CN103936530A - Compound regulating agent for remediating cadmium-contaminated soil and application method of compound regulating agent - Google Patents
Compound regulating agent for remediating cadmium-contaminated soil and application method of compound regulating agent Download PDFInfo
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- CN103936530A CN103936530A CN201410176885.0A CN201410176885A CN103936530A CN 103936530 A CN103936530 A CN 103936530A CN 201410176885 A CN201410176885 A CN 201410176885A CN 103936530 A CN103936530 A CN 103936530A
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Abstract
The invention discloses a compound regulating agent for remediating cadmium-contaminated soil. The compound regulating agent is prepared by evenly mixing 45.45%-88.89% of calcium magnesium phosphate, 0-50% of carbon base fertilizer and 0-20% of limestone together in proportion. The compound regulating agent is capable of effectively reducing the content of effective-state Cd in the contaminated soil so that the biological effective-state cadmium content in the contaminated soil can be reduced by 44.47%-86.53%, the cadmium content in vegetable products can be reduced by about 20-70%, and meanwhile, the pH value of the soil also can be increased by 0.6-1.7; the compound regulating agent has functions of passivating heavy metals in the soil, remediating the acidized soil and improving the soil fertility, and thus can be mainly applied to treatment of vast heavy metal cadmium-contaminated farmland soil.
Description
Technical field
The invention belongs to contaminated soil recovery technique field, what more specifically relate to is a kind of compound adjusting control agent and application method thereof of restoring cadmium polluted agricultural land soil.
Background technology
Due to industrial develop rapidly, the problem of heavy metal cadmium soil is subject to the attention of countries in the world, and China's cadmium pollution problem is particularly outstanding.Heavy metal contamination be current contaminated area the widest, endanger one of maximum environmental problem, according to incompletely statistics, the heavy metal contamination cultivated area of China nearly 2.0 × 10
8hm
2, account for 1/5 of total area under cultivation, being wherein subject to cadmium pollution cultivated area is 1.33 × l0
4hm
2, relate to 11 and economize 25 areas.The cadmium pollution of paddy soil not only affects growth, grain yield and the quality of rice crop, but also will enter body by the direct or indirect mode of food chain relation, serious threat HUMAN HEALTH.Cadmium pollution environment event taking the sixties in last century ' itai-itai disease ' that Toyama County, Japan occurs for typical, event root is exactly that local people have eaten cadmium pollution rice, this time event makes japanese people suffer grievous injury, and Japanese government and enterprise have also paid huge economic cost for this reason.Therefore, the Sustainable development and the grain security that affect agriculture production are produced in paddy soil cadmium pollution.
Along with the raising of people's living standard, people more and more pay close attention to vegetables quality and safety problem.Cause the bad factor of vegetables quality a lot, it is the important root that causes vegetables quality safety problem that heavy metal content in soil exceeds standard.Hangzhou Vegetable Base heavy metal content in soil far exceedes local background value.Tianjin vegetable soil contents of heavy metal elements is higher than this city's agricultural soil background value more than one times.Nanning City's some Vegetable Bases soil pollutant is mainly cadmium.Part base, Yuhong District, Shenyang City oneself reach in, serious pollution.Also there is the slight pollution of different sorts heavy metal element Dongting Lake Area.Although there are some researches show heavy metal content in soil along with the growing vegetables time limit increases and increases to some extent, it is less, still particularly outstanding with cadmium pollution problem at present that Cadmium in Soil content increases variation with Planting Years.
The heavy metal contamination of soil has disguise, chronicity and irreversibility, and therefore, in the contaminated situation in farmland, it is to prevent that heavy metal contamination 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, because of its advantage such as easy, quick, efficient, is the better selection of repairing big area heavy metal contamination agricultural land soil.The present invention uses fused(calcium magnesium)phosphate, charcoal base manure and Wingdale mixing material, to reach the dual purpose of heavy metal-passivated cadmium and improvement soil.
Summary of the invention
Technical problem to be solved by this invention is compound adjusting control agent and the application method thereof that a kind of cadmium pollution soil repair is provided for the deficiency of above-mentioned prior art existence, compound adjusting control agent of the present invention can effectively reduce available Cd content in contaminated soil, effectively reduce the cadmium content in vegetable products, 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 fused(calcium magnesium)phosphate 45.45%-88.89%, charcoal base manure 0-50%, Wingdale 0-20%, and described fused(calcium magnesium)phosphate, charcoal base manure and Wingdale are mixed in proportion and formed.
