CN103752604A - Method for repairing heavy metal contaminated soil by combination of biochar and iron-reducing bacteria agent - Google Patents
Method for repairing heavy metal contaminated soil by combination of biochar and iron-reducing bacteria agent Download PDFInfo
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- CN103752604A CN103752604A CN201410026686.1A CN201410026686A CN103752604A CN 103752604 A CN103752604 A CN 103752604A CN 201410026686 A CN201410026686 A CN 201410026686A CN 103752604 A CN103752604 A CN 103752604A
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Abstract
The invention discloses a method for repairing heavy metal contaminated soil by combination of biochar and an iron-reducing bacteria agent. Adsorption of the biochar and oxidation-reduction of iron-reducing bacteria are fully exerted, and the bioremediation process of the heavy metal contaminated soil is greatly accelerated by the synergistic effect. An organic waste for preparing the biochar disclosed by the invention is wide in source, and low in cost; the iron-reducing bacteria agent is simple in preparation method, aeration facilities do not need to be added in the soil repairing process by the anaerobic metabolism ability, and operation is facilitated. The method for repairing the heavy metal contaminated soil by combination of the biochar and the iron-reducing bacteria agent has the advantages of a bioremediation technology, is outstanding in heavy metal fixing, passivating and ageing effects, and has a good application prospect.
Description
Technical field
The invention belongs to soil remediation technical field, particularly a kind of method of utilizing charcoal and iron-reducing bacterium agent renovation of heavy metal polluted soil with combined.
Background technology
Heavy metal pollution of soil not only causes the reduction of degeneration, crop yield and the quality of soil, and may threaten human health by directly contact, food chain etc.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: the one, and the existence of change heavy metal, reduces its animal migration and bioavailability in environment, i.e. heavy metal passivation; The 2nd, by engineering means, heavy metal is become to soluble state, free state, through drip washing, then collect the heavy metal in leacheate, thereby reach the dual purpose that reclaims and reduce heavy metal in soil; In addition, can 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, electronic reparation, microorganism are repaired with phytoremediation etc.
Heavy-metal contaminated soil microorganism recovery technique is generally to utilize microorganism adsorption effect and biological oxidation-reduction to realize the reparation to heavy-metal contaminated soil; Wherein, application comparatively generally original position microorganism is repaired, and refers to the in the situation that of spoiled soil basic structure not, depends on original inhabitants or inoculating microbe heavy metal in soil is converted into the form that toxicity is low or makes heavy metal aging fixing with soil mineral effect; In addition, also can utilize heavy metal in the metabolite activating soil of certain micro-organisms, thereby improve the utilization ratio of plant to heavy metal, by plant, absorb the object that reaches rehabilitating soil.Compared with conventional physical chemical repair method, microorganism recovery project is simple, and disposal cost is lower, little to soil fertility and metabolic activity negative effect, can avoid because pollutant shifts, human health and environment being exerted an influence.But, although microorganism recovery technique draws attention day by day, owing to being difficult to seek, get suitable bacterial strain, the repairing method of microorganism effects that great majority have been reported not significantly, take effect slow, repairing effect is unstable, has limited 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 iron-reducing bacterium agent synergy to make heavy metal in soil fix passivation, realize the original position microorganism of heavy-metal contaminated soil and repair.
The technical solution used in the present invention is:
A method for charcoal and iron-reducing bacterium agent renovation of heavy metal polluted soil with combined, is characterized in that: in every 1kg contaminated soil, add 50～200g charcoal and living bacteria count>=6 × 10
9iron-reducing bacterium agent, mix, bank up, repair.
Preferably, iron-reducing bacterium agent contains Corynebacterium humireducens (CGMCC 2452), comamonas (CCTCC AB 2011133) and iron reduction spring bacillus (CCTCC M 2011498).
Preferably, in iron-reducing bacterium agent, the living bacteria count ratio of Corynebacterium humireducens, comamonas and iron 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, in repair process, maintaining soil moisture is 50～70% of field saturation moisture capacity.
Preferably, repairing efficiency is 60～120 days.
Preferably, in contaminated soil, add charcoