CN104117533B - Containing selenium Agrotechnical formulation and the use in conjunction of heavy metal-polluted soil renovation agent - Google Patents

Containing selenium Agrotechnical formulation and the use in conjunction of heavy metal-polluted soil renovation agent Download PDF

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CN104117533B
CN104117533B CN201310668985.0A CN201310668985A CN104117533B CN 104117533 B CN104117533 B CN 104117533B CN 201310668985 A CN201310668985 A CN 201310668985A CN 104117533 B CN104117533 B CN 104117533B
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application described
soil
preparation
lentinan
heavy metal
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CN104117533A (en
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何其明
国锦琳
杨锡良
詹绍军
廖立群
姜勇
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Chengdu new Chaoyang Crop Science Co., Ltd
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Chengdu NewSun Crop Science Co Ltd
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Abstract

The invention provides the Agrotechnical formulation containing selenium and the use in conjunction of heavy metal-polluted soil renovation agent, wherein the use in conjunction heavy metal-polluted soil renovation agent of heavy metal-polluted soil renovation agent includes lentinan and chitosan.After use in conjunction, additionally it is possible to strengthen the effect of heavy metal-polluted soil renovation agent, significantly reduce the content of the heavy metals such as cadmium in plant (especially plant seed).

Description

Containing selenium Agrotechnical formulation and the use in conjunction of heavy metal-polluted soil renovation agent
Technical field
The invention belongs to Pollutant Treatment field and agriculturally useful compositions field, specifically, the present invention relates to containing selenium agricultural Preparation and the use in conjunction of heavy metal-polluted soil renovation agent.
Background technology
In recent years, the heavy metal pollution problem of China's soil shows especially day by day, to ecological environment, food safety and health Constitute serious threat, can not be ignored.Dyestuff, chemical industry, process hides, exploitation of mineral resources, smelt and the industrial discharge such as processing Waste gas, waste water, waste residue contain substantial amounts of heavy metal, by (particularly dirty filling), solid waste (mud, the rubbish etc.) heap of pouring water The modes such as long-pending and atmospheric sedimentation enter soil, cause heavy metal in soil content to increase, especially the heavy metal of exchangeable species, Directly absorbed by crops, be enriched with, directly threatened health.
At present, carry out rehabilitating soil by chemical method, be based primarily upon heavy metal chelant, such as chitosan, make soil In the heavy metal of exchangeable species be changed into the heavy metal of stable state, reduce the absorbtivity of crops heavy metal, thus play Administer the effect of heavy metal pollution of soil.
Such as, Chinese patent 200310108910 discloses the chemical regulator administering soil pollution, and it is low-molecular-weight Chitosan, but the inventors discovered that, and it has the strongest complexing power to metallic zinc, and mainly makees when administering soil pollution Use for eluent;
Chinese patent 200910115020 discloses the method for soil remediation, by excavating fluid injection well and constructing reaction wall, Being injected inside soil by chitosan leacheate, but the inventors discovered that, this mode quantities is big, uses inconvenience, it is difficult to Promote;
Chinese patent 201110413145 discloses the method for remediating heavy metal cadmium pollution soil, utilizes the Nicotiana tabacum L. product of resistance to cadmium In kind, chitosan solution and activating soil, the microorganism of heavy metal cadmium acts on jointly, but its applicable surface is narrow and is difficult to weight Multiple enforcement;
Chinese patent 201210231422 discloses heavy metal adsorption flocculant, and it is the acid water of chitosan and sophorolipid Solution, but although finally can soil protection environment, but be substantially the heavy metal in adsorbed water body.
Studying for a long period of time and groping the experience obtained according to the present inventor, first finds, the heavy metal chelating of existing wide spectrum The harmful heavy metals such as the lead in soil, chromium, cadmium are not only adsorbed in agent, and can adsorb to fall ZINC IN SOIL etc. in the most non-zinc-rich of China Element the most useful on farmland, causes the underproduction so that the heavy metal chelant actual effect of existing wide spectrum is very bad;Secondly send out Existing, make up by adding zinc fertilizer, harmful huge sum of moneys such as the heavy metal chelant Adsorption of Lead of existing wide spectrum, chromium, cadmium will be substantially reduced The efficiency belonged to, also contains a certain amount of harmful heavy metal, so being excessively used zinc fertilizer do not have reality in addition conventional zinc fertilizer Meaning;Also finding, the effect of the means used also extreme influence popularization and application, the especially Main Ingredients and Appearance of eluent is water, will Expend a large amount of manpower to spray, very inconvenient.Through the present inventor's painstaking efforts, in conjunction with some fortune that God helps those who help themselves, make us Extremely have unexpectedly discovered that the compounding upper lentinan of chitosan, it is possible to optionally adsorb to fall harmful weights such as the chromium in soil, cadmium The harmful heavy metal of metal, especially exchangeable species, and have substantially no effect on the Zn content in soil, keep the zinc fertilizer power of soil, The farmland being particularly suited for planting the plants such as Camellia sinensis uses.
