CN112920802A - Application of manganese dioxide as repair material in reducing bioavailability of Cd in weakly alkaline soil - Google Patents
Application of manganese dioxide as repair material in reducing bioavailability of Cd in weakly alkaline soil Download PDFInfo
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Abstract
The invention provides application of manganese dioxide as a repairing material in reducing bioavailability of Cd in weakly alkaline soil, and relates to the technical field of soil heavy metal pollution prevention and control. According to the invention, manganese dioxide is used as a repairing material to be applied to alkalescent soil, so that the bioavailability of heavy metal Cd in the alkalescent soil can be effectively reduced, the alkalescent soil can be prevented from being too strong in alkalinity, and the long-term stability is realized; and the manganese dioxide is easy to obtain, is a commodity which can be produced in large scale in the existing factory, and has market popularization value. Furthermore, the application amount of the manganese dioxide as the repair material is 0.15-0.4 wt%, and the low application amount can effectively reduce the content of the heavy metal effective state in the weak alkaline soil, so that the method has good economic benefit and application prospect.
Description
Technical Field
The invention relates to the technical field of soil heavy metal pollution prevention and treatment, in particular to application of manganese dioxide as a repairing material in reducing bioavailability of alkalescent soil Cd.
Background
In recent years, the heavy metal pollution of cultivated land soil in China is more serious, wherein the primary pollutant is heavy metal Cd. Cd has strong toxicity and is one of the major heavy metals affecting human health. The alkalescent soil is mainly distributed in the north of China, wheat which is the main crop planted in the alkalescent soil is one of the most important grain crops in the world, Cd in the soil is easily absorbed by the wheat and is enriched in plants, and Cd accumulated in wheat grains can enter human bodies through food chains and cause serious harm to human health. Therefore, the remediation of Cd pollution in weakly alkaline soil is a difficult problem to be solved urgently.
At present, the methods for treating the heavy metal pollution of soil are more, and comprise chemical leaching, phytoremediation, chemical passivation and the like. The chemical passivation is mainly used for treating heavy metal pollution by reducing the activity of heavy metal in soil, and the method has the advantages of good technical effect, short period, simple and easy operation, and is a cheap and environment-friendly treatment method. The chemical passivation repair technology for acid soil in the south is mature, the applied passivation repair material mainly takes the improvement of the pH value of the soil as a main material, the activity of heavy metal is reduced by increasing the pH value of the soil, and the biological effectiveness of the heavy metal is further reduced, and the widely used passivation repair material comprises lime, hydroxyapatite, plant ash and the like. And the pH value of the weak alkaline soil in the north is higher, if alkaline materials such as phosphor lime, lime or plant ash are added, the pH value of the soil can be increased to more than 7.5 due to the large improvement range of the materials on the pH value of the soil, so that the alkalinity of the soil is too strong, and the risks of soil hardening and soil salinization are increased. At present, almost no method for effectively restoring alkalescent farmland soil polluted by Cd for a long time exists.
Disclosure of Invention
In view of the above, the invention aims to provide an application of manganese dioxide as a repair material in reducing bioavailability of Cd in weakly alkaline soil. According to the invention, manganese dioxide is used as a repairing material for weakly alkaline soil, so that the bioavailability of heavy metal Cd in the weakly alkaline soil can be effectively reduced, the over-strong alkalinity of the weakly alkaline soil can be avoided, the pH value of the soil is controlled to be below 7.5, and the long-term stability is achieved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides application of manganese dioxide as a repair material in reducing bioavailability of Cd in weakly alkaline soil; the pH value of the weakly alkaline soil is 7.1-7.5.
Preferably, the pH value of the weakly alkaline soil is 7.1-7.2.
Preferably, the purity of the manganese dioxide is greater than 90%; the mass content of Pb in the manganese dioxide is less than 0.005 percent, and the mass content of Fe in the manganese dioxide is less than 0.02 percent; the particle size of the manganese dioxide is less than or equal to 50 mu m.
