CN105199736A - Calcium-iron-silicon-based composite material for restoring heavy metal polluted acid soil and application thereof - Google Patents
Calcium-iron-silicon-based composite material for restoring heavy metal polluted acid soil and application thereof Download PDFInfo
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Abstract
The invention discloses a calcium-iron-silicon-based composite material for restoring heavy metal polluted acid soil and application thereof. The mass ratio of component elements of the composite material is calcium:iron:silicon:manganese:magnesium:phosphorus:aluminum= 30-40:19-25:8-12:1-3:5-6:1-3:2-5, the composite material is particularly prepared from, by volume, 55-70% of calcium silicate, 20-30% of calcium ferrite and 5-15% of compound mixture, and the compound mixture is a mixture of calcium-iron-aluminum oxides, calcium iron silicate, calcium aluminate, calcium-aluminum oxides, calcium-manganese-iron oxides, hydroxyl aluminium phosphate and hydroxyl manganese phosphate. The composite material is used for improving and restoring the heavy metal polluted acid soil, the pH value of the soil can be increased by 0.5-2.5 units, the content of effective state heavy metal in the soil is reduced by 64-98%, the content of heavy metal in agricultural products is reduced by 33-94% compared with a control group, and the yield of the agricultural products is increased by 16-1412% compared with the control group.
Description
Technical field
The invention belongs to soil pollution recovery technique field.More specifically, a kind of calcium iron silicon based composite material and application thereof of repairing heavy metal pollution acid soil is related to.
Background technology
Along with socioeconomic fast development, the demand of the mankind to Mineral resources is growing, and the environmental problem that mining activity brings is also more and more serious.
The unreasonable discharge of the acid mine water of digging up mine and formed in Metal smelting process, cause ecology of mining areas to be degenerated, farmland pollution is serious.Mainly there is the pH value of Extreme acid and the problem of too high two aspects of heavy metal content in acid mine water polluted agricultural land.Heavy metal contamination farmland, not only causes Soil degradation, also can threaten human health by food chain.Especially it should be noted that in great majority, low stain farmland is still producing, if do not take suitable counter-measure, these agricultural-food produced in middle low stain farmland, may produce serious harm to HUMAN HEALTH because China arable land lacks.Especially for the crop of the heavy metals such as this cadmium of paddy rice, environmental risk is larger.
Summary of the invention
The technical problem to be solved in the present invention is the defect and the recovery technique deficiency that overcome existing heavy metal pollution of soil, a kind of formula of calcium iron silicon based composite material is provided, and this matrix material heavy metal (Cd, Pb, As, Cr, Cu or Zn) combined pollution or monometallic pollute acid soil, especially rice field and dryland soil are (as vegetables, corn, the cash crop such as fruit tree or sugarcane land used) method of repairing, improve soil acidity by calcium base agent modulates acid heavy metal contaminated soil pH(and reduce heavy metal activity), agricultural-food are regulated and controled as paddy rice by iron-based and silicon base substance, the build-up effect of vegetables heavy metal, while improving edatope, reduce the enrichment of agricultural-food heavy metal, realize repairing polluted soil, reduce triple benefits of agricultural-food edible safety risk and raising agricultural output, produce heavy metal content in agricultural-food and reach national food security standard, for south China heavy-metal contaminated soil especially rice field and vegetable field soil reparation provide the high restorative procedure of a kind of cost performance.
The object of this invention is to provide a kind of calcium iron silicon based composite material of repairing heavy metal pollution acid soil.
Another object of the present invention is to provide the application of above-mentioned calcium iron silicon based composite material in repairing heavy metal pollution acid soil.
Another object of the present invention is to provide the method utilizing above-mentioned calcium iron silicon based composite material repairing heavy metal pollution acid soil.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A calcium iron silicon based composite material for repairing heavy metal pollution acid soil, the mass ratio of its constitution element is: calcium: iron: silicon: manganese: magnesium: phosphorus: aluminium=30 ~ 40:19 ~ 25:8 ~ 12:1 ~ 3:5 ~ 6:1 ~ 3:2 ~ 5.
Preferably, the mass ratio of the constitution element of described calcium iron silicon based composite material is: calcium: iron: silicon: manganese: magnesium: phosphorus=35:22:10:2:4:2.
