CN103936530B - A kind of compound adjusting control agent and application process thereof of cadmium pollution soil repair - Google Patents
A kind of compound adjusting control agent and application process thereof of cadmium pollution soil repair Download PDFInfo
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Abstract
The invention discloses a kind of compound adjusting control agent of cadmium pollution soil repair, it comprises calcium magnesium phosphate 45.45%-88.89%, charcoal base manure 0-50%, lime stone 0-20%, mixes in proportion and forms. Compound adjusting control agent of the present invention can effectively reduce available state Cd content in contaminated soil, can make biologically effective state cadmium content decline 44.47%-86.53% in contaminated soil, cadmium content in the victual about 20-70% that declines, also make soil pH value improve 0.6-1.7 simultaneously, have passivation heavy metal-polluted soil concurrently, repair acidified soil and improve the several functions such as soil fertility, be mainly used in administering the agricultural land soil of vast heavy metal cadmium.
Description
Technical field
The invention belongs to contaminated soil recovery technique field, what more specifically relate to is a kind of restoring cadmium polluted agricultural land soilCompound adjusting control agent and application process thereof.
Background technology
Due to industrial develop rapidly, the problem of heavy metal cadmium soil is subject to the attention of countries in the world, China's cadmium dirtThe problem of dying is particularly outstanding. Heavy metal pollution be current contaminated area the widest, endanger one of maximum environmental problem, according to incomplete systemMeter, the heavy metal pollution cultivated area of China nearly 2.0 × 108hm2, account for 1/5 of total area under cultivation, ploughed by cadmium pollutionGround area is 1.33 × l04hm2, relate to 11 and economize 25 areas. The cadmium pollution of paddy soil not only affects the life of rice cropLength, grain yield and quality, but also will enter body by the direct or indirect mode of food chain relation, serious threat human body is strongHealth. Cadmium pollution environment event taking the sixties in last century Toyama County, Japan occur ' Itai-itai diseases ' for typical case, event root be exactly oughtThe ground people have eaten cadmium pollution rice, and this time event makes japanese people suffer grievous injury, and Japanese government and enterprise are also for this reasonPay huge economic cost. Therefore, paddy soil cadmium pollution will affect sustainable development and the grain security of agricultural productionProduce.
Along with the raising of people's living standard, people more and more pay close attention to vegetables quality and safety problem. Cause vegetables qualityBad factor is a lot, and it is the important root that causes vegetables quality safety problem that heavy metal content in soil exceeds standard. Hangzhou vegetablesBase heavy metal content in soil far exceedes local background value. Tianjin vegetable soil contents of heavy metal elements is higher than this city's agriculturalSoil background is more than one times. Nanning City's some Vegetable Bases soil pollutant is mainly cadmium. Part base, Yuhong District, Shenyang CityDuring oneself reaches, serious pollution. Also there is the slight pollution of variety classes heavy metal element Dongting Lake Area. Although there are some researches show soilContent of beary metal is along with the growing vegetables time limit increases and increases to some extent, and Cadmium in Soil content increases and changes with Planting YearsLittle, but still particularly outstanding with cadmium pollution problem at present.
The heavy metal pollution of soil has disguise, chronicity and irreversibility, therefore, and the contaminated situation in farmlandUnder, it is to prevent that heavy metal pollution from affecting the key of human health that the transfer enrichment behavior of Removed In Soil-crop System is regulated and controled. ?In numerous recovery techniques, chemical passivation recovery technique is because of its advantage such as easy, quick, efficient, is that to repair large area heavy metal-pollutedDye the better selection of agricultural land soil. The present invention uses calcium magnesium phosphate, charcoal base manure and lime stone composite material, to reach a passivation huge sum of moneyBelong to the dual purpose of cadmium and improvement soil.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of cadmium of repairing for the deficiency of above-mentioned prior art existenceCompound adjusting control agent and the application process thereof of contaminated soil, compound adjusting control agent of the present invention can effectively reduce in contaminated soilAvailable Cd content, effectively reduces the cadmium content in victual, can also repair acidified soil simultaneously.
