CN110810181A - Research and development method of influence mechanism of sulfur addition on arsenic migration and transformation in soil rice system - Google Patents

Research and development method of influence mechanism of sulfur addition on arsenic migration and transformation in soil rice system Download PDF

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CN110810181A
CN110810181A CN201911201567.4A CN201911201567A CN110810181A CN 110810181 A CN110810181 A CN 110810181A CN 201911201567 A CN201911201567 A CN 201911201567A CN 110810181 A CN110810181 A CN 110810181A
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soil
arsenic
rice
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陈力嘉
许丽媛
赖冠宇
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G22/00—Cultivation of specific crops or plants not otherwise provided for
    • A01G22/20—Cereals
    • A01G22/22—Rice
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence
    • G01N21/6404—Atomic fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/12—Circuits of general importance; Signal processing
    • G01N2201/129—Using chemometrical methods

Abstract

The invention discloses a research and development method of an influence mechanism of sulfur addition on arsenic migration and transformation in a soil rice system, which researches the influence of sulfate treatment in different forms on the arsenic absorption and accumulation of rice and the form of arsenic at the rhizosphere by the steps of rice variety selection, experimental soil preparation, rice planting, continuous extraction and analysis of arsenic in soil, analysis of arsenic in a plant sample, measurement of iron film on the surface of rice roots, data analysis and the like, and analyzes the correlation among the steps and the mechanism in the correlation. By analyzing and evaluating the bioavailability of the sulfate to arsenic in the rhizosphere environment, theoretical basis is provided for searching for agricultural and technical measures for reducing the absorption and accumulation of arsenic by rice, guaranteeing food safety and the like.

Description

Research and development method of influence mechanism of sulfur addition on arsenic migration and transformation in soil rice system
Technical Field
The invention relates to the technical field of agricultural production, in particular to a research and development method of an influence mechanism of sulfur addition on arsenic migration and transformation in a soil rice system.
Background
Sulfur (S) is one of the major elements essential for the growth and development of plants, and the redox process of sulfur can directly or indirectly affect the bioavailability of heavy metals in soil. In the absence of sulfur, the growth and development of rice are seriously affected, and the stress resistance of the rice is obviously reduced. The absorption and accumulation of heavy metals in rice depends to a great extent on the form and bioavailability of heavy metals in the rhizosphere microenvironment. Therefore, the regulation and control of the content and the existing form of sulfur in the soil have important significance for the prevention and control of the excessive accumulation of heavy metals in rice.
Some researches show that exogenous addition of thionin can reduce absorption and accumulation of arsenic in rice by improving thiol metabolism in rice and enhancing an antioxidant system. However, the mechanism of how sulfur affects the existing form of arsenic in paddy soil and thus affects the absorption and accumulation of arsenic in rice is not completely understood. In the paddy soil, the existence of abundant iron makes the biochemical cycle among arsenic, sulfur and iron more complicated. The application of sulfur can increase the content of iron film on the rice root surface, and in a reducing environment, the increase of the content of sulfate can reduce the dissimilatory reduction of ferric iron and pentavalent arsenic. Soil and rhizosphere microorganisms play an important role in sulfur form conversion of reductive soil, root system absorption of arsenic and the like. The existing state of arsenic in soil is obviously influenced by conditions such as soil pH value, oxidation-reduction potential, iron-manganese oxide and the like, and the application of elemental sulfur and gypsum can cause changes of soil pH, Eh and the like, so that the processes of oxidation-reduction, adsorption-desorption, precipitation-dissolution, methylation-demethylation, biological enrichment and the like of arsenic are changed, and the content of iron-manganese adhesive films is influenced, so that the activity and the bioavailability of arsenic are influenced.
At present, a great deal of research is carried out on the influence of sulfur with different forms on the growth and development of rice, and the research on the influence of the sulfur on the absorption, accumulation and distribution of arsenic in soil-rice polluted by arsenic is also carried out. However, no clear result is found in the aspect of exploring the influence of different forms of sulfur application on arsenic distribution and transfer in a soil-rice system. Therefore, a research and development method of an influence mechanism of sulfur addition on arsenic migration and transformation in a soil rice system is needed.
