CN114214074B - Selenium-rich soil conditioner for restoring soil heavy metals, and preparation method and application thereof - Google Patents
Selenium-rich soil conditioner for restoring soil heavy metals, and preparation method and application thereof Download PDFInfo
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- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 125
- 239000011669 selenium Substances 0.000 title claims abstract description 125
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000002689 soil Substances 0.000 title claims abstract description 69
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 55
- 239000003516 soil conditioner Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 42
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 39
- 235000010755 mineral Nutrition 0.000 claims abstract description 39
- 239000011707 mineral Substances 0.000 claims abstract description 39
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000292 calcium oxide Substances 0.000 claims abstract description 20
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 20
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004113 Sepiolite Substances 0.000 claims abstract description 11
- 229960000892 attapulgite Drugs 0.000 claims abstract description 11
- 239000004021 humic acid Substances 0.000 claims abstract description 11
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 11
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 11
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 11
- 238000003971 tillage Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000012423 maintenance Methods 0.000 claims abstract description 6
- 238000005067 remediation Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 4
- 230000007480 spreading Effects 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000013305 food Nutrition 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 241000209094 Oryza Species 0.000 description 24
- 235000007164 Oryza sativa Nutrition 0.000 description 24
- 235000009566 rice Nutrition 0.000 description 24
- 238000011282 treatment Methods 0.000 description 12
- 229910052785 arsenic Inorganic materials 0.000 description 11
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910052793 cadmium Inorganic materials 0.000 description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 10
- 230000004720 fertilization Effects 0.000 description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 10
- 229910052753 mercury Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000003337 fertilizer Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 238000006388 chemical passivation reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 206010039921 Selenium deficiency Diseases 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000006587 Glutathione peroxidase Human genes 0.000 description 1
- 108700016172 Glutathione peroxidases Proteins 0.000 description 1
- 208000012659 Joint disease Diseases 0.000 description 1
- 208000019926 Keshan disease Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical class [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000009700 ping-tang Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012954 risk control Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- 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
- C09K2101/00—Agricultural use
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention belongs to the technical field of farmland soil remediation, and particularly discloses a selenium-rich soil conditioner for soil heavy metal remediation and a preparation method and application thereof. The selenium-rich soil conditioner is prepared by mixing the following raw materials in parts by weight: 20-40 parts of active selenium mineral powder, 10-20 parts of quicklime, 10-20 parts of attapulgite, 10-20 parts of sepiolite and 20-30 parts of humic acid. The selenium-rich soil conditioner is applied before crop planting, uniformly applied to the soil surface, irrigated and rotary tillage cured. The selenium-rich soil conditioner can fully react with heavy metals in soil during maintenance, solidify and stabilize, obviously reduce the effective state content of the heavy metals in the soil and reduce the heavy metal content in crops; the content of the heavy metal in the soil is reduced, and the content of the water-soluble selenium in the soil is increased, so that the planted crops are agricultural products which achieve the selenium-rich effect and meet the national food safety standard GB 2762-2017.
Description
Technical Field
The invention belongs to the technical field of farmland soil remediation, and particularly relates to a selenium-rich soil conditioner for soil heavy metal remediation and a preparation method and application thereof.
Background
With the rapid development of modern science and technology and economy, the discharge of industrial three wastes, sewage irrigation, sludge agriculture, and the long-term unreasonable application of pesticides and fertilizers, which cause heavy metal pollution of farmland soil, become a widely focused problem. Heavy metals in the soil can be absorbed by plants to enter a food chain, so that serious threat to human health is formed.
