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CN103752604B - A kind of method of charcoal and Fe3+ reduction microbial inoculum renovation of heavy metal polluted soil with combined - Google Patents

A kind of method of charcoal and Fe3+ reduction microbial inoculum renovation of heavy metal polluted soil with combined Download PDF

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CN103752604B
CN103752604B CN201410026686.1A CN201410026686A CN103752604B CN 103752604 B CN103752604 B CN 103752604B CN 201410026686 A CN201410026686 A CN 201410026686A CN 103752604 B CN103752604 B CN 103752604B
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soil
charcoal
microbial inoculum
heavy metal
reduction
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CN103752604A (en
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余震
周顺桂
岳艳丽
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Guangdong Institute of Eco Environmental Science and Technology
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Guangdong Institute of Eco Environment and Soil Sciences
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Abstract

The invention discloses a kind of method of charcoal and Fe3+ reduction microbial inoculum renovation of heavy metal polluted soil with combined, give full play to the absorption of charcoal and the redox of iron-reducing bacterium, the two synergy greatly accelerates the biological prosthetic process of heavy-metal contaminated soil.The present invention is for the preparation of the debirs wide material sources of charcoal, with low cost; The preparation method of Fe3+ reduction microbial inoculum is simple, and its anaerobic metabolism ability also makes in soil remediation process, do not need additional aeration facility, and operation is convenient.Charcoal of the present invention and iron-reducing bacterium renovation of heavy metal polluted soil with combined are in-situ remediation methods, and this method has the advantage of microorganism remediation technology, and heavy metal is fixed, passivation and aging effect are given prominence to, and has a good application prospect.

Description

A kind of method of charcoal and Fe3+ reduction microbial inoculum renovation of heavy metal polluted soil with combined
Technical field
The invention belongs to technical field of soil remediation, particularly a kind of method utilizing charcoal and Fe3+ reduction microbial inoculum renovation of heavy metal polluted soil with combined.
Background technology
Heavy metal pollution of soil not only causes the reduction of the degeneration of soil, crop yield and quality, and can by directly contact, food chain etc. threaten human health.Therefore, heavy-metal contaminated soil reparation is the focus that recent domestic is paid close attention to.At present, heavy metal pollution reparation mainly contains following approach: one is change the existence of heavy metal, reduces its animal migration in the environment and bioavailability, i.e. heavy metal passivation; Two is, by engineering means, heavy metal is become soluble state, free state, through drip washing, then collects the heavy metal in leacheate, thus reaches the dual purpose reclaiming and reduce heavy metal in soil; In addition, utilize enriching plant to absorb heavy metal in soil by agronomic measures, then this plant is removed.The concrete measure of soil remediation has: chemistry is fixing, Soil leaching, thermal desorption, electro reclamation, microorganism remediation and phytoremediation etc.
Heavy-metal contaminated soil microorganism remediation technology is generally the reparation utilizing microorganism adsorption effect and biological oxidation-reduction to realize heavy metal contaminated soil; Wherein, application comparatively generally original position microorganism remediation, namely refers to when not spoiled soil basic structure, depends on original inhabitants or heavy metal in soil is converted into the low form of toxicity by inoculating microbe or make heavy metal aging fixing with soil mineral effect; In addition, also can utilize heavy metal in the metabolite activating soil of certain micro-organisms, thus improve the utilization ratio of plant heavy metal, be reached the object of rehabilitating soil by plant absorption.Compared with conventional physical chemical repair method, microorganism remediation engineering is simple, and disposal cost is lower, to soil fertility and metabolic activity negative effect little, can avoid because pollutant transfer human health and environmental effects.But, although microorganism remediation technology draws attention day by day, get Suitable strains owing to being difficult to seek, the repairing method of microorganism effect reported of great majority not significantly, take effect slow, repairing effect is unstable, limits applying of this technology.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, utilize charcoal and the synergy of Fe3+ reduction microbial inoculum to make heavy metal in soil fix passivation, realize the original position microorganism remediation of heavy-metal contaminated soil.
The technical solution used in the present invention is:
A method for charcoal and Fe3+ reduction microbial inoculum renovation of heavy metal polluted soil with combined, is characterized in that: add 50 ~ 200g charcoal and living bacteria count>=6 × 10 in every 1kg contaminated soil 9fe3+ reduction microbial inoculum, mix, bank up, repair.
