CN112898979A - Application of potassium calcium magnesium sulfate as repair material in reducing bioavailability of Cd in weakly alkaline soil - Google Patents
Application of potassium calcium magnesium sulfate as repair material in reducing bioavailability of Cd in weakly alkaline soil Download PDFInfo
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- CN112898979A CN112898979A CN202110080293.9A CN202110080293A CN112898979A CN 112898979 A CN112898979 A CN 112898979A CN 202110080293 A CN202110080293 A CN 202110080293A CN 112898979 A CN112898979 A CN 112898979A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention provides application of potassium calcium magnesium sulfate 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. The potassium sulfate calcium magnesium is a natural fertilizer, the sulfate radical contained in the fertilizer can form strong acid weak base salt with ammonium ions in weak alkaline soil, and H is generated after hydrolysis+The pH value of the alkalescent soil can be reduced, and the over-strong alkalinity of the soil can be avoided; calcium oxide and magnesium oxide in the potassium calcium magnesium sulfate can form a stable structure with Cd, so that the proportion of Cd in a soil residue state is improved, and the bioavailability of Cd is reduced; the potassium sulfate calcium magnesium can provide potassium, calcium, magnesium, sulfur and other nutrients necessary for the growth of crops, improve the soil fertility, improve the agglomeration capability of soil particles after being applied to the soil, and improve the soil buffering capacity, thereby improving the soil moisture value and the soil adaptability. The inventionThe potassium calcium magnesium sulfate is applied to the alkalescent soil as a repairing material, so that the bioavailability of heavy metal Cd in the alkalescent soil can be effectively reduced, and the soil fertility can be improved.
Description
Technical Field
The invention relates to the technical field of soil heavy metal pollution prevention and treatment, in particular to application of potassium sulfate calcium magnesium 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 is a non-essential element of organisms and is considered as a heavy metal with the strongest biological toxicity due to its high mobility, high toxicity, high accumulation and difficult elimination.
For the soil polluted by heavy metal in large area, especially the farmland soil polluted by medium and light degree, the in-situ chemical passivation restoration technology has the advantages of simple implementation, low cost and high treatment speed. For in-situ fixation passivation repair of Cd pollution of soil, the passivation repair materials widely used at present are alkaline materials such as lime, hydroxyapatite and the like. However, these remediation materials are generally used for remediating Cd pollution in acidic soil, and the action of the remediation materials is mainly to raise the pH of the soil, and reduce the activity of heavy metals by raising the pH of the soil, thereby reducing the bioavailability of the heavy metals. For weakly alkaline soil (the pH value is 7.1-7.5), the pH value of the soil background is relatively high, and if alkaline materials such as phosphor lime or lime are added, the pH value of the soil can be increased to more than 7.5 due to the large lifting amplitude of the materials for the pH value of the soil, so that the soil alkalinity is too strong, the risks of soil hardening and soil salinization are increased, and at present, almost no in-situ fixation passivation restoration method for effectively reducing the bioavailability of Cd in the soil for a long time aiming at the Cd-polluted weakly alkaline soil exists. In addition, these passivating remediation materials tend to reduce soil fertility.
Disclosure of Invention
In view of the above, the invention aims to provide an application of potassium calcium magnesium sulfate as a repair material in reducing the bioavailability of alkalescent soil Cd. The invention applies potassium-calcium-magnesium sulfate as a repairing material to alkalescent soil, can effectively reduce the bioavailability of heavy metal Cd in the alkalescent soil, and can improve the soil fertility.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an application of potassium calcium magnesium sulfate 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.
Preferably, the potassium calcium magnesium sulfate is granular, and the particle size is 2-4 mm.
Preferably, the method of application comprises the steps of:
applying the potassium sulfate calcium magnesium in a plough layer of weakly alkaline soil;
and watering and irrigating the plough layer after the application, and balancing to uniformly mix the potassium, calcium and magnesium sulfate and the soil of the plough layer.
Preferably, the plough layer is a weak alkaline soil surface layer with the depth of 0-20 cm.
Preferably, the application amount of the potassium sulfate, calcium and magnesium sulfate is 0.2-0.45% of the dry weight of the soil mass of the plough layer.
Preferably, the application amount of the potassium calcium magnesium sulfate is 0.4% 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 an application of potassium calcium magnesium sulfate 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. The potassium sulfate calcium magnesium is a natural fertilizer with a molecular formula of K2Ca2Mg(SO4)4·2(H2O), sulfate radical contained in potassium sulfate calcium and magnesium can form strong acid weak base salt with ammonium ion in weak alkaline soil, H is generated after hydrolysis+The pH value of the alkalescent soil can be reduced, and the over-strong alkalinity of the soil is avoided; calcium ions and magnesium ions in the potassium calcium magnesium sulfate can form a stable structure with heavy metal Cd in soil (Ca)2+And Mg2+Can be reacted with Cd2+A displacement reaction is carried out to lead Cd2+Formation of Cd (OH)2Precipitation separation), the proportion of the soil residue state Cd is improved, and thus the bioavailability of the soil Cd is reduced; in addition, potassium sulfate, calcium and magnesium, which is a natural fertilizer, can provide nutrient elements such as potassium, calcium, magnesium, sulfur and the like necessary for the growth of crops, improve the soil fertility, improve the agglomeration capability of soil particles after being applied into soil, improve the buffering capability of the soil, and further improve the soil moisture value and the tiltability of the soil. The invention applies potassium-calcium-magnesium sulfate as a repairing material to alkalescent soil, can effectively reduce the bioavailability of heavy metal Cd in the alkalescent soil, and can improve the soil fertility.
