CN110163424B - Rice grain cadmium pollution risk early warning method based on gradient film diffusion technology - Google Patents
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Abstract
The invention relates to the field of agricultural product quality safety, and discloses a rice grain cadmium pollution risk early warning method based on a gradient film diffusion technology, which comprises the following steps: s1: before rice planting, collecting a soil sample, detecting the content X1 of effective cadmium in the soil by using a gradient film diffusion technology, and simultaneously detecting the pH value X2, the content X3 of silicon oxide, the content X4 of iron oxide and the content X5 of calcium oxide of the soil; s2: substituting X1-X5 into the prediction model to obtain a predicted value Y of the cadmium content in rice grains in the mature period; s3: according to the early warning value J = Y ÷ 0.2mg/kg and the related judgment rule; and predicting the risk. The method has the characteristics of high prediction accuracy, convenience in operation and the like. When the safety of the rice is monitored, the safety of cadmium in rice grains can be early warned before planting, and problems can be found in advance.
Description
Technical Field
The invention relates to the technical field of agricultural product quality safety, in particular to a rice grain cadmium pollution risk early warning method based on a gradient film diffusion technology.
Background
Since the 20 th century, with the great increase of population, the rapid development of mining, smelting, manufacturing and other industries, the use of a large amount of agricultural chemicals and the discharge of urban sewage, the pollution problem of cadmium (Cd) in soil is becoming more serious. According to statistics, the cultivated land polluted by heavy metal in the world is about 2.35 hundred million hm2And Cd entering the soil is about 2.2 million tons per year.
Many studies have shown that cadmium uptake and accumulation in crops depends mainly on its bioavailability in soil (the content that can be taken up by plants) and not on the total amount. How to scientifically characterize the biological effectiveness of cadmium, so that a soil-rice cadmium pollution risk prediction model is established on the basis of the biological effectiveness, and the method has important significance for guaranteeing the diet safety of the masses.
The extraction technology commonly used in the effective state of the heavy metal in the soil is a chemical method, although the method has effect, the method is limited by a series of external factors, the universality is poor, and the form distribution of the heavy metal can be changed in the determination process. The gradient film diffusion technique is a new morphological analysis technique, developed mainly by Davison and Zhang, university of Lancaster, uk, in the middle of the 90's of the last century. The appearance of the gradient film diffusion technology overcomes the defects of a chemical extraction method, and can achieve ideal effect on the extraction of the effective state of cadmium in the environment. In recent years, many researches also prove that the cadmium effective state content extracted by the gradient film diffusion technology is a better index for evaluating the bioavailability of the cadmium in the soil. However, the early warning method for researching the cadmium pollution risk of soil-rice by using the gradient film diffusion technology has not been reported yet.
Disclosure of Invention
In order to solve the technical problems, the invention provides a rice grain cadmium pollution risk early warning method based on a gradient film diffusion technology, and the method has the characteristics of high prediction accuracy, convenience in operation and the like. When the safety of the rice is monitored, the safety of cadmium in rice grains can be early warned before planting, and problems can be found in advance.
The specific technical scheme of the invention is as follows: a rice grain cadmium pollution risk early warning method based on a gradient film diffusion technology comprises the following steps:
s1: before rice planting, collecting a soil sample, detecting the content X1 of effective cadmium in the soil by using a gradient film diffusion technology, and simultaneously detecting the pH value X2, the content X3 of silicon oxide, the content X4 of iron oxide and the content X5 of calcium oxide of the soil.
S2: and substituting X1, X2, X3, X4 and X5 into a prediction model shown in the following table to obtain a predicted value Y of the cadmium content in the rice grains in the mature period.
S3: calculating an early warning value according to the food safety national standard GB2762-2017 that the cadmium limit in food is less than 0.2 mg/kg: the early warning value J is the predicted value Y/0.2 mg/kg of cadmium content in rice grains in the mature period; no risk is present if J < 0.7, warning if J < 1.0.7, low risk if J < 2.0, medium risk if J < 3.0, and high risk if J < 3.0.
The invention adopts a gradient film diffusion technology to represent the biological effectiveness of cadmium in soil, and creatively searches the relationship between the accumulation amount of cadmium in mature rice grains and the content of effective cadmium and the physicochemical properties of soil in the mature rice grains, on the basis, a Cubist mixed linear regression method is respectively adopted, the content of the effective cadmium in the soil and the physicochemical indexes (pH, silicon oxide content, iron oxide content and calcium oxide content) of the soil are taken as variables, the cadmium content in the rice grains in the mature period is taken as a dependent variable, a prediction model is established, after the cadmium content in the rice grains is predicted, an early warning value is calculated, the safety of the rice grains is judged according to the early warning value, the prediction accuracy is high, the operation is convenient, the safety of the cadmium in the rice grains can be early warned before planting, and problems can be found in advance.