Preferably, the method of application comprises the steps of:
applying the manganese dioxide in a plough layer of weakly alkaline soil;
and watering and irrigating the plough layer soil after the application, and then balancing to uniformly mix the manganese dioxide and the plough layer soil.
Preferably, the plough layer is a weak alkaline soil surface layer with the depth of 0-20 cm.
Preferably, the application amount of the manganese dioxide is 0.15-0.4% of the dry weight of the soil mass of the plough layer.
Preferably, the application amount of the manganese dioxide is 0.2% of the dry weight of the soil mass of the plough layer.
Preferably, the watering irrigation maintains the water content of the plough layer soil to be not less than 30% of the saturated water holding capacity of the plough layer soil.
Preferably, the balancing time is 4-6 days.
The invention provides application of manganese dioxide as a repair material in reducing bioavailability of Cd in weakly alkaline soil; the pH value of the weakly alkaline soil is 7.1-7.5. In the invention, the pH value of the soil is only slightly increased (below 7.5) in a short period of time when the manganese dioxide is applied to the weakly alkaline soil, and the pH value of the weakly alkaline soil is gradually reduced by the manganese dioxide along with the passage of time; therefore, when the manganese dioxide is applied to the alkalescent soil as the repair material, the over-strong alkalinity of the soil can be avoided, and the soil is prevented from being pollutedRisk of hardening and salting. The surface of the manganese dioxide contains a large number of negative charges, strong affinity can be generated for Cd ions with positive charges, the manganese dioxide has certain oxidizability, and Mn in the manganese dioxide4+Will change into Mn2+Under weakly alkaline conditions, Mn2+Can make Cd adsorbed on the surface of manganese dioxide2+Forming a DCS configuration, increasing the distance of Cd-Mn, and further increasing the stability of the manganese dioxide for adsorbing Cd; in addition, the specific surface area of the manganese dioxide is large, after the manganese dioxide is applied to weakly alkaline soil, the protonation and hydroxylation characteristics of the surface of manganese oxide can show chemical adsorption, the specific adsorption plays an important role in controlling migration and enrichment of Cd, and the two modes reduce the content of available Cd in the soil. Therefore, the manganese dioxide is used as the repair material to be applied to the alkalescent soil, so that the bioavailability of the heavy metal Cd in the alkalescent soil can be effectively reduced, the alkalescent soil can be prevented from being too strong in alkalinity, and the long-term stability is realized. And the manganese dioxide is easy to obtain, is a commodity which can be produced in large scale in the existing factory, and has market popularization value.
Furthermore, the application amount of the manganese dioxide as the repair material is 0.15-0.4 wt% of the dry weight of the soil in the plough layer, and the lower application amount can effectively reduce the biological effective state content of Cd in the weak alkaline soil, so that the method has better economic benefit and can avoid the risk of secondary pollution to the soil caused by excessive application of materials.
Drawings
FIG. 1 is a graph showing the change in the respective forms of Cd in the soil after 30 days of incubation with manganese dioxide according to examples 1 and 2;
FIG. 2 is a graph showing the change in the respective forms of Cd in the soil after 90 days of incubation with manganese dioxide in examples 1 and 2.
Detailed Description
The invention provides application of manganese dioxide as a repair material in reducing bioavailability of Cd in weakly alkaline soil; the pH value of the weakly alkaline soil is 7.1-7.5.
In the invention, the pH value of the weakly alkaline soil is preferably 7.1-7.2. The invention has no special requirements on the source of the weak alkaline soil, and the soil in the pH value range is suitable for the invention.
In the present invention, the purity of the manganese dioxide is preferably greater than 90%; the mass content of Pb in the manganese dioxide is preferably less than 0.005%, and the mass content of Fe in the manganese dioxide is preferably less than 0.02%; the particle size of the manganese dioxide is 50 μm or less, preferably 40 μm or less. In the invention, the content of mercury, arsenic, Cd, lead, chromium and the like in the manganese dioxide is lower than the screening value of GB15618-2018 soil pollution risk control standard for soil environment quality agricultural land, the environmental risk is lower, the bioavailability of the Cd in the weakly alkaline soil is reduced, and the secondary pollution can be avoided.
