CN104119924A - Soil heavy metal repairing agent and application thereof to highly contaminated soil - Google Patents

Soil heavy metal repairing agent and application thereof to highly contaminated soil Download PDF

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Publication number
CN104119924A
CN104119924A CN201310677304.7A CN201310677304A CN104119924A CN 104119924 A CN104119924 A CN 104119924A CN 201310677304 A CN201310677304 A CN 201310677304A CN 104119924 A CN104119924 A CN 104119924A
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soil
heavy metal
application
lentinan
plant
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何其明
国锦琳
杨锡良
廖立群
詹绍军
姜勇
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Chengdu NewSun Crop Science Co Ltd
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Chengdu NewSun Crop Science Co Ltd
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  • Processing Of Solid Wastes (AREA)
  • Fertilizers (AREA)
  • Cultivation Of Plants (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides an application of a repairing composition used in heavy metal contamination of soil. The composition comprises lentinan and chitosan and can be used for improving the growth situations and/or quality of plants such as bitter gourds and the like on the soil highly contaminated by heavy metals. Besides, the invention also provides a preparation and the like based on the composition.

Description

Heavy metal-polluted soil renovation agent and the application to high pollution soil thereof
Technical field
The invention belongs to Pollutant Treatment field and agricultural composition field, particularly, the Selective repair agent that the present invention relates to heavy metal pollution of soil with and the application of high pollution soil.
Background technology
In recent years, the heavy metal pollution problem of China's soil shows especially day by day, and ecotope, food safety and HUMAN HEALTH have been formed to serious threat, can not be ignored.Waste gas, waste water, the waste residue of the industrial discharges such as dyestuff, chemical industry, process hides, exploitation of mineral resources, smelting and processing contain a large amount of heavy metals, by pouring water, the modes such as (particularly dirty filling), solid waste (mud, rubbish etc.) accumulation and atmospheric precipitation enter soil, cause heavy metal in soil content to increase, especially the heavy metal of exchangeable species, directly, by farm crop are absorbed, enrichment, directly threaten HUMAN HEALTH.
At present, carry out rehabilitating soil by chemical process, mainly based on heavy metal chelant, as chitosan, make the heavy metal of the exchangeable species in soil change the heavy metal of stable state into, reduce the absorbed dose of farm crop to heavy metal, thereby play the effect of administering heavy metal pollution of soil.
For example, Chinese patent 200310108910 discloses the chemical regulator of administering soil pollution, and it is low-molecular weight chitoglycan, but the inventor finds, it has very strong complex ability to metallic zinc, and administers when soil pollution and mainly use as eluent;
Chinese patent 200910115020 discloses the method for soil remediation, by excavating fluid injection well and constructing reaction wall, chitosan leacheate is injected to soil inside, but inventor's discovery, and this mode quantities is large, uses inconvenience, is difficult to promote;
Chinese patent 201110413145 discloses the method for remediating heavy metal cadmium pollution soil, utilizes the microorganism of heavy metal cadmium in tobacco bred, chitosan solution and the activating soil of resistance to cadmium to carry out acting in conjunction, but its applicable surface is narrow and be difficult to repeat implement;
Chinese patent 201210231422 discloses heavy metal adsorption flocculation agent, and it is the acidic aqueous solution of chitosan and sophorolipid, although finally can soil protection environment, but be for the heavy metal of adsorbed water body in essence.
According to the inventor's the experience that studies for a long period of time and grope to obtain, first find, the heavy metal chelant of existing wide spectrum not only adsorbs the harmful heavy metals such as lead in soil, chromium, cadmium, and can adsorb to fall the very useful element on the most non-rich zinc of China farmland such as ZINC IN SOIL, cause the underproduction, make the heavy metal chelant actual effect of existing wide spectrum very bad; Secondly find, make up by adding zinc fertilizer, by greatly reducing the efficiency of the harmful heavy metals such as the heavy metal chelant Adsorption of Lead, chromium, cadmium of existing wide spectrum, in conventional zinc fertilizer, also contain a certain amount of harmful heavy metal, so excessive use zinc fertilizer does not have realistic meaning in addition; Also find, the major ingredient of the means of using effect, especially eluent that also greatly impact is applied is water, will expend a large amount of manpowers and spray, very inconvenient.Through inventor's painstaking efforts, in conjunction with some fortune that God helps those who help themselves, make us being extremely surprised to find that the composite upper lentinan of chitosan, can optionally adsorb to fall the harmful heavy metal such as chromium, cadmium in soil, especially the harmful heavy metal of exchangeable species, and substantially do not affect the zinc content in soil, and keep the zinc fertilizer power of soil, be particularly useful for planting the farmland use of the plants such as tea tree.
And in the prior art, the composition that comprises chitosan and lentinan is for people's pharmaceutical composition aspect, the mushroom polysaccharide chitosan nanoparticle with antitumor action and immuno-potentiation as disclosed in Chinese patent 200910154959, with the disclosed bioactive polysaccharide self-assembly modified material with anti-microbial activity and cell compatibility of Chinese patent 201010112065, do not use in agricultural land soil as agricultural composition, and the cost of these prior aries is high, also cannot serve as agricultural composition commercial application in agricultural land soil.
Along with the recent inventor constantly obtains new test-results, find unexpectedly again, even for the soil of height heavy metal contamination, agricultural composition of the present invention is except reducing the heavy-metal residual in plant materials, improve outside plant quality, can also effectively alleviate the suffered coercion of plant-growth, improve vegetation growth state, making to make full use of the normal planting plants of some soil that are subject to heavy metal contamination (especially polluting is not very serious soil) becomes possibility.
