CN109762573A - A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter and preparation method thereof - Google Patents

A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter and preparation method thereof Download PDF

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CN109762573A
CN109762573A CN201910119558.4A CN201910119558A CN109762573A CN 109762573 A CN109762573 A CN 109762573A CN 201910119558 A CN201910119558 A CN 201910119558A CN 109762573 A CN109762573 A CN 109762573A
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hydroxyapatite
zeolite
agricultural land
land soil
paecilomyces lilacinus
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CN109762573B (en
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孙燕
张燕
王江帆
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Jiangxi Xiashi Spring Environmental Ltd By Share Ltd
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Jiangxi Xiashi Spring Environmental Ltd By Share Ltd
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  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
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Abstract

The invention discloses a kind of agricultural land soil microorganism-compound renovation agents of inorganic matter, include hydroxyapatite-Zeolite modifying object and Paecilomyces lilacinus bacterium solution, and the hydroxyapatite-Zeolite modifying object passes through NH by the mixture of hydroxyapatite and zeolite4Cl, KCl are modified to be obtained, and cell concentration is 10 in the Paecilomyces lilacinus bacterium solution5~107CFU/mL.The present invention closes Paecilomyces lilacinus using hydroxyapatite-Zeolite modifying Internet of Things and carries out soil remediation to Cd polluted agricultural land, and significant effect, repairing effect more independent than inorganic matter or microorganism is stronger, and simple process, is conducive to promote.

Description

A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter and preparation method thereof
Technical field
The invention belongs to technical field of soil remediation more particularly to a kind of agricultural land soil microorganism-, inorganic matter is compound repairs Multiple agent and preparation method thereof.
Background technique
With the excavation in a large amount of mines, the random row of industrial waste gas, waste water, waste residue, agricultural fertilizer is sprayed, day refuse Heap abandoning etc., will endlessly heavy metal slowly penetrate into agricultural land soil, and biocoene upset, soil organic substance is caused to subtract Less, stable soil environment is destroyed, and causes great threat to survival and development of mankind.According to the relevent statistics, currently, I State reaches 20,000,000 hm by the cultivated area of heavy metal pollution2, this situation alreadys exceed the 1/6 of national cultivated area.I Annual contaminated by heavy metals grain up to 12,000,000 t of state, and because the grain yield of the annual reduction of this pollution situation is also higher by 10000000 t add up to property loss to exceed 20,000,000,000 yuan.And gradually growth trend is presented in the situation.Heavy metal is very steady in the soil It is fixed, difficult mobile, it is not easy to by aqueous dissolution, and to be difficult to be decomposed by the microorganisms, deposition is difficult to remove in the soil, in soil It is accumulated step by step in earth-plant-animal, high risks finally is caused to human health.The accumulation of heavy metal in the soil, not only The biomass, biological species and bio-diversity of soil are reduced, while destroying soil texture again, has upset soil ecology system System, reduces soil function.
Common heavy-metal contaminated soil reclamation activities includes chemical passivation, Soil leaching and biological prosthetic etc..Microorganism Reparation is one kind of bioremediation technology, using some functional microorganisms to the absorption of heavy metal, conversion, it is fixed the effects of drop Low heavy metal toxicity, and the microorganism of Different groups is different to the repair mechanisms of different heavy metals.Relative to traditional object For Physicochemical restorative procedure, microorganism remediation technology has unique advantage: microorganism individual is small, and naked eyes difficulty is shown in, compares table Area is big, and eucaryotic cell structure is complicated, and distributed in nature is wide, resourceful in soil, can quickly handle rnetal contamination problem, simultaneously Handle the composite pollution of various heavy;Remediating heavy metal ability is strong, will not pollute again to Zinc fractions, to soil texture, Soil function and microorganism ecological environment influence small;Microbial reproduction is very fast, and metabolic capability is strong, and rehabilitation expense is few.
It is an extremely complex process using microorganism remediation heavy-metal contaminated soil, is directed not only to microbial molecular Effect further includes that microorganism and metal generation physics, chemistry etc. react.Wherein, repair mechanisms are also diversification, including biology is inhaled A variety of effects such as attached, enrichment, redox, dissolution precipitating, mycorrhizal fungi.Optimize multiple combinations recovery technique, building is such as organic The combination such as object-microorganism, inorganic matter-microorganism, plant-microorganism, in conjunction with the advantage of each restorative procedure, more effectively More rapidly solve various heavy metal pollution problems.The foundation of a variety of method combination recovery techniques will be that the following remediating heavy metal is dirty The primary selection of dye.