Particularly, above-mentioned constitution element is with its oxide basis, and described calcium is in CaO, and described iron is with Fe
2o
3meter, described silicon is with SiO
2meter, described manganese is in MnO, and described magnesium is in MgO, and described phosphorus is with P
2o
5meter, aluminium is with Al
2o
3meter.
More specifically, as the enforceable preferred version of one, described calcium iron silicon based composite material is made up of the component of following volume percent: 55 ~ 70% Calucium Silicate powder, 20 ~ 30% calcium ferrites and 5 ~ 15% compounding mixtures; Described compounding mixture is calcium iron-aluminium oxide (Ca
2[Fe (Fe
0.866al
0.134) O
5]), Calucium Silicate powder iron (CaFe
3si
2o
8(OH)), calcium aluminate (Ca
11.3al
14o
32.3), calcium aluminum oxide (Ca
3al
2o
6), calcium manganese iron axinite (Ca
3mn
1.2fe
1.8o
8), Adju-Phos (Al
4(PO
4)
3(OH)
39H
2and di manganese (Mn O)
5(PO
3) (OH)
2(PO
4)
2(H
2o)
4) mixture.
Wherein, described Calucium Silicate powder is tricalcium silicate Ca
3siO
5and/or Dicalcium Phosphate (Feed Grade) Ca
2siO
4; Described calcium ferrite is calcium ferriferous oxide CaFe
2o
4and/or black calcium nutrition Ca
2fe
2o
5.
Preferably, described Calucium Silicate powder is the tricalcium silicate Ca of 3 ~ 5:5 ~ 7
3siO
5with Dicalcium Phosphate (Feed Grade) Ca
2siO
4mixture; Described calcium ferrite is the calcium ferriferous oxide CaFe of 3 ~ 5:5 ~ 7
2o
4with black calcium nutrition Ca
2fe
2o
5mixture.
Preferably, each volume components ratio of described compounding mixture is: calcium iron-aluminium oxide: Calucium Silicate powder iron: calcium aluminate: calcium aluminum oxide: calcium manganese iron axinite: Adju-Phos: di manganese=1 ~ 5:20 ~ 30:1 ~ 3:1 ~ 3:2 ~ 6:2 ~ 6:2 ~ 6.
More preferably, described calcium iron silicon based composite material is made up of the component of following volume percent: 65% Calucium Silicate powder, 25% calcium ferrite and 10% compounding mixture; Each volume components ratio of wherein said compounding mixture is: calcium iron-aluminium oxide: Calucium Silicate powder iron: calcium aluminate: calcium aluminum oxide: calcium manganese iron axinite: Adju-Phos: di manganese=1:5:0.5:0.5:1:1:1.
In addition, preferably, each component in above-mentioned Calucium Silicate powder, calcium ferrite and compounding mixture is all crushed to Powdered, and crosses 0.2mm sieve.We study discovery, when utilizing calcium iron silicon based composite material of the present invention to hinder control plant absorption heavy metal, when the mixing of described component is crushed to the fine particle of 0.2mm, be the best to the improvement of soil and repairing effect.
The application of above-mentioned calcium iron silicon based composite material in improvement rehabilitating soil, also within protection scope of the present invention.
Preferably, described soil is heavy metal contamination (comprising slight to serious pollution) soil, acidified soil, lacks silicon or iron deficiency soil.
Preferably, described heavy metal is Cd and/or Pb and/or As and/or Cu and/or Zn and/or Cr.
More preferably, described soil is the cash crop soil such as the paddy soil that pollutes of Cd and/or Pb and/or As or vegetables, corn, fruit tree or sugarcane.
Specifically preferably, the method of described application (namely utilizes the method for this composite repair contaminated soil, also be described utilizing calcium iron silicon based composite material to improve soil and intercept the method for rice from absorbing heavy metal) be: at plant transplantation before one week, polluted soil is carried out turn over smooth after, according to 1.8tha
-1~ 3.6tha
-1amount of application, calcium iron silicon based composite material base is imposed on polluted soil, ploughs a field and calcium iron silicon based composite material and 0 ~ 20cm topsoil soils are fully mixed.