Summary of the invention
The technical problem to be solved in the present invention is the soil selectivity heavy metal remediation composition capable that provides new or the preparation that comprises it improving the growing state of plant on the highly polluted soil of heavy metal and/or the application in quality.Optionally chromium and/or cadmium pollution in rehabilitating soil of new soil-repairing agent provided by the invention (soil conditioner), the chromium and/or the cadmium that improve the plant of planting are residual, but simultaneously substantially do not reduce the zinc content in soil, do not reduce the useful plant quality of zinc institute energy.In addition, the present invention also provides the application of this soil-repairing agent, comprises soil remediation (conditioning), planting plants and improves the application of the aspects such as plant quality.
Particularly, in first aspect, the invention provides soil selectivity heavy metal remediation composition capable, it comprises lentinan and chitosan.In inventor's research, chance on the composite of lentinan and chitosan, optionally chromium and/or cadmium pollution in rehabilitating soil, the chromium and/or the cadmium that improve the plant of planting are residual, but substantially do not reduce the zinc content in soil simultaneously, are a significant benefit to and apply.In this article, as indicated without contrary, term " reparation " can exchange and use with " conditioning ", refers to the residual quantity that reduces heavy metal in soil, especially reduce the residual quantity of the heavy metal of exchangeable species in soil, thereby reduce the biological effectiveness (availability) of heavy metal.
Because heavy metal exists with stable state and these two kinds of forms of exchangeable species in soil, the former is difficult to discharge by plant utilization, substantially can not cause the residual of heavy metal in plant; And the latter is due to its biological effectiveness, be the arch-criminal of Accumulation of heavy metals in plant, its mobility in addition, so the heavy metal of exchangeable species is the object of repairing.So in this article, the reparation of heavy metal pollution of soil refers to the heavy metal that reduces exchangeable species in soil.In this article, as indicated without contrary, term " heavy metal " and concrete heavy metal, what refer to is all heavy metals of corresponding exchangeable species.For the heavy metal in plant, be all considered to be exchangeable species.
The composition of first aspect present invention can also comprise other and be of value to the renovation agent that heavy metal-polluted soil is repaired, as metallo-chelates such as EDTA, but the effect of the Selective repair of the composition of first aspect present invention is pretty good, for the consideration on cost, can no longer comprise other renovation agents.Therefore preferred, the composition of first aspect present invention is made up of lentinan and chitosan.
Preferably in the composition of first aspect present invention, lentinan: the weight ratio of chitosan is 5 ~ 100:1 ~ 25, is preferably 10 ~ 60:2 ~ 15, more preferably 15 ~ 40:3 ~ 10, are more preferably 20 ~ 30:5 ~ 8, most preferably are 25:6.5.
Chitosan, comprises small molecules amount chitosan and the crosslinked macromolecule chitosan etc. of degraded, has reported for work for the reparation of soil.Existing research is more, and corresponding comparative maturity (as described in Chinese patent 01107664) of products production, from the chitosan of pharmaceutical grade, the chitosan of food grade, chitosan to technical grade has, so can buy from the market the inexpensive chitosan product that is applicable to the present invention's needs.In the present invention, chitosan is preferably non-pharmaceutical grade chitosan, also nonfood grade chitosan preferably.In the specific embodiment of the present invention, chitosan is the chitosan purchased from the high molecular of Qi Mei bio tech ltd, Chengdu (100kDa), although do not have the heavy metal joint efficiency of the low-molecular weight chitoglycan that now technical popular degraded obtains afterwards high, can be competent at completely with lentinan composite and work in coordination with the residual of exchangeable species heavy metal in reduction soil.
In the present invention, lentinan is non-pharmaceutical grade lentinan, also nonfood grade lentinan preferably.Lentinan, existing research is mainly used in health care, and at present commercially available product is the lentinan (as described in Chinese patent 92109345) of food grade and even pharmaceutical grade substantially, does not have the industrial applicability in field under the present invention on cost.So, in the specific embodiment of the present invention, lentinan is (as sporophore, mycorhiza, stem or their combination by edible mushrooms, preferably edible mushrooms entirety or mycorhiza, stem) hold back through immersion extraction, ultrafiltration the lentinan of preparing with concentrate drying,, the preparation method of this lentinan comprises the steps or is made up of following steps:
(1) soak edible mushrooms (as sporophore, mycorhiza, stem or its entirety, preferably edible mushrooms entirety or mycorhiza, stem) the extraction of pulverizing, preferably in the water of 70 ~ 95 DEG C, soak the edible mushrooms of pulverizing and extract reservation clear liquid;
(2) clear liquid is carried out to ultrafiltration, hold back high molecular weight product, as be not less than the product of 10kDa, be preferably not less than the product of 20kDa, be more preferably not less than the product of 30kDa; With,
(3) concentrate and be dried.
In this article, term " pharmaceutical " refers to the medical applications taking human or animal as object.Medicinal product and product agricultural or that agricultural chemicals is used are that technical field is distinguished huge variant production completely, and those skilled in the art in the invention can not produce and anyly obscure.In this article, preferably material used (as, chitosan and/or lentinan) foreign matter content higher than the high limit standard of pharmaceutical products or food, and/or homogeneity (purity) is lower than the lower bound standard of pharmaceutical products or food.
 