Among the factors that influence the pH, silica content, iron oxide content, and calcium oxide content of the soil in the present invention are: the inventor discovers through a large amount of previous researches that the pH value of soil is an important factor influencing the cadmium enrichment of rice, and as the pH value of the soil is increased, organic matters in the soil are chelated with the cadmium to generate chelate, so that the biological effectiveness of the cadmium is reduced, and the absorption and accumulation of the rice on the cadmium are reduced. The pH value of the soil has obvious positive correlation with the content of calcium oxide in the soil, and the pH value of the soil also shows an ascending trend along with the increase of the content of calcium oxide, so that the content of calcium oxide in the soil is also an important factor influencing the cadmium enrichment of rice. Silicon oxide in soil can form coprecipitation with cadmium, which causes the solubility of cadmium in soil to be reduced, thereby affecting the enrichment of cadmium in rice. Besides soil calcium oxide and silicon oxide, iron oxide can form an iron film on the surface of rice roots to prevent cadmium absorption, so that rice is influenced to be enriched with cadmium.
In addition, in the prediction model of the present invention, the reason why the calculation formula needs to be selected in 3 cases is that:
the inventor finds that the pH value of the soil and the content of the cadmium in the effective state are the two most important factors influencing the enrichment of the cadmium in the rice in practical research, and under the conditions of different pH values and the content of the cadmium in the effective state, the weight of the soil factors influencing the cadmium content in the rice is different, so that the pH value and the content of the cadmium in the effective state need to be independently used as the basis for selecting different calculation formulas, and the accuracy is higher. If the calculation is uniformly performed by using a calculation formula, the accuracy is greatly reduced.
In the invention, the judgment method is as follows: the early warning value J is the predicted value Y/0.2 mg/kg of cadmium content in rice grains in the mature period; no risk is present if J < 0.7, warning if J < 1.0.7, low risk if J < 2.0, medium risk if J < 3.0, and high risk if J < 3.0.
Preferably, in S2, the prediction model is established by the correlation between the earlier-measured X1, X2, X3, X4 and X5 and the cadmium content in rice grains in the mature period, and the correlation coefficient is 0.95.
Preferably, in S2, the soil sample is tested continuously for at least 2 years while the predictive model is established.
Preferably, the soil sample is taken from 0-20cm of topsoil.
Preferably, in the detection of X1-X5, the soil sample is air-dried at natural room temperature, fully mixed, removed of impurities, ground manually and sieved.
Preferably, the soil sample is sieved through a sieve of 80 to 120 meshes.
Preferably, when a prediction model is established to detect the cadmium content in rice grains in the mature period, taking the rice ears of the mature rice and then pretreating: air drying the rice ears indoors, threshing into brown rice with a thresher, grinding into polished rice with a polished rice machine, drying to constant weight, pulverizing into polished rice flour, and sieving.
Preferably, the rice ears are naturally air-dried indoors for 25-35 days; drying the polished rice to constant weight at 65-75 ℃; sieving the fine rice flour with a sieve of 80-120 meshes.
Preferably, the cadmium element in the rice grains in the mature period adopts HNO3-HClO4Wet digestion method, extracting method of total cadmium in soil sample using HF-HCLO4-HNO3The method respectively takes a rice national standard substance NCSZC73008 and a soil national standard substance GBW07457 as internal standards to control the analysis quality.
Preferably, the pH of the soil sample is measured with a pH meter, water: the mass ratio of the soil is 2.4-2.6: 1.
Compared with the prior art, the invention has the beneficial effects that: the method has the characteristics of high prediction accuracy, convenience in operation and the like. When the safety of the rice is monitored, the safety of cadmium in rice grains can be early warned before planting.
Drawings
FIG. 1 is a graph showing the correlation between cadmium in the active state of soil DGT and cadmium in rice in examples;
FIG. 2 is a graph showing the correlation between the cadmium detection value of rice and the prediction value of the model in the embodiment.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A rice kernel cadmium pollution risk early warning method characterizes the bioavailability of cadmium in soil based on a gradient thin film diffusion technology (DGT), and searches for the relationship establishment between the accumulation amount of cadmium in rice kernels, the content of cadmium in an effective state in soil and the physical and chemical properties of soil.
