed by the following formula (0 < t), wherein t is the number of days (d) of ending the accumulation phase):
enrichment factor (BCF), the ratio of the equilibrium concentration of a contaminant in an organism to the concentration of that contaminant in its environment of living, is an important indicator describing the tendency of a chemical to accumulate in an organism. BCF can be found by the following formula:
when enrichment reaches equilibrium, the metal content C in the organism Amax Expressed by the formula:
C Amax =BCF×C w
treating C with the corresponding heavy metal concentration w And the corresponding in-vivo C obtained by calculation Amax And drawing and modeling to obtain an offshore heavy metal biotoxicity prediction model represented by oyster, and carrying out model reliability inspection according to field research. Thereby achieving the aim of predicting the heavy metal content in the oyster body and evaluating the biological toxicity of the oyster by measuring the heavy metal content in the sea water.
The study carried out double-box model fitting on the relevant study data, the fitting formula is shown in the double-box model, the fitting result is shown in fig. 2, and relevant fitting parameters are shown in table 1.
Table 1 three offshore unitsFitting parameters and corresponding enrichment factors (BCF) related to double-box models of shellfish and cadmium-containing seawater, and heavy metal content (C) in organisms Amax ) Calculation result
S03, obtaining parameters of a prediction model of the heavy metal content in the offshore organism through linear fitting based on a double-box model fitting result. C according to Table 1 w And C Amax The value of the obtained solution can obtain the corresponding heavy metal treatment concentration C w And the corresponding in-vivo C obtained by calculation Amax Is a graph of the relationship of (1).
The formula applies: c (C) Amax =22.03θkC w This was fitted linearly and the results are shown in figure 3. k represents the enrichment capability of oyster to specific heavy metals, and the k value of cadmium is calculated to be 8.15. The parameter theta represents species difference index, and represents the capability of enriching seawater heavy metals of different organisms, and theta values of the crassostrea gigas, the crassostrea gigas and the crassostrea gigas are respectively 1, 4.34 and 2.95, so that crassostrea gigas > are indicated.
S04, correcting parameters of a prediction model of the heavy metal content in the offshore organism based on field data. The model is constructed based on a double-box model, so that the model is suitable for laboratory culture experiments, and under laboratory conditions, because the concentration of added heavy metal is usually about 100-10000 times that of the wild heavy metal, the influence except the heavy metal exchange between seawater and oyster is negligible. However, the accumulation and transformation of heavy metals in the field are complex and are not a two-box model environment, and because the concentration of seawater in the field is low, the concentration of heavy metals in oysters enriched by other sources such as surrounding sediments cannot be ignored, and in this case, if the concentration of heavy metals in the seawater is only considered to estimate the concentration of heavy metals in oysters, the accumulated amount of heavy metals in oysters is likely to be misestimated.
In order to correct the coefficient sigma in the formula, field data are obtained through a literature retrieval method or field investigation, and further fitting is performed based on field experiment data; the fitting result is shown in fig. 4, and the slope value in the fitting result divided by the corresponding slope value in fig. 3 is the coefficient sigma value;
the corrected prediction model is: c (C) Amax =22.03σθkC w The method comprises the steps of carrying out a first treatment on the surface of the In the formula, C Amax Is the content (mg/kg) of heavy metals in the offshore shellfish to be predicted; c (C) w The concentration value (mg/kg) of heavy metals in the sea water obtained by measurement; the coefficient σ is a correction coefficient between acquisition of field data by a literature search method and field investigation. .
S05, calculating a heavy metal eating safety threshold and an acute biotoxicity threshold based on an offshore biotoxicity prediction model suitable for the field. The method comprises the following steps: (1) edible safety threshold: the corresponding standard is formulated for the heavy metals in the mariculture water body in China, the water quality requirement of the mariculture water is regulated by the Ministry of agriculture (NY 5052-2001), the upper limit of the content of various heavy metals is related, wherein the mariculture regulated concentration of cadmium ions is 0.005mg/L, and the concentration is C w Value calculating the content C of the heavy metal cadmium in the offshore shellfish Amax 3.90mg/kg of crassostrea gigas and 0.90mg/kg of crassostrea gigas. (2) acute biotoxicity threshold: studies show that the concentration of half-rate of cadmium in crassostrea gigas is 0.611mg/L in 48 hours, so that the cadmium content in crassostrea gigas under the acute toxicity condition can be calculated; 0.611mg/L as C w The result is brought into the fitting formula of the crassostrea gigas in figure 4 to obtain a model for predicting the heavy metal content in crassostrea gigas to be 1.27 multiplied by 10 4 mg/kg, i.e.acute biotoxicity threshold of Cd in soft tissue is 1.27X10 4 mg/kg。
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.