Summary of the invention
The present invention provides a kind of agricultural land soil microorganism-compound renovation agents of inorganic matter, include hydroxyapatite-zeolite Modifier and Paecilomyces lilacinus bacterium solution, the hydroxyapatite-Zeolite modifying object by hydroxyapatite and zeolite mixture Pass through NH4Cl, KCl are modified to be obtained, and cell concentration is 10 in the Paecilomyces lilacinus bacterium solution5~107 CFU/mL。
Further, the hydroxyapatite-Zeolite modifying object is used cooperatively with Paecilomyces lilacinus bacterium solution, hydroxy-apatite Stone-Zeolite modifying object usage amount is 10~20t/hm2, the usage amount of Paecilomyces lilacinus bacterium solution is 500~2000mL/m2
Further, the culture medium of the Paecilomyces lilacinus is mentioned comprising beef extract, peptone, sodium chloride, elsholtzia splendens Object, zinc nitrate and distilled water are taken, the mass ratio of each component in culture medium are as follows:
Beef extract: peptone: sodium chloride: elsholtzia splendens extract: zinc nitrate: distilled water=5~10g:12~18g:2~5g:1 ~2g:3~5mg:1000g.
Further, the elsholtzia splendens extract the preparation method comprises the following steps:
(1) the whole strain of fresh elsholtzia splendens is cleaned, removes root, then mashes in a reservoir;
(2) aqueous citric acid solution is added in Xiang Suoshu container to mix with elsholtzia splendens, then container is sealed, the mixing in container Object is heated to 120~140 DEG C of heat preservation 5h or more, naturally cools to room temperature after heat preservation;
(3) mixture in container is taken out, filtering removal solid phase residue, liquid phase is concentrated under reduced pressure, obtains the elsholtzia splendens and mention Take object.
Further, the mass percentage of citric acid is 10%~18% in the aqueous citric acid solution, and citric acid is water-soluble The addition weight of liquid is 8~15 times of fresh elsholtzia splendens total weight be added in container, in the step (3), liquid phase decompression It is concentrated into the 1/6~1/8 of liquid phase volume.
The invention also discloses above-mentioned agricultural land soil microorganism-inorganic matter compound renovation agent preparation method, the hydroxyls Base apatite-Zeolite modifying object the preparation method comprises the following steps:
1) according to hydroxyapatite: zeolite mass ratio=1:3~7 amount uniformly mixes hydroxyapatite and zeolite, is mixed Close object A;
2) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.5~0.8mol/L, and KCl concentration is 0.20~0.60mol/L, remaining is deionized water;The mixture A is immersed in the NH4In Cl, KCl solution, ultrasonic wave 2~3h is shaken, then 80 ± 10 DEG C of water bath with thermostatic control, keeps the temperature 3h or more;
3) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains the hydroxyapatite-Zeolite modifying Object;
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configure the culture medium, Paecilomyces lilacinus strain is accessed and is trained It supports in base, 30 DEG C, 60~70h of 200r/min shaking table culture;Then bacterium solution is collected by centrifugation again, bacterium solution is washed with phosphate buffer 3 times, then control cell concentration is resuspended to 10 with phosphate buffer5~107 CFU/mL。
Further, in the step 2), the NH4The quality of Cl, KCl solution is to be immersed in mixture A matter therein 8 times or more of amount.
The invention also discloses above-mentioned agricultural land soil microorganism-inorganic matter compound renovation agent application method, steps Are as follows:
A. by the hydroxyapatite-Zeolite modifying object according to 10~20t/hm2Amount be uniformly sprinkling upon Cd pollution agricultural land soil On, hydroxyapatite-Zeolite modifying object is mixed agricultural land soil scarifying with soil, adjusts soil moisture to soil moisture content It is 10% or more;
B. 500~2000mL/m is pressed2Amount the Paecilomyces lilacinus bacterium solution is sprayed to the agricultural land soil of Cd pollution On, it is primary every sprinkling in 7~10 days, it sprays 3~5 times altogether.
Further, before the hydroxyapatite-Zeolite modifying object to be sprinkling upon to the agricultural land soil of Cd pollution, lemon is first sprayed Sour thin liquid, the fountain height of the citric acid thin liquid are 5000~10000mL/m2, the quality percentage of citric acid in citric acid thin liquid Content is 5%~10%.