Press such scheme, the optimum ratio of the compound adjusting control agent of described cadmium pollution soil repair is: by mass percentage, it comprises fused(calcium magnesium)phosphate 45.45-66.70%, charcoal base manure 31.25-50%, Wingdale 0-10%.This optimum ratio is suitable for the situation that cadmium pollution soil is agricultural land soil very much.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 fused(calcium magnesium)phosphate 62.50%, charcoal base manure 31.25%, Wingdale 6.25%, and the mass ratio of fused(calcium magnesium)phosphate, charcoal base manure 31.25% and Wingdale is about 10:5:1.This optimum ratio is especially suitable for the situation that cadmium pollution soil is Plantula Brassicae chinensis and bag vegetable field soil.
Press such scheme, P in described fused(calcium magnesium)phosphate
2o
5mass content be 15%-20%.Fused(calcium magnesium)phosphate, claims that again melting contains magnesium-phosphorus fertilizer, is a kind of sillico aluminate glass body that contains phosphate radical, and main component comprises Ca
3(PO
4)
2, CaSiO
3, MgSiO
3, be a kind of multi-element fertilizer, the aqueous solution is alkalescence, can improve acid soil, and fine as base fertilizer effect when cultivating large seedling, plant can slowly absorb required nutrient.
Press such scheme, described charcoal base manure is charcoal base fertilizer, and its carbon content is between 10%-30%.Charcoal base manure, a kind of taking biomass charcoal as matrix, according to different zones land characteristics, Different Crop growth characteristic and the principle that applies fertilizers scientifically, add organic matter or/and the formulated ecological environment-friendly type fertilizer of inanimate matter.Charcoal base manure is divided into three large base types: charcoal base fertilizer; Charcoal base inorganic fertilizer; Charcoal base composite organic-inorganic fertilizer (Chemical Mixed Fertilizer).Charcoal base fertilizer is the straw charcoal being produced after decomposing by wastes of crops stalk, as the base-material of fertilizer, and the fertilizer of producing, its main role is to have certain adsorption, execute in soil and can improve fertilizer efficiency, keep good soil fertility, realize the carbon balance in soil.
Press such scheme, described Wingdale main component is CaCO
3, its content is more than 90%.
Press such scheme, the granularity requirements of described fused(calcium magnesium)phosphate, charcoal base manure, Wingdale 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 method 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, composite passivant is applied to described cadmium pollution soil, mixes.
Principle of the present invention: the compound adjusting control agent of cadmium pollution soil repair of the present invention, is mixed in proportion and formed by fused(calcium magnesium)phosphate, charcoal base manure and Wingdale.Fused(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 fused(calcium magnesium)phosphate, and form the similar Cd that solubleness is very low
3(PO
4)
2the mineral hard to tolerate that OH is the same, the simultaneously M in fused(calcium magnesium)phosphate
g 2+, Ca
2+deng with Cd
2+antagonistic action, alleviated Cd
2+the effect of poisoning, thus make the Cd in plant materials
2+content declines.Joining of fused(calcium magnesium)phosphate and biomass charcoal, Wingdale executed, and can obtain higher passivation effect, and when wherein fused(calcium magnesium)phosphate and biomass charcoal, Wingdale mass ratio are about 10:5:1, effect is best.Its reason is except calcium base material works, also be organic adding in biomass charcoal, the a large amount of oxygen of decomposition and consumption makes soil may form the precipitations such as CdS in reduced state on the one hand, the intermediate product and the heavy metal formation stability complex compound that improve on the other hand microorganism active reduction soil Eh and its decomposition generation also obviously reduce cadmium activity, reduce plant it is absorbed.Using of biomass charcoal, also helps the function of improving Soil structure, regulating soil nutrient, coordinate plant growth.Execute the joining of Wingdale and fused(calcium magnesium)phosphate can with soil in available state Cd form stable Cd-CaO-P structural system, anti-leaching is strong, heavy metal adsorption is strong.Applying total amount fixing in the situation that, fused(calcium magnesium)phosphate and biomass charcoal and or execute joining of Wingdale, can also reduce the amount of application of phosphate fertilizer and 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:
First, 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 vegetable products 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.
The second, raw material sources of the present invention are extensive, and preparation method is simple, Yi Hang, easy to use.Through pot experiment, in vegetable products, heavy metal cadmium content is lower than state food safety standards value, significant to Ensuring Food Safety, has a extensive future.