In second aspect, the invention provides selectivity soil heavy metal preparation for repairing, the composition that it comprises first aspect present invention and agricultural acceptable auxiliary material.In this article, term " agricultural acceptable auxiliary material " refers to the agricultural complementary material of permission that does not affect agricultural active material performance effect.Agricultural acceptable accessory package is containing pH adjusting agent, weighting agent, solvent, solubility promoter, emulsifying agent, dispersion agent, co-emulsifier, frostproofer, defoamer, thickening material, stablizer and/or binding agent.
Preferably, in the preparation of second aspect present invention, pH adjusting agent is alkaline pH mediator agent, as one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.
In this article, weighting agent can exchange and use with carrier, can be one or more in kaolin, light calcium carbonate, white carbon black, montmorillonite, diatomite, clay, atlapulgite, nakrite, talcum powder, rice husk, corncob cellulose and the peat composed of rotten mosses conventionally.
Preferably the preparation of second aspect present invention comprises pH adjusting agent and/or weighting agent, as comprises salt of wormwood and/or the peat composed of rotten mosses.In the specific embodiment of the present invention, the agricultural acceptable auxiliary material in said preparation is made up of salt of wormwood and the peat composed of rotten mosses.
Preferably the preparation of second aspect present invention is solid preparation, as pulvis.Inventor's discovery, the preparation of second aspect present invention can be used as solid preparation and spreads fertilizer over the fields, and still can reach effect that soil selectivity heavy metal is repaired.This is with respect to tank solution preparation of the prior art, can reduce solvent shared spill in a large number, the amount of spraying, for the continuous downward trend of China's rural area working population, advantage is more obvious.
More preferably in the preparation of second aspect present invention, the composition of first aspect present invention: pH adjusting agent: the weight ratio of weighting agent is 5 ~ 100:1 ~ 10:10 ~ 500, be preferably 10 ~ 60:2 ~ 8:25 ~ 100, more preferably 20 ~ 40:3 ~ 7:45 ~ 80, be more preferably 25 ~ 35:4 ~ 6:55 ~ 70, most preferably be 31.5:5:63.5.
 