As can be seen from the above technical solutions, the invention has the advantages that the present invention uses hydroxyapatite-Zeolite modifying object Joint Paecilomyces lilacinus carries out soil remediation to Cd polluted agricultural land, and significant effect individually repairs effect than inorganic matter or microorganism Fruit is stronger, and simple process, is conducive to promote.
Specific embodiment
It is described in detail below with reference to embodiment:
Embodiment 1
A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter includes hydroxyapatite-Zeolite modifying object and pale purple quasi- blueness Mould bacterium solution, the hydroxyapatite-Zeolite modifying object pass through NH by the mixture of hydroxyapatite and zeolite4Cl, KCl are modified It obtains, cell concentration is 5 × 10 in the Paecilomyces lilacinus bacterium solution6 CFU/mL。
The hydroxyapatite-Zeolite modifying object the preparation method comprises the following steps:
1) according to hydroxyapatite: zeolite mass ratio=1:3 amount uniformly mixes hydroxyapatite and zeolite, obtains mixture A;
2) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.5mol/L, and KCl concentration is 0.20mol/L, remaining is deionized water;The mixture A is immersed in the NH4In Cl, KCl solution, ultrasonic oscillation 2h, Then 80 ± 10 DEG C of water bath with thermostatic control keep the temperature 3h;
3) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains the hydroxyapatite-Zeolite modifying Object.
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configuration culture medium, by Paecilomyces lilacinus strain access train It supports in base, 30 DEG C, 200r/min shaking table culture 60h;Then bacterium solution is collected by centrifugation again, bacterium solution is washed 3 times with phosphate buffer, Control cell concentration is resuspended to 5 × 10 with phosphate buffer again6 CFU/mL。
Above-mentioned culture medium includes beef extract, peptone, sodium chloride, elsholtzia splendens extract, zinc nitrate and distilled water, culture The mass ratio of each component in base are as follows:
Beef extract: peptone: sodium chloride: elsholtzia splendens extract: zinc nitrate: distilled water=5g:12g:2g:1g:3mg:1000g.
Above-mentioned elsholtzia splendens extract the preparation method comprises the following steps:
(1) the whole strain of fresh elsholtzia splendens is cleaned, removes root, then mashes in a reservoir;
(2) aqueous citric acid solution that Solute mass percentage composition is 10% is added in Xiang Suoshu container to mix with elsholtzia splendens, lemon The addition weight of lemon aqueous acid is 8 times of the fresh elsholtzia splendens total weight being added in container;Container is sealed again, in container Mixture be heated to 120~140 DEG C of heat preservation 5h, naturally cool to room temperature after heat preservation;
(3) mixture in container is taken out, filtering removal solid phase residue, liquid phase is concentrated under reduced pressure into the 1/6 of liquid phase volume, obtains Obtain the elsholtzia splendens extract.
Embodiment 2
A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter includes hydroxyapatite-Zeolite modifying object and pale purple quasi- blueness Mould bacterium solution, the hydroxyapatite-Zeolite modifying object pass through NH by the mixture of hydroxyapatite and zeolite4Cl, KCl are modified It obtains, cell concentration is 5 × 10 in the Paecilomyces lilacinus bacterium solution6 CFU/mL。
The hydroxyapatite-Zeolite modifying object the preparation method comprises the following steps:
1) according to hydroxyapatite: zeolite mass ratio=1:5 amount uniformly mixes hydroxyapatite and zeolite, obtains mixture A;
2) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.6mol/L, and KCl concentration is 0.40mol/L, remaining is deionized water;The mixture A is immersed in the NH4In Cl, KCl solution, ultrasonic oscillation 2h, Then 80 ± 10 DEG C of water bath with thermostatic control keep the temperature 3h;
3) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains the hydroxyapatite-Zeolite modifying Object.