The 3rd, the charcoal base manure in the present invention adopts biomass energy stalk to process, and is a kind of new resource utilization method, and it is nutritious, contain the required macroelement of vegetable growth, contribute to improve Soil structure, increase soil nutrient effect, improve the biomass of vegetables.So the present invention has very high economic benefit and Ecological Society effect.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not limitation of the present invention, all any this areas 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 that the ZEEnit700P type Atomic Absorption Spectroscopy AAS that uses Analytik Jena AG to produce is measured, and measuring method is respectively the mensuration (GB/T5009.15-2003) of standard of soil environment quality (GB15618-1995), cadmium in foods; PH in soil is that the STARTER3100 type pH meter that uses Ohaus Instrument (Shanghai) Co., Ltd. to produce is measured.
In following embodiment, fused(calcium magnesium)phosphate, charcoal base manure, Wingdale 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 Wingdale CaCO adopting
3content is more than 90%.
Embodiment 1
Soil incubation test: the present embodiment adopts the impact of soil incubation experimental study the present invention on available Cd passivation effect in cadmium pollution soil.Essential 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 as blank group.In the test of 2-9 group, in the compound adjusting control agent of the cadmium pollution soil repair of using, the concrete proportioning of fused(calcium magnesium)phosphate, charcoal base manure and Wingdale is as shown in table 2, and every group of test repeats 3 times, and data results 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, apply in the flowerpot that holds described cadmium pollution rice soil, fully mix, add deionized water by rice soil water retaining capacity 60%, add later every day appropriate amount of deionized water to maintain this humidity.Acquisition test soil after 28 days, carries out Cd available state content measuring, and carries out pH measurement, and test-results is as shown in table 3.
Table 3
| Test group number | pH | Primary 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.Compared with the 1st group of blank group, use adjusting control agent of the present invention and all can significantly reduce soil available Cd content.Especially the 9th group, in the time that the mass ratio of fused(calcium magnesium)phosphate, charcoal base manure, Wingdale in described adjusting control agent is about 10:5:1, soil available Cd content has reduced by 86.53%, pH than blank group and has increased by 1.17.
Embodiment 2
The pot experiment of in-situ passivation: the present embodiment adopts the pot experiment passivation effect of research the present invention on the acid-soluble state of cadmium in rice soil and the impact of vegetables absorption and accumulation cadmium, test arranges 8 groups of tests.Essential 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 fused(calcium magnesium)phosphate 62.5%, charcoal base manure 31.25%, Wingdale 6.25%.
Plantula Brassicae chinensis test group
1.1, the paddy rice soil sample that takes 2.5Kg cadmium pollution is put into clean plastic flowerpot, compound adjusting control agent prepared by the present embodiment applies the ratio of 5g according to every kilogram of soil, apply in described rice soil, stir and fully mix, add deionized water by rice soil water retaining capacity 60%, add appropriate amount of deionized water to maintain this humidity every day later, stablize after two weeks and carry out Plantula Brassicae chinensis sowing., as fertilizer, potted plant management is undertaken by greenhouse routine operation in sowing forward direction soil, to add analytical pure ammonium nitrate (calculating with N content 100mg/Kg) and potassium primary phosphate (calculating taking P content 80mg/Kg).After plant growth maturation, gather in crop edible part, gather 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 the ratio of 10g according to every kilogram of soil, apply 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 the ratio of 20g according to every kilogram of soil, apply 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 embodiment applies the ratio of 5g according to every kilogram of soil, apply in the rice soil of described cadmium pollution, stir and fully mix, add deionized water by rice soil water retaining capacity 60%, add appropriate amount of deionized water to maintain this humidity every day later, stablize after two weeks and carry out cabbage sowing., as fertilizer, potted plant management is undertaken by greenhouse routine operation in sowing forward direction soil, to add analytical pure ammonium nitrate (calculating with N content 100mg/Kg) and potassium primary phosphate (calculating taking P content 80mg/Kg).After plant growth maturation, gather in crop edible part, gather 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 the ratio of 10g according to every kilogram of soil, apply 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 the ratio of 20g according to every kilogram of soil, apply 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 results of the present embodiment Plantula Brassicae chinensis test group and cabbage test group is as shown in table 4, known: use the compound adjusting control agent of the present invention on cadmium content impact in the acid-soluble state of rice soil cadmium and Plantula Brassicae chinensis and cabbage body significantly.Compared with not executing the control group that meets adjusting control agent, use adjusting control agent of the present invention and all can reduce acid-soluble state cadmium content in soil.Use after the compound adjusting control agent of the present invention acid-soluble state cadmium content in soil and do not reduced 8.82%-19.03% and 7.53%-21.71% than contrast component; In Plantula Brassicae chinensis, cadmium content 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%, and soil pH value has increased 0.60-1.24.