And in the prior art, comprise the compositions of chitosan and lentinan for human medicine Composition Aspects, as The mushroom polysaccharide chitosan nanometer with antitumor action and immunological enhancement disclosed in Chinese patent 200910154959 Grain, and the bioactive polysaccharide self assembly with antibacterial activity and cell compatibility disclosed in Chinese patent 201010112065 Decorative material, does not uses in agricultural land soil as agriculturally useful compositions, and the cost of these prior aries is high, also cannot As agriculturally useful compositions commercial application in agricultural land soil.
Along with recent the present inventor constantly obtains new result of the test, confirming again, the agriculturally useful compositions of the present invention is not tied Close the feature of the beneficial elements such as selenium so that the agriculturally useful compositions of the present invention can not reduce the efficiency containing selenium Agrotechnical formulation so that Both can be applied jointly;More surprisingly, after use in conjunction, additionally it is possible to strengthen heavy metal-polluted soil renovation agent Effect, thus significantly reduce the content of the heavy metals such as the cadmium in plant (especially plant seed).And prior art, such as China Patent 200410009345,200410084878,200610086308 and 200910213516 etc., be substantially all so that Plant increases the content (as produced rice rich in selenium) of selenium, there is no any enlightenment being used in combination with heavy metal-polluted soil renovation agent.
Summary of the invention
The technical problem to be solved in the present invention is to provide new soil selectivity heavy metal remediation composition and containing selenium Agriculturally useful compositions combine the plant on planting soil or improve grown on soil plant quality in application.The present invention also carries Supply new soil selectivity heavy metal remediation composition, the most maybe will use agriculturally useful compositions containing selenium repairing Application in the cadmium of soil and/or pollution of chromium.Preferably this soil selectivity heavy metal remediation composition can optionally be repaired Chromium in Soil and/or cadmium pollution, improve chromium and/or the cadmium residual of the plant planted, but the most do not reduce selenium institute energy simultaneously Useful plant quality, even can work in coordination with onset with the agriculturally useful compositions containing selenium.
Specifically, in first aspect, the invention provides soil selectivity heavy metal remediation composition, it includes Lentinus Edodes Polysaccharide and chitosan.The present inventor's research chances on the compounding of lentinan and chitosan, it is possible to optionally repair soil Chromium and/or cadmium pollution in earth, improve chromium and/or the cadmium residual of the plant planted, but the most do not reduce in soil simultaneously Zn content, is a significant benefit to popularization and application.In this article, as without contrary instruction, term " is repaired " to exchange with " conditioning " and is made With, refer to reduce the residual quantity of heavy metal in soil, especially reduce the residual quantity of the heavy metal of exchangeable species in soil, from And reduce the biological effectiveness (availability) of heavy metal.
Owing to heavy metal exists with stable state and exchangeable species both forms in soil, the former is difficult to release by plant Utilize, substantially without causing the residual of heavy metal in plant;And the latter is due to its biological effectiveness, it it is Accumulation of heavy metals in plant Arch-criminal, its mobility in addition, thus the heavy metal of exchangeable species be repair object.So, in this article, soil The reparation of heavy metal pollution refers to reduce the heavy metal of exchangeable species in soil.The most in this article, as without contrary instruction, term " heavy metal " and concrete heavy metal, refer to is all the heavy metal of corresponding exchangeable species.For the heavy metal in plant, all It is considered to be exchangeable species.
The compositions 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 The metallo-chelates such as EDTA, but the effect of the Selective repair of the compositions of first aspect present invention is the most pretty good, goes out Consideration on cost, can no longer comprise other renovation agents.Therefore preferred, the compositions of first aspect present invention is many by Lentinus Edodes Sugar and chitosan form.
Preferably in the compositions of first aspect present invention, lentinan: the weight ratio of chitosan is 5 ~ 100:1 ~ 25, excellent Elect 10 ~ 60:2 ~ 15 as, more preferably 15 ~ 40:3 ~ 10, more preferably 20 ~ 30:5 ~ 8, most preferably 25:6.5.
Chitosan, including degraded small-molecular-weight chitosan and the macromolecule chitosan etc. of crosslinking, reported for work for The reparation of soil.Existing research is more, and corresponding production comparative maturity is (such as Chinese patent 01107664 institute State), from the chitosan of pharmaceutical grade, the chitosan of food stage, the chitosan to technical grade has, it is possible to purchase from the market Buy the inexpensive chitosan product of applicable present invention needs.In the present invention, chitosan is preferably non-pharmaceutical grade chitosan, the most excellent Choosing is nonfood grade chitosan.In the detailed description of the invention of the present invention, it is limited that chitosan is available from Chengdu flag U.S. biotechnology The chitosan of the high molecular (100kDa) of company, although the low-molecular-weight shell obtained after not having the most popular degraded The heavy metal joint efficiency of polysaccharide is high, but be fully able to competent compounding with lentinan work in coordination with reduce in soil commutative The residual of state heavy metal.