Furthermore, the application amount of the potassium calcium magnesium sulfate used as a repair material is 0.15-0.4% of the dry weight of the soil in the plough layer, and the low application amount can effectively reduce the biological available state content of heavy metal Cd in the weak alkaline soil, so that the method has good economic benefit.
Drawings
FIG. 1 is a graph showing the change in the forms of Cd in soil after 30 days of incubation with potassium calcium magnesium sulfate in examples 1 and 2;
FIG. 2 is a graph showing the change in the forms of Cd in the soil occurring in examples 1 and 2 after 90 days of incubation with potassium calcium magnesium sulfate.
Detailed Description
The invention provides an application of potassium calcium magnesium sulfate 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.
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 invention, the potassium sulfate calcium magnesium is a pure natural fertilizer (Polysulphte) produced by Israel chemical group and mined in England, and the molecular formula is K2Ca2Mg(SO4)4·2(H2O). In the invention, the potassium sulfate calcium magnesium is preferably granular, and the grain size is preferably 2-4 mm. In the invention, sulfate radicals contained in potassium sulfate calcium and magnesium can be mixed with weakly alkaline soilThe ammonium ion forms strong acid and weak base salt, and H is generated after hydrolysis+The pH value of the alkalescent soil can be reduced, and the over-strong alkalinity of the soil can be avoided; calcium oxide and magnesium oxide in the potassium calcium magnesium sulfate can form a stable structure with heavy metal Cd, so that the proportion of soil residue state Cd is improved, and the bioavailability of the soil Cd is reduced; in addition, potassium sulfate calcium magnesium is used as a natural fertilizer, can provide nutrients such as potassium, calcium, magnesium, sulfur and the like necessary for the growth of crops, improves the soil fertility, and can also improve the agglomeration capability of soil particles and the buffer capability of soil after being applied to the soil, thereby improving the moisture value and the tiltability of the soil. The invention applies potassium-calcium-magnesium sulfate as a repairing material to alkalescent soil, can effectively reduce the bioavailability of heavy metal Cd in the alkalescent soil, and can improve the soil fertility. In addition, the potassium calcium magnesium sulfate is used as a repairing material, the heavy metal content of the potassium calcium magnesium sulfate is very low, the content of mercury, arsenic, Cd, lead, chromium and the like is lower than the screening value of GB15618-2018 'soil pollution risk control standard for soil environmental quality agricultural land soil', the environmental risk is low, the bioavailability of Cd in weakly alkaline soil is reduced, and secondary pollution to the soil is avoided.
In the present invention, the method of application preferably comprises the steps of:
applying the potassium sulfate calcium magnesium 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 potassium, calcium and magnesium sulfate 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 potassium sulfate, calcium and magnesium sulfate is preferably 0.2-0.45% of the dry weight of the soil mass of the plough layer, and more preferably 0.4%.
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. 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 potassium calcium magnesium sulfate 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 present 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.
500g of soil to be tested is sieved by a sieve with the aperture of 2mm, potassium calcium magnesium sulfate (the particle size is 2-4 mm, produced by Israel chemical group) is added into the soil to be tested, the potassium calcium magnesium sulfate accounts for 0.2 wt% of the dry weight of the soil, the potassium calcium magnesium sulfate is uniformly mixed in a culture container, three parallel treatments are set, and the soil to be tested without the addition of the potassium calcium magnesium sulfate is 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
The balance of potassium sulfate calcium magnesium is 0.4 wt% of the dry weight of the soil as in example 1.
The effect of potassium calcium magnesium sulfate applied to weak alkaline soil in example 1 and example 2 was examined and analyzed:
influence on pH of weakly alkaline soil after potassium sulfate calcium magnesium is applied
The soil pH was directly read on a pH meter using a potentiometric method (water to soil ratio 2.5: 1), and the test results are shown in Table 2:
TABLE 2 examples 1-2 Effect on weakly alkaline soil pH after Potassium calcium magnesium sulfate application
As can be seen from table 2, the pH of the soil decreased after 30 days of application of both calcium magnesium sulfate in example 1 and example 2, the pH of the soil decreased by 0.11 units for the 0.2 wt% addition treatment group (example 1) and by 0.16 units for the 0.4 wt% addition soil (example 2) compared to the blank. 90 days after application of the potassium calcium magnesium sulfate repair material, the reduction in soil pH was increased by the potassium calcium magnesium sulfate-added treatment, the soil pH of the 0.2 wt% added treatment group (example 1) was reduced by 0.44 units compared to the blank control, and the soil pH of the 0.4 wt% added soil was reduced by 0.69 units compared to the blank control.