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configuration culture medium, by Paecilomyces lilacinus strain access train It supports in base, 30 DEG C, 200r/min shaking table culture 65h;Then bacterium solution is collected by centrifugation again, bacterium solution is washed 3 times with phosphate buffer, Control cell concentration is resuspended to 5 × 10 with phosphate buffer again6 CFU/mL。
Above-mentioned culture medium includes beef extract, peptone, sodium chloride, elsholtzia splendens extract, zinc nitrate and distilled water, culture The mass ratio of each component in base are as follows:
Beef extract: peptone: sodium chloride: elsholtzia splendens extract: zinc nitrate: distilled water=7g:14g:3g:1.4g:4mg: 1000g。
Above-mentioned elsholtzia splendens extract the preparation method comprises the following steps:
(1) the whole strain of fresh elsholtzia splendens is cleaned, removes root, then mashes in a reservoir;
(2) aqueous citric acid solution that Solute mass percentage composition is 12% is added in Xiang Suoshu container to mix with elsholtzia splendens, lemon The addition weight of lemon aqueous acid is 11 times of the fresh elsholtzia splendens total weight being added in container;Container is sealed again, container Interior mixture is heated to 120~140 DEG C of heat preservation 5h, naturally cools to room temperature after heat preservation;
(3) mixture in container is taken out, filtering removal solid phase residue, liquid phase is concentrated under reduced pressure into the 1/7 of liquid phase volume, obtains Obtain the elsholtzia splendens extract.
Embodiment 3
A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter includes hydroxyapatite-Zeolite modifying object and pale purple quasi- blueness Mould bacterium solution, the hydroxyapatite-Zeolite modifying object pass through NH by the mixture of hydroxyapatite and zeolite4Cl, KCl are modified It obtains, cell concentration is 5 × 10 in the Paecilomyces lilacinus bacterium solution6 CFU/mL。
The hydroxyapatite-Zeolite modifying object the preparation method comprises the following steps:
1) according to hydroxyapatite: zeolite mass ratio=1:6 amount uniformly mixes hydroxyapatite and zeolite, obtains mixture A;
2) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.7mol/L, and KCl concentration is 0.50mol/L, remaining is deionized water;The mixture A is immersed in the NH4In Cl, KCl solution, ultrasonic oscillation 3h, Then 80 ± 10 DEG C of water bath with thermostatic control keep the temperature 3h;
3) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains the hydroxyapatite-Zeolite modifying Object.
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configuration culture medium, by Paecilomyces lilacinus strain access train It supports in base, 30 DEG C, 200r/min shaking table culture 66h;Then bacterium solution is collected by centrifugation again, bacterium solution is washed 3 times with phosphate buffer, Control cell concentration is resuspended to 5 × 10 with phosphate buffer again6 CFU/mL。
Above-mentioned culture medium includes beef extract, peptone, sodium chloride, elsholtzia splendens extract, zinc nitrate and distilled water, culture The mass ratio of each component in base are as follows:
Beef extract: peptone: sodium chloride: elsholtzia splendens extract: zinc nitrate: distilled water=8g:16g:4g:1.8g:4mg: 1000g。
Above-mentioned elsholtzia splendens extract the preparation method comprises the following steps:
(1) the whole strain of fresh elsholtzia splendens is cleaned, removes root, then mashes in a reservoir;
(2) aqueous citric acid solution that Solute mass percentage composition is 16% is added in Xiang Suoshu container to mix with elsholtzia splendens, lemon The addition weight of lemon aqueous acid is 13 times of the fresh elsholtzia splendens total weight being added in container;Container is sealed again, container Interior mixture is heated to 120~140 DEG C of heat preservation 5h, naturally cools to room temperature after heat preservation;
(3) mixture in container is taken out, filtering removal solid phase residue, liquid phase is concentrated under reduced pressure into the 1/8 of liquid phase volume, obtains Obtain the elsholtzia splendens extract.
Embodiment 4
A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter includes hydroxyapatite-Zeolite modifying object and pale purple quasi- blueness Mould bacterium solution, the hydroxyapatite-Zeolite modifying object pass through NH by the mixture of hydroxyapatite and zeolite4Cl, KCl are modified It obtains, cell concentration is 5 × 10 in the Paecilomyces lilacinus bacterium solution6 CFU/mL。
The hydroxyapatite-Zeolite modifying object the preparation method comprises the following steps:
1) according to hydroxyapatite: zeolite mass ratio=1:7 amount uniformly mixes hydroxyapatite and zeolite, obtains mixture A;
2) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.8mol/L, and KCl concentration is 0.60mol/L, remaining is deionized water;The mixture A is immersed in the NH4In Cl, KCl solution, ultrasonic oscillation 3h, Then 80 ± 10 DEG C of water bath with thermostatic control keep the temperature 3h;
3) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains the hydroxyapatite-Zeolite modifying Object.