In the present invention, lentinan is non-pharmaceutical grade lentinan, preferably also nonfood grade lentinan.Lentinus Edodes is many Sugar, existing research is mainly used in health care, and presently commercially available product is substantially the lentinan of food stage or even pharmaceutical grade (as described in Chinese patent 92109345), does not have industrial applicability of the art on cost.So, In the detailed description of the invention of the present invention, lentinan is (such as sporophore, mycorhiza, stem or combinations thereof, excellent by edible fungi Choosing is that edible fungi is overall or mycorhiza, stem) soaking extraction, ultrafiltration retain and concentrate drying and the lentinan prepared, i.e. should The preparation method of lentinan comprises the steps or is made up of following steps:
(1) edible fungi pulverized is soaked (such as sporophore, mycorhiza, stem or its entirety, preferably edible fungi entirety or bacterium Root, stem) and extract, in the water of 70 ~ 95 DEG C, preferably soak the edible fungi of pulverizing and extract reservation clear liquid;
(2) clear liquid is carried out ultrafiltration, retain high molecular weight product, such as the product not less than 10kDa, be preferably not less than The product of the product of 20kDa, more preferably no less than 30kDa;With,
(3) it is concentrated and dried.
In this article, term " pharmaceutical " refers to the medical applications with human or animal as object.Medicinal product with agricultural or The product of person's pesticide is entirely the different product that technical field difference is huge, and those skilled in the art in the invention will not produce Life is any to be obscured.In this article, the impurity content of material (e.g., chitosan and/or lentinan) preferably used is higher than medicinal Product or the high limit standard of food, and/or homogeneity (purity) is less than pharmaceutical products or the lower bound standard of food.
In second aspect, the invention provides selectivity heavy metal-polluted soil preparation for repairing, it comprises first aspect present invention Compositions and agricultural acceptable adjuvant.In this article, term " agricultural acceptable adjuvant " refers to not affect agricultural work Property material play effect allow agricultural auxiliary substances.Agricultural acceptable accessory package is containing pH adjusting agent, filler, molten Agent, cosolvent, emulsifying agent, dispersant, co-emulsifier, antifreezing agent, defoamer, thickening agent, stabilizer and/or binding agent.
Preferably in the preparation of second aspect present invention, pH adjusting agent is alkaline pH mediator agent, such as sodium hydroxide, hydroxide One or more in potassium, sodium carbonate and potassium carbonate.
In this article, filler can with carrier exchange use, can be generally Kaolin, precipitated calcium carbonate, white carbon, One or many in montmorillonite, kieselguhr, clay, active hargil, nacrite, Pulvis Talci, rice husk, corncob cellulose and the peat composed of rotten mosses Kind.
The preferably preparation of second aspect present invention comprises pH adjusting agent and/or filler, as comprised potassium carbonate and/or grass Charcoal.In the detailed description of the invention of the present invention, the agricultural acceptable adjuvant in said preparation is made up of potassium carbonate and the peat composed of rotten mosses.
The preferably preparation of second aspect present invention is solid preparation, such as powder.The inventors discovered that, second aspect present invention Preparation can spread fertilizer over the fields as solid preparation, and still can reach soil selectivity heavy metal repair effect.This is relative to existing For having the tank solution preparation in technology, it is possible to reduce spilling in a large number shared by solvent, the amount of spraying, for China rural area work people For mouth constantly downward trend, advantage is the most obvious.
More preferably in the preparation of second aspect present invention, the compositions of first aspect present invention: pH adjusting agent: filler Weight ratio be 5 ~ 100:1 ~ 10:10 ~ 500, preferably 10 ~ 60:2 ~ 8:25 ~ 100, more preferably 20 ~ 40:3 ~ 7:45 ~ 80, more Add preferably 25 ~ 35:4 ~ 6:55 ~ 70, most preferably 31.5:5:63.5.
In the third aspect, the invention provides the compositions of first aspect present invention in rehabilitating soil cadmium and/or pollution of chromium In application;And/or, it is provided that the compositions of first aspect present invention in preparation for rehabilitating soil cadmium and/or pollution of chromium Application in preparation (preferably said preparation is the preparation of second aspect present invention);And/or, it is provided that the system of second aspect present invention Agent application 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 Be (reduce soil pollution residual) to as if the harmful heavy metal such as cadmium and/or chromium rather than it has been generally acknowledged that plant useful The useful heavy metal such as zinc.This farmland vast for China is all for non-zinc-rich soil to be particularly advantageous.Certainly, the present invention The compositions of first aspect or the preparation of second aspect present invention also have certain effect to rehabilitating soil lead contamination.
In fourth aspect, the invention provides in the compositions of the first aspect present invention plant on planting soil should With;And/or, it is provided that the compositions of first aspect present invention (preferably should at the preparation of the plant that preparation is used on planting soil Preparation is the preparation of second aspect present invention) in application;And/or, it is provided that the preparation of second aspect present invention is at planting soil The application in plant on earth.