Claims (1)

1. A method for predicting the biotoxicity of off-shore organisms in the wild, which is characterized by comprising the following steps:
s01, acquiring the data of the heavy metal enrichment kinetics of the offshore organisms;
s02, constructing a water body-organism heavy metal fitting model based on a two-phase distribution model;
s03, obtaining parameters of a model for predicting the content of heavy metal in the offshore organism through linear fitting based on a double-box model fitting result;
s04, correcting parameters of a prediction model of the heavy metal content in the offshore organism based on field data;
s05, calculating a heavy metal eating safety threshold and an acute biotoxicity threshold based on an offshore biotoxicity prediction model suitable for the field;
in the step S01, heavy metal enrichment kinetic data related to heavy metals and offshore organisms are obtained mainly based on literature investigation or control experiments; the main research object is heavy metal enrichment kinetics of soft tissue;
in the step S02, the action process between the water body and the offshore organisms is described by a two-phase distribution model, and a good result is obtained; neglecting volatilization of heavy metals in the water body, and expressing the concentration of the heavy metals in the offshore organism as 0< t by the following formula, wherein t is the number of days (d) of ending the accumulation phase:
wherein k1 and k2 are respectively an enrichment rate constant and a biological discharge rate constant of organisms on a certain heavy metal;
in addition, the parameter to be acquired is the enrichment coefficient BCF; further, when the enrichment reaches equilibrium, the metal content C in the organism Amax Expressed by the formula:
C Amax =BCF×C w
treating C with the corresponding heavy metal concentration w And the corresponding in-vivo C obtained by calculation Amax Drawing and modeling to obtain a fitted offshore heavy metal biotoxicity prediction model, and carrying out model reliability inspection according to field research; thereby achieving the aim of predicting the heavy metal content in the offshore organism and evaluating the biotoxicity by measuring the heavy metal content in the sea water;
in the step S03, according to C obtained in S02 w And C Amax Obtaining the corresponding heavy metal treatment concentration C w And the corresponding in-vivo C obtained by calculation Amax Is a relationship diagram of (1);
the formula applies: c (C) Amax =22.03θkC w Performing linear fitting on the heavy metals, wherein k represents the enrichment capacity of offshore organisms on specific types of heavy metals, and calculating to obtain the k value of the heavy metals; the parameter theta represents a species difference index, represents the capability of enriching the heavy metals in the seawater by different organisms, and obtains theta values of the different organisms through calculation;
in step S04, the model is constructed based on a two-box model; correcting a coefficient sigma in the formula, acquiring field data through a literature retrieval method or field investigation, and fitting based on field experimental data; dividing the slope value in the fitting result by the corresponding slope value in the step S03 to obtain a coefficient sigma value; the corrected prediction model is: c (C) Amax =22.03σθkC w The method comprises the steps of carrying out a first treatment on the surface of the In the formula, C Amax Is the content of heavy metals in the offshore organisms to be predicted; c (C) w The concentration value of heavy metals in the sea water obtained by measurement; the physical meaning of the coefficient sigma represents the ratio of the amount of the heavy metal enriched by the offshore organism from the outside of the seawater to the heavy metal enriched by the offshore organism from the seawater;
in the step S05, a heavy metal eating safety threshold and an acute biotoxicity threshold are calculated, specifically: (1) edible safety threshold: the upper limit of the content of various heavy metals in the mariculture water is regulated according to pollution-free food mariculture water quality (NY 5052-2001) of the department of agriculture of China, and an edible safety threshold is obtained; if the sea area exceeds the safety threshold, the sea area is considered to have edible safety risk corresponding to the offshore shellfish variety; (2) acute biotoxicity threshold: and predicting the content of heavy metals in the offshore organism based on a field model according to water heavy metal concentration data corresponding to 48h half-mortality of the offshore organism, namely, the acute biotoxicity threshold of the heavy metals in the soft tissue.
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