Selenium is a trace element necessary for human body, and is a component of erythrocyte glutathione peroxidase, and has the main functions of participating in enzyme synthesis, protecting the structure and function of cell membranes from excessive oxidation injury, and vitamin E interaction can play an anticancer role, and simultaneously has various biological activities of antagonizing heavy metals, stress resistance and the like, selenium deficiency can cause more than 40 diseases such as keshan disease, bone joint disease and the like, and selenium supplementation can prevent diseases caused by selenium deficiency. Over 72% of the regions in our country belong to the selenium-deficient region, and 16 regions in our province and city are severely deficient in selenium. Selenium belongs to rare dispersive elements, and is enriched only in certain sedimentary rocks and sulphide ores, so that world selenium resources are quite lacking, only Hubei Enshi and Shanxi Ziyang have relatively rich selenium resources in China, especially Enshi, the selenium resources are relatively rich and concentrated, the selenium ore in the double river fish pond dam in the New pond countryside is called as a ' world rare and unique independent industrial selenium deposit ', the selenium content in the ore is tens to thousands milligrams per kilogram ', but the selenium in the ore is mostly in a combined state, and only a very small amount of selenium can be absorbed and utilized by plants to be converted into organic selenium which is nontoxic and harmless to human bodies. Selenium in the ore must be activated to be absorbed and utilized by animals and plants, however, in the reported selenium activation technology, the activation rate of selenium is low, the soluble selenium is only more than 20%, and the bioavailability is low. To increase the utilization of limited selenium resources, the activation technology of selenium needs to be further studied. In addition, in the existing crop planting process, in order to achieve the effect of selenium enrichment, the foliar fertilizer is sprayed on crops, and the foliar fertilizer spraying mode is greatly influenced by weather and has limited absorption capacity; in addition, the prior art also increases the selenium absorption of crops by the selenium in the soil through applying an activating agent to the roots of the crops, but the original selenium content in the soil in partial areas is less, the activating mode is unstable, and the selenium absorption amount of the crops is limited.
At present, the chemical passivation restoration in the restoration technology of heavy metal contaminated soil is to add a conditioner into the soil to change the physical and chemical properties of the soil, and the existence state of heavy metal in the soil is changed and the biological activity is reduced by virtue of the actions of the conditioner on the adsorption, precipitation, ion exchange, complexation and the like of the heavy metal. The chemical passivation repair technology is valued for the advantages of low cost, quick repair, simple operation and the like, and is suitable for repairing large-area heavy metal contaminated soil. Conditioning agents commonly used in chemical passivation remediation techniques include alkaline materials, phosphorous containing materials, minerals rich in iron and manganese oxides, organic materials, and the like. However, the commonly used conditioning agents have respective limitations, such as long-term application of phosphorus-containing materials can make soil strongly alkaline and induce eutrophication of water; minerals rich in iron-manganese oxides have relatively high cost, and Fe and Mn have toxic risks to crops; in addition, the existing conditioner can not only reduce the heavy metal absorption of crops to soil, but also ensure the selenium-rich effect of crops.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a selenium-rich soil conditioner for restoring soil heavy metals, and a preparation method and application thereof.
In order to achieve the above object, the present invention adopts the following technical scheme.
A selenium-rich soil conditioner for restoring soil heavy metals (cadmium, mercury, arsenic, lead and chromium) is prepared from the following raw materials in parts by weight: 20-40 parts of active selenium mineral powder, 10-20 parts of quicklime, 10-20 parts of attapulgite, 10-20 parts of sepiolite and 20-30 parts of humic acid.
Preferably, the material is prepared from the following raw materials in parts by weight: 30 parts of active selenium mineral powder, 15 parts of quicklime, 15 parts of attapulgite, 15 parts of sepiolite and 25 parts of humic acid.
Further, the preparation method of the active selenium mineral powder comprises the following steps: a) Crushing and drying selenium ore to obtain selenium ore powder with water content of 15% or less and total selenium content of 200mg/kg or more (selenium is measured by selenium element, and the same applies below); b) Adding quicklime into the selenium mineral powder obtained in the step a), and then crushing the selenium mineral powder into 80-mesh selenium mineral powder; c) And (3) feeding reaction: dissolving potassium permanganate in hot water at 70 ℃, adding hydrogen peroxide, uniformly mixing, and spraying into the selenium mineral powder obtained in the step b); d) Stacking and activating: and (3) putting the charged selenium mineral powder into a reaction tank, controlling the temperature to be 70-80 ℃, and ending the whole reaction when the temperature starts to drop to obtain the active selenium mineral powder.