In the third aspect, the application of the composition that the invention provides first aspect present invention in rehabilitating soil cadmium and/or pollution of chromium; And/or, the application of the composition that first aspect present invention is provided in the preparation for the preparation of rehabilitating soil cadmium and/or pollution of chromium (preferably said preparation is the preparation of second aspect present invention); And/or, the application of the preparation that second aspect present invention is provided in rehabilitating soil cadmium and/or pollution of chromium.
Preferably, in the application of third aspect present invention, reparation is Selective repair.In this article, term " selectivity " refers to (reducing soil pollution residual) to liking the harmful heavy metals such as cadmium and/or chromium, instead of it has been generally acknowledged that the useful heavy metals such as the zinc useful to plant.This is all that non-rich zinc soil is useful especially for the vast farmland of China.Certainly, the composition of first aspect present invention or the preparation of second aspect present invention also have certain effect to rehabilitating soil Lead contamination.
In fourth aspect, the application in the plant of the composition that the invention provides first aspect present invention on planting soil; And/or, the application of the composition of first aspect present invention in the preparation of the plant for the preparation of on planting soil (preferably said preparation is the preparation of second aspect present invention) is provided; And/or, the application in the plant of the preparation that second aspect present invention is provided on planting soil.
Preferably in the application of fourth aspect present invention, plant is the plant that plant edible or medicinal part are easy to accumulate cadmium and/or chromium, be the plant of growth and development of plants to cadmium and/or pollution of chromium sensitivity, and/or be the plant that zinc is useful to plant, as paddy rice, tea tree etc.In the specific embodiment of the present invention, plant is tea tree.
Aspect the 5th, the invention provides the composition of first aspect present invention in the application improving in the plant quality of planting on soil; And/or the composition that first aspect present invention is provided is in the application for the preparation of improving in the preparation (preferably said preparation is the preparation of second aspect present invention) of the plant quality of planting on soil; And/or, provide the preparation of second aspect present invention in the application improving in the plant quality of planting on soil.
Preferably in the application of fifth aspect present invention, plant quality is the quality of cadmium and/or chromium residues in plant.Certainly, the composition of first aspect present invention or the preparation of second aspect present invention also have certain effect to improving plumbous residual quality in plant.Also preferred in the application of fifth aspect present invention, plant quality is the tea leaf quality of tea tree.In the specific embodiment of the present invention, improve tea leaf quality and refer to and under the prerequisite that does not affect the quality such as aminoacids content and caffeine content, reduce the residual of cadmium and/or chromium (and/or plumbous).
Preferably, in the application aspect the present invention the 3rd, the 4th and/or the 5th, soil is non-rich zinc soil.Such soil distributes very wide in China, can more embody the advantage that selectivity of the present invention is brought.
Although the present invention is to still old certain effect of lead, because remediation efficiency is lower, therefore, in preferred application aspect the present invention the 3rd, the 4th and/or the 5th, unless soil is also the soil of cadmium and/or pollution of chromium simultaneously, otherwise soil is non-lead pollution of soil.
Preferably in the application aspect the present invention the 3rd, the 4th and/or the 5th, application is directly to the application of (as, pulvis) of soil application solid preparation.As described above, for the continuous downward trend of China's rural area working population, advantage is more obvious.
In the inventor's research, find unexpectedly, the composition of the present invention of middle dosage or preparation are even better than high dosage to the reduction effect of cadmium in plant materials and/or chromium residues, although soil remediation presents certain dose-effect proportional relation, but cost is considered in addition, using especially of middle dosage has superiority.Therefore in preferred application aspect the present invention the 3rd, the 4th and/or the 5th, application is the 8 ~ 15kg/ mu (preferably 9 ~ 14kg/ mu in lentinan, more preferably 10 ~ 13kg/ mu, is more preferably 10.5 ~ 12kg/ mu, most preferably 11.25kg/ mu) dosage to the application of soil application.In this article, the amount of application that term " in lentinan " refers to composition of the present invention or preparation calculates with the amount of application of lentinan, and not only uses lentinan.
 