When the acid soil by heavy metal contamination is water paddy soil, at plant transplantation before one week, the acid paddy soil by heavy metal contamination is turned over smooth after, according to 1.8tha
-1~ 3.6tha
-1amount of application, calcium iron silicon based composite material base is imposed on the acid paddy soil by heavy metal contamination, ploughs a field and calcium iron silicon based composite material and 0 ~ 20cm topsoil soils are fully mixed, pour water, keep 2 ~ 3cm waterflooding state, balance about one week; Transplanting rice rice shoot, follow-up rice cultivating technique routinely rice does management implementation.
During practical application, concrete amount of application adjusts according to the contaminated degree of heavy metal in soil.Preferably, can refer to following standard to carry out:
When heavy metal in soil exceeds standard less than 2 times (as total Cd content is less than 0.6mgkg
-1) time, calcium iron silicon based composite material application dosage is 1.8tha
-1; When heavy metal in soil exceed standard 2 times ~ 4 times time (if total Cd content is 0.6mgkg
-1<Cd<2.0mgkg
-1), calcium iron silicon based composite material application dosage is 3.6tha
-1.
And method of application can singly be executed, or execute with other fertilizer is mixed; Amount of application can be grasped as the case may be flexibly.
The present invention is through large quantity research, develop a kind of formula of calcium iron silicon based composite material, this matrix material heavy metal is polluted acid paddy soil and is had excellent repairing performance, confirm through long term field experiment, after this calcium iron silicon based composite material is applied to the acid paddy soil of heavy metal contamination, can not only improve the physico-chemical property of contaminated soil, the acid heavy metal in soil of passivation is active, and can significantly reduce heavy metal content in rice, reach national food hygienic safety production standard.
Rich using of calcium substance can form Ca (OH) within a short period of time
2significantly improve the pH of soil Deng alkaline matter, passivation heavy metal in soil is active; Meanwhile, paddy rice is happiness silicon crop, Silicon-rich material use the content that can increase effective silicon in soil and plant, the pH of raising soil, the activity of passivation heavy metal in soil, and the photosynthesis and the anti-adversity that improve paddy rice, have the effect of volume increase; In addition, rich iron modifying agent use the content that can improve available iron in soil and plant, promote the formation of iron and manganese oxides, thus heavy metal ion in absorption soil, make Heavy Metals to indissoluble state or residual form conversion, reduce the bioavailability of paddy rice heavy metal.
In addition, research is had also to show, cadmium can utilize the absorption and transport passage of paddy rice to iron to enter in rice plant body by Competition, therefore apply rich iron substance iron may be suppressed to be correlated with the expression of high-affinity transporter gene, thus the absorption and transport path of part blocks cadmium, reach the object significantly reducing cadmium content in rice.
Experimental result shows, and calcium iron silicon based composite material of the present invention is applied to by heavy metal (Cd, Pb, Cr, As, Cu, Zn) paddy soil of light-serious pollution, soil pH can be made to improve 0.5 ~ 2.5 unit, and soil available heavy metal content significantly reduces 64% ~ 94%; The content of the Cd in first three Growing season polished rice all reaches national food safety standard (GB2762-2012), declines 33% ~ 50% than space management; Rice yield is respectively than space management volume increase 16% ~ 38%.
This matrix material is for improveing the acid dryland soil of repairing heavy metal pollution, cadmium arsenic can be made to pollute acid dryland soil pH and to improve 0.70 ~ 2.37 unit, soil available arsenic declines 71.76 ~ 85.29%, available Cd declines 90.48 ~ 97.88%, the edible part Cd content of vegetables declines 38 ~ 87% than control group, and arsenic declines 45 ~ 94%; Vegetable crop is than control group volume increase 169 ~ 1412%.