The present invention for the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
A compound adjusting control agent for cadmium pollution soil repair, by mass percentage, it comprises calcium magnesium phosphate 45.45%-88.89%, charcoal base manure 0-50%, lime stone 0-20%, mixes in proportion described calcium magnesium phosphate, charcoal base manure and lime stoneForm.
Press such scheme, the optimum ratio of the compound adjusting control agent of described cadmium pollution soil repair is: by mass percentage,It comprises calcium magnesium phosphate 45.45-66.70%, charcoal base manure 31.25-50%, lime stone 0-10%. This optimum ratio is very applicableCadmium pollution soil is the situation of agricultural land soil. Described agricultural land soil comprises rice soil and red soil etc.
Press such scheme, the best proportioning of the compound adjusting control agent of described cadmium pollution soil repair is: by mass percentage,It comprises calcium magnesium phosphate 62.50%, charcoal base manure 31.25%, lime stone 6.25%, i.e. calcium magnesium phosphate, charcoal base manure 31.25% and stoneThe mass ratio of lime stone is about 10:5:1. This optimum ratio is especially suitable for the feelings that cadmium pollution soil is pakchoi and bag vegetable field soilCondition.
Press such scheme, P in described calcium magnesium phosphate2O5Mass content be 15%-20%. Calcium magnesium phosphate, claims that again melting containsMagnesium-phosphorus fertilizer, is a kind of sillico aluminate glass body that contains phosphate radical, and main component comprises Ca3(PO4)2、CaSiO3、MgSiO3, beA kind of multi-element fertilizer, the aqueous solution is alkalescence, can improve acid ground, fine as base fertilizer effect when cultivating large seedling, plant energyThe required nutrient of enough slowly absorptions.
Press such scheme, described charcoal base manure is charcoal base fertilizer, and its carbon content is between 10%-30%. Charcoal base manure, onePlant taking biomass carbon as matrix, according to zones of different land characteristics, Different Crop growth characteristic and the principle that applies fertilizers scientifically, addOrganic matter is or/and the formulated ecological environment-friendly type fertilizer of inanimate matter. Charcoal base manure is divided into three large fundamental types: charcoal base fertilizer;Charcoal base inorganic fertilizer; Charcoal base composite organic-inorganic fertilizer (Chemical Mixed Fertilizer). Charcoal base fertilizer is to be produced after decomposing by wastes of crops stalkRaw straw charcoal, as the base-material of fertilizer, the fertilizer of producing, its main role is to have certain suction-operated,Execute in soil and can improve fertilizer efficiency, keep good soil fertility, realize the carbon balance in soil.
Press such scheme, described lime stone main component is CaCO3, its content is more than 90%.
Press such scheme, the granularity requirements of described calcium magnesium phosphate, charcoal base manure, lime stone is below 60 orders.
Press such scheme, in described cadmium pollution soil, cadmium concentration is less than 2mg/kg, preferably 1-1.6mg/kg.
The application process of above-mentioned compound adjusting control agent, applies the ratio of the compound adjusting control agent of 5-20g according to every kilogram of soil, will answerClose passivator and apply described cadmium pollution soil, mix.