Preferably, Fe3+ reduction microbial inoculum contains Corynebacterium humireducens (CGMCC2452), comamonas (CCTCCAB2011133) and Fe3+ reduction spring bacillus (CCTCCM2011498).
Preferably, the living bacteria count ratio of Corynebacterium humireducens in Fe3+ reduction microbial inoculum, comamonas and Fe3+ reduction spring bacillus is (0.5 ~ 1.0): (0.5 ~ 1.5): 1.
Preferably, the particle diameter of charcoal is less than or equal to 5mm.
Preferably, maintain in repair process that soil moisture is field saturation moisture capacity 50 ~ 70%.
Preferably, repairing efficiency is 60 ~ 120 days.
Preferably, in contaminated soil, add charcoal, mix, after banking up 20 ~ 30 days, inoculate Fe3+ reduction microbial inoculum, mix, continue reparation of banking up.
Preferably, contaminated soil, through air-dry, that mistake aperture is less than or equal to 5mm mesh screen, then adds charcoal.
The invention has the beneficial effects as follows:
(1) heavy metal (Cu, Cr etc.) can be reduced to the lower valence state of toxicity by the valence state that toxicity is high by iron-reducing bacterium, the interaction of microorganism-soil mineral can also be utilized to make heavy metal (Pb, Cd, Zn etc.) aging, reach the object of passivation, fixing heavy metal; Combine in heavy-metal contaminated soil and apply charcoal and Fe3+ reduction microbial inoculum, except the redox of the absorption and iron-reducing bacterium that can play charcoal, the applying of charcoal can also maintain and improve each heavy metal species in soil physico-chemical property, absorption fixing soil, favourable perch place and a large amount of electron transfer mediators for iron-reducing bacterium provides simultaneously, for the iron-reducing bacterium isoreactivity microorganism in soil provides advantage, the two synergy greatly accelerates the biological prosthetic process of heavy-metal contaminated soil.
(2) the present invention is for the preparation of the debirs wide material sources of charcoal, with low cost; The preparation method of Fe3+ reduction microbial inoculum is simple, and its anaerobic metabolism ability also makes in soil remediation process, do not need additional aeration facility, and operation is convenient.Charcoal of the present invention and iron-reducing bacterium renovation of heavy metal polluted soil with combined are in-situ remediation methods, and this method has the advantage of microorganism remediation technology, and heavy metal is fixed, passivation and aging effect are given prominence to, and has a good application prospect.
Detailed description of the invention
Below in conjunction with embodiment, set forth content of the present invention further.
Charcoal is prepared from by agricultural wastes stalk: be that the air-dry rice straw of 5000g is placed in carbonizing apparatus by quality, inflated with nitrogen deaeration, at 600 DEG C of temperature, it is made to carbonize completely afterwards, take out after being cooled to room temperature, mixing grinding, the charcoal quality obtained is 2269g(productive rate is 45.4%), its physicochemical property is as follows: pH7.98, ash content 4.57wt%, organic carbon 66.52wt%.
Fe3+ reduction microbial inoculum by Corynebacterium humireducens ( corynebacteriumhumireducenscGMCC2452), comamonas ( comamonasguangdongensiscCTCCAB2011133) and Fe3+ reduction spring bacillus ( fontibacterferrireducenscCTCCM2011498) 3 strain bacterial strain Mixed culture are made, and exemplary, Spawn incubation method is as follows: LB culture medium, pH7.0,30 DEG C of aerobic cultivation 48 ~ 72h; LB culture medium consists of: peptone 10g/L, yeast extract 5g/L, sodium chloride 10g/L.
In embodiment, contaminated soil takes from Dong Tang town, Renhua County, Guangdong Province demonstration pilot project.After soil removes the impurity such as stone, tree root, natural air drying is for subsequent use.This soil types is sand loam, and concrete physicochemical property is as follows: pH6.2, machine matter content 9.8g/kg, full nitrogen 0.49g/kg, rapid available phosphorus 11.8g/kg and available potassium 89.4g/kg.The concentration of heavy metal Zn, Pb and Cd is respectively 2578.3,942.5 and 15.7mg/kg.Wherein, the concentration of Zn, Pb and Cd of bioavailable state is respectively 774.5,309.8 and 3.4mg/kg; The medium concentration of Zn, Pb and Cd of state that utilizes is respectively 1535.5,524.3 and 10.4mg/kg; Difficulty utilizes the concentration of Zn, Pb and Cd of state to be respectively 268.3,108.5 and 1.9mg/kg.