The present invention has following beneficial effect:
1, calcium iron silicon based composite material of the present invention can be used as soil conditioner, is applied to the agricultural land soil of gently acid-severe heavy metal (as Cd, Pb, As, Cr, Cu, Zn) combined pollution or monometallic pollution.Its application does not change Soil structure and composition substantially, can improve soil pH value, and can promote that in soil, water-soluble state heavy metal ion transforms to the non-soluble state such as silicate, phosphoric acid salt, oxyhydroxide, reduces the activity of heavy metal.Use calcium iron silicon based composite material relevant with the amount of application of calcium iron silicon based composite material with the influence degree reducing heavy metal activity to improving soil pH, consumption is larger, heavy metal resistance control effect is more remarkable, but excessively use the problem may bringing soil compaction, concrete consumption should according to the target determination amount of application of local soil physical chemistry feature and reparation (generally at 1.8 ~ 3.6tha
-1in scope all can).
2, the present invention utilizes calcium iron silicon based composite material to intercept the method for rice Metal uptake, is one and improves heavy metal contamination farmland paddy growth, reduce the absorption and accumulation of paddy rice heavy metal, ensures the method for the economical and efficient of rice safety in production.The mechanism of the method mainly comprises: 1) described above, uses the environment that calcium iron silicon based composite material improves soil, significantly improves acid soil pH, promote paddy growth; 2) contain abundant calcium and silicon in calcium iron silicon based composite material, paddy rice typically likes calcium, happiness silicon crop, uses the silica-based fertilizer of calcium iron and be conducive to improving paddy rice anti contravariance performance; 3) for paddy rice, silicon is not only important nutritive element, but also by forming silicon-heavy metal complex with the heavy metal in paddy rice body, the heavy metal activity in passivation paddy rice body, alleviates its murder by poisoning to paddy rice, and suppresses it to the transhipment of rice; Iron in matrix material, manganese, phosphorus are also conducive to promoting that heavy metal-polluted soil transforms to SA indissoluble or residual form.
3, the present invention utilizes calcium iron silicon based composite material to improve soil and intercepts the method for rice from absorbing heavy metal, emphasize chemistry and biological coupling in soil-plant system, in matrix material, calcium, iron, silicon, manganese etc. can regulate and control the heavy metal activity in contaminated soil environment on the one hand, extremely significantly reduce its toxicity; Calcium, iron and silicon can strengthen paddy rice anti contravariance performance, the build-up effect of adjusting and controlling rice plant heavy metal on the other hand, realize the reparation of heavy metal contamination agricultural land soil, guarantee that rice is kept the safety in production and triple benefits that rice is increased production.
4, the method for calcium iron silicon based composite material improvement soil provided by the invention, is also applicable to alleviate soil acidification, or uses as calcareous fertilisers, siliceous fertilizer and iron fertilizer.Method of application can singly be executed, or executes with other fertilizer is mixed; Amount of application and time of application can be grasped as the case may be flexibly.
5, calcium iron silicon based composite material provided by the present invention intercepts the method for rice absorbing heavy metal, is also applicable to other crops except paddy rice, is particularly useful for the cash crop such as vegetables, corn, fruit tree, sugarcane.
Embodiment
Further illustrate the present invention below in conjunction with specific embodiment, but embodiment does not limit in any form to the present invention.Unless stated otherwise, the present invention adopts reagent, method and apparatus are the art conventional reagent, method and apparatus.
Unless stated otherwise, following examples agents useful for same and material are commercial.
embodiment 1 calcium iron silicon based composite material
A calcium iron silicon based composite material for repairing heavy metal pollution acid soil, is made up of the component of following volume percent: 65% Calucium Silicate powder, 25% calcium ferrite and 10% compounding mixture.
Wherein, described Calucium Silicate powder is the tricalcium silicate Ca of 8:13
3siO
5with Dicalcium Phosphate (Feed Grade) Ca
2siO
4mixture; Described calcium ferrite is the calcium ferriferous oxide CaFe of 4:5
2o
4with black calcium nutrition Ca
2fe
2o
5mixture.
Described compounding mixture is made up of each component of following volume ratio: calcium iron-aluminium oxide (Ca
2[Fe (Fe
0.866al
0.134) O
5]): Calucium Silicate powder iron (CaFe
3si
2o
8(OH)): calcium aluminate (Ca
11.3al
14o
32.3): calcium aluminum oxide (Ca
3al
2o
6): calcium manganese iron axinite (Ca
3mn
1.2fe
1.8o
8): Adju-Phos (Al
4(PO
4)
3(OH)
39H
2o): di manganese (Mn
5(PO
3) (OH)
2(PO
4)
2(H
2o)
4)=1:5:0.5:0.5:1:1:1.