Aspect the 6th, be also the most important aspect of the present invention, the composition that the invention provides first aspect present invention is improving the growing state of plant on the highly polluted soil of heavy metal and/or the application in quality; And/or, provide the composition of first aspect present invention in the application for the preparation of improving in the growing state of plant on the highly polluted soil of heavy metal and/or the preparation of quality (preferably said preparation is the preparation of second aspect present invention); And/or the preparation that second aspect present invention is provided is improving the growing state of plant on the highly polluted soil of heavy metal and/or the application in quality.
Preferably, in the application of sixth aspect present invention, heavy metal is cadmium and/or chromium, preferably chromium.Inventor's discovery, the heavy metal (the especially heavy metal of high density) in soil, except meeting causes heavy metal contamination in plant materials, affects plant quality, also can produce coercion to plant, affects plant-growth, causes the plant underproduction, even total crop failure.The composition of first aspect present invention and preparation thereof can significantly be alleviated the coercion of heavy metal on plants, improve the growing state of plant.
Preferably in the application of sixth aspect present invention, heavy metal is highly polluted is that heavy metal content is greater than 30mg/kg soil (earth), is preferably greater than 50mg/kg soil (earth), more preferably greater than 80mg/kg soil (earth), more preferably greater than 120mg/kg soil (earth), as be 150mg/kg soil (earth).For the sake of clarity, the upper limit of the highly polluted heavy metal content of heavy metal can be to be no more than 200mg/kg soil (earth), as is no more than 180mg/kg soil (earth).The growth that it is the upper plant of 150mg/kg soil (earth) that embodiments of the invention have proved at heavy metal content improves, and therefore the application on more oligosaprobic soil of the composition of first aspect present invention and preparation thereof is also predictable.
Preferably, in the application of sixth aspect present invention, growing state is survival rate and/or plant height; Preferred in addition in the application of sixth aspect present invention, quality is residual quantity of heavy metal, and improving quality is to reduce residual quantity of heavy metal.
In the application of sixth aspect present invention, plant can be non-edible plant, as forest, for plant or the ornamental plant etc. of papermaking or industrial abstract.For food plant, plant can be the less plant of amount, as balsam pear.Certainly, if on more oligosaprobic soil planting plants, even if a large amount of edible plant is also fine.In addition, inventor's discovery, balsam pear is very strong to the accumulation ability of the heavy metals such as the chromium in soil, can absorb more heavy metal in its plant body, so plantation balsam pear itself also contributes to the heavy metal reparation to soil.As long as can be by the growth of this plant of composition for improved of the present invention, a large amount of plantations also can enrichment be fallen the heavy metal in soil.Therefore, preferably, in the application of sixth aspect present invention, plant is balsam pear.
 
Beneficial effect of the present invention is mainly that composition of the present invention or preparation have selective advantage: chromium and/or cadmium in rehabilitating soil (and/or plumbous) pollute, the chromium and/or the cadmium (and/or plumbous) that improve the plant of planting are residual, and have the effect of synergy; Simultaneously substantially do not reduce the zinc content in soil, do not reduce the useful plant quality of zinc institute energy, be conducive to the popularization on the agricultural land soil of the vast non-rich zinc of China.That is, the amount of application that selective advantage on the one hand can potential minimizing zinc fertilizer, has improved the remediation efficiency that soil Cr and/or cadmium (and/or plumbous) are polluted on the other hand, and the requirement of realistic application, is convenient to promote.In addition, beneficial effect of the present invention is also: composition of the present invention or preparation can, with solid preparation form directly to soil application, can alleviate and use required labor force and cost; Composition of the present invention or preparation are preferably used with the amount of application of non-high dosage, can alleviate and use required labor force and cost, also can reduce the cost of product storage and transport; The preferred composition of the present invention or preparation production cost are low, are more conducive to promote the use of in the wide agricultural land soil of China.For what is more important of the present invention, can be used for improving growing state and/or the quality of plant on the highly polluted soil of heavy metal, contribute for making full use of the limited land resources of China.
 