Preferably in the application of fourth aspect present invention, plant is plant edible or medicinal effects be prone to accumulate cadmium and/ Or the plant of chromium, the plant that to be growth and development of plants sensitive to cadmium and/or pollution of chromium, and/or be the plant that zinc is useful to plant, Such as Oryza sativa L., Camellia sinensis etc..In the detailed description of the invention of the present invention, plant is Camellia sinensis.
At the 5th aspect, the compositions that the invention provides first aspect present invention is improving the plant product of grown on soil Application in matter;And/or, it is provided that the compositions of first aspect present invention is used for improving the plant product of grown on soil in preparation Application in the preparation (preferably said preparation is the preparation of second aspect present invention) of matter;And/or, it is provided that second aspect present invention Preparation application in the plant quality improving grown on soil.
Preferably in the application of fifth aspect present invention, plant quality is cadmium and/or the quality of chromium residues in plant.When So, the compositions of first aspect present invention or the preparation of second aspect present invention also have one to improving the quality of lead residual in plant Determine effect.It is also preferred that in the application of fifth aspect present invention, plant quality is the tea leaf quality of Camellia sinensis.Concrete in the present invention In embodiment, improve tea leaf quality and refer to reduce on the premise of not affecting the quality such as amino acid content and caffeine content Cadmium and/or the residual of chromium (and/or lead).
Preferably in the application of the present invention the three, the 4th and/or the 5th aspect, soil is non-zinc-rich soil.Such soil Earth is the widest in China's distribution, it is possible to more embody the advantage that the selectivity of the present invention is brought.
Although the present invention certain effect the most old to lead, but owing to remediation efficiency is relatively low, the most preferably in the present invention Three, in the application of the 4th and/or the 5th aspect, unless soil is also the soil of cadmium and/or pollution of chromium simultaneously, otherwise soil right and wrong Lead-contaminated soil.
Preferably in the application of the present invention the three, the 4th and/or the 5th aspect, application is directly to soil application solid system The application of agent (e.g., powder).As described above, for China's continuous downward trend of rural area labouring population, advantage is more Send out significantly.
Surprisingly, it was found that the compositions of the present invention of middle dosage or preparation are to plant in the research of the present inventor The reducing effect of interior cadmium and/or chromium residues is even better than high dose, although soil remediation presents a certain amount, effect direct ratio closes System, but cost viewpoint in addition, using of middle dosage is especially advantageous.The most preferably in the present invention the three, the 4th and/or In the application of the 5th aspect, application is 8 ~ 15kg/ mu (preferably 9 ~ 14kg/ mu, the more preferably 10 ~ 13kg/ in terms of lentinan Mu, more preferably 10.5 ~ 12kg/ mu, most preferably 11.25kg/ mu) dosage to the application of soil application.In this article, term " in terms of lentinan " refers to the compositions of the present invention or the amount of application of preparation calculates with the amount of application of lentinan, and also Non-only use lentinan.
At the 6th aspect, also it is the most important aspect of the present invention, the invention provides the compositions of first aspect present invention With the agriculturally useful compositions containing selenium combine the plant on planting soil or improve grown on soil plant quality in application;Or Person, it is provided that the compositions of first aspect present invention, the most maybe will use the soil of the agriculturally useful compositions containing selenium repairing Application in the cadmium of earth and/or pollution of chromium.
The compositions of the first aspect present invention of the present inventor's invention has substantially no effect on the beneficial elements such as the selenium shadow to plant Ring, thus different from soil-repairing agent of the prior art, it is possible to the agriculturally useful compositions use in conjunction containing selenium.In this article, The soil using the agriculturally useful compositions containing selenium can be the agriculturally useful compositions directly containing selenium to soil application, in order to improve plant pair The absorption efficiency of selenium, preferably directly uses to the plant (e.g., the blade face of plant) of grown on soil, thus indirectly to soil application Agriculturally useful compositions containing selenium.
Preferably in the application of sixth aspect present invention, described agriculturally useful compositions includes containing selenium inorganic compound.Typically The inorganic compound containing selenium is selenate (such as sodium salt, potassium salt or ammonium salt) or selenite (such as sodium salt, potassium salt or ammonium salt).At this In bright detailed description of the invention, described agriculturally useful compositions includes sodium selenite.The amount of application of described agriculturally useful compositions, with spray for Example, spraying concentration is 1 ~ 1000ppm(1/1000000th, weight), preferably 10 ~ 500ppm, more preferably 50 ~ 300ppm, as 100ppm;Do not converge into water droplet and drop down to cover plant leaf surface and be advisable.
Preferably in the application of sixth aspect present invention, described compositions provides with dosage form.Such as, the present invention first The compositions of aspect can provide with selectivity heavy metal-polluted soil preparation for repairing form, wherein selectivity heavy metal-polluted soil reparation system Agent can be the preparation of second aspect present invention.
And for example, the agriculturally useful compositions containing selenium provides with the Agrotechnical formulation form containing selenium, and described preparation comprises described containing selenium Agriculturally useful compositions and agricultural acceptable adjuvant.In the most described preparation, agricultural acceptable accessory package contains pH adjusting agent, filling Agent, solvent, cosolvent, emulsifying agent, dispersant, co-emulsifier, antifreezing agent, defoamer, thickening agent, stabilizer and/or bonding Agent.In the detailed description of the invention of the present invention, described preparation comprises solvent, such as water.Additionally it is also preferred that described preparation is liquid system Agent, such as foliage spraying agent.