Further, the mass ratio of the selenium mineral powder, the quicklime, the potassium permanganate, the water and the hydrogen peroxide obtained in the step a) is 1:10%:2%:32%:1.5%.
Further, the quicklime: producing the Chinese medicinal materials with the main component of calcium oxide with the content of more than 75 percent, crushing and sieving with a 80-mesh sieve;
further, the attapulgite: produced from Xiangtan, the main component is magnesium-rich aluminosilicate, crushed and sieved by a 80-mesh sieve;
further, the sepiolite: produced from Xiangtan, the main component is hydrated magnesium silicate, crushed and sieved by a 80-mesh sieve;
further, the humic acid: the organic matter produced from Shanxi Fen is more than 60% and the water content is less than 15%, and the organic matter is delivered through a 60-mesh sieve.
The preparation method of the selenium-enriched soil conditioner for restoring the heavy metals in the soil comprises the following steps: and uniformly mixing the active selenium mineral powder, quicklime, attapulgite, sepiolite and humic acid according to the weight ratio to obtain the selenium-rich soil conditioner.
The method for repairing the heavy metal in the soil by using the selenium-enriched soil conditioner or the selenium-enriched soil conditioner prepared by the method comprises the following steps of:
(1) Soil tillage: ploughing heavy metal polluted farmland soil, wherein the ploughing depth is 10-20cm;
(2) Application of soil conditioner: uniformly broadcasting the selenium-rich soil conditioner into soil; the broadcast amount is 200-250 kg/mu;
(3) And (3) moisture control: controlling the water content of soil in farmland to 15-50%;
(4) Rotary tillage maintenance: rotary tillage, crushing and stirring are carried out on the soil by a rotary cultivator (provided with a common rotary blade), the balance is carried out for 5-8 days, and the water content of the soil is kept at 15-50%.
Further, after the step (4) of watering maintenance is finished and 5 to 14 days later, crops can be planted as required.
The principle of the invention is as follows: according to the invention, the selenium-rich soil conditioner is uniformly spread on the soil surface and then irrigated, and then rotary tillage is carried out, so that the selenium-rich soil conditioner can be fully contacted with the soil, and a sufficient reaction condition is provided for the selenium-rich soil conditioner and heavy metals in the soil. The selenium-rich soil conditioner can fully react with heavy metals in soil during balanced maintenance, so that solidification and stabilization are realized, the effective state content of the heavy metals in the soil is obviously reduced, and the heavy metal content in crops is reduced; the content of the heavy metal in the soil is reduced, and the content of the water-soluble selenium in the soil is increased, so that the planted crops are agricultural products which achieve the selenium-rich effect and meet the national food safety standard GB 2762-2017.
The invention has the advantages and beneficial effects that:
1. the invention can reduce the effective state content of heavy metals in soil so as to reduce the heavy metal content in crops.
2. The raw material of the selenium-enriched soil conditioner is mineral materials or materials which are simply processed by the mineral materials, so that the effective heavy metals in the soil are reduced, the soil structure is not damaged, the organic matter content of the soil is increased, and the water-soluble selenium content in the soil is improved.
3. The selenium-rich soil conditioner is sprayed before crop planting, so that farming time is not delayed.
4. The method is safe and reliable, and can continuously and effectively reduce the heavy metal content in crops.
5. The method is ecological, environment-friendly, economical and effective, low in cost, extremely high in universality and suitable for large-scale popularization and use.
Detailed Description
The following applicant describes further the technical solution of the present invention in connection with specific implementations, but the scope of the invention claimed is not limited thereto.
According to the regulations of soil environmental quality agricultural land pollution risk management and control standard (trial run) (GB 15618-2018), agricultural land pollution risk screening values and control values are regulated, wherein the risk screening values and control value standard requirements for five heavy metals are respectively as follows in tables 1 and 2 (unit: mg/kg): the amount of contaminants in the food was defined according to the regulations of the food safety national standard food limit (GB 2762-2017), wherein the heavy metal content in the grains was specified as in Table 3.
TABLE 1 agricultural soil risk screening values
Table 2 agricultural land soil risk control values
TABLE 3 heavy metal limitation criteria in grains
| Contaminant project | Quantity limited (mg/kg) |
| Cadmium (Cd) | 0.1 (Rice 0.2) |
| Mercury | 0.02 |
| Arsenic (inorganic arsenic) | 0.2 |
| Lead | 0.2 |
| Chromium (Cr) | 1.0 |
The contents of heavy metals cadmium, lead, arsenic, chromium and mercury in the selenium-enriched soil conditioner used in the following examples all meet the requirements of standard Q/XHbQ01-2019, the cultivation management adopts a heavy metal detection method specified in soil environmental quality standard (GB 15618-1995) to determine the contents of five conventional heavy metals in soil samples according to a conventional management mode, and the contents of five conventional heavy metals and selenium in foods are detected according to GB 5009-2014.
Example 1: the experimental land is a field block for paddy rice planting in 3.47 mu of a field dam of the dental boat town in Pingtang county of Guizhou, and the pH of the soil of the land is as follows: 5.97, heavy metal content is: cadmium: 0.821mg/kg, 11.6mg/kg of mercury, 50.2mg/kg of arsenic, 48.8mg/kg of lead and 94.5mg/kg of chromium, wherein the content of cadmium, mercury and arsenic exceeds the risk screening value in the soil environment quality agricultural land soil pollution risk management and control standard (trial run) (GB 15618-2018), paddy rice is planted in the farmland, and the produced paddy rice has the risk of exceeding the standard of the content of cadmium, mercury, arsenic and the like.
And (3) test design: the test was performed in 4 treatments, 3 replicates, and a total of 12 test fields, randomly arranged in groups. The cell is 10m long, 20m wide and 200m in area 2 2.5 m wide protection rows are arranged around the test area, ridges (width is 20cm and height is 30 cm) are arranged between every two areas of the paddy field, and plastic films are covered on the ridges to prevent water and fertilizer from being mixed in different areas; drainage ditches (width 20cm, depth 30 cm) are arranged between every two cells of the dry land.
Control group: blank (CK), normal fertilization;
treatment 1: conventional fertilization and selenium-rich soil conditioner application are carried out for 100 kg/mu;
treatment 2: conventional fertilization and selenium-rich soil conditioner application are carried out at a rate of 150 kg/mu;
treatment 3: conventional fertilization and selenium-rich soil conditioner application of 200 kg/mu;
treatment 4: conventional fertilization and selenium-rich soil conditioner application are carried out at a rate of 250 kg/mu.
The method for repairing soil heavy metal and safely planting crops by using the selenium-enriched soil conditioner comprises the following steps:
(1) Ploughing test field soil, wherein the ploughing depth is as follows: 10-15cm;
(2) Uniformly spreading the selenium-rich soil conditioner into soil, wherein the one-time spreading is completed;
the preparation method of the selenium-enriched soil conditioner comprises the following steps:
a: raw material sources and pretreatment:
quicklime: producing the Chinese medicinal materials with the main component of calcium oxide with the content of more than 75 percent, crushing and sieving with a 80-mesh sieve;
attapulgite: produced from Xiangtan, the main component is magnesium-rich aluminosilicate, crushed and sieved by a 80-mesh sieve;
sepiolite: produced from Xiangtan, the main component is hydrated magnesium silicate, crushed and sieved by a 80-mesh sieve;
humic acid: the organic matter produced from Shanxi Fen is more than 60% and the water content is less than 15%, and the organic matter is delivered through a 60-mesh sieve.
The preparation method of the active selenium mineral powder comprises the following steps in sequence: a) Crushing and drying selenium ore (Hubei enroishi) to control the water content in the selenium ore powder to be within 15 percent and the total selenium element content to be more than 200 mg/kg; b) Adding quicklime with the mass of 10% of selenium mineral powder into the selenium mineral powder, mixing the quicklime and the selenium mineral powder, and then crushing the mixture into selenium mineral powder which is sieved by an 80-mesh sieve; c) And (3) feeding reaction: dissolving potassium permanganate accounting for 2% of the mass of selenium mineral powder in hot water with the mass of potassium permanganate being 70 ℃ which is 16 times that of the selenium mineral powder, adding hydrogen peroxide accounting for 1.5% of the mass of the selenium mineral powder (the concentration is 30 wt%), uniformly mixing, and spraying the mixture into the selenium mineral powder obtained in the step b); d) Stacking and activating: and (3) putting the charged selenium mineral powder into a reaction tank, controlling the temperature to be 70-80 ℃, and after about 24 hours, ending the whole reaction when the temperature starts to drop, thus obtaining the active selenium mineral powder.
B: and (3) uniformly mixing 30 parts by weight of active selenium mineral powder, 15 parts by weight of quicklime, 15 parts by weight of attapulgite, 15 parts by weight of sepiolite and 25 parts by weight of humic acid according to the parts by weight to obtain the selenium-rich soil conditioner.
(3) The water content of soil in farmland is controlled at 30%;
(4) Rotary tillage maintenance: operating a rotary cultivator to crush and stir the field spread with the soil conditioner in all directions without dead angles, wherein the rotary cultivator moves back and forth along a straight line; balancing the farmland for 5 days after rotary tillage is finished, and keeping the water content of soil to be 30 percent during the period;
(5) After 7 days of curing, the rice (variety: yixiangyou 1108) is transplanted in the year 2020, 6 and 21 days, and conventional water and fertilizer management is carried out during the growth period of crops;
(6) Rice was harvested during the harvest period of rice (10 months, 15 days in 2020), and the heavy metal content and selenium content of rice were measured, and the heavy metal content and selenium content of rice in the control group and 4 treated groups are shown in Table 4.
Table 4 heavy metal content and selenium content (unit: mg/kg) in comparative group and 4 treated group rice
Note that: the test results were averaged over 3 replicates.
Example 2: the experimental land is a 3.5 mu paddy rice planting field block in the county of Qingzhou Pingzhou province, and the pH value of the soil of the land is: 6.85, heavy metal content is: cadmium: 1.563mg/kg, 9.48mg/kg of mercury, 39.2mg/kg of arsenic, 41.0mg/kg of lead and 98.6mg/kg of chromium, wherein the content of cadmium, mercury and arsenic exceeds the risk screening value in the soil environment quality agricultural land soil pollution risk management and control standard (trial run) (GB 15618-2018), paddy rice is planted in the farmland, and the produced paddy rice has the risk of exceeding the standard of the content of cadmium, mercury and arsenic.
And (3) test design: the test was performed in 4 treatments, 3 replicates, and a total of 12 test fields, randomly arranged in groups. The cell is 10m long, 20m wide and 200m in area 2 2.5 m wide protection rows are arranged around the test area, ridges (width is 20cm and height is 30 cm) are arranged between every two areas of the paddy field, and plastic films are covered on the ridges to prevent water and fertilizer from being mixed in different areas; drainage ditches (width 20cm, depth 30 cm) are arranged between every two cells of the dry land.
Control group: blank (CK), normal fertilization;
treatment 1: conventional fertilization and soil conditioner application of 100 kg/mu;
treatment 2: conventional fertilization and soil conditioner application of 150 kg/mu;
treatment 3: conventional fertilization and soil conditioner application of 200 kg/mu;
treatment 4: conventional fertilization and soil conditioner application are carried out at a rate of 250 kg/mu.
The preparation steps of the soil conditioner and the method for applying the soil conditioner to soil heavy metal restoration and crop safe planting are the same as those of the embodiment 1. The only difference is that the preparation of the added soil conditioner omits the activation step of selenium mineral powder, the water content is controlled within 15 percent and the total selenium is more than 200mg/kg, the selenium mineral powder after being crushed and sieved by a 80-mesh sieve is uniformly mixed with quicklime, attapulgite, sepiolite and humic acid, and the soil conditioner is prepared.
Rice is collected in the harvesting period of the rice, the heavy metal content and the selenium content of the rice are detected, and the heavy metal content and the selenium content of the rice in the control group and the rice in the 4 treatment groups are shown in table 5.