The mass ratio of the constitution element of above-mentioned calcium iron silicon based composite material is: calcium: iron: silicon: manganese: magnesium: phosphorus: aluminium=35:22:10:2:4:2:4.(particularly, described constitution element is with its oxide basis, and described calcium is in CaO, and described iron is with Fe
2o
3meter, described silicon is with SiO
2meter, described manganese is in MnO, and described magnesium is in MgO, and described phosphorus is with P
2o
5meter, described aluminium is with Al
2o
3meter).
In addition, each component in above-mentioned Calucium Silicate powder, calcium ferrite and compounding mixture is all crushed to Powdered shape, and crosses 0.2mm sieve.
embodiment 2 calcium iron silicon based composite material
A calcium iron silicon based composite material for repairing heavy metal pollution acid soil, is made up of the component of following volume percent: 65% Calucium Silicate powder, 30% calcium ferrite and 5% compounding mixture.
Wherein, described Calucium Silicate powder is the tricalcium silicate Ca of 5:13
3siO
5with Dicalcium Phosphate (Feed Grade) Ca
2siO
4mixture; Described calcium ferrite is the calcium ferriferous oxide CaFe of 3:5
2o
4with black calcium nutrition Ca
2fe
2o
5mixture.
Described compounding mixture is made up of each component of following volume ratio: calcium iron-aluminium oxide: Calucium Silicate powder iron: calcium aluminate: calcium aluminum oxide: calcium manganese iron axinite: Adju-Phos: di manganese=2:20:1:1:2:2:2.
In addition, each component in above-mentioned Calucium Silicate powder, calcium ferrite and compounding mixture is all crushed to Powdered shape, and crosses 0.2mm sieve.
embodiment 3 calcium iron silicon based composite material
A calcium iron silicon based composite material for repairing heavy metal pollution acid soil, is made up of the component of following volume percent: 65% Calucium Silicate powder, 20% calcium ferrite and 15% compounding mixture.
Wherein, described Calucium Silicate powder is the tricalcium silicate Ca of 9:13
3siO
5with Dicalcium Phosphate (Feed Grade) Ca
2siO
4mixture; Described calcium ferrite is the calcium ferriferous oxide CaFe of 5:5
2o
4with black calcium nutrition Ca
2fe
2o
5mixture.
Described compounding mixture is made up of each component of following volume ratio: calcium iron-aluminium oxide: Calucium Silicate powder iron: calcium aluminate: calcium aluminum oxide: calcium manganese iron axinite: Adju-Phos: di manganese=2:30:3:3:6:6:6.
In addition, each component in above-mentioned Calucium Silicate powder, calcium ferrite and compounding mixture is all crushed to Powdered shape, and crosses 0.2mm sieve.
embodiment 4 calcium iron silicon based composite material
A calcium iron silicon based composite material for repairing heavy metal pollution acid soil, is made up of the component of following volume percent: 55% Calucium Silicate powder, 30% calcium ferrite and 15% compounding mixture.
Wherein, described Calucium Silicate powder is the tricalcium silicate Ca of 5:13
3siO
5with Dicalcium Phosphate (Feed Grade) Ca
2siO
4mixture; Described calcium ferrite is the calcium ferriferous oxide CaFe of 5:5
2o
4with black calcium nutrition Ca
2fe
2o
5mixture.
Described compounding mixture is made up of each component of following volume ratio: calcium iron-aluminium oxide: Calucium Silicate powder iron: calcium aluminate: calcium aluminum oxide: calcium manganese iron axinite: Adju-Phos: di manganese=1:5:0.5:0.5:1:1:1.
In addition, each component in above-mentioned Calucium Silicate powder, calcium ferrite and compounding mixture is all crushed to Powdered shape, and crosses 0.2mm sieve.
embodiment 5 calcium iron silicon based composite material
A calcium iron silicon based composite material for repairing heavy metal pollution acid soil, is made up of the component of following volume percent: 70% Calucium Silicate powder, 20% calcium ferrite and 10% compounding mixture.