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configuration culture medium, by Paecilomyces lilacinus strain access train It supports in base, 30 DEG C, 200r/min shaking table culture 70h;Then bacterium solution is collected by centrifugation again, bacterium solution is washed 3 times with phosphate buffer, Control cell concentration is resuspended to 5 × 10 with phosphate buffer again6 CFU/mL。
Above-mentioned culture medium includes beef extract, peptone, sodium chloride, elsholtzia splendens extract, zinc nitrate and distilled water, culture The mass ratio of each component in base are as follows:
Beef extract: peptone: sodium chloride: elsholtzia splendens extract: zinc nitrate: distilled water=10g:18g:5g:2g:5mg: 1000g。
Above-mentioned elsholtzia splendens extract the preparation method comprises the following steps:
(1) the whole strain of fresh elsholtzia splendens is cleaned, removes root, then mashes in a reservoir;
(2) aqueous citric acid solution that Solute mass percentage composition is 18% is added in Xiang Suoshu container to mix with elsholtzia splendens, lemon The addition weight of lemon aqueous acid is 10 times of the fresh elsholtzia splendens total weight being added in container;Container is sealed again, container Interior mixture is heated to 120~140 DEG C of heat preservation 5h, naturally cools to room temperature after heat preservation;
(3) mixture in container is taken out, filtering removal solid phase residue, liquid phase is concentrated under reduced pressure into the 1/8 of liquid phase volume, obtains Obtain the elsholtzia splendens extract.
Comparative example 1
A kind of microorganism agricultural land soil renovation agent, the renovation agent are Paecilomyces lilacinus bacterium solution, the Paecilomyces lilacinus bacterium Cell concentration is 5 × 10 in liquid6 CFU/mL。
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configuration culture medium, by Paecilomyces lilacinus strain access train It supports in base, 30 DEG C, 200r/min shaking table culture 66h;Then bacterium solution is collected by centrifugation again, bacterium solution is washed 3 times with phosphate buffer, Control cell concentration is resuspended to 5 × 10 with phosphate buffer again6 CFU/mL。
Above-mentioned culture medium includes beef extract, peptone, sodium chloride, elsholtzia splendens extract, zinc nitrate and distilled water, culture The mass ratio of each component in base are as follows:
Beef extract: peptone: sodium chloride: elsholtzia splendens extract: zinc nitrate: distilled water=8g:16g:4g:1.8g:4mg: 1000g。
Above-mentioned elsholtzia splendens extract the preparation method comprises the following steps:
(1) the whole strain of fresh elsholtzia splendens is cleaned, removes root, then mashes in a reservoir;
(2) aqueous citric acid solution that Solute mass percentage composition is 16% is added in Xiang Suoshu container to mix with elsholtzia splendens, lemon The addition weight of lemon aqueous acid is 13 times of the fresh elsholtzia splendens total weight being added in container;Container is sealed again, container Interior mixture is heated to 120~140 DEG C of heat preservation 5h, naturally cools to room temperature after heat preservation;
(3) mixture in container is taken out, filtering removal solid phase residue, liquid phase is concentrated under reduced pressure into the 1/8 of liquid phase volume, obtains Obtain the elsholtzia splendens extract.
Comparative example 2
A kind of agricultural land soil hydroxyapatite-Zeolite modifying object renovation agent, the hydroxyapatite-Zeolite modifying object preparation side Method are as follows:
1) according to hydroxyapatite: zeolite mass ratio=1:6 amount uniformly mixes hydroxyapatite and zeolite, obtains mixture A;
2) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.7mol/L, and KCl concentration is 0.50mol/L, remaining is deionized water;The mixture A is immersed in the NH4In Cl, KCl solution, ultrasonic oscillation 3h, Then 80 ± 10 DEG C of water bath with thermostatic control keep the temperature 3h;
3) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains the hydroxyapatite-Zeolite modifying Object.
Comparative example 3
A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter includes Zeolite modifying object and Paecilomyces lilacinus bacterium solution, institute It states Zeolite modifying object and NH is passed through by zeolite4Cl, KCl are modified to be obtained, and cell concentration is 5 × 10 in the Paecilomyces lilacinus bacterium solution6 CFU/mL。
The Zeolite modifying object the preparation method comprises the following steps:
1) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.7mol/L, and KCl concentration is 0.50mol/L, remaining is deionized water;Zeolite is immersed in the NH4In Cl, KCl solution, ultrasonic oscillation 3h is then permanent 80 ± 10 DEG C of tepidarium, keep the temperature 3h;
2) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains Zeolite modifying object.