embodiment 1
Only charcoal is added in contaminated soil:
Contaminated soil is crossed 2.36mm mesh screen, get 2000g, add straw biological charcoal (crossing 4.0mm mesh screen) prepared by 200g, Homogeneous phase mixing; Soil moisture is regulated to be 60% of field saturation moisture capacity by deionized water afterwards, naturally bank up under room temperature after 60d and (regulate soil moisture content to initial value by deionized water in good time), measuring can biological utilisation state, the medium concentration value utilizing Zn, Pb and Cd of form with difficulty utilizing state in soil.
Result shows: soil pH value rises to 7.4; The concentration of Zn, Pb and Cd of bioavailable state is respectively 469.8,207.5 and 2.1mg/kg, have dropped 39.3,33.1 and 37.0% respectively; The medium concentration of Zn, Pb and Cd of state that utilizes is respectively 1767.3,456.5 and 7.4mg/kg, and the concentration that wherein Zn rises 15.1%, Pb and Cd have dropped 13.2 and 28.6% respectively; Difficulty utilizes the concentration of Zn, Pb and Cd of state to be respectively 274.3,287.5 and 5.5mg/kg, rises 2.2,164.9 and 183.1% respectively.
embodiment 2
Only Fe3+ reduction microbial inoculum is added in contaminated soil:
Contaminated soil is crossed 2.36mm mesh screen, get 2000g, (living bacteria count is 1.75 × 10 to inoculation 80mL Fe3+ reduction microbial inoculum 10wherein, the living bacteria count ratio of Corynebacterium humireducens, comamonas and Fe3+ reduction spring bacillus is 0.8:1.3:1), then soil moisture is regulated to be 60% of field saturation moisture capacity by deionized water, naturally bank up under room temperature after 60d and (regulate soil moisture content to initial value by deionized water in good time), measuring can biological utilisation state, the medium concentration value utilizing Zn, Pb and Cd of form with difficulty utilizing state in soil.
Result shows: soil pH value rises to 6.5; The concentration of Zn, Pb and Cd of bioavailable state is respectively 643.3,247.8 and 2.9mg/kg, have dropped 16.9,20.2 and 41.0% respectively; Medium utilize the concentration of Zn, Pb and Cd of state be respectively 1502.8,506.3 and 9.8mg/kg, Zn, Pb and Cd concentration have dropped 2.1,3.4 and 6.2% respectively; Difficulty utilizes the concentration of Zn, Pb and Cd of state to be respectively 354.0,188.8 and 2.9mg/kg, rises 31.9,73.9 and 51.9% respectively.
embodiment 3
Apply charcoal and Fe3+ reduction microbial inoculum in contaminated soil simultaneously:
Contaminated soil is crossed 2.36mm mesh screen, get 2000g, add straw biological charcoal (crossing 4.0mm mesh screen) prepared by 200g, Homogeneous phase mixing; Add 80mL Fe3+ reduction microbial inoculum (with embodiment 2) afterwards again, soil moisture is regulated to be 60% of field saturation moisture capacity by deionized water, naturally bank up under room temperature after 60d and (regulate soil moisture content to initial value by deionized water in good time), measuring can biological utilisation state, the medium concentration value utilizing Zn, Pb and Cd of form with difficulty utilizing state in soil.
Result shows: soil pH value rises to 7.0; The concentration of Zn, Pb and Cd of bioavailable state is respectively 408.8,185.9 and 1.2mg/kg, have dropped 47.2,40.0 and 65.9% respectively; The medium concentration of Zn, Pb and Cd of state that utilizes is respectively 1732.3,430.0 and 8.7mg/kg, and the concentration that wherein Zn rises 12.8%, Pb and Cd have dropped 17.9 and 16.8% respectively; Difficulty utilizes the concentration of Zn, Pb and Cd of state to be respectively 397.5,338.8 and 5.6mg/kg, rises 48.1,212.2 and 192.2% respectively.