Wherein, described Calucium Silicate powder is the tricalcium silicate Ca of 9:13
3siO
5with Dicalcium Phosphate (Feed Grade) Ca
2siO
4mixture; Described calcium ferrite is the calcium ferriferous oxide CaFe of 3:5
2o
4with black calcium nutrition Ca
2fe
2o
5mixture.
Described compounding mixture is made up of each component of following volume ratio: calcium iron-aluminium oxide: Calucium Silicate powder iron: calcium aluminate: calcium aluminum oxide: calcium manganese iron axinite: Adju-Phos: di manganese=1.5:25:2:2:4:4:4.
In addition, each component in above-mentioned Calucium Silicate powder, calcium ferrite and compounding mixture is all crushed to Powdered shape, and crosses 0.2mm sieve.
embodiment 6 calcium iron silicon based composite material is to the repair of the acid paddy soil of heavy Cd contamination
1, the present embodiment is with acid paddy soil (the total Cd=4.2mgkg of heavy Cd contamination
-1, pH=4.5) and for repairing object, study calcium iron silicon based composite material of the present invention to the repair of soil, experimental group uses calcium iron silicon based composite material, arranges space management control group simultaneously, does multiple revision test to ensure the confidence level of result.
Method is as follows:
(1) at plant transplantation before one week, acid for heavy Cd contamination paddy soil is carried out turn over smooth after, according to 3.6tha
-1amount of application, calcium iron silicon based composite material is evenly manured into soil, ploughs a field after calcium iron silicon based composite material and 0 ~ 20cm topsoil soils are fully mixed, pour water, keep 2 ~ 3cm waterflooding state, balance about one week.
(2), after balance terminates, the transplanting of rice seedling is carried out.The management such as the water during paddy growth, fertilizer, transplanting, results is undertaken by local usual manner.Four rice growing seasons have been carried out in test continuously, and period no longer adds calcium iron silicon based composite material, and other way to manages routinely rice are done to carry out.
2, soil pH change
The change of the real time measure soil pH, result shows, and at continuous four rice growing seasons, applies calcium iron silicon based composite material and significantly improves the stronger sour environment condition of contaminated soil, make soil pH improve 0.5 ~ 2.5 unit.
3, the change of Active Heavy Metals content in soil
The change of Active Heavy Metals content in the real time measure soil, result shows, apply calcium iron silicon based composite material and significantly reduce soil activation heavy metal content, compared with space management control group, the soil available heavy metal Cd content of calcium iron silicon based composite material process significantly reduces 64 ~ 94%.
And test-results finds, apply calcium iron silicon based composite material and obviously facilitate heavy metal in soil Cd ion to precipitation conversions such as silicate, phosphoric acid salt, oxyhydroxide.
4, the output of paddy rice is added up
Result shows, and applies the growth that calcium iron silicon based composite material significantly promotes polluted agricultural land paddy rice, and continuous four rice growing season rice yields are respectively than space management volume increase 16 ~ 38%.
5, the impact of the transhipment of calcium iron silicon based composite material heavy metal in paddy rice body
(1) measure the transhipment situation of heavy metal in paddy rice body, concrete grammar is:
By paddy rice pot experiment, before rice harves, more than rice root base portion, stem is chopped at 3 ~ 4cm place off, blots wound fluid with filter paper, then immediately on fracture portion cover bore and Culm of Rice suitable, be about 5cm, clean silicone tube.A small amount of Vaseline is coated, in case bleeding sap runs off bottom pipe; Pipe top absorbent cotton jam-pack, collect 3h, the sucking-off of every 1h micropipet once.It is a sample that paddy rice Xylem sap under same treatment condition collects, and loads in the plastics tubing of 2.5ml to be measured.
(2) result display, the process applying calcium iron silicon based composite material significantly reduces the content of the heavy metal such as zinc, cadmium, arsenic in paddy rice Xylem sap, and the applied amount of this matrix material larger reduction amplitude is larger.Illustrate thus, supply calcium iron silicon based composite material effectively can reduce the loading of the heavy metals such as zinc, cadmium, arsenic to xylem, and then reduces the efficiency of heavy metal to the transhipment of overground part.Especially in the water culture experiment adding silicon element resistance control heavy metal zinc, compared with not executing the process of silicon element, from the line sweep X-ray energy spectrum graph discovery adding silicon process paddy rice sample, in root, leaf sheath and Transverse section of leaf blade, the characteristic signal of zinc and silicon all can be detected simultaneously, can infer that adding silicon process may facilitate zinc and be present in paddy rice body with the form of Zn-Si mixture thus.Therefore probed into silicon element in calcium iron silicon based composite material further and paddy rice resistance has been controlled to the mechanism of action of Metal uptake.