Table 5 heavy metal content and selenium content (unit: mg/kg) in comparative group and 4 treated group rice
Note that: the test results were averaged over 3 replicates.
As can be seen from table 4, after the selenium-rich soil conditioner is applied to the paddy field to repair the heavy metals in the soil, the content of each heavy metal (cadmium, mercury, arsenic, lead and chromium) in the harvested rice is obviously lower than that of the control group, the selenium-rich soil conditioner is not applied, and the regulation of pollutant limit in food safety national standard food (GB 2762-2017) is achieved; the selenium content in the harvested rice is obviously higher than that of the control group, the selenium-rich soil conditioner is not applied, and the selenium-rich effect is achieved. From Table 4, it can be seen that the optimal application amount of the selenium-rich soil conditioner is about 200 kg/mu for treatment 3. As can be seen from Table 5, by applying the soil conditioner to the paddy field (in which the selenium ore powder component is not activated), the content of each heavy metal in the harvested rice is significantly lower than that in the control group without applying the soil conditioner, and the regulations of the limit of pollutants in food safety national standard food (GB 2762-2017) are satisfied. The application of the soil conditioner in the embodiment 2 can reduce the content of various heavy metals in rice, meets the regulations of the pollutant limit in food safety national standard food (GB 2762-2017), but has no obvious effect on the selenium content in rice. The application of the selenium-enriched soil conditioner disclosed by the invention can be used for repairing soil heavy metals and enabling agricultural products to achieve a selenium-enriched effect.
Claims (4)
1. The soil conditioner for restoring the heavy metal in the paddy field soil is characterized by being prepared from the following raw materials in parts by weight: 20-40 parts of active selenium mineral powder, 10-20 parts of quicklime, 10-20 parts of attapulgite, 10-20 parts of sepiolite and 20-30 parts of humic acid;
the quicklime comprises the following components: the calcium oxide content is more than 75%, and the mixture is sieved by a 80-mesh sieve; the attapulgite is powder which is sieved by an 80-mesh sieve; the sepiolite is powder which is sieved by an 80-mesh sieve; the humic acid: more than 60% of organic matters and less than 15% of water are sieved by a 60-mesh sieve;
the preparation method of the active selenium mineral powder comprises the following steps: a) Crushing and drying selenium ore to obtain selenium ore powder with water content of 15% or less and total selenium content of 200mg/kg or more; b) Adding quicklime into the selenium mineral powder obtained in the step a), and then crushing the selenium mineral powder into 80-mesh selenium mineral powder; c) And (3) feeding reaction: dissolving potassium permanganate in hot water at 70 ℃, adding hydrogen peroxide, uniformly mixing, and spraying into the selenium mineral powder obtained in the step b); d) Stacking and activating: and (3) putting the charged selenium mineral powder into a reaction tank, controlling the temperature to be 70-80 ℃, and ending the whole reaction when the temperature starts to drop to obtain the active selenium mineral powder.
2. The soil conditioner according to claim 1, which is prepared from the following raw materials in parts by weight: 30 parts of active selenium mineral powder, 15 parts of quicklime, 15 parts of attapulgite, 15 parts of sepiolite and 25 parts of humic acid.
3. The soil conditioner according to claim 1, wherein the mass ratio of selenium ore powder, quicklime, potassium permanganate, water and hydrogen peroxide obtained in the step a) is 1:10%:2%:32%:1.5%.
4. A method of using a soil conditioner according to any one of claims 1 to 3 for paddy field soil heavy metal remediation, comprising the steps of:
(1) Soil tillage: ploughing heavy metal polluted farmland soil, wherein the ploughing depth is 10-20cm;
(2) Application of soil conditioner: uniformly spreading the soil conditioner into the soil, wherein the spreading amount of the soil conditioner is 200-250 kg/mu, and the soil conditioner is completely spread at one time;
(3) And (3) moisture control: controlling the water content of soil in farmland to 15-50%;
(4) Rotary tillage maintenance: rotary tillage, crushing and stirring are carried out on the soil by using a rotary cultivator, the balance is carried out for 5-8 days, and the water content of the soil is kept at 15-50%.
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