Disclosure of Invention
The invention aims to provide a research and development method for reasonably designing an influence mechanism of sulfur addition on arsenic migration and transformation in a soil rice system, aiming at the defects and shortcomings of the prior art. The research aims to apply different forms of thionin, simulate the arsenic pollution experiment of rice, and provide theoretical basis for researching agronomic measures for reducing the absorption and accumulation of arsenic by the rice and guaranteeing the food safety by analyzing and evaluating the bioavailability of the sulfur with different forms to the arsenic in the rhizosphere environment.
In order to achieve the purpose, the invention adopts the following technical scheme: the operation steps are as follows:
step 1, rice variety selection
The rice seeds are selected from super-excellent 524 (hereinafter referred to as TY 524).
Step 2, preparing experimental soil
The soil to be tested in the test is selected from the As contaminated soil added from an external source. Exogenous addition of As contaminated soil: the soil is collected from non-polluted paddy soil (0-20 cm) in Xinyang city, Henan province, and the background As concentration of the soil is (12.5 soil 0.02) mg.kg-1. The collected paddy soil is air-dried and ground, and 60 mg/kg-1 of As (As Na) is added to the soil3AsO4Form (d) by spraying Na3AsO4·12H2And spraying the O solution into the soil to uniformly mix the heavy metal solution and the soil. And adding base fertilizer into the mixed soil according to the standard of 2 g of compound fertilizer per kilogram of soil, fully and uniformly mixing, and balancing for one month for later use.
Step 3, planting rice
The selected rice seeds were air-dried for two days, and then 30% H was used2O2Soaking for 15 minutes, washing with tap water for three times till completely clean, placing into a culture dish, soaking in full water for two days, and transferring the white seeds with broken breasts to prepared pollution-free soil for seedling for 30 days. Seedlings with the same size are selected and transplanted into rhizosphere bags (300 meshes, height 15 cm multiplied by diameter 8 cm), and each bag contains two seedlings. Set 3 sets of treatments: a. adding 120 mg/kg before transplanting-1Na2SO4(ii) a b. Adding 120 mg/kg before transplanting-1Elemental sulfur (S); c. and (4) a control group. Each group was replicated 4 times, with a plant spacing of 20cm and a row spacing of 20cm, all replicates were randomly distributed. And (3) performing conventional management on the rice, such as regular irrigation, drainage, fertilization, weeding and insect pest prevention. After 12 months, the plants are cleaned by tap water and collected according to root, stem leaf, seed and other parts. Drying the stem leaf and seed samples in an oven at 60 deg.C, and treating with stainless steelCrushing by a steel crusher to be detected; the roots were blotted dry with filter paper and stored in a freezer at-20 ℃ for testing. The soil sample in the rhizosphere bag is considered to be rhizosphere soil, the soil sample with the surface layer below 3 cm is collected uniformly, is frozen and then is sieved by a 20-mesh sieve, and is stored in a refrigeration house at the temperature of minus 20 ℃ for standby.