(1) Sampling: rice ears and corresponding surface soil (0-20cm) samples of rice ears and soil samples of 143 samples of rice ears and soil samples of Hangzhou Fuyang, Shaoxing Yuancheng, Ningbo Fengcheng, Ningbo Jianbei, Quzhou Longyou and the like in 2017 and 2018 are collected continuously for two years respectively. Sampling points are all representative local fields, the rice variety is a local main cultivated variety, the sampling time is the rice maturity, and each point is sampled randomly. The rice varieties and the number of samples collected in each region are shown in the following table.
The name of the rice variety and the number of samples at each sampling point
(2) Pretreatment: naturally air drying the rice ears indoors for 30 days, threshing into brown rice by a threshing machine, grinding into polished rice by a polished rice machine, drying the polished rice in a constant temperature oven at 70 ℃ for about 48h to constant weight, crushing into polished rice powder by a stainless steel crusher, and sieving with a 100-mesh sieve. And (3) air-drying the soil sample at natural room temperature, fully mixing, manually grinding after removing impurities such as small stones, residual roots and the like, and sieving by a 100-mesh sieve.
(3) And (3) sample determination: the cadmium element in the rice sample adopts HNO3-HClO4Wet digestion method, extracting method of total cadmium in soil, selecting aged and pregnant HF-HCLO4-HNO3The method respectively uses a rice national standard substance NCSZC73008 and a soil national standard substance GBW07457 as internal standards to control the analysis quality. The effective cadmium in the soil is extracted by a DGT device developed by environmental protection, scientific research and monitoring in the rural areas of agriculture, and the cadmium content in the extracting solution is determined by an inductively coupled plasma mass spectrometry. The pH value of the soil is measured by a pH meter, the ratio of water to soil is 2.5: 1, the soil organic matter is measured by a potassium dichromate volumetric method, the soil cation exchange amount is measured by an ammonium acetate exchange method, and reference values of other elements in the soil are measured by an X-ray energy spectrum method.
(4) Data analysis and prediction model construction: and (4) carrying out variance analysis on the data in the step (3), wherein the regression equation is remarkably different through linear regression analysis (shown in figure 1). The DGT technology can effectively predict the biological effectiveness of the cadmium in the paddy soil.
Through Cubist mixed linear regression analysis, the relation of the cadmium content in rice grains, the DGT effective cadmium content in soil and the soil physical and chemical indexes (pH, silicon oxide content, iron oxide content and calcium oxide content) can be fitted by using a multiple linear regression equation, the content of the effective Cd in the soil and the soil physical and chemical indexes (pH, silicon oxide content, iron oxide content and calcium oxide content) are used as variables, the cadmium content in rice grains in the mature period is used as a dependent variable, and a related function prediction model system is established, and is shown in the following table:
rice cadmium prediction model
The rice cadmium prediction model constructed by Cubist has 3 regular conditions, and the pH value of soil and the content of DGT active cadmium in the soil determine the form of the prediction model. The correlation coefficient of the model reaches 0.95, which shows that the degree of conformity of the analysis model with the reality is high and the model can be applied.
(5) And (3) verification of a prediction model: in order to verify the feasibility of the prediction model, 4 soil-rice samples in different areas are collected, and the correlation between the Cd detection value of rice and the prediction value of the model is analyzed. As can be seen from the graph 2, the correlation between the Cd detection value of the rice and the model prediction value reaches 94.8%, the ratio of the predicted value to the detection value is in the range of 85-122%, the excessive data is not predicted to be a coincidence value according to the comparison of the excessive limit values, and the percentage of the coincidence value which is predicted to be excessive is only 4.76%, so that the cadmium content in rice grains can be well predicted based on the established prediction model.
(6) Risk prediction: actual data of DGT (cadmium content), pH (potential of hydrogen) and contents of silicon oxide, iron oxide and calcium oxide in soil are obtained by sampling, the actual data are input into a corresponding calculation formula of the mathematical prediction model to predict the cadmium content in rice grains, and an early warning value (the early warning value J is equal to the predicted value Y of the cadmium content in the rice grains divided by 0.2mg/kg) is calculated according to the regulations of the pollutant limit in national standard food for food safety on the cadmium content of rice (GB2762-2017, the Cd limit value is less than 0.2mg/kg), J is less than 0.7, J is more than or equal to 0.7 and less than 1.0, is warning, J is more than or equal to 1.0 and less than 2.0, is low risk, J is more than or equal to 2 and less than 3.0, is medium risk, and J is more than or equal to 3.0 and less than or equal to high risk, so that the safety of the rice grains is judged.