The source of the manganese dioxide is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used; the manganese dioxide is easy to obtain, is a commodity which can be produced in large scale in the existing factory, and has market popularization value.
In the invention, the pH value of the soil is only slightly increased (below 7.5) in a short period of time when the manganese dioxide is applied to the weakly alkaline soil, and the pH value of the weakly alkaline soil is gradually reduced by the manganese dioxide along with the passage of time; therefore, when the manganese dioxide is applied to weakly alkaline soil as a repairing material, the over-strong alkalinity of the soil can be avoided, and the risks of soil hardening and salinization are avoided. The surface of the manganese dioxide contains a large number of negative charges, strong affinity can be generated for Cd ions with positive charges, the manganese dioxide has certain oxidizability, and Mn in the manganese dioxide4+Will change into Mn2+Under weakly alkaline conditions, Mn2+Can make Cd adsorbed on the surface of manganese dioxide2+Forming a DCS configuration, increasing the distance of Cd-Mn, and further increasing the stability of the manganese dioxide for adsorbing Cd; in addition, the specific surface area of the manganese dioxide is large, after the manganese dioxide is applied to weakly alkaline soil, the protonation and hydroxylation characteristics of the surface of manganese oxide can show chemical adsorption, the specific adsorption plays an important role in controlling migration and enrichment of Cd, and the two modes reduce the content of available Cd in the soil. Therefore, the manganese dioxide is used as the repair material to be applied to the weakly alkaline soil, and the manganese dioxide can be used for repairing the weakly alkaline soilEffectively reduces the bioavailability of heavy metal Cd in the alkalescent soil, can avoid the alkalescent soil from being too strong in alkalinity, and has long-term stability.
In the present invention, the method of application preferably comprises the steps of:
applying the manganese dioxide in a plough layer of weakly alkaline soil;
and watering and irrigating the plough layer soil after the application, and then balancing to uniformly mix the manganese dioxide and the plough layer soil.
In the invention, the plough layer is preferably a weakly alkaline soil surface layer with the depth of 0-20 cm. In the invention, the application amount of the manganese dioxide is preferably 0.15-0.4% of the dry weight of the soil mass of the plough layer, and more preferably 0.2%. Manganese dioxide is used as a repairing material, the content of the biological available state of heavy metal Cd in the alkalescent soil can be effectively reduced by a lower application amount, and the method has better economic benefit.
In the invention, the watering irrigation ensures that the water content of the soil of the plough layer is preferably kept to be not less than 30% of the saturated water holding capacity of the soil of the plough layer, and more preferably 30-40% of the saturated water holding capacity. According to the invention, the water content of the plough layer is controlled within the range, so that the full action of the alkalescent soil and the manganese dioxide can be ensured, and the repairing effect of the manganese dioxide on the alkalescent soil can be improved.
In the present invention, the equilibration time is preferably 4 to 6 days, and more preferably 5 days.
The following examples are provided to illustrate the application of manganese dioxide as a remediation material in reducing the bioavailability of Cd in weakly alkaline soil in detail, but they should not be construed as limiting the scope of the invention.
Example 1
The soil to be tested is collected from the sand ginger black soil in the range of 0-20 cm on the surface layer of the farmland in the area of Quwang in Jiangzhou, Xuzhou, Jiangsu province, the Cd content of the soil reaches 1.12mg/kg, the basic physicochemical properties are shown in Table 1, and the soil is alkalescent soil. According to the soil environment quality agricultural land soil pollution risk control standard (GB 15618-.
Table 1 example 1 basic physicochemical properties of the soil tested
In Table 1, the Cation Exchange Content (CEC) was 8.21 mol. L-1Sodium acetate-flame photometry; the soil quick-acting phosphorus is 0.03mol/LNH4F-0.02mol/L HCl leaching method; the quick-acting potassium is extracted by ammonium acetate-flame photometry; the alkaline hydrolysis nitrogen adopts an alkaline hydrolysis diffusion method; and titrating the total nitrogen of the soil by adopting a Kelvin method-Kjeldahl apparatus.