For verifying the repairing effect of this implementation method heavy metal, after the soil remediation process of 60d terminates, transplant pakchoi seedling respectively in non-rehabilitating soil and rehabilitating soil, pakchoi nursery growth period is 20 days.By detecting the heavy metal concentration of pakchoi overground part and subterranean root, in rehabilitating soil, the concentration of pakchoi overground part and root Zn is respectively 256.8 and 177.6mg/kg, compared to 613.2 and 255.2mg/kg of non-rehabilitating soil, have dropped 58.1 and 30.4% respectively; The concentration of overground part and root Pb is respectively 13.9 and 46.0mg/kg, compared to 22.9 and 77.6mg/kg of non-rehabilitating soil, have dropped 39.3 and 40.7% respectively; The concentration of overground part and root Cd is respectively 3.4 and 9.9mg/kg, compared to 7.1 and 24.8mg/kg of non-rehabilitating soil, have dropped 52.1 and 60.1% respectively.
embodiment 4
In contaminated soil, substep applies biological carbon and Fe3+ reduction microbial inoculum:
Contaminated soil is crossed 2.36mm mesh screen, get 2000g, first add straw biological charcoal (crossing 4.0mm mesh screen) prepared by 200g, with soil Homogeneous phase mixing, and regulate soil moisture to be 60% of field saturation moisture capacity by deionized water, bank up under room temperature 30d; Afterwards, bank up add 80mL Fe3+ reduction microbial inoculum (with embodiment 2) in soil after 30d again, bank up period, regulate soil moisture content to initial value by deionized water, measuring can biological utilisation state, the medium concentration value utilizing Zn, Pb and Cd of form with difficulty utilizing state in soil in good time.
Result shows: soil pH value rises to 7.2; The concentration of Zn, Pb and Cd of bioavailable state is respectively 390.1,147.1 and 0.9mg/kg, have dropped 49.6,52.5 and 74.7% respectively; The medium concentration of Zn, Pb and Cd of state that utilizes is respectively 1738.5,481.3 and 8.6mg/kg, and the concentration that wherein Zn rises 13.2%, Pb and Cd have dropped 8.2 and 17.1% respectively; Difficulty utilizes the concentration of Zn, Pb and Cd of state to be respectively 385.3,368.3 and 6.1mg/kg, rises 45.6,239.8 and 216.9% respectively.
For verifying the repairing effect of this implementation method heavy metal, after repair process terminates, transplant pakchoi seedling respectively in non-rehabilitating soil and rehabilitating soil, pakchoi nursery growth period is 20 days.By detecting the concentration of the heavy metal of pakchoi overground part and subterranean root, overground part and the root concentration of Zn are respectively 270.9 and 118.4mg/kg, compared to 613.2 and 255.2mg/kg of non-rehabilitating soil, have dropped 55.8 and 53.6% respectively; Overground part and the root concentration of Pb are respectively 10.9 and 37.8mg/kg, compared to 22.9 and 77.6mg/kg of non-rehabilitating soil, have dropped 52.4 and 51.3% respectively; Overground part and the root concentration of Cd are respectively 2.6 and 6.9mg/kg, compared to 7.1 and 24.8mg/kg of non-rehabilitating soil, have dropped 63.4 and 72.2% respectively.
The reparation result of comparative example 1 ~ 4 is known, compared to applying separately charcoal or inoculation iron-reducing bacterium, in heavy-metal contaminated soil charcoal and Fe3+ reduction microbial inoculum combined remediation method can in more effective reduction soil the heavy metal such as Zn, Pb and Cd can biological utilisation state concentration, and reduce the uptake of cultivated plant heavy metal in soil, thus reach the object of biological prosthetic heavy-metal contaminated soil.And, add Fe3+ reduction microbial inoculum again after applying charcoal 30d and there is more significant repairing effect.
embodiment 5
After contaminated soil being crossed 4.0mm mesh screen, get 2000g, first add straw biological charcoal (crossing 4.75mm mesh screen) prepared by 100g, with soil Homogeneous phase mixing, and regulate soil moisture to be 50% of field saturation moisture capacity by deionized water, bank up under room temperature 30d; Afterwards, (living bacteria count is 1.64 × 10 in soil, to add Fe3+ reduction microbial inoculum 10wherein, the living bacteria count ratio of Corynebacterium humireducens, comamonas and Fe3+ reduction spring bacillus is 0.5:0.5:1) after to bank up again 70d, bank up period, regulate soil moisture content to initial value by deionized water, measuring can biological utilisation state, the medium concentration value utilizing Zn, Pb and Cd of form with difficulty utilizing state in soil in good time.