Step 4, continuously extracting and analyzing arsenic in soil
Taking out rhizosphere soil, sieving the rhizosphere soil by a sieve of 80 meshes, and weighing 0.4000 g of soil sample from the rhizosphere soil into a centrifugal tube. 10mL of 0.05 mol. L was added-1（NH4）2SO4Shaking at room temperature for 4 h. Centrifuging at 8000rpm for 10min after shaking is finished, and taking supernatant to obtain F1 non-specific adsorption state arsenic solution. The remaining precipitate was rinsed with 10mL of ultrapure water, shaken at room temperature for 10min, and then centrifuged at 8000rpm for 10 min. The supernatant was decanted. The remaining precipitate was added to 10mL of 0.05 mol. L-1NH4H2PO4Shaking at room temperature for 16h, and centrifuging at 8000rpm for 10min after shaking. And taking the supernatant to obtain the F2 specific adsorption state arsenic solution. The remaining precipitate was rinsed with 10mL of ultrapure water, shaken at room temperature for 10min, and then centrifuged at 8000rpm for 10 min. The supernatant was decanted. The remaining precipitate was added to 10mL of 0.2 mol. L-1Ammonium oxalate buffer (pH = 3), shaken at room temperature for 4 h, then centrifuged at 8000rpm for 10 min. Taking the supernatant to obtain an F3 amorphous or weak crystalline iron-aluminum hydrated oxide combined arsenic solution. The remaining precipitate was rinsed with 10mL of ultrapure water, shaken at room temperature for 10min, and then centrifuged at 8000rpm for 10 min. The supernatant was decanted. The remaining precipitate was added to 10mL of 0.2 mol. L-1Ammonium oxalate and 0.1 mol. L-1The ascorbic acid mixed solution (pH = 3) was shaken in a water bath at 96 ℃ for 30min, and then centrifuged at 8000rpm for 10 min. And taking the supernatant to obtain F4 crystalline iron-aluminum hydrated oxide combined arsenic-dissolved supernatant. And drying the rest precipitate in a 60 ℃ oven, transferring the precipitate into a digestion tube, adding 5 mL of aqua regia for digestion at 140 ℃ for 9 h, removing acid until 0.5 mL of solution remains in the digestion tube, filtering, and finally fixing the volume to 25 mL to obtain the F5 residue arsenic solution. The arsenic content in each solution was determined using Atomic Fluorescence Spectroscopy (AFS).
Step 5, analyzing arsenic in plant sample
Digestion of stem leaves, seeds and rootsThe system is HNO3(superior purity), digesting for 9 h at 140 ℃, dispelling acid until 0.5 mL of solution is left in the digestive tube, filtering, fixing the volume to 15 mL, and storing at 4 ℃. And measuring the arsenic content in the solution by using an Atomic Fluorescence Spectrometer (AFS).
Step 6, measuring the iron membrane on the surface of the rice root
0.6 g sodium hydrosulfite (sodium hydrosulfite) is added into 30mL solution containing 0.03 mol.L-1Sodium citrate and 0.125 mol.L-1And (3) adding the solution of sodium bicarbonate to obtain a DCB extract. Washing rice root with ultrapure water, soaking in 30mL of the extractive solution of LDCB, extracting at 25 deg.C for 2 hr, filtering, diluting to 50 mL, and storing at 4 deg.C. And measuring the contents of iron and manganese in the sample by using an inductively coupled plasma emission spectrometer (ICP-OES). And (4) measuring the arsenic content in the solution by utilizing AFS.
Step 7, data analysis
One-way analysis of variance (ANO-VA) was performed using SPSS 22.0 software, and the analysis of significant differences between different values in treated samples and controls was determined by the Least Significant Difference (LSD) assay. The data were all mean ± sd of 3 replicates.
Further, the compound fertilizer in the step (2) comprises the following components: the application amount of the deionized water and the nitrogen, phosphorus and potassium are respectively P2O5[Ca（H2PO4）2]0.5 g·kg-1，N[CO（NH2）2]And K2O (KCl) 0.2 g/kg-1 in each case.
The invention has the advantages and positive effects that:
1. the research discusses the absorption and accumulation of arsenic by different parts in rice plants under different adding conditions of the sulfur element and various morphological contents of arsenic in rhizosphere soil, tries to know the influence and mechanism of the sulfur on the accumulation of the arsenic in the rice, and hopefully provides data support for solving the problem of arsenic pollution of large-area rice fields at present and provides theoretical basis for future research.
2. According to the determination result, a novel fertilizer beneficial to reducing the arsenic absorption of rice can be produced.
3. According to the determination result, a new method for planting rice in the arsenic-polluted rice field can be provided.
4. According to the determination result, a new idea for screening varieties of rice planted in the arsenic-polluted rice field can be provided.
Detailed Description
The present invention is further described in detail below with reference to specific examples.
Step 1, rice variety selection
The rice seeds are selected from super-excellent 524 (hereinafter referred to as TY 524).