For the ease of understanding, below will be described in detail the present invention by specific embodiment.It needs to be noted, these descriptions are only exemplary descriptions, do not form limitation of the scope of the invention.According to the discussion of this specification sheets, many variations of the present invention, change have been all obviously concerning one of ordinary skill in the art.In addition, the open source literature that the present invention quotes is in order more clearly to describe the present invention, and their full text content is all included in and carried out reference herein, just looks like that repeated description is excessively the same in this article for their full text.
 
Embodiment
By specific embodiment, the present invention is carried out to exemplary description below, if any not using up part, can be with reference to corresponding laboratory manual, equipment and the operation instruction of reagent and the relevant guide standard of the Ministry of Agriculture.
 
The preparation of embodiment 1 soil-repairing agent of the present invention
Chitosan (Qi Mei bio tech ltd, Chengdu) and lentinan that soil-repairing agent of the present invention contains all can adopt commercially available product, but preferably wherein the lentinan of large usage quantity can be according to following method preparation, make its cost lower, be more suitable for applying.
(1) preparation of lentinan
Get mushroom fruiting body and pulverize, cross 30 mesh sieves, get particle that the powder 200kg(that can sieve can not sieve and return pulverizer and pulverize), add 1000L water to soak 1 hour in 80 DEG C, stir during this time, then filter and retain clear liquid; The residue once soaking adds 1000L water in 80 DEG C of immersions 1 hour, stirs during this time, then filters and retains clear liquid; The residue that secondary soaks adds 1000L water in 80 DEG C of immersions 1 hour, stirs during this time, then filters and retains clear liquid.Merge above-mentioned clear liquid, the Hollow Fiber Ultrafiltration system that is 30kDa by molecular weight cut-off (can be purchased from Millipore company of the U.S., Biomax-30) ultrafiltration, the part that obtains holding back is concentrated into 1/10th volumes through dual-effect concentrator (can purchased from Shaanxi Chang Tai Industrial Co., Ltd.), then be dried to water content through vacuum drier (can purchased from Shaanxi Chang Tai Industrial Co., Ltd.) and be not more than 10%(w/w), obtain lentinan of the present invention.
(2) preparation of soil-repairing agent
Get lentinan 25kg and chitosan 6.5kg, add salt of wormwood (as pH adjusting agent, can be purchased from Zhengzhou Lan Yu fine product Chemical Co., Ltd.) powder 5kg, after mixing, adding the peat composed of rotten mosses (is peat, as weighting agent, can praise gloomy garden spot purchased from Pixian County) 63.5kg, mix, pack, obtains soil-repairing agent of the present invention (pulvis).
In addition, get chitosan 6.5kg, add potassium carbonate powder 5kg, after mixing, add peat composed of rotten mosses 88.5kg, mix, as positive control 1; Get lentinan 25kg, add potassium carbonate powder 5kg, after mixing, add peat composed of rotten mosses 70kg, mix, as positive control 2; Get potassium carbonate powder 5kg and peat composed of rotten mosses 95kg, mix, as negative control.
 