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configuration culture medium, by Paecilomyces lilacinus strain access train It supports in base, 30 DEG C, 200r/min shaking table culture 66h;Then bacterium solution is collected by centrifugation again, bacterium solution is washed 3 times with phosphate buffer, Control cell concentration is resuspended to 5 × 10 with phosphate buffer again6 CFU/mL。
Above-mentioned culture medium includes beef extract, peptone, sodium chloride, elsholtzia splendens extract, zinc nitrate and distilled water, culture The mass ratio of each component in base are as follows:
Beef extract: peptone: sodium chloride: elsholtzia splendens extract: zinc nitrate: distilled water=8g:16g:4g:1.8g:4mg: 1000g。
Above-mentioned elsholtzia splendens extract the preparation method comprises the following steps:
(1) the whole strain of fresh elsholtzia splendens is cleaned, removes root, then mashes in a reservoir;
(2) aqueous citric acid solution that Solute mass percentage composition is 16% is added in Xiang Suoshu container to mix with elsholtzia splendens, lemon The addition weight of lemon aqueous acid is 13 times of the fresh elsholtzia splendens total weight being added in container;Container is sealed again, container Interior mixture is heated to 120~140 DEG C of heat preservation 5h, naturally cools to room temperature after heat preservation;
(3) mixture in container is taken out, filtering removal solid phase residue, liquid phase is concentrated under reduced pressure into the 1/8 of liquid phase volume, obtains Obtain the elsholtzia splendens extract.
Comparative example 4
A kind of agricultural land soil microorganism-compound renovation agent of inorganic matter includes hydroxyapatite-Zeolite modifying object and pale purple quasi- blueness Mould bacterium solution, the hydroxyapatite-Zeolite modifying object pass through NH by the mixture of hydroxyapatite and zeolite4Cl, KCl are modified It obtains, cell concentration is 5 × 10 in the Paecilomyces lilacinus bacterium solution6 CFU/mL。
The hydroxyapatite-Zeolite modifying object the preparation method comprises the following steps:
1) according to hydroxyapatite: zeolite mass ratio=1:6 amount uniformly mixes hydroxyapatite and zeolite, obtains mixture A;
2) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.7mol/L, and KCl concentration is 0.50mol/L, remaining is deionized water;The mixture A is immersed in the NH4In Cl, KCl solution, ultrasonic oscillation 3h, Then 80 ± 10 DEG C of water bath with thermostatic control keep the temperature 3h;
3) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains the hydroxyapatite-Zeolite modifying Object.
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configuration culture medium, by Paecilomyces lilacinus strain access train It supports in base, 30 DEG C, 200r/min shaking table culture 66h;Then bacterium solution is collected by centrifugation again, bacterium solution is washed 3 times with phosphate buffer, Control cell concentration is resuspended to 5 × 10 with phosphate buffer again6 CFU/mL。
Above-mentioned culture medium includes beef extract, peptone, sodium chloride and distilled water, the mass ratio of each component in culture medium are as follows:
Beef extract: peptone: sodium chloride: distilled water=8g:16g:4g:1000g.
Embodiment 5
Cadmium pollution soil is taken to be divided into several pieces, every part of soil group has soil 1kg, measures cadmium content in soil and is 168.32mg/kg.Examples 1 to 4 and the resulting renovation agent of comparative example 1~4 are separately repaired into above-mentioned cadmium pollution soil Soil in group, the wherein restorative procedure of Examples 1 to 4 and comparative example 3~4 are as follows:
A. first 50g hydroxyapatite-Zeolite modifying object (or Zeolite modifying object) is sufficiently mixed with cadmium pollution soil, adjusts soil Earth moisture to soil moisture content is 20%;
B. Paecilomyces lilacinus bacterium solution described in 100mL is sprayed on cadmium pollution soil, it is primary every sprinkling in 7 days, 4 are sprayed altogether It is secondary.
The wherein restorative procedure of comparative example 1 are as follows:
A. by cadmium pollution soil scarifying, adjusting soil moisture to soil moisture content is 20%;
B. Paecilomyces lilacinus bacterium solution described in 100mL is sprayed on cadmium pollution soil, it is primary every sprinkling in 7 days, 4 are sprayed altogether It is secondary.