Result shows: soil pH value rises to 7.1; The concentration of Zn, Pb and Cd of bioavailable state have dropped 45.8,49.5 and 71.1% respectively; The medium concentration utilizing the Zn of state to rise 15.3%, Pb and Cd have dropped 7.4 and 15.4% respectively; Difficulty utilizes the concentration of Zn, Pb and Cd of state to rise 39.8,198.7 and 186.4% respectively.
embodiment 6
Contaminated soil is crossed 4.75mm mesh screen, get 2000g, first add straw biological charcoal (crossing 4.75mm mesh screen) prepared by 400g, with soil Homogeneous phase mixing, and regulate soil moisture to be 70% of field saturation moisture capacity by deionized water, bank up under room temperature 20d; Afterwards, (living bacteria count is 1.3 × 10 in soil, to add Fe3+ reduction microbial inoculum 10wherein, the living bacteria count ratio of Corynebacterium humireducens, comamonas and Fe3+ reduction spring bacillus is 1.0:1.2:1) after to bank up again 100d, bank up period, regulate soil moisture content to initial value by deionized water, measuring can biological utilisation state, the medium concentration value utilizing Zn, Pb and Cd of form with difficulty utilizing state in soil in good time.
Result shows: soil pH value rises to 7.4; The concentration of Zn, Pb and Cd of bioavailable state have dropped 58.3,65.4 and 91.2% respectively; The medium concentration utilizing the Zn of state to rise 7.5%, Pb and Cd have dropped 14.3 and 27.6% respectively; Difficulty utilizes the concentration of Zn, Pb and Cd of state to rise 58.1,289.4 and 257.6% respectively.
embodiment 7
Contaminated soil is crossed 4.0mm mesh screen, get 2000g, first add straw biological charcoal (crossing 2.8mm mesh screen) prepared by 300g, with soil Homogeneous phase mixing, and regulate soil moisture to be 60% of field saturation moisture capacity by deionized water, bank up under room temperature 20d; Afterwards, (living bacteria count is 1.82 × 10 in soil, to add Fe3+ reduction microbial inoculum 10wherein, the living bacteria count ratio of Corynebacterium humireducens, comamonas and Fe3+ reduction spring bacillus is 0.8:1.5:1) after to bank up again 80d, bank up period, regulate soil moisture content to initial value by deionized water, measuring can biological utilisation state, the medium concentration value utilizing Zn, Pb and Cd of form with difficulty utilizing state in soil in good time.
Result shows: soil pH value rises to 7.3; The concentration of Zn, Pb and Cd of bioavailable state have dropped 53.6,57.9 and 82.4% respectively; The medium concentration utilizing the Zn of state to rise 9.1%, Pb and Cd have dropped 9.6 and 22.4% respectively; Difficulty utilizes the concentration of Zn, Pb and Cd of state to rise 52.7,254.1 and 239.8% respectively.

Claims (7)

1. a method for charcoal and Fe3+ reduction microbial inoculum renovation of heavy metal polluted soil with combined, is characterized in that: add 50 ~ 200g charcoal and living bacteria count>=6 × 10 in every 1kg contaminated soil 9fe3+ reduction microbial inoculum, mix, bank up, repair; Wherein, Fe3+ reduction microbial inoculum contains Corynebacterium humireducens (CGMCC2452), comamonas (CCTCCAB2011133) and Fe3+ reduction spring bacillus (CCTCCM2011498).
2. method according to claim 1, is characterized in that: the living bacteria count ratio of Corynebacterium humireducens in Fe3+ reduction microbial inoculum, comamonas and Fe3+ reduction spring bacillus is (0.5 ~ 1.0): (0.5 ~ 1.5): 1.
3. method according to claim 1, is characterized in that: the particle diameter of charcoal is less than or equal to 5mm.
4. method according to claim 1, is characterized in that: maintain in repair process that soil moisture is field saturation moisture capacity 50 ~ 70%.
5. method according to claim 1, is characterized in that: repairing efficiency is 60 ~ 120 days.
6. the method according to Claims 1 to 5 any one, is characterized in that: in contaminated soil, add charcoal, mix, and after banking up 20 ~ 30 days, inoculates Fe3+ reduction microbial inoculum, mixes, continue reparation of banking up.
7. method according to claim 1, is characterized in that: contaminated soil, through air-dry, that mistake aperture is less than or equal to 5mm mesh screen, then adds charcoal.
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