The compositions of first aspect present invention and the agriculturally useful compositions containing selenium can be used in combination, such as preparation in groups Compound is used.But, in order to improve the absorption efficiency of Selenium By The Plants, also for improving the efficiency using soil-repairing agent to repair, Preferably the compositions of first aspect present invention and the agriculturally useful compositions containing selenium are separate administration.Preferably first aspect present invention Compositions directly to soil application and is used containing the agriculturally useful compositions directly plant leaf surface on soil of selenium.
Preferably in the application of sixth aspect present invention, plant is Oryza sativa L..It is also preferred that in the application of sixth aspect present invention In, improve plant quality and include reducing cadmium and/or the residual of chromium.
Beneficial effect of the present invention essentially consists in the compositions of the present invention or preparation has a selective advantage: chromium in rehabilitating soil And/or cadmium (and/or lead) pollutes, improve chromium and/or cadmium (and/or lead) residual of the plant planted, and there is collaborative increasing The effect of effect;Simultaneously the most do not reduce the Zn content in soil, do not reduce the plant quality that zinc institute can be useful, beneficially in China Popularization on the agricultural land soil of vast non-zinc-rich.That is, selective advantage on the one hand can the amount of application of potential minimizing zinc fertilizer, another Aspect improves the remediation efficiency polluting soil Cr and/or cadmium (and/or lead), meets the requirement of actual application, it is simple to promote. It addition, beneficial effect of the present invention also resides in: the compositions of the present invention or preparation directly can be executed to soil with solid dosage form With, it is possible to alleviate and use required labour force and cost;The compositions of the present invention or preparation are preferably with the amount of application of non-high dose Use, it is possible to alleviate and use required labour force and cost, also can reduce the cost of product storage and transport;The present invention is preferred Compositions or preparation production cost low, be more beneficial for promoting the use of in the wide agricultural land soil of China.For the present invention more It is essential that the compositions of the present invention with the agriculturally useful compositions use in conjunction containing selenium, not only can not make mutual beneficial effect support Disappear, and onset can be worked in coordination with, the Accumulation of heavy metals being greatly reduced in plant seed.
By specific embodiment, the present invention will be described in detail in order to make it easy to understand, following.Needs refer in particular to Going out, these describe the description being merely exemplary, are not intended that limitation of the scope of the invention.Opinion according to this specification Stating, many changes of the present invention, change are all obviously for one of ordinary skill in the art.It addition, the present invention quotes Open source literature be to more clearly describe the present invention, their entire contents is all included in and is carried out reference herein, just looks like it Full text repeated description the most in this article excessively as.
Detailed description of the invention
Below by way of specific embodiment, the present invention is carried out exemplary description, if any not most part, be referred to phase The operation instruction of laboratory manual, equipment and the reagent answered and the relevant guide standard of the Ministry of Agriculture.
The preparation of the soil-repairing agent of embodiment 1 present invention
Chitosan (Qi Mei bio tech ltd, Chengdu) and lentinan that the soil-repairing agent of the present invention contains are equal Commercially available product can be used, but the lentinan of large usage quantity can be prepared according to following method preferably wherein so that it is become This is lower, is more suitable for popularization and application.
(1) preparation of lentinan
Take mushroom fruiting body to pulverize, cross 30 mesh sieves, take the granule that the powder 200kg(that can sieve can not sieve and return pulverizer Pulverize), add 1000L water and soak 1 hour in 80 DEG C, period stirs, and then filters and retains clear liquid;The residue once soaked adds 1000L water soaks 1 hour in 80 DEG C, and period stirs, and then filters and retains clear liquid;Secondary soak residue add 1000L water in 80 DEG C are soaked 1 hour, and period stirs, and then filter and retain clear liquid.Merge above-mentioned clear liquid, be 30kDa's by molecular cut off Hollow Fiber Ultrafiltration system (being purchased from Millipore company of the U.S., Biomax-30) ultrafiltration, the part obtaining retaining is through economic benefits and social benefits Concentrator (being purchased from Shaanxi Chang Tai Industrial Co., Ltd.) is concentrated into 1/10th volumes, and the most vacuum dried device (is purchased from Shaanxi Chang Tai Industrial Co., Ltd.) be dried to water content be not more than 10%(w/w), obtain the lentinan of the present invention.
(2) preparation of soil-repairing agent
Take lentinan 25kg and chitosan 6.5kg, add potassium carbonate and (as pH adjusting agent, be purchased from Zhengzhou indigo plant space essence Thin product Chemical Co., Ltd.) powder 5kg, after mix homogeneously, (i.e. peat, as filler, is purchased from Pixian County and praises to add the peat composed of rotten mosses Gloomy garden spot) 63.5kg, mix homogeneously, pack, obtain the soil-repairing agent (powder) of the present invention.