Step 2, preparing experimental soil
The soil to be tested in the test is selected from the As contaminated soil added from an external source. Exogenous addition of As contaminated soil: the soil is collected from non-polluted paddy soil (0-20 cm) in Xinyang city, Henan province, and the background As concentration of the soil is (12.5 soil 0.02) mg.kg-1. The collected paddy soil is air-dried and ground, 60 mg/kg-1 of As (in the form of Na 3 AsO 4) is added into the soil, and the Na 3 AsO 4.12H2O solution is sprayed into the soil by a spraying method, so that the heavy metal solution is uniformly mixed with the soil. Adding base fertilizer into the mixed soil according to the standard of 2 g of compound fertilizer per kilogram of soil, weighing 2.5 kg (in terms of dry weight) of each barrel of soil, fully and uniformly mixing, and balancing for one month for later use. The compound fertilizer comprises the following components: the application amount of the deionized water and the nitrogen, phosphorus and potassium are respectively P2O5[Ca（H2PO4）2]0.5 g·kg-1，N[CO（NH2）2]And K2O (KCl) 0.2 g/kg-1 in each case.
Step 3, planting rice
The selected rice seeds were air-dried for two days, and then 30% H was used2O2Soaking for 15 minutes, washing with tap water for three times till completely clean, placing into a culture dish, soaking in full water for two days, and transferring the white seeds with broken breasts to prepared pollution-free soil for seedling for 30 days. Seedlings with the same size are selected and transplanted into rhizosphere bags (300 meshes, height 15 cm multiplied by diameter 8 cm), and each bag contains two seedlings. Set 3 sets of treatments: a. adding 120 mg/kg before transplanting-1Na2SO4(ii) a b. Adding 120 mg/kg before transplanting-1Elemental sulfur (S); c. and (4) a control group. Each group was replicated 4 times, with a plant spacing of 20cm and a row spacing of 20cm, all replicates were randomly distributed. Often timesThe rice is regularly managed, such as regular irrigation, drainage, fertilization, weeding and insect pest prevention. After 12 months, the plants are cleaned by tap water and collected according to root, stem leaf, seed and other parts. Drying the stem leaf and seed samples in a 60 ℃ oven, and crushing the stem leaf and seed samples by a stainless steel crusher to be detected; the roots were blotted dry with filter paper and stored in a freezer at-20 ℃ for testing. The soil sample in the rhizosphere bag is considered to be rhizosphere soil, the soil sample with the surface layer below 3 cm is collected uniformly, is frozen and then is sieved by a 20-mesh sieve, and is stored in a refrigeration house at the temperature of minus 20 ℃ for standby.
Step 4, continuously extracting and analyzing arsenic in soil
Taking out rhizosphere soil, sieving the rhizosphere soil by a sieve of 80 meshes, and weighing 0.4000 g of soil sample from the rhizosphere soil into a centrifugal tube. 10mL of 0.05 mol. L was added-1（NH4）2SO4Shaking at room temperature for 4 h. Centrifuging at 8000rpm for 10min after shaking is finished, and taking supernatant to obtain F1 non-specific adsorption state arsenic solution. The remaining precipitate was rinsed with 10mL of ultrapure water, shaken at room temperature for 10min, and then centrifuged at 8000rpm for 10 min. The supernatant was decanted. The remaining precipitate was added to 10mL of 0.05 mol. L-1NH4H2PO4Shaking at room temperature for 16h, and centrifuging at 8000rpm for 10min after shaking. And taking the supernatant to obtain the F2 specific adsorption state arsenic solution. The remaining precipitate was rinsed with 10mL of ultrapure water, shaken at room temperature for 10min, and then centrifuged at 8000rpm for 10 min. The supernatant was decanted. The remaining precipitate was added to 10mL of 0.2 mol. L-1Ammonium oxalate buffer (pH = 3), shaken at room temperature for 4 h, then centrifuged at 8000rpm for 10 min. Taking the supernatant to obtain an F3 amorphous or weak crystalline iron-aluminum hydrated oxide combined arsenic solution. The remaining precipitate was rinsed with 10mL of ultrapure water, shaken at room temperature for 10min, and then centrifuged at 8000rpm for 10 min. The supernatant was decanted. The remaining precipitate was added to 10mL of 0.2 mol. L-1Ammonium oxalate and 0.1 mol. L-1The ascorbic acid mixed solution (pH = 3) was shaken in a water bath at 96 ℃ for 30min, and then centrifuged at 8000rpm for 10 min. And taking the supernatant to obtain F4 crystalline iron-aluminum hydrated oxide combined arsenic-dissolved supernatant. Drying the rest precipitate in 60 deg.C oven, transferring into digestion tube, adding 5 mL aqua regia for digestion at 140 deg.C for 9 hr, removing acid until 0.5 mL solution in digestion tube remains, filtering, and finallyThe volume is determined to be 25 mL, and F5 residue arsenic solution is obtained. The arsenic content in each solution was determined using Atomic Fluorescence Spectroscopy (AFS).