Above result shows, calcium iron silicon based composite material can suppress the transhipment of heavy metal in paddy rice body, and the metal ion promoting physiologically active stronger transforms to metal-silicon composite precipitation, can also increase the distribution of complex precipitate at cell walls, alleviate the murder by poisoning to paddy rice.
6, the content of Cd in rice is detected
Through measuring, through the paddy soil of calcium iron silicon based composite material improvement in the present embodiment, the content of the Cd in first three Growing season polished rice all reaches national food safety standard (GB2762-2012), declines 33 ~ 50% than space management.
embodiment 7 calcium iron silicon based composite material is to the repair of arsenic cadmium combined pollution acid soil
1, the present embodiment is with arsenic cadmium combined pollution acid soil (total Cd=0.41mgkg
-1, total As=138.8mgkg
-1pH=4.4) for repairing object, study calcium iron silicon based composite material of the present invention to the repair of vegetable field soil, experimental group uses calcium iron silicon based composite material, space management control group is set simultaneously, planting vegetable Brassica rapa L, three revision tests, to ensure the confidence level of result.
Method is as follows:
(1) at vegetable transplanting before one week, by crossing the arsenic cadmium pollution acid soil of 2mm sieve, according to 0g/kg, 3g/kg, the amount of application of 6g/kg, 10g/kg, is evenly manured into soil calcium iron silicon based composite material, after calcium iron silicon based composite material and soil are fully mixed, keep 60% moisture content, balance about one week.
(2), after balance terminates, the transplanting of vegetables Shanghai young crops is carried out.The management such as the water during vegetable growth, fertilizer, results is carried out in the usual way.2 Growing season have been carried out in test continuously, and period no longer adds calcium iron silicon based composite material.
2, soil pH change
The change of the real time measure soil pH, result shows, and at continuous 2 Growing season, applies calcium iron silicon based composite material and significantly improves the stronger acidic conditions of contaminated soil, make soil pH improve 0.70 ~ 2.37 unit.
3, the change of Active Heavy Metals content in soil
The change of Active Heavy Metals content in the real time measure soil, result shows, apply calcium iron silicon based composite material and significantly reduce soil activation heavy metal content, compared with space management group, the process of calcium iron silicon based composite material makes the bio-available Zn concentration of Arsenic in Soil decline 71.76% ~ 85.29%, makes the bio-available Zn concentration of Cd decline 90.48% ~ 97.88%.
And test-results finds, apply calcium iron silicon based composite material and obviously facilitate heavy metal in soil ion to precipitation conversions such as silicate, phosphoric acid salt, oxyhydroxide.
4, the output of vegetables is added up
Result shows, and applies the growth that calcium iron silicon based composite material significantly promotes contaminated soil vegetables, and continuous 2 Growing season vegetable crop are respectively than space management volume increase 169% ~ 1412% and 436% ~ 731%.
6, the content of As, Cd in vegetables is detected
Through measuring, through the soil of calcium iron silicon based composite material improvement in the present embodiment, the content of As, Cd in continuous two Growing season vegetables all reaches national food safety standard (GB2762-2012), compared with space management, makes edible portion As content decline 84% ~ 94%.Cd content declines 38% ~ 87%.
Claims (10)
1. the calcium iron silicon based composite material of a repairing heavy metal pollution acid soil, it is characterized in that, the mass ratio of described calcium iron silicon based composite material constitution element is: calcium: iron: silicon: manganese: magnesium: phosphorus: aluminium=30 ~ 40:19 ~ 25:8 ~ 12:1 ~ 3:5 ~ 6:1 ~ 3:2 ~ 5.