The wherein restorative procedure of comparative example 2 are as follows:
A. 50g hydroxyapatite-Zeolite modifying object (or Zeolite modifying object) is sufficiently mixed with cadmium pollution soil, adjusts soil Moisture to soil moisture content is 20%;
B. after 30 days in testing soil cadmium form.
Embodiment 6
Soil group (handling without renovation agent) in embodiment 5 is separately taken into portion, it is micro- with the resulting agricultural land soil of embodiment 3 The compound renovation agent of biological-inorganic object is according to following repair mode reparations:
A. citric acid thin liquid is sprayed to cadmium pollution soil, the fountain height of citric acid thin liquid is 100mL, and citric acid thin liquid is lemon The aqueous solution that the mass percentage of acid is 8%;
B. 50g hydroxyapatite-Zeolite modifying object (or Zeolite modifying object) is sufficiently mixed with cadmium pollution soil, adjusts soil Moisture to soil moisture content is 20%;
C. 100mL Paecilomyces lilacinus bacterium solution is sprayed on cadmium pollution soil, it is primary every sprinkling in 7 days, it sprays 4 times altogether.
Cd fractionation of the soil of each soil group in embodiment 5 and embodiment 6 after repair process in testing soil, cadmium Morphological analysis is measured using improved BCR method (Zhang Chaoyang etc.), is divided into weak acid bound residue, can reduction-state, oxidable state, residue State.Structure is as shown in table 1:
Table 1
Experimental group Bound residue percentage composition Oxidable state percentage composition It can reduction-state percentage composition Residual form percentage composition
Untreated soil 73.52% 9.35% 11.68% 5.45%
Embodiment 1 43.87% 8.19% 26.33% 21.61%
Embodiment 2 41.69% 8.02% 29.84% 20.45%
Embodiment 3 40.73% 7.80% 28.53% 22.94%
Embodiment 4 45.96% 8.31% 28.62% 17.11%
Comparative example 1 63.47% 10.17% 15.55% 10.81%
Comparative example 2 58.94% 8.66% 26.29% 6.11%
Comparative example 3 51.72% 9.03% 24.47% 14.78%
Comparative example 4 53.33% 8.51% 29.34% 8.82%
Embodiment 6 39.38% 7.67% 21.19% 31.76%
As shown in Table 1, by renovation agent prepared by the present invention treated cadmium pollution soil, cadmium in soil can be made from weak acid Bound residue and oxidable state cadmium to residual form and can the conversion of reduction-state cadmium, reduce the validity of cadmium, thereby reduce cadmium to agriculture The ability of crop top migration, plays the role of reparation to the cadmium in soil.Comparative example 3, comparative example 1 and comparative example 2 can Know, hydroxyl is compared using hydroxyapatite prepared by the present invention-Zeolite modifying object and Paecilomyces lilacinus bacterium solution complex repairation soil Apatite-Zeolite modifying object or Paecilomyces lilacinus bacterium solution are more preferable separately as the repairing effect of renovation agent, this may be due to Hydroxyapatite-Zeolite modifying object and Paecilomyces lilacinus bacterium solution produce synergistic effect in repair process.Comparative example 3 With comparative example 3 it is found that hydroxyapatite-zeolite composite modified object common zeolite one-component renovation agent is repaired than in the prior art Multiple effect is more preferable, is more advantageous to Cd fractionation and converts to residual form.Restorative procedure and embodiment 6 in comparative example 5 it is found that The cadmium that dilute citric acid is conducive in soil is sprayed before repairing in the soil in advance more to convert to residual form.
Technical solution provided by the present invention is described in detail above, for those of ordinary skill in the art, Thought according to an embodiment of the present invention, there will be changes in the specific implementation manner and application range, in conclusion this theory Bright book content should not be construed as limiting the invention.

Claims (9)

1. a kind of agricultural land soil microorganism-compound renovation agent of inorganic matter, which is characterized in that change comprising hydroxyapatite-zeolite Property object and Paecilomyces lilacinus bacterium solution, the hydroxyapatite-Zeolite modifying object are led to by the mixture of hydroxyapatite and zeolite Cross NH4Cl, KCl are modified to be obtained, and cell concentration is 10 in the Paecilomyces lilacinus bacterium solution5~107 CFU/mL。
2. a kind of agricultural land soil microorganism-compound renovation agent of inorganic matter according to claim 1, which is characterized in that institute It states hydroxyapatite-Zeolite modifying object to be used cooperatively with Paecilomyces lilacinus bacterium solution, the use of hydroxyapatite-Zeolite modifying object Amount is 10~20t/hm2, the usage amount of Paecilomyces lilacinus bacterium solution is 500~2000mL/m2
3. a kind of agricultural land soil microorganism-compound renovation agent of inorganic matter according to claim 1 or 2, which is characterized in that The culture medium of the Paecilomyces lilacinus includes beef extract, peptone, sodium chloride, elsholtzia splendens extract, zinc nitrate and distillation Water, the mass ratio of each component in culture medium are as follows:
Beef extract: peptone: sodium chloride: elsholtzia splendens extract: zinc nitrate: distilled water=5~10g:12~18g:2~5g:1 ~2g:3~5mg:1000g.