Step 5, analyzing arsenic in plant sample
The digestive system of stem leaves, seeds and roots is HNO3(superior purity), digesting for 9 h at 140 ℃, dispelling acid until 0.5 mL of solution is left in the digestive tube, filtering, fixing the volume to 15 mL, and storing at 4 ℃. And measuring the arsenic content in the solution by using an Atomic Fluorescence Spectrometer (AFS).
Step 6, measuring the iron membrane on the surface of the rice root
0.6 g sodium hydrosulfite (sodium hydrosulfite) is added into 30mL solution containing 0.03 mol.L-1Sodium citrate and 0.125 mol.L-1And (3) adding the solution of sodium bicarbonate to obtain a DCB extract. Washing rice root with ultrapure water, soaking in 30mL of the extractive solution of LDCB, extracting at 25 deg.C for 2 hr, filtering, diluting to 50 mL, and storing at 4 deg.C. And measuring the contents of iron and manganese in the sample by using an inductively coupled plasma emission spectrometer (ICP-OES). And (4) measuring the arsenic content in the solution by utilizing AFS.
Step 7, data analysis
One-way analysis of variance (ANO-VA) was performed using SPSS 22.0 software, and the analysis of significant differences between different values in treated samples and controls was determined by the Least Significant Difference (LSD) assay. The data were all mean ± sd of 3 replicates.
Results and analysis:
1. influence of sulfur fertilizers with different forms on arsenic forms
The result shows that the As form of the soil is that the proportion of F1 non-specific adsorption state arsenic accounts for 2.2-5.3%, the proportion of F2 specific adsorption state arsenic accounts for 32.1-36.5%, the proportion of F3 amorphous or weak crystal form iron-aluminum hydrated oxide binding state arsenic accounts for 29.2-39.5%, and the proportion of F4 crystal form iron-aluminum hydrated oxide binding state arsenic accounts for 11.8-15.2%; the proportion of F5 residue arsenic is 9.6% -22.3%. The proportion of F2 and F3 reaches 61.3% -76.0%, and the proportion of F1 is the lowest.
In rhizosphere soil, the As chemical morphology of the soil is less changed under S treatment, while Na2SO4Under the treatment, the non-specific adsorption state, amorphous iron oxide state and crystalline iron oxide state As in the soil are all obviously reduced, and the residue state As is obviously increased (P)<0.05）。
The arsenic form classification of the soil can reflect the information of potential mobility, biological effectiveness, pollution hazard level and the like of arsenic. Wherein F1 non-specific adsorption arsenic is easy to be absorbed by organism and has larger harmfulness; the specific adsorption arsenic of F2 and the amorphous or weak crystal arsenic in iron-aluminum oxide hydrate binding state of F3 can be released into effective arsenic when the soil physicochemical conditions change, while the specific adsorption arsenic of F4 and the amorphous or weak crystal arsenic in iron-aluminum oxide hydrate binding state of F5 are not easy to release and bioabsorb, and have low hazard. The research shows that in rhizosphere soil, the addition of the sulfur fertilizer reduces several forms with higher bioavailability and promotes the conversion of As to a stable state.