Principle of the present invention: the compound adjusting control agent of cadmium pollution soil repair of the present invention, by calcium magnesium phosphate, charcoal base manure andLime stone mixes in proportion and forms. Calcium magnesium phosphate raises soil pH can reduce Cd available state content in soil. In addition,The adsorbable divalence class heavy metal in insoluble phosphate surface in calcium magnesium phosphate, and form the similar Cd that solubility is very low3(PO4)2OHThe same mineral hard to tolerate, the simultaneously M in calcium magnesium phosphateg 2+、Ca2+Deng with Cd2+Antagonism, alleviated Cd2+The effect of poisoning,Thereby make the Cd in plant2+Content declines. Joining of calcium magnesium phosphate and biomass carbon, lime stone executed, and can obtain higher bluntChange effect, when wherein calcium magnesium phosphate and biomass carbon, lime stone mass ratio are about 10:5:1, effect is best. Its reason is except calcium baseOutside material works, be also organic adding in biomass carbon, a large amount of oxygen of decomposition and consumption makes soil in going back on the one handPrevious status may form the precipitations such as CdS, improves on the other hand middle the producing that microbial activity reduction soil Eh and its decomposition produceThing and heavy metal form stability complex compound and also obviously reduce cadmium activity, reduce plant it is absorbed. Using of biomass carbon, alsoThe function that be conducive to improve soil texture, regulates soil nutrient, coordinate plant growth. Execute the joining of lime stone and calcium magnesium phosphate passableForm stable Cd-CaO-P structural system with the available state Cd in soil, anti-leaching is strong, and heavy metal adsorption is strong. ExecutingAdd in the fixing situation of total amount, calcium magnesium phosphate and biomass carbon and or execute joining of lime stone, can also reduce the amount of application of phosphate fertilizerAnd prevent the phosphorus loss, the secondary pollution problems that excessively use phosphate fertilizer to cause.
Compared with prior art, the invention has the beneficial effects as follows:
The first, compound adjusting control agent of the present invention can effectively reduce available state Cd content in contaminated soil, can make dirtDye biologically effective state cadmium content decline 44.47%-86.53% in soil, the about 20-70% that declines of the cadmium content in victual,Also make soil pH value improve 0.6-1.7 simultaneously, have passivation heavy metal-polluted soil concurrently, repair acidified soil and improve soil fertility etc.Several functions, is mainly used in administering the agricultural land soil of vast heavy metal cadmium.
The second, raw material sources of the present invention are extensive, and preparation method is simple, Yi Hang, easy to use. Through pot experiment, vegetablesIn product, heavy metal cadmium content is lower than state food safety standard value, significant to Ensuring Food Safety, application prospectWide.
The 3rd, the charcoal base manure in the present invention adopts biomass energy stalk to process, and is a kind of new recyclingMethod, and it is nutritious, contains the required a great number of elements of vegetable growth, contributes to improve soil texture, increases soil nutrientEffect, improves the biomass of vegetables. So the present invention has very high economic benefit and Ecological Society effect.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but is not limitation of the present invention, all complying withAny this area of doing according to the disclosure of invention be equal to replacement, all belong to protection scope of the present invention.
The concentration of Cadmium in Soil concentration and Cadmium in Vegetables is all to use Analytik Jena AG to produceZEEnit700P type Atomic Absorption Spectrometer is measured, and measuring method is respectively standard of soil environment quality (GB15618-1995), the mensuration of cadmium in foods (GB/T5009.15-2003); PH in soil uses the limited public affairs of Ao Haosi instrument (Shanghai)The STARTER3100 type pH meter that department produces is measured.
In following embodiment, calcium magnesium phosphate, charcoal base manure, lime stone are marketable material, and granularity is all processed to 60 orders.The charcoal base fertilizer adopting in following embodiment, its carbon content is between 10%-30%; The lime stone CaCO adopting3Content existsMore than 90%.
Embodiment 1
Soil incubation test: the present embodiment adopts soil incubation experimental study the present invention to available Cd in cadmium pollution soilThe impact of passivation effect. Fundamental property for examination soil sees the following form shown in 1.
Table 1
The rice soil of cadmium pollution is contained in flowerpot and is tested, and test arranges 9 groups of tests, and the 1st group right as blankAccording to group. In the test of 2-9 group, calcium magnesium phosphate, charcoal base manure and lime in the compound adjusting control agent of the cadmium pollution soil repair of usingThe concrete proportioning of stone is as shown in table 2, and every group of test repeats 3 times, and data result is averaged.
Table 2
By the compound adjusting control agent of above-mentioned different proportionings, apply the ratio of the compound adjusting control agent of 10g according to every kilogram of soil, applyHold in the flowerpot of described cadmium pollution rice soil, fully mix, add deionized water by rice soil maximum water-holding capacity 60%,Add appropriate amount of deionized water to maintain this humidity every day later. Acquisition test soil after 28 days, carries out Cd available state containing measuringExamination, and carry out pH measurement, result of the test is as shown in table 3.
Table 3
| Test group number | pH | Initial soil cadmium available state concentration (ppm) | Cadmium in Soil available state concentration (ppm) after processing | Deactivation rate (%) |
| 1 | 6.53 | 0.3661 | / | / |
| 2 | 7.73 | 0.3661 | 0.1391 | 62.00 |
| 3 | 7.16 | 0.3661 | 0.2033 | 44.47 |
| 4 | 7.48 | 0.3661 | 0.0973 | 73.42 |
| 5 | 7.57 | 0.3661 | 0.0876 | 76.07 |
| 6 | 7.74 | 0.3661 | 0.1460 | 60.12 |
| 7 | 7.78 | 0.3661 | 0.1356 | 62.96 |
| 8 | 7.66 | 0.3661 | 0.0667 | 81.78 |
| 9 | 7.70 | 0.3661 | 0.0493 | 86.53 |
As shown in Table 3: use the compound adjusting control agent of the present invention on the impact of Cadmium in Soil available state significantly. With blank group the 1stGroup is compared, and uses adjusting control agent of the present invention and all can significantly reduce soil available Cd content. Especially the 9th group, when described regulation and controlWhen in agent, the mass ratio of calcium magnesium phosphate, charcoal base manure, lime stone is about 10:5:1, soil available Cd content is than blank groupReduce by 86.53%, pH and increased by 1.17.
Embodiment 2
The pot experiment of in-situ passivation: the present embodiment adopts pot experiment research the present invention to the acid-soluble state of cadmium in rice soilThe impact of passivation effect and vegetables absorption and accumulation cadmium, test arranges 8 groups of tests. Fundamental property for examination soil is shown in Table 1.
The compound adjusting control agent of cadmium pollution soil repair in the present embodiment, by mass percentage, it comprises calcium magnesium phosphate62.5%, charcoal base manure 31.25%, lime stone 6.25%.
Pakchoi test group
1.1, the paddy rice soil sample that takes 2.5Kg cadmium pollution is put into clean plastic flowerpot, and prepared by the present embodiment answersClose adjusting control agent and apply the ratio of 5g according to every kilogram of soil, apply in described rice soil, stir and fully mix, by rice soilMaximum water-holding capacity 60% adds deionized water, adds later every day appropriate amount of deionized water to maintain this humidity, stablize two weeks laggardThe sowing of row pakchoi. In sowing forward direction soil, add and analyze pure ammonium nitrate (calculating with N content 100mg/Kg) and potassium dihydrogen phosphate(calculating taking P content 80mg/Kg), as fertilizer, potted plant management is undertaken by greenhouse routine operation. After plant growth maturation, gather in workThing edible part, gathers pedotheque. Test repeats 3 times, results averaged.
1.2, be from the different of test group 1.1: compound adjusting control agent prepared by the present embodiment applies according to every kilogram of soilThe ratio of 10g, applies in the rice soil of described cadmium pollution.
1.3, be from the different of test group 1.1: compound adjusting control agent prepared by the present embodiment applies according to every kilogram of soilThe ratio of 20g, applies in the rice soil of described cadmium pollution.
1.4, be from the different of test group 1.1: do not use compound adjusting control agent prepared by the present embodiment.