It addition, take chitosan 6.5kg, adding potassium carbonate powder 5kg, after mix homogeneously, add peat composed of rotten mosses 88.5kg, mixing is all Even, as positive control 1;Take lentinan 25kg, add potassium carbonate powder 5kg, after mix homogeneously, add peat composed of rotten mosses 70kg, mixed Close uniformly, as positive control 2;Taking potassium carbonate powder 5kg and peat composed of rotten mosses 95kg, mix homogeneously, as negative control.
The research that heavy metal-polluted soil reparation and plant quality are improved by the soil-repairing agent of embodiment 2 present invention
Inst. of Soil Fertilizer, Sichuan Academy of Agriculture Science is entrusted to carry out in the tea place of plantation river No. 9 kinds of tea in Pujiang County Field test, directly spreads fertilizer over the fields following soil-repairing agent or comparison, and covering of digging in the plot of random packet when starting to test, Remaining is 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: the soil-repairing agent of the present invention, 22.5kg/ mu;
E, middle dosage experiments group: the soil-repairing agent of the present invention, 45kg/ mu;
F, high dose experimental group: the soil-repairing agent of the present invention, 90kg/ mu.
After on-test 90 days, take each group of soil and carry out heavy metal element analysis;150 days (i.e. tea after on-test The leaf collecting period), pluck Folium Camelliae sinensis and carry out heavy metal element and index of quality analysis.
Heavy metal-polluted soil analysis result is as shown in table 1:
The tea garden soil Analysis of Heavy Metal result table of the different group of table 1
Result shows, chitosan individually can non-selectively reduce the content of the heavy metal of exchangeable species in soil, with Heavy dose is used, and lead, cadmium, chromium and zinc can be reduced about about 10%;Lentinan individually reduction to heavy metal in soil Effect does not then have rule, has substantially no effect on the content of lead and zinc, but can reduce the content of chromium and cadmium.Unexpectedly, shell Polysaccharide and the compositions of lentinan, it is possible to the content of chromium and cadmium is optionally greatly reduced, and the reducing effect of middle dosage is even Being better than chitosan and the summation that is administered alone of lentinan of heavy dose, collaborative to reduce effect obvious;And, said composition is basic Do not affect the Zn content in soil, and Camellia sinensis is highly profitable by zinc.So, although said composition reduces the most in the lump to soil The absorbability of the lead of exchangeable species in earth, but to non-lead contamination but the advantage ten of the soil of chromium and/or cadmium pollution is clearly demarcated for it Aobvious.
In Folium Camelliae sinensis, the analysis result of heavy metal and the index of quality is as shown in table 2:
The heavy metal of the Folium Camelliae sinensis of the different group of table 2 and the analysis result table of the index of quality
Result shows, chitosan individually can non-selectively reduce the residual quantity of the harmful heavy metal in Folium Camelliae sinensis, with greatly Dosage is used, and lead, cadmium and chromium can be reduced about about 10%;Lentinan is individually to the reduction of harmful heavy metal in Folium Camelliae sinensis Effect does not then have rule, and it has substantially no effect on the content of lead, but can reduce the residual quantity of chromium and cadmium.Unexpectedly, shell Polysaccharide and the compositions of lentinan, it is possible to the residual quantity of chromium and cadmium is optionally greatly reduced, have the collaborative effect that reduces, more Surprisingly, the reducing effect of the middle dosage effect that even better than heavy dose is used, this awaits studying further;And And, said composition, owing to having substantially no effect on the content of zinc useful to Camellia sinensis in soil, does not the most reduce Folium Camelliae sinensis its He has slight rising at the index of quality, even part;And chitosan is administered alone, owing to decreasing exchangeable species in soil Zinc, cause aminoacid and the caffeine etc. of Folium Camelliae sinensis by other index of quality that zinc is affected decline about 10% even more than.So, Said composition has and obviously acts on reducing chromium and/or cadmium residual quantity in plant, also has certain effect to reducing lead content, And the rareest, this is in the condition not reducing the index of quality such as Amino Acids in Tea and caffeine that even increased Lower realization, it is very beneficial for application;It addition, the effect that middle dosage is used is the most obvious, the highest dose Amount can increase on the contrary every the residual index with chromium in Folium Camelliae sinensis after using, and in conjunction with cost consideration, therefore the compositions of the present invention is preferred With 45kg/ mu (chitosan 2.925kg/ mu+lentinan 11.25kg/ mu), tea place is used.
The preparation of the selenium Agrotechnical formulation of embodiment 3 present invention
Taking sodium selenite 0.1g, be added to the water, complement to 1L with water, mix homogeneously can be used as the blade face spray of the present invention Execute agent to use.This foliage spraying agent is preferably at prepared before use.