Sieving 500g of soil to be tested by a sieve with the aperture of 2mm, adding manganese dioxide (the particle size is 50 mu m, the purity is 95 percent, the Pb content is less than 0.005wt percent, and the Fe content is less than 0.02wt percent) into the soil to be tested, uniformly mixing the manganese dioxide in a culture container, and carrying out three parallel treatments; the test soil without manganese dioxide was used as a blank control. The experiment is carried out in an incubator, the saturated water holding capacity is kept at 30%, the cultivation lasts for 90 days (the first 5 days are balance time, the main growth period of general field crops is about 90 days, if the repair material still has good passivation effect on soil after being cultivated for 90 days, the effect of the repair material can be proved to be continuous and stable, and is matched with the period of absorption of soil nutrient substances in the main growth period of general field crops), partial soil is taken every 30 days, and then the soil is air-dried, ground, sieved by a 2 mm-aperture sieve and is to be analyzed.
Example 2
Manganese dioxide makes up 0.4% by weight of the dry weight of the soil, the remainder being the same as in example 1.
The effect of manganese dioxide applied to weakly alkaline soil in example 1 and example 2 was examined and analyzed:
influence on pH value of weakly alkaline soil after application of manganese dioxide
The pH value of the soil is directly read on a pH meter by adopting a potential method (the water-soil ratio is 2.5: 1), and the test results are shown in a table 2:
TABLE 2 results of the effect of manganese dioxide application on the pH of weakly alkaline soil in examples 1-2
As can be seen from Table 2, the pH of weakly alkaline soils increased 30 days after the application of examples 1 and 2, the pH of the soil of the treated group added at 0.2 wt% (example 1) was 0.05 units higher than that of the blank control, and the pH of the soil of the treated group added at 0.4 wt% (example 2) was 0.1 units higher than that of the blank control. However, after 90 days, the soil pH values of the two treatment groups were significantly reduced compared to the blank control, and the soil pH values of the treatment groups at different application rates were reduced by 0.16 units compared to the blank control. It can be seen that the pH of the weakly alkaline soil increased only slightly over time with the application of manganese dioxide, and gradually decreased over time.
(II) influence of manganese dioxide on effective Cd content in weakly alkaline soil
The effective state of the heavy metal Cd in the soil is extracted by a DTPA method, the content of the heavy metal Cd is measured by an inductively coupled plasma emission spectrometer (ICP-OES), and a standard substance (GBW07445) purchased from Beijing institute of physics and geochemistry is repeatedly combined with reagent blank analysis in the digestion process to ensure the accuracy and precision of the digestion program. The test results are shown in table 3:
TABLE 3 results of the effect of manganese dioxide application on Cd content in soil available state (. mu.g/L) in examples 1-2
As can be seen from Table 3, after manganese dioxide is applied to the samples 1 and 2, the content of Cd in an available state in weakly alkaline soil is significantly reduced compared with that in a blank sample, after 30 days of culture, the Cd in the available state can be reduced by 10.87% by the treatment group with 0.2 wt% of addition amount (sample 1), and can be reduced by 19.57% by the treatment group with 0.4 wt% of addition amount (sample 2); after 90 days of culture, the treatment group with 0.2 wt% addition (example 1) can reduce the available Cd by 20.67%, and the treatment group with 0.4 wt% addition (example 2) can reduce the available Cd by 14.11%. Therefore, the stability of the treatment effect of the 0.2% additive amount is better than that of the 0.4 wt% additive amount, and when the additive amount is 0.2 wt%, the content of the available state Cd in the weak alkaline soil is gradually reduced along with the prolonging of the time, which shows that the additive amount has better stability for reducing the available state of the Cd in the weak alkaline soil.