Cabbage test group
2.1, take 2.5Kg paddy rice soil sample and put into clean plastic flowerpot, compound adjusting control agent prepared by the present embodimentApply the ratio of 5g according to every kilogram of soil, apply in the rice soil of described cadmium pollution, stir and fully mix, by rice soilMaximum water-holding capacity 60% adds deionized water, adds later every day appropriate amount of deionized water to maintain this humidity, stablize two weeks laggardThe sowing of row cabbage. The pure ammonium nitrate of interpolation analysis (calculating with N content 100mg/Kg) and potassium dihydrogen phosphate in sowing forward direction soil (withP content 80mg/Kg calculates) be fertilizer, potted plant management is undertaken by greenhouse routine operation. After plant growth maturation, gathering in crop canEdible part, gathers pedotheque. Test repeats 3 times, results averaged.
2.2, be from the different of test group 2.1: compound adjusting control agent prepared by the present embodiment applies according to every kilogram of soilThe ratio of 10g, applies in the rice soil of described cadmium pollution.
2.3, be from the different of test group 2.1: compound adjusting control agent prepared by the present embodiment applies according to every kilogram of soilThe ratio of 20g, applies in the rice soil of described cadmium pollution.
2.4, be from the different of test group 2.1: do not use compound adjusting control agent prepared by the present embodiment.
The data result of the present embodiment pakchoi test group and cabbage test group is as shown in table 4, known: use the present invention againClose adjusting control agent on cadmium content impact in the acid-soluble state of rice soil cadmium and pakchoi and cabbage body significantly. Meet the right of adjusting control agent with not executingCompare according to group, use adjusting control agent of the present invention and all can reduce acid-soluble state cadmium content in soil. Use soil after the compound adjusting control agent of the present inventionIn earth, acid-soluble state cadmium content has not reduced 8.82%-19.03% and 7.53%-21.71% than contrast component; In pakchoi, cadmium containsAmount has reduced 21.47%-60.73%, and soil pH value has increased 0.68-1.39; In cabbage, cadmium content has reduced 21.74%-70.65%, soil pH value has increased 0.60-1.24.
Table 4
Embodiment 3
The pot experiment of in-situ passivation: the present embodiment employing pot experiment research the present invention is blunt to the acid-soluble state of cadmium in red soilChange the impact of effect and vegetables absorption and accumulation cadmium, test arranges 8 groups of tests. Fundamental property for examination soil is shown in Table 5.
Table 5
The compound adjusting control agent of cadmium pollution soil repair in the present embodiment, by mass percentage, it comprises calcium magnesium phosphate62.5%, charcoal base manure 31.25%, lime stone 6.25%.
Pakchoi test group
3.1, take 2.5Kg red soil soil sample and put into clean plastic flowerpot, compound adjusting control agent prepared by the present embodimentApply the ratio of 5g according to every kilogram of soil, apply in the rice soil of described cadmium pollution, stir and fully mix, by rice soilMaximum water-holding capacity 60% adds deionized water, adds later every day appropriate amount of deionized water to maintain this humidity, stablize two weeks laggardThe sowing of row pakchoi. In sowing forward direction soil, add and analyze pure ammonium nitrate (calculating with N content 100mg/Kg) and potassium dihydrogen phosphate(calculating taking P content 80mg/Kg), as fertilizer, potted plant management is undertaken by greenhouse routine operation. After plant growth maturation, gather in workThing edible part, gathers pedotheque. Test repeats 3 times, results averaged.
3.2, be from the different of test group 1.1: compound adjusting control agent prepared by the present embodiment applies according to every kilogram of soilThe ratio of 10g, applies in the rice soil of described cadmium pollution.
3.3, be from the different of test group 1.1: compound adjusting control agent prepared by the present embodiment applies according to every kilogram of soilThe ratio of 20g, applies in the rice soil of described cadmium pollution.
3.4, be from the different of test group 1.1: do not use compound adjusting control agent prepared by the present embodiment.