Heavy metal-polluted soil reparation and plant quality are changed by foliage spraying agent and the soil-repairing agent of embodiment 4 present invention Kind research
Shifang City, Sichuan Province learn something in history town one at serious grown on soil Oryza sativa L. Gangyou725 (Hybrid) of cadmium pollution Carrying out field test, the cadmium severe contamination of this soil, the cadmium content of exchangeable species is more than 3mg/kg.When starting to test directly with Soil-repairing agent of the invention below or comparison, and covering of digging are spread fertilizer over the fields in the plot of machine packet, in Oryza sativa L. booting early stage to filling Spray the foliage spraying agent of the present invention during the slurry phase with the interval of 7 days/time, to spray, sprayed dose knows that blade face is formed without water droplet Trickling is limited (for not spraying the group of foliage spraying agent, to spray the water replacement of respective amount), and remaining liquid manure, insect protected management are all Unification is carried out:
A, negative control group: negative control 30kg/ mu;
B, positive controls 1: the soil-repairing agent 30kg/ mu of the present invention;
C, positive controls 2: the foliage spraying agent of the present invention;
D, experimental group: the foliage spraying agent of the soil-repairing agent 30kg/ mu+present invention of the present invention;
After Rise's boot period starts 14 days (after i.e. having sprayed three foliage spraying agents), take each group of soil and carry out heavy metal Elementary analysis;Gather in the crops after Oryza sativa L. maturation, and weigh its yield the content of beary metal measuring in seed.
Heavy metal-polluted soil analysis result is as shown in table 3:
The analysis result table of the cadmium pollution soil of the different group of table 3
Result shows, the chitosan of the present invention and the compositions of lentinan, even if being administered alone, it is also possible to be greatly reduced Cadmium content in soil;Repeatedly spray the foliage spraying agent of the present invention, to the cadmium in soil almost without reduction effect;It is worth closing Note, when the foliage spraying agent use in conjunction of the soil-repairing agent of the present invention and the present invention when, it is possible to collaborative reduce soil Cadmium content in earth about 1%, this soil-repairing agent being probably the present invention how much can promote selenium exchange soil in cadmium, be allowed to from Exchangeable species is transformed into stable state.
The heavy metal of the rice paddy seed of the different group of table 4 and the analysis result table of yield index
Result shows, the chitosan of the present invention and the compositions of lentinan, when being administered alone, causes hardly increasing Produce, but do not interfere with yet the foliage spraying agent of the present invention rich in selenium to the effect of increasing production of Oryza sativa L. (the most slightly improve, but Total effect of increasing production is the most obvious), show that the soil-repairing agent of the present invention does not the most produce " reparation " effect to beneficial elements such as selenium Should, it is possible to they are played a role;The cadmium residual quantity reduced in rice only can be ignored by the foliage spraying agent of the present invention The effect disregarded, but it is with the soil-repairing agent use in conjunction of the present invention when, it is possible to collaborative cadmium residual is greatly reduced Amount, the collaborative effect improved improves nearly 20%, it is expected to be promotes selenium and occupies the reason in the Metal-accumulation site in plant. So, both use in conjunction are highly beneficial.

Claims (53)

1. soil selectivity heavy metal remediation composition and the agriculturally useful compositions containing selenium are combined the plant on planting soil or change Application in the plant quality of kind grown on soil, wherein said soil selectivity heavy metal remediation composition includes lentinan And chitosan.
2. the application described in claim 1, wherein said soil selectivity heavy metal remediation composition is gathered by lentinan and shell Sugar composition.
3. the application described in claim 1, the wherein said plant quality improving grown on soil is reduce cadmium and/or chromium residual Stay.
4. the application described in claim 1, wherein lentinan: the weight ratio of chitosan is 5 ~ 100:1 ~ 25.
5. the application described in claim 4, wherein lentinan: the weight ratio of chitosan is 10 ~ 60:2 ~ 15.
6. the application described in claim 5, wherein lentinan: the weight ratio of chitosan is 15 ~ 40:3 ~ 10.
7. the application described in claim 6, wherein lentinan: the weight ratio of chitosan is 20 ~ 30:5 ~ 8.
8. the application described in claim 7, wherein lentinan: the weight ratio of chitosan is 25:6.5.
9. the application described in claim 1, wherein lentinan is non-pharmaceutical grade lentinan.
10. the application described in claim 1, wherein lentinan is nonfood grade lentinan.
Application described in 11. claim 1, wherein lentinan is to be retained and concentrate dry by the soaking extraction of edible fungi, ultrafiltration Dry and the lentinan prepared.
Application described in 12. claim 1, wherein said agriculturally useful compositions includes containing selenium inorganic compound.
Application described in 13. claim 12, wherein said agriculturally useful compositions includes sodium selenite.
Application described in 14. claim 1, wherein soil selectivity heavy metal remediation composition is repaiied with selectivity heavy metal-polluted soil Multiple dosage form provides, and described preparation comprises described soil selectivity heavy metal remediation composition and agricultural acceptable adjuvant.
Application described in 15. claim 14, in wherein said preparation, agricultural acceptable accessory package contains pH adjusting agent, filling Agent, solvent, cosolvent, emulsifying agent, dispersant, antifreezing agent, defoamer, thickening agent, stabilizer and/or binding agent.