Table 4
Embodiment 3
The pot experiment of in-situ passivation: the present embodiment adopts the pot experiment passivation effect of research the present invention on the acid-soluble state of cadmium in red soil and the impact of vegetables absorption and accumulation cadmium, test arranges 8 groups of tests.Essential 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 fused(calcium magnesium)phosphate 62.5%, charcoal base manure 31.25%, Wingdale 6.25%.
Plantula Brassicae chinensis 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 embodiment applies the ratio of 5g according to every kilogram of soil, apply in the rice soil of described cadmium pollution, stir and fully mix, add deionized water by rice soil water retaining capacity 60%, add appropriate amount of deionized water to maintain this humidity every day later, stablize after two weeks and carry out Plantula Brassicae chinensis sowing., as fertilizer, potted plant management is undertaken by greenhouse routine operation in sowing forward direction soil, to add analytical pure ammonium nitrate (calculating with N content 100mg/Kg) and potassium primary phosphate (calculating taking P content 80mg/Kg).After plant growth maturation, gather in crop edible part, gather 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 the ratio of 10g according to every kilogram of soil, apply 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 the ratio of 20g according to every kilogram of soil, apply 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 embodiment applies the ratio of 5g according to every kilogram of soil, apply in the rice soil of described cadmium pollution, stir and fully mix, add deionized water by rice soil water retaining capacity 60%, add appropriate amount of deionized water to maintain this humidity every day later, stablize after two weeks and carry out cabbage sowing., as fertilizer, potted plant management is undertaken by greenhouse routine operation in sowing forward direction soil, to add analytical pure ammonium nitrate (calculating with N content 100mg/Kg) and potassium primary phosphate (calculating taking P content 80mg/Kg).After plant growth maturation, gather in crop edible part, gather 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 the ratio of 10g according to every kilogram of soil, apply 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 the ratio of 20g according to every kilogram of soil, apply 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 results of the present embodiment Plantula Brassicae chinensis test group and cabbage test group is as shown in table 6, known: use the compound adjusting control agent of the present invention on cadmium content impact in the acid-soluble state of cadmium in red soil and Plantula Brassicae chinensis and cabbage body significantly.Compared with not executing the control group of adjusting control agent, use adjusting control agent of the present invention and all can reduce acid-soluble state cadmium content in soil.Use after the compound adjusting control agent of the present invention acid-soluble state cadmium content in soil and do not reduced 8.21%-18.89% and 5.31%-16.27% than contrast component; In Plantula Brassicae chinensis, cadmium content has reduced 27.24%-63.42%, and soil pH value has increased 0.70-1.64; In cabbage, cadmium content has reduced 31.36%-65.50%, and 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 for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. the compound adjusting control agent of a cadmium pollution soil repair, it is characterized in that: by mass percentage, it comprises fused(calcium magnesium)phosphate 45.45%-88.89%, charcoal base manure 0-50%, Wingdale 0-20%, and described fused(calcium magnesium)phosphate, charcoal base manure and Wingdale are mixed in proportion and formed.
2. the compound adjusting control agent of a kind of cadmium pollution soil repair according to claim 1, it is characterized in that: the proportioning of the compound adjusting control agent of described cadmium pollution soil repair is: by mass percentage, it comprises fused(calcium magnesium)phosphate 45.45-66.70%, charcoal base manure 31.25-50%, Wingdale 0-10%.
3. the compound adjusting control agent of a kind of cadmium pollution soil repair according to claim 1, it is characterized in that: the proportioning of the compound adjusting control agent of described cadmium pollution soil repair is: by mass percentage, it comprises fused(calcium magnesium)phosphate 62.50%, charcoal base manure 31.25%, Wingdale 6.25%.
4. according to the compound adjusting control agent of any one cadmium pollution soil repair described in claim 1-3, it is characterized in that: P in described fused(calcium magnesium)phosphate
2o
5mass content be 15%-20%.
5. according to the compound adjusting control agent of any one cadmium pollution soil repair described in claim 1-4, it is characterized in that: described charcoal base manure is charcoal base fertilizer, and its carbon content is 10%-30%.
6. according to the compound adjusting control agent of any one cadmium pollution soil repair described in claim 1-5, it is characterized in that: the granularity requirements of described fused(calcium magnesium)phosphate, charcoal base manure, Wingdale is below 60 orders.
7. according to the compound adjusting control agent of any one cadmium pollution soil repair described in claim 1-6, it is characterized in that: in described cadmium pollution soil, cadmium concentration is less than 2mg/kg.
8. according to the application method of the compound adjusting control agent of any one cadmium pollution soil repair described in claim 1-7, it is characterized in that: apply the ratio of the compound adjusting control agent of 5-20g according to every kilogram of soil, composite passivant is applied to described cadmium pollution soil.
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