(III) change of alkalescent soil Cd occurrence form after manganese dioxide application
The method comprises the steps of extracting water-soluble state, acetate extraction state, reducible state, oxidizable state and residue state of soil Cd by improving a BCR method, determining the content by adopting an inductively coupled plasma mass spectrometer-liquid chromatography system (ICP-MS), and repeatedly combining standard substances (GBW07445) purchased from Beijing physical and geochemical institute with reagent blank analysis in the digestion process to ensure the accuracy and precision of the digestion program. The specific measurement method is shown in table 4:
TABLE 4 extraction method of various occurrence forms of Cd in soil
The contents of various appearance forms of Cd in the soil after the manganese dioxide is applied for 30d and 90d are shown in the table 5:
TABLE 5 content of Cd in soil (μ g/L) after application of manganese dioxide for 30d and 90d
Fig. 1 and 2 are respectively plotted according to the test results of table 5. It can be seen that after 30 days of culture, the treatment effect of the treatment groups with different addition amounts was not significantly different from that of the blank control, and the WD value and CA value of the soil (example 2) of the treatment group with 0.4 wt% addition amount were respectively reduced by 24% and 25%, and the RE value, OX value and REs value were respectively increased by 16%, 15% and 3%; the WD value and CA value of the soil of the treatment group (example 1) added at 0.2 wt% were also reduced by 22% and 27%, respectively, the RE value was not significantly changed, and the OX value and RES value were increased by 13% and 6%, respectively. After 90 days of culture, the WD value and CA value of the 0.4 wt% added soil (example 2) were reduced by 23.2% and 17.5%, respectively, the RE value was not significantly changed, and the OX value and REs value were increased by 37.9% and 5.4%, respectively, as compared to the blank control; while the WD and CA values of the soil treated with the 0.2 wt% addition (example 1) were reduced by 24.7% and 19.2%, respectively, the RE value was not significantly changed, and the OX and RES values were increased by 38% and 5.7%. It can be seen that the treatment effect was gradually improved with time at the addition amount of 0.2 wt%, and was more stable than at the addition amount of 0.4 wt%.
The embodiment shows that the manganese dioxide is used as the repair material to be applied to the alkalescent soil, so that the bioavailability of the heavy metal Cd in the alkalescent soil can be effectively reduced, the alkalescent soil can be prevented from being too strong in alkalinity, and the long-term passivation stability is realized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The application of manganese dioxide as a repair material in reducing the bioavailability of Cd in weakly alkaline soil; the pH value of the weakly alkaline soil is 7.1-7.5.
2. The use according to claim 1, wherein the pH of the weakly alkaline soil is 7.1 to 7.2.
3. Use according to claim 1, wherein said manganese dioxide has a purity of greater than 90%; the mass content of Pb in the manganese dioxide is less than 0.005 percent, and the mass content of Fe in the manganese dioxide is less than 0.02 percent; the particle size of the manganese dioxide is less than or equal to 50 mu m.
4. The application according to claim 1, 2 or 3, characterized in that the method of application comprises the steps of:
applying the manganese dioxide in a plough layer of weakly alkaline soil;
and watering and irrigating the plough layer soil after the application, and then balancing to uniformly mix the manganese dioxide and the plough layer soil.
5. The use according to claim 4, wherein the layer of tillage is a weak alkaline soil surface layer within a depth of 0-20 cm.
6. The use according to claim 4, wherein the manganese dioxide is applied in an amount of 0.15 to 0.4% by mass dry weight of the soil in the plough layer.
7. The use according to claim 6, wherein the manganese dioxide is applied in an amount of 0.2% by mass dry weight of the soil of the plough layer.
8. The use according to claim 4, wherein the watering irrigation maintains the moisture content of the topsoil at no less than 30% of the saturated water holding capacity of the topsoil.
9. The use of claim 4, wherein the equilibration time is 4 to 6 days.
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| CN108130087A (en) * | 2018-01-02 | 2018-06-08 | 湖南金旅环保股份有限公司 | A kind of soil conditioner and application process for repairing cadmium-arsenic combined pollution |
| CN109575926A (en) * | 2018-11-26 | 2019-04-05 | 华中农业大学 | Cadmium arsenic combined contamination soil renovation agent |
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