According to the prediction method, if the early warning value is higher than the risk critical value, the risk that the Cd of the rice produced on the fields exceeds the standard is higher. The prediction model of the invention has important guiding function for planning and selecting the rice production base, and simultaneously can purposefully take some agricultural measures in advance to reduce the effectiveness of cadmium in soil or reduce the accumulation of cadmium in rice, improve the sanitary safety level of rice and ensure the physical health of consumers.
Comparative example 1
At present, the most common method for measuring the effective cadmium in the soil is a chemical extraction method, and common extracting agents comprise DTPA, HCl and HNO3、CaCl2、NH4Ac, and the like. However, the chemical extraction method has the phenomena of cadmium redistribution and secondary adsorption in the determination process, thereby influencing the accuracy of the extraction result. Therefore, the quality of the effective state determination method is evaluated by comparing the linear correlation degree between the soil effective state cadmium content and the rice grain cadmium content determined by the DGT technology and the 5 chemical extraction methods. According to the linear regression result, the linear correlation (R) between the cadmium content measured by the DGT technology and the cadmium content of the rice grains20.755) is superior to other 5 chemical extraction states (CaCl)2：R2＝0.679；HCl：R2＝0.657；HNO3： R2＝0.635；DTPA：R2＝0.616；NH4Ac：R20.588), so that the DGT can better simulate the process of absorbing the soil cadmium by the rice compared with the traditional chemical extraction method.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A rice grain cadmium pollution risk early warning method based on a gradient film diffusion technology is characterized by comprising the following steps:
s1: before rice planting, collecting a soil sample, detecting the content X1 of effective cadmium in the soil by using a gradient film diffusion technology, and simultaneously detecting the pH value X2, the content X3 of silicon oxide, the content X4 of iron oxide and the content X5 of calcium oxide of the soil;
s2: substituting X1-X5 into a prediction model shown in the following table to obtain a predicted value Y of cadmium content in rice grains in the mature period;
s3: calculating an early warning value according to the food safety national standard GB2762-2017 that the cadmium limit in food is less than 0.2 mg/kg: the early warning value J is the predicted value Y/0.2 mg/kg of cadmium content in rice grains in the mature period; no risk is present if J < 0.7, warning if J < 1.0.7, low risk if J < 2.0, medium risk if J < 3.0, and high risk if J < 3.0.
2. The rice grain cadmium pollution risk early warning method based on the gradient thin film diffusion technology as claimed in claim 1, wherein in S2, the prediction model is established by the correlation between the previously measured X1-X5 and the cadmium content in the rice grain in the mature period, and the correlation coefficient is 0.95.
3. The rice grain cadmium pollution risk early warning method based on the gradient thin film diffusion technology as claimed in claim 1, wherein in S2, the soil sample is continuously detected for at least 2 years when the prediction model is established.
4. The rice grain cadmium pollution risk early warning method based on the gradient thin film diffusion technology as claimed in claim 1 or 3, wherein the soil sample is taken from surface soil of 0-20 cm.
5. The rice grain cadmium pollution risk early warning method based on the gradient film diffusion technology as claimed in claim 1 or 2, wherein when detecting X1-X5, a soil sample is air-dried at a natural room temperature, fully mixed, ground manually after removing impurities, and sieved.
6. The rice grain cadmium pollution risk early warning method based on the gradient film diffusion technology as claimed in claim 5, wherein the soil sample is sieved by a sieve of 80-120 meshes.
7. The rice grain cadmium pollution risk early warning method based on the gradient thin film diffusion technology as claimed in claim 2, wherein when a prediction model is established to detect cadmium content in rice grains in a mature period, mature rice ears are taken and then pretreated: air drying the rice ears indoors, threshing into brown rice with a thresher, grinding into polished rice with a polished rice machine, drying to constant weight, pulverizing into polished rice flour, and sieving.
8. The rice grain cadmium pollution risk early warning method based on the gradient thin film diffusion technology as claimed in claim 7, wherein the rice ears are naturally air-dried indoors for 25-35 days; drying the polished rice to constant weight at 65-75 deg.C; sieving the fine rice flour with 80-120 mesh sieve.
9. The rice grain cadmium pollution risk early warning method based on the gradient thin film diffusion technology as claimed in claim 1 or 2, wherein cadmium element in rice grains in the mature period adopts HNO3-HClO4Wet digestion method, extracting method of total cadmium in soil sample using HF-HCLO4-HNO3The method respectively takes a rice national standard substance NCSZC73008 and a soil national standard substance GBW07457 as internal standards to control the analysis quality.
10. The rice grain cadmium pollution risk early warning method based on the gradient film diffusion technology as claimed in claim 1 or 2, wherein the pH of a soil sample is measured by a pH meter, and the mass ratio of water to soil is 2.4-2.6: 1.
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