4. a kind of agricultural land soil microorganism-compound renovation agent of inorganic matter according to claim 3, which is characterized in that institute State elsholtzia splendens extract the preparation method comprises the following steps:
(1) the whole strain of fresh elsholtzia splendens is cleaned, removes root, then mashes in a reservoir;
(2) aqueous citric acid solution is added in Xiang Suoshu container to mix with elsholtzia splendens, then container is sealed, the mixing in container Object is heated to 120~140 DEG C of heat preservation 5h or more, naturally cools to room temperature after heat preservation;
(3) mixture in container is taken out, filtering removal solid phase residue, liquid phase is concentrated under reduced pressure, obtains the elsholtzia splendens and mention Take object.
5. a kind of agricultural land soil microorganism-compound renovation agent of inorganic matter according to claim 4, which is characterized in that institute The mass percentage for stating citric acid in aqueous citric acid solution is 10%~18%, and the addition weight of aqueous citric acid solution is to be added to hold 8~15 times of fresh elsholtzia splendens total weight in device, in the step (3), liquid phase be concentrated under reduced pressure into liquid phase volume 1/6~ 1/8。
6. agricultural land soil microorganism-inorganic matter compound renovation agent preparation method as described in any one of claim 3~5, Be characterized in that, the hydroxyapatite-Zeolite modifying object the preparation method comprises the following steps:
1) according to hydroxyapatite: zeolite mass ratio=1:3~7 amount uniformly mixes hydroxyapatite and zeolite, is mixed Close object A;
2) NH is configured4Cl, KCl solution, the NH4NH in Cl, KCl solution4Cl concentration is 0.5~0.8mol/L, and KCl concentration is 0.20~0.60mol/L, remaining is deionized water;The mixture A is immersed in the NH4In Cl, KCl solution, ultrasonic wave 2~3h is shaken, then 80 ± 10 DEG C of water bath with thermostatic control, keeps the temperature 3h or more;
3) it is separated by solid-liquid separation after keeping the temperature, solid phase is washed with deionized, and drying obtains the hydroxyapatite-Zeolite modifying Object;
The Paecilomyces lilacinus bacterium solution the preparation method comprises the following steps: configure the culture medium, Paecilomyces lilacinus strain is accessed and is trained It supports in base, 30 DEG C, 60~70h of 200r/min shaking table culture;Then bacterium solution is collected by centrifugation again, bacterium solution is washed with phosphate buffer 3 times, then control cell concentration is resuspended to 10 with phosphate buffer5~107 CFU/mL。
7. a kind of preparation method of agricultural land soil microorganism-compound renovation agent of inorganic matter according to claim 6, special Sign is, in the step 2), the NH4The quality of Cl, KCl solution be immersed in 8 times of mixture A mass therein with On.
8. agricultural land soil microorganism-inorganic matter compound renovation agent application method as described in any one of Claims 1 to 5, It is characterized in that, the steps include:
A. by the hydroxyapatite-Zeolite modifying object according to 10~20t/hm2Amount be uniformly sprinkling upon Cd pollution agricultural land soil On, hydroxyapatite-Zeolite modifying object is mixed agricultural land soil scarifying with soil, adjusts soil moisture to soil moisture content It is 10% or more;
B. 500~2000mL/m is pressed2Amount the Paecilomyces lilacinus bacterium solution is sprayed on the agricultural land soil of Cd pollution, It is primary every sprinkling in 7~10 days, it sprays 3~5 times altogether.
9. a kind of application method of agricultural land soil microorganism-compound renovation agent of inorganic matter according to claim 8, special Sign is, before the hydroxyapatite-Zeolite modifying object to be sprinkling upon to the agricultural land soil of Cd pollution, first sprays citric acid thin liquid, institute The fountain height for stating citric acid thin liquid is 5000~10000mL/m2, in citric acid thin liquid the mass percentage of citric acid be 5%~ 10%。
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