The research of embodiment 2 soil-repairing agent of the present invention to heavy metal-polluted soil reparation and plant quality improvement
Entrust Inst. of Soil Fertilizer, Sichuan Academy of Agriculture Science to carry out field test in Pujiang County in the tea place of No. 9 kinds of plantation river tea, while starting to test, directly in the plot of random packet, spread fertilizer over the fields following soil-repairing agent or contrast, and the covering of digging, all the other are with reference to tea place Routine Management:
A, negative control group: negative control, 90kg/ mu;
B, positive controls 1: positive control 1,90kg/ mu;
C, positive controls 2: positive control 2,90kg/ mu;
D, low dosage experimental group: soil-repairing agent of the present invention, 22.5kg/ mu;
E, middle dosage experiments group: soil-repairing agent of the present invention, 45kg/ mu;
F, high dosage experimental group: soil-repairing agent of the present invention, 90kg/ mu.
After on-test 90 days, get each group of soil and carry out metal element analyse; After on-test 150 days (being the tea picking phase), pluck tealeaves and carry out heavy metal element and quality parameter analysis.
Heavy metal-polluted soil analytical results is as shown in table 1:
Not tea garden soil Analysis of Heavy Metal result table on the same group of table 1
Result shows, chitosan can non-selectively reduce separately the content of the heavy metal of exchangeable species in soil, uses with heavy dose, can both reduce approximately 10% left and right to lead, cadmium, chromium and zinc; Lentinan does not have rule to the reduction effect of heavy metal in soil separately, does not substantially affect the content of plumbous and zinc, but can reduce the content of chromium and cadmium.Unexpectedly, the composition of chitosan and lentinan, can optionally significantly reduce the content of chromium and cadmium, and the reduction effect of middle dosage is even better than the summation that heavy dose of chitosan and lentinan are used separately, and it is collaborative that to reduce effect obvious; And said composition does not affect the zinc content in soil substantially, and zinc is highly profitable to tea tree.So although said composition has also weakened the plumbous adsorptive power to exchangeable species in soil in the lump, it is to non-Lead contamination but the advantage of the soil of chromium and/or cadmium pollution is fairly obvious.
In tealeaves, the analytical results of heavy metal and quality parameter is as shown in table 2:
The not heavy metal of tealeaves and the analytical results table of quality parameter on the same group of table 2
Result shows, chitosan can non-selectively reduce separately the residual quantity of the harmful heavy metal in tealeaves, uses with heavy dose, can both reduce approximately 10% left and right to plumbous, cadmium and chromium; Lentinan does not have rule to the reduction effect of harmful heavy metal in tealeaves separately, and it does not affect plumbous content substantially, but can reduce the residual quantity of chromium and cadmium.Unexpectedly, the composition of chitosan and lentinan, can optionally significantly reduce the residual quantity of chromium and cadmium, there is the collaborative effect that reduces, more surprisingly, the reduction effect of middle dosage is even better than the effect that heavy dose is used, and this awaits further research; And said composition, owing to substantially not affecting the content to the useful zinc of tea tree in soil, does not therefore reduce other quality parameter of tealeaves substantially, even part has slight rising; And use separately chitosan, owing to having reduced the zinc of the exchangeable species in soil, cause amino acid and the trimethyl-xanthine etc. of tealeaves be subject to other quality parameter that zinc affects decline 10% left and right even more than.So, said composition has very significantly effect to chromium and/or cadmium residual quantity in reduction plant, also there is certain effect to reducing lead content, and more rare be, this is to realize under the condition that does not reduce the quality parameter such as Amino Acids in Tea and trimethyl-xanthine that even increased, and is very beneficial for application; In addition, the effect that middle dosage is used is in general obvious, especially high dosage after using, can increase on the contrary in tealeaves every with the residual index of chromium, in conjunction with cost consideration, therefore composition of the present invention is preferably used tea place with 45kg/ mu (chitosan 2.925kg/ mu+lentinan 11.25kg/ mu).
 
Embodiment 3 soil-repairing agent of the present invention is to planting the research of balsam pear on the soil of height heavy metal contamination
Entrust Chengdu University of Technology to carry out indoor pot experiment, the long white Varieties of Balsam Pear of plantation (purchased from Sichuan Academy of Agricultural Sciences).Test soil is taken from farmland, San Shenghua township, Chengdu, Sichuan, and wherein Cr content is 5.2mg/kg after testing, and Cd content is 0.04mg/kg, is the good soil that is not subject to heavy metal contamination; For the soil of simulated altitude heavy metal contamination, by CrCl 3be dissolved in hot water, evenly add in above-mentioned soil, make Cr content reach 150mg/kg, and be substantially exchangeable species.Soil-repairing agent or contrast below directly inciting somebody to action in the basin of random packet while starting to test are admixed in corresponding soils, then transplant balsam pear seedling:
A, pollution-free control group: be not subject to the soil of heavy metal contamination, do not admix soil-repairing agent of the present invention;
B, pollutes control group: the soil of height heavy metal contamination, do not admix soil-repairing agent of the present invention;
C, low dosage experimental group: the soil of height heavy metal contamination, admix soil-repairing agent 10g/kg soil of the present invention;
D, high dosage experimental group: the soil of height heavy metal contamination, admix soil-repairing agent 20g/kg soil of the present invention.
After on-test 90 days, whole strain balsam pear plant is gathered in the crops, measure after growth indexes, clean surface and also weigh, in 70 DEG C of oven dry, then measure respectively heavy metal content.
The analytical results of the growth indexes of balsam pear and wherein heavy metal content is as shown in table 3:
The not heavy metal of balsam pear and the analytical results table of quality parameter on the same group of table 3
Result shows, even the soil for pollution of chromium up to 150mg/kg, the composition of chitosan of the present invention and lentinan also can significantly reduce the chromium residues amount in balsam pear, even use with low dosage, also can reduce chromium residues amount more than 20%, along with the rising of amount of application, chromium residues amount also reduces thereupon; Pollution of chromium has on the growth of balsam pear the impact of coercing, and shows that plant yellow, survival rate reduce and plant is short and small upper, and wherein, in the time not using soil-repairing agent of the present invention, survival rate reduces approximately 17%, and the plant height half that almost declined; And used soil-repairing agent of the present invention, and can significantly alleviate the impact of pollution of chromium, improve survival rate and plant height and effect and amount of application correlation.
Although this experiment is to carry out on the soil of high pollution, can significantly alleviate the impact of heavy metal contamination on plant-growth for abundant demonstration soil-repairing agent of the present invention, those skilled in the art can expect that soil-repairing agent of the present invention also can be applied on the lower soil of heavy metal contamination degree.