2. calcium iron silicon based composite material according to claim 1, is characterized in that, the preferred mass ratio of described calcium iron silicon based composite material constitution element is: calcium: iron: silicon: manganese: magnesium: phosphorus: aluminium=35:22:10:2:4:2:3.5.
3. calcium iron silicon based composite material according to claim 1 and 2, is characterized in that, described calcium is in CaO, and described iron is with Fe
2o
3meter, described silicon is with SiO
2meter, described manganese is in MnO, and described magnesium is in MgO, and described phosphorus is with P
2o
5meter, described aluminium is with Al
2o
3meter.
4. calcium iron silicon based composite material according to claim 1 and 2, is characterized in that, described calcium iron silicon based composite material is made up of the component of following volume percent: 55 ~ 70% Calucium Silicate powder, 20 ~ 30% calcium ferrites and 5 ~ 15% compounding mixtures; Described compounding mixture is the mixture of calcium iron-aluminium oxide, Calucium Silicate powder iron, calcium aluminate, calcium aluminum oxide, calcium manganese iron axinite, Adju-Phos and di manganese.
5. calcium iron silicon based composite material according to claim 4, is characterized in that, described Calucium Silicate powder is tricalcium silicate Ca
3siO
5and/or Dicalcium Phosphate (Feed Grade) Ca
2siO
4; Described calcium ferrite is calcium ferriferous oxide CaFe
2o
4and/or black calcium nutrition Ca
2fe
2o
5; Each volume components ratio of described compounding mixture is: calcium iron-aluminium oxide: Calucium Silicate powder iron: calcium aluminate: calcium aluminum oxide: calcium manganese iron axinite: Adju-Phos: di manganese=1 ~ 5:20 ~ 30:1 ~ 3:1 ~ 3:2 ~ 6:2 ~ 6:2 ~ 6.
6. calcium iron silicon based composite material according to claim 5, is characterized in that, the tricalcium silicate Ca of described Calucium Silicate powder to be volume ratio be 3 ~ 5:5 ~ 7
3siO
5with Dicalcium Phosphate (Feed Grade) Ca
2siO
4mixture; Described calcium ferrite is the calcium ferriferous oxide CaFe of volume ratio 3 ~ 5:5 ~ 7
2o
4with black calcium nutrition Ca
2fe
2o
5mixture.
7. calcium iron silicon based composite material according to claim 4, is characterized in that, described calcium iron silicon based composite material is made up of the component of following volume percent: 65% Calucium Silicate powder, 25% calcium ferrite and 10% compounding mixture; Each volume components ratio of wherein said compounding mixture is: calcium iron-aluminium oxide: Calucium Silicate powder iron: calcium aluminate: calcium aluminum oxide: calcium manganese iron axinite: Adju-Phos: di manganese=1:5:0.5:0.5:1:1:1.
8. calcium iron silicon based composite material according to claim 4, is characterized in that, each component in described Calucium Silicate powder, calcium ferrite and compounding mixture is all crushed to Powdered, and crosses 0.2mm sieve.
9. the application of the arbitrary described calcium iron silicon based composite material of claim 1 ~ 8 in improvement rehabilitating soil.
10. apply according to claim 9, it is characterized in that, the method for application is: at plant transplantation before one week, polluted soil is carried out turn over smooth after, according to 1.8tha
-1~ 3.6tha
-1amount of application, calcium iron silicon based composite material base is imposed on polluted soil, ploughs a field and calcium iron silicon based composite material and 0 ~ 20cm topsoil soils are fully mixed.
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| CN113667486A (en) * | 2021-08-25 | 2021-11-19 | 济南大学 | Acidic soil remediation agent and preparation method and application thereof |
| CN113817473A (en) * | 2021-09-23 | 2021-12-21 | 河南农业大学 | Stabilizing agent for repairing heavy metal contaminated soil, preparation method and application thereof, and repairing method of heavy metal contaminated soil |
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| CN105199736B (en) | 2018-12-25 |
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Application publication date: 20151230 Assignee: Nongfengbao Group Co., Ltd Assignor: SUN YAT-SEN University Contract record no.: X2020440000067 Denomination of invention: Calcium-iron-silicon-based composite material for restoring heavy metal polluted acid soil and application thereof Granted publication date: 20181225 License type: Common License Record date: 20200414 |