2. Influence of different forms of sulfur fertilizer on rice growth
The results show that the addition of the sulfur fertilizer has no obvious influence on the plant height of the underground part of the rice, the length of the overground part of the rice is obviously increased, and S and Na are added2SO4The treatment increased the length of the overground part of rice by 19.5% and 12.4%, respectively, as compared with the control group (P)<0.05), to a certain extent, the overground part of the rice is promoted to grow. The addition of the thionin has a certain promotion effect on the fresh weight of the rice. The addition of thionin obviously increases the fresh weight of the overground part, and increases the fresh weight of the overground part by S and Na2SO4The treatment increased 20.5% and 28.1%, respectively, compared to the control group (P)<0.05）。
S and Na2SO4The method can obviously improve the plant height of the overground part of the rice and the fresh weight of the rice under the As pollution, and shows that the toxic action of the As on the growth and development of the rice can be relieved by applying the S fertilizer. Applying elemental sulfur and Na as a whole2SO4There was no significant difference between treatments, but elemental sulfur was slightly more effective than Na2SO4This is probably because the simple substance is chalcogenic to the reducing substance.
3. Effect of Thionin on As distribution in Rice plants
The results showed that the As content in the rice roots was the highest in all treatments. The accumulation of As in rice at different positions is roughly ordered by root, leaf, stem, husk and rice grain. The thionin addition had no significant effect on the accumulation of rice root As. The addition of elemental sulphur significantly reduced the accumulation of As in the rice stem by 30.2% (P < 0.05), whereas the addition of sodium sulphate did not have a significant effect (P > 0.05). The addition of thionin significantly reduced the accumulation of As in rice leaves, and the addition of sodium sulfate changed the accumulation of rice leaves and stems, with leaves > stem in the control treatment and leaves ≈ stem in the sodium sulfate treatment. The addition of thionin has no effect on As in the husk.
S can influence the absorption of As by rice and the transportation and transfer of As in rice plants by changing the pH value, the oxidation-reduction state and the like of the rhizosphere environment of rice. The results show that the application of the S fertilizer can obviously reduce the content of As in stems and leaves and grains of overground parts of rice, and the effect of applying the elemental sulfur is better than that of applying sodium sulfate.
4. Influence of sulfur fertilizer on element content of rice root surface adhesive film and on adsorption amount of As
The results show that the iron-manganese oxide glue film on the surface of the rice root system is mainly Fe film, and the Mn film is relatively less (P > 0.05). The content of the ferro-manganese glue film on the surface of the rice root system can be increased by applying the S. The elemental sulfur can promote the formation of Fe film, and has certain inhibiting effect on Mn film (P > 0.05).
The application of the thionin reduces As and Fe in the rhizosphere soil solution to a certain extent, and reduces the mobility of As; as in the soil solution is also reduced to a certain extent; the addition of the thionin obviously reduces the effective state of As in rhizosphere soil; the effect of sodium sulfate at the same sulfur content was more pronounced than elemental sulfur (P < 0.05).
The addition of elemental sulphur significantly increased the Fe content of the root surface glue film (P < 0.05), and the addition of sodium sulphate increased the Fe content but did not reach a significant level (P > 0.05). The addition of different thionin obviously increases the rice root surface glue film As and Fe to be in extremely obvious positive correlation (r =0.828, P < 0.01). The addition of thionin significantly increased S in the root surface glue film, and S was very significantly positively correlated with both As (r =0.831, P < 0.01) and Fe (r =0.876, P < 0.01). The addition of the thionin promotes the formation of a rice root surface adhesive film, and increases the retention of As in the rhizosphere environment and the rice root surface.
5. Correlation analysis
And (3) carrying out correlation analysis on the chemical form of the rhizosphere soil solution and the As absorbed by the rice, and investigating factors influencing the As absorption of the rice. Both Fe and S in the root surface coating were significantly negatively correlated with As in rice leaves (P < 0.05). As in the soil solution has a certain correlation with the absorption of As in rice, total As in the soil solution is obviously and negatively correlated with As in rice grains, and the As is obviously and positively correlated with As in rice stems and leaves. The chemical form of As in soil has a certain significant correlation with the absorption of As by rice and the mobility of As and Fe in soil solution.