Cabbage test group
4.1, take 2.5Kg red soil soil sample and put into clean plastic flowerpot, compound adjusting control agent prepared by the present embodimentApply the ratio of 5g according to every kilogram of soil, apply in the rice soil of described cadmium pollution, stir and fully mix, by rice soilMaximum water-holding capacity 60% adds deionized water, adds later every day appropriate amount of deionized water to maintain this humidity, stablize two weeks laggardThe sowing of row cabbage. The pure ammonium nitrate of interpolation analysis (calculating with N content 100mg/Kg) and potassium dihydrogen phosphate in sowing forward direction soil (withP content 80mg/Kg calculates) be fertilizer, potted plant management is undertaken by greenhouse routine operation. After plant growth maturation, gathering in crop canEdible part, gathers pedotheque. Test repeats 3 times, results averaged.
4.2, be from the different of test group 2.1: compound adjusting control agent prepared by the present embodiment applies according to every kilogram of soilThe ratio of 10g, applies in the rice soil of described cadmium pollution.
4.3, be from the different of test group 2.1: compound adjusting control agent prepared by the present embodiment applies according to every kilogram of soilThe ratio of 20g, applies in the rice soil of described cadmium pollution.
4.4, be from the different of test group 2.1: do not use compound adjusting control agent prepared by the present embodiment.
The data result of the present embodiment pakchoi test group and cabbage test group is as shown in table 6, known: use the present invention againClose adjusting control agent on cadmium content impact in the acid-soluble state of cadmium in red soil and pakchoi and cabbage body significantly. With do not execute contrasting of adjusting control agentGroup is compared, and uses adjusting control agent of the present invention and all can reduce acid-soluble state cadmium content in soil. Use soil after the compound adjusting control agent of the present inventionIn acid-soluble state cadmium content do not reduced 8.21%-18.89% and 5.31%-16.27% than contrast component; Cadmium content in pakchoiReduced 27.24%-63.42%, soil pH value has increased 0.70-1.64; In cabbage, cadmium content has reduced 31.36%-65.50%, soil pH value has increased 0.60-1.52.
Table 6
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent, as defined herein for those skilled in the art to the multiple amendment of these embodimentGeneral Principle can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments. Therefore, the present inventionTo can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty phase oneThe widest scope causing.
Claims (7)
1. a compound adjusting control agent for cadmium pollution soil repair, is characterized in that: by mass percentage, it comprises calcium magnesium phosphate45.45-66.70%, charcoal base manure 31.25-50%, lime stone 0-10%, by described calcium magnesium phosphate, charcoal base manure and lime stone in proportionMix and form.
2. the compound adjusting control agent of a kind of cadmium pollution soil repair according to claim 1, is characterized in that: described reparation cadmiumThe proportioning of the compound adjusting control agent of contaminated soil is: by mass percentage, it comprises calcium magnesium phosphate 62.50%, charcoal base manure31.25%, lime stone 6.25%.
3. the compound adjusting control agent of a kind of cadmium pollution soil repair according to claim 1, is characterized in that: described calcium magnesium phosphorusP in fertilizer2O5Mass content be 15%-20%.
4. the compound adjusting control agent of a kind of cadmium pollution soil repair according to claim 1, is characterized in that: described charcoalBase manure is charcoal base fertilizer, and its carbon content is 10%-30%.
5. the compound adjusting control agent of a kind of cadmium pollution soil repair according to claim 1, is characterized in that: described calcium magnesium phosphorusThe granularity requirements of fertilizer, charcoal base manure, lime stone is below 60 orders.
6. the compound adjusting control agent of a kind of cadmium pollution soil repair according to claim 1, is characterized in that: described cadmium pollutionCadmium in Soil concentration is less than 2mg/kg.
7. the application process of the compound adjusting control agent of a kind of cadmium pollution soil repair according to claim 1, is characterized in that:Apply the ratio of the compound adjusting control agent of 5-20g according to every kilogram of soil, compound adjusting control agent is applied to described cadmium pollution soil.
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