Application described in 16. claim 15, in wherein said preparation, agricultural acceptable accessory package containing pH adjusting agent and/or Filler.
Application described in 17. claim 16, in wherein said preparation, agricultural acceptable accessory package contains potassium carbonate and/or grass Charcoal.
Application described in 18. claim 14, wherein said preparation is solid preparation.
Application described in 19. claim 18, wherein said preparation is powder.
Application described in 20. claim 1, wherein the agriculturally useful compositions containing selenium provides with the Agrotechnical formulation form containing selenium, described Preparation comprises the described agriculturally useful compositions containing selenium and agricultural acceptable adjuvant.
Application described in 21. claim 20, in wherein said preparation, agricultural acceptable accessory package contains pH adjusting agent, filling Agent, solvent, cosolvent, emulsifying agent, dispersant, antifreezing agent, defoamer, thickening agent, stabilizer and/or binding agent.
Application described in 22. claim 21, in wherein said preparation, agricultural acceptable accessory package contains solvent.
Application described in 23. claim 22, in wherein said preparation, agricultural acceptable accessory package is aqueous.
Application described in 24. claim 20, wherein said preparation is liquid preparation.
Application described in 25. claim 24, wherein said preparation is foliage spraying agent.
Application described in 26. claim 1, wherein soil selectivity heavy metal remediation composition and the agriculturally useful compositions containing selenium are Separate administration.
Application described in 27. claim 26, wherein soil selectivity heavy metal remediation composition directly to soil application and Agriculturally useful compositions containing the selenium directly plant leaf surface on soil is used.
Application described in 28. claim 1, wherein plant is Oryza sativa L..
29. soil selectivity heavy metal remediation compositions, the most maybe will use agriculturally useful compositions containing selenium repairing Application in the cadmium of soil and/or pollution of chromium, wherein said soil selectivity heavy metal remediation composition include lentinan and Chitosan.
Application described in 30. claim 29, wherein said soil selectivity heavy metal remediation composition is by lentinan and shell Polysaccharide forms.
Application described in 31. claim 29, wherein lentinan: the weight ratio of chitosan is 5 ~ 100:1 ~ 25.
Application described in 32. claim 31, wherein lentinan: the weight ratio of chitosan is 10 ~ 60:2 ~ 15.
Application described in 33. claim 32, wherein lentinan: the weight ratio of chitosan is 15 ~ 40:3 ~ 10.
Application described in 34. claim 33, wherein lentinan: the weight ratio of chitosan is 20 ~ 30:5 ~ 8.
Application described in 35. claim 34, wherein lentinan: the weight ratio of chitosan is 25:6.5.
Application described in 36. claim 29, wherein lentinan is non-pharmaceutical grade lentinan.
Application described in 37. claim 29, wherein lentinan is nonfood grade lentinan.
Application described in 38. claim 29, wherein lentinan is to be retained and concentrate dry by the soaking extraction of edible fungi, ultrafiltration Dry and the lentinan prepared.
Application described in 39. claim 29, wherein said agriculturally useful compositions includes containing selenium inorganic compound.
Application described in 40. claim 39, wherein said agriculturally useful compositions includes sodium selenite.
Application described in 41. claim 29, wherein soil selectivity heavy metal remediation composition is with selectivity heavy metal-polluted soil Preparation for repairing form provides, and described preparation comprises described soil selectivity heavy metal remediation composition and agricultural acceptable auxiliary Material.
Application described in 42. claim 41, in wherein said preparation, agricultural acceptable accessory package contains pH adjusting agent, filling Agent, solvent, cosolvent, emulsifying agent, dispersant, antifreezing agent, defoamer, thickening agent, stabilizer and/or binding agent.
Application described in 43. claim 42, in wherein said preparation, agricultural acceptable accessory package containing pH adjusting agent and/or Filler.
Application described in 44. claim 43, in wherein said preparation, agricultural acceptable accessory package contains potassium carbonate and/or grass Charcoal.
Application described in 45. claim 41, wherein said preparation is solid preparation.
Application described in 46. claim 45, wherein said preparation is powder.
Application described in 47. claim 29, wherein the agriculturally useful compositions containing selenium provides with the Agrotechnical formulation form containing selenium, described Preparation comprises the described agriculturally useful compositions containing selenium and agricultural acceptable adjuvant.
Application described in 48. claim 47, in wherein said preparation, agricultural acceptable accessory package contains pH adjusting agent, filling Agent, solvent, cosolvent, emulsifying agent, dispersant, antifreezing agent, defoamer, thickening agent, stabilizer and/or binding agent.
Application described in 49. claim 48, in wherein said preparation, agricultural acceptable accessory package contains solvent.
Application described in 50. claim 49, in wherein said preparation, agricultural acceptable accessory package is aqueous.
Application described in 51. claim 47, wherein said preparation is liquid preparation.
Application described in 52. claim 51, wherein said preparation is foliage spraying agent.
Application described in 53. claim 29, wherein soil selectivity heavy metal remediation composition and the agriculturally useful compositions containing selenium It it is separate administration.
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