In soil, F1 non-specific adsorption state arsenic, F3 amorphous or weak crystal form iron-aluminum hydrated oxide combined state arsenic As are all in significant positive correlation with Fe in a soil solution, wherein F3 amorphous or weak crystal form iron-aluminum hydrated oxide combined state arsenic As is also in significant positive correlation with As in the soil solution, which indicates that the forms are not stable in the culture process and are the main part of Fe reduction and dissolution, and the residue state As is in significant negative correlation with As and Fe in the soil solution, which indicates that only the residue state is in an As stable state in the contaminated soil added with As. The addition of the thionin obviously reduces the unstable state in the rhizosphere soil and reduces the effective state of rhizosphere As, thereby relieving the toxicity of As to plants.
Through the research, the research and development method is feasible, and theoretical basis is provided for searching for agricultural technical measures for reducing the absorption and accumulation of arsenic in rice, guaranteeing food safety and the like.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.

Claims (2)

1. A research and development method of an influence mechanism of sulfur addition on arsenic migration and transformation in a soil rice system is characterized by comprising the following steps:
step 1, rice variety selection
The rice seeds are selected from super-excellent 524 (hereinafter referred to as TY 524);
step 2, preparing experimental soil
The tested soil is selected from the As contaminated soil added from an external source;
exogenous addition of As contaminated soil: the soil is collected from non-polluted rice soil (0-20 cm) in Xinyang city, Henan province, and the background As concentration of the soil is (12.5 soil 0.02) mg.kg-1;
the collected paddy field soil is air-dried and ground, 60 mg/kg-1 of As (in the form of Na 3 AsO 4) is added into the soil, and the Na 3 AsO 4.12H2O solution is sprayed into the soil by adopting a spraying method, so that the heavy metal solution is uniformly mixed with the soil;
adding base fertilizer into the mixed soil according to the standard of 2 g of compound fertilizer per kilogram of soil, fully and uniformly mixing, and balancing for one month for later use;
step 3, planting rice
The selected rice seeds were air-dried for two days, and then 30% H was used2O2Soaking for 15 minutes, washing with tap water for three times till the seeds are completely clean, placing the seeds into a culture dish, adding the culture dish, soaking the seeds in full water for two days, and transferring the seeds with white skin exposed on the chest into prepared pollution-free soil for seedling for 30 days;
selecting seedlings with consistent size to transplant to rhizosphere bag (300)
Mesh, height 15 cm x diameter 8 cm), two seedlings per bag;
set 3 sets of treatments: a. adding 120 mg/kg before transplanting-1Na2SO4(ii) a b. Adding 120 mg/kg before transplanting-1Elemental sulfur (S); c. a control group;
each group is repeated for 4 times, the plant spacing is 20cm, the row spacing is 20cm, and all the repetitions are randomly distributed;
conventionally managing the rice, such as regular irrigation, drainage, fertilization, weeding and insect pest prevention;
after 12 months, the plants enter a mature period, are cleaned by tap water and are respectively collected according to the root, the stem leaves, the seeds and the like;
drying the stem leaf and seed samples in a 60 ℃ oven, and crushing the stem leaf and seed samples by a stainless steel crusher to be detected; the roots are stored in a refrigeration house with the temperature of minus 20 ℃ to be tested after absorbing water by filter paper;
the soil sample in the rhizosphere bag is considered to be rhizosphere soil, the soil sample with the surface layer being less than 3 cm is collected uniformly, is filtered through a 20-mesh sieve after freeze-drying, and is stored in a refrigeration house at the temperature of minus 20 ℃ for standby;
step 4, continuously extracting and analyzing arsenic in soil
Taking out rhizosphere soil, sieving the rhizosphere soil by a sieve of 80 meshes, and weighing 0.4000 g of soil sample from the rhizosphere soil into a centrifugal tube;