(II) influence of potassium calcium magnesium sulfate 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 influence of potassium calcium magnesium sulfate application on Cd content in soil available state (μ g/L) in examples 1-2
As can be seen from Table 3, after the potassium-calcium-magnesium sulfate is applied, the content of Cd in the effective state in the soil of the treatment groups of examples 1 and 2 is significantly reduced compared with that of the blank control, after 60 days of culture, the Cd in the effective state in the soil can be reduced by 12.21% by the treatment group with 0.2 wt% of addition amount (example 1), and the Cd in the effective state in the soil can be reduced by 15.95% by the treatment group with 0.4 wt% of addition amount (example 2); after 90 days of culture, the treatment group with 0.2 wt% of addition amount (example 1) can reduce the Cd in the effective state of the soil by 15.37%, and the treatment group with 0.4 wt% of addition amount (example 2) can reduce the Cd in the effective state of the soil by 13.53%. As can be seen from Table 3, the effective Cd content in the soil can be effectively reduced by 0.2 wt% and 0.4 wt%.
(III) the change of the occurrence form of Cd in weakly alkaline soil after potassium calcium magnesium sulfate is applied
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 Cd in the soil after the potassium sulfate calcium magnesium is applied for 30 days and 90 days are shown in Table 5:
TABLE 5 content of Cd in soil (μ g/L) after applying potassium sulfate calcium magnesium for 30 days and 90 days
The data of table 5 is plotted as shown in fig. 1 and 2, respectively. As can be seen from Table 5 and FIG. 1, after 30 days of culture, the treatment group (example 2) added at 0.4 wt% showed better treatment effects than the blank control, with 39%, 24% and 23% reductions in the soil WD value, CA value and RE value, and 19% and 9% increases in the OX value and RES value, respectively; the WD, CA and RE values of the soil were also reduced by 35%, 21% and 20% and the OX and RES values increased by 17% and 8%, respectively, in the 0.2% addition treatment group (example 1). As can be seen from table 5 and fig. 2, after 90 days of culture, the WD value, CA value and RE value of the soil (example 2) at 0.4% addition were decreased by 33.9%, 20.7% and 5.1%, respectively, and the OX value and REs value were increased by 60.9% and 6.4%, respectively, compared to the blank control; while the WD, CA and RE values of the soil treated with 0.2% addition (example 1) were reduced by 31.3%, 15.5% and 0.7%, respectively, and the OX and RES values were increased by 47.1 and 4.9%. From this, it can be seen that the effect of the treatment was not much different between the 0.2% addition amount and the 0.4% addition amount, but the effect of the treatment was better at the 0.4% addition amount.
The above embodiments show that the potassium calcium magnesium sulfate is used as a repairing material for weakly alkaline soil, so that the biological effectiveness of heavy metal Cd in the weakly alkaline soil can be effectively reduced, and the potassium calcium magnesium sulfate is used as a natural fertilizer, so that potassium, calcium, magnesium, sulfur and other nutrient elements necessary for crop growth can be provided, and the soil fertility is improved. The invention applies potassium-calcium-magnesium sulfate as a repairing material to alkalescent soil, can effectively reduce the bioavailability of heavy metal Cd in the alkalescent soil, and can improve the soil fertility.
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 (8)
1. The potassium calcium magnesium sulfate is used as a repairing material to reduce 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 potassium calcium magnesium sulfate is in the form of particles having a particle size of 2 to 4 mm.
3. The application according to claim 1, characterized in that the method of application comprises the steps of:
applying the potassium sulfate calcium magnesium in a plough layer of weakly alkaline soil;
and watering and irrigating the soil of the plough layer after the application, and then balancing to uniformly mix the potassium, calcium and magnesium sulfate and the soil of the plough layer.
4. The use according to claim 3, wherein the plough layer is a weak alkaline soil surface layer with a depth in the range of 0-20 cm.
5. The use according to claim 3 or 4, wherein the potassium calcium magnesium sulphate is applied in an amount of 0.2-0.45% by mass dry weight of the soil in the plough layer.
6. The use according to claim 5, wherein the potassium calcium magnesium sulphate is applied in an amount of 0.4% by mass dry weight of the soil in the plough layer.
7. Use according to claim 3, wherein the watering irrigation maintains the moisture content of the topsoil at not less than 30% of the saturated water capacity of the topsoil.
8. Use according to claim 3, wherein the equilibration time is 4 to 6 days.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018185706A2 (en) * | 2017-04-05 | 2018-10-11 | Ali Hadia | Production & protection compositions (ppc) |
| CN108863645A (en) * | 2018-06-30 | 2018-11-23 | 格丰科技材料有限公司 | A kind of soil conditioner and its method of administration |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018185706A2 (en) * | 2017-04-05 | 2018-10-11 | Ali Hadia | Production & protection compositions (ppc) |
| CN108863645A (en) * | 2018-06-30 | 2018-11-23 | 格丰科技材料有限公司 | A kind of soil conditioner and its method of administration |
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