Claims (10)

1. soil selectivity heavy metal remediation composition capable or the preparation that comprises it are improving the growing state of plant on the highly polluted soil of heavy metal and/or the application in quality, wherein, described composition comprises lentinan and chitosan, and preferably it is made up of lentinan and chitosan.
2. application claimed in claim 1, wherein lentinan: the weight ratio of chitosan is 5 ~ 100:1 ~ 25, is preferably 10 ~ 60:2 ~ 15, more preferably 15 ~ 40:3 ~ 10, are more preferably 20 ~ 30:5 ~ 8, most preferably are 25:6.5.
3. the application described in claim 1 or 2, wherein lentinan is non-pharmaceutical grade lentinan, also nonfood grade lentinan preferably, be more preferably by edible mushrooms extract through soaking, ultrafiltration holds back the lentinan of preparing with concentrate drying.
4. application claimed in claim 1, wherein preparation comprises described soil selectivity heavy metal remediation composition capable and agricultural acceptable auxiliary material;
Preferably wherein, agricultural acceptable accessory package is containing pH adjusting agent, weighting agent, solvent, solubility promoter, emulsifying agent, dispersion agent, co-emulsifier, frostproofer, defoamer, thickening material, stablizer and/or binding agent, preferably comprise pH adjusting agent and/or weighting agent, as comprise salt of wormwood and/or the peat composed of rotten mosses;
Also preferably said preparation is solid preparation, as pulvis.
5. application claimed in claim 4, wherein said soil selectivity heavy metal remediation composition capable: pH adjusting agent: the weight ratio of weighting agent is 5 ~ 100:1 ~ 10:10 ~ 500, be preferably 10 ~ 60:2 ~ 8:25 ~ 100, more preferably 20 ~ 40:3 ~ 7:45 ~ 80, be more preferably 25 ~ 35:4 ~ 6:55 ~ 70, most preferably be 31.5:5:63.5.
6. application claimed in claim 1, wherein heavy metal is cadmium and/or chromium, preferably chromium.
7. application claimed in claim 1, wherein heavy metal is highly polluted is that heavy metal content is greater than 30mg/kg, is preferably greater than 50mg/kg, more preferably greater than 80mg/kg, more preferably greater than 120mg/kg, 150mg/kg in this way.
8. application claimed in claim 1, wherein growing state is survival rate and/or plant height.
9. application claimed in claim 1, wherein quality is residual quantity of heavy metal.
10. application claimed in claim 1, wherein plant is balsam pear.
CN201310677304.7A 2013-04-25 2013-12-13 Soil heavy metal repairing agent and application thereof to highly contaminated soil Pending CN104119924A (en)

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CN201310668985.0A Active CN104117533B (en) 2013-04-25 2013-12-11 Containing selenium Agrotechnical formulation and the use in conjunction of heavy metal-polluted soil renovation agent
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