10mL of 0.05 mol. L was added-1（NH4）2SO4Oscillating for 4 hours at room temperature;
centrifuging at 8000rpm for 10min after shaking is finished, and taking supernatant to obtain F1 nonspecific adsorption state arsenic solution;
rinsing the rest precipitate with 10mL of ultrapure water, oscillating for 10min at room temperature, and centrifuging for 10min at 8000 rpm;
pouring the supernatant;
the remaining precipitate was added to 10mL of 0.05 mol. L-1NH4H2PO4Oscillating for 16h at room temperature, and centrifuging for 10min at 8000rpm after oscillation is finished;
taking the supernatant to obtain F2 specific adsorption state arsenic solution;
rinsing the rest precipitate with 10mL of ultrapure water, oscillating for 10min at room temperature, and centrifuging for 10min at 8000 rpm;
pouring the supernatant;
the remaining precipitate was added to 10mL of 0.2 mol. L-1Ammonium oxalate buffer (pH = 3), shaking at room temperature for 4 h, then centrifuging at 8000rpm for 10 min;
taking the supernatant to obtain an F3 amorphous or weak crystalline form iron-aluminum hydrated oxide combined arsenic solution;
rinsing the rest precipitate with 10mL of ultrapure water, oscillating for 10min at room temperature, and centrifuging for 10min at 8000 rpm;
pouring the supernatant;
the remaining precipitate was added to 10mL of 0.2 mol. L-1Ammonium oxalate and 0.1 mol. L-1Ascorbic acid mixed solution (pH = 3), shaken in a water bath at 96 ℃ for 30min, and then centrifuged at 8000rpm for 10min；
Taking the supernatant to obtain F4 crystalline ferroaluminum hydrated oxide combined arsenic-dissolved supernatant;
drying the rest precipitate in a 60 ℃ oven, transferring to a digestion tube, adding 5 mL of aqua regia for digestion at 140 ℃ for 9 h, removing acid until 0.5 mL of solution remains in the digestion tube, filtering, and finally fixing the volume to 25 mL to obtain F5 residue state arsenic solution;
measuring the arsenic content in each solution by using an Atomic Fluorescence Spectrometer (AFS);
step 5, analyzing arsenic in plant sample
The digestive system of stem leaves, seeds and roots is HNO3(superior purity), digesting for 9 h at 140 ℃, dispelling acid until 0.5 mL of solution remains in the digestive tube, filtering, fixing the volume to 15 mL, and storing at 4 ℃;
measuring the arsenic content in the solution by using an Atomic Fluorescence Spectrometer (AFS);
step 6, measuring the iron membrane on the surface of the rice root
0.6 g sodium hydrosulfite (sodium hydrosulfite) is added into 30mL solution containing 0.03 mol.L-1Sodium citrate and 0.125 mol.L-1To obtain a DCB extract;
washing rice roots with ultrapure water, soaking the rice roots into 30mL of LDCB extracting solution, extracting for 2 hours at 25 ℃, filtering, fixing the volume to 50 mL, and storing at 4 ℃;
measuring the contents of iron and manganese in the sample by using an inductively coupled plasma emission spectrometer (ICP-OES);
determining the arsenic content in the solution by using AFS;
step 7, data analysis
Single-factor analysis of variance (ANO-VA) using SPSS 22.0 software, the analysis of significant differences between different values in treated samples and controls was determined by the Least Significant Difference (LSD) assay;
the data were all mean ± sd of 3 replicates.
2. The method for developing the mechanism of influence of sulfur addition on arsenic migration transformation in soil rice system as claimed in claim 1, wherein said step (a), (b), (c), (d2) The medium-sized compound fertilizer comprises the following components: the application amount of the deionized water and the nitrogen, phosphorus and potassium are respectively P2O5[Ca（H2PO4）2]0.5 g·kg-1，N[CO（NH2）2]And K2O (KCl) 0.2 g/kg-1 in each case.
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Publication number Priority date Publication date Assignee Title
CN111899624A (en) * 2020-06-30 2020-11-06 河海大学 Device and method for simulating influence of external environment change on occurrence of sulfur element in sediment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111899624A (en) * 2020-06-30 2020-11-06 河海大学 Device and method for simulating influence of external environment change on occurrence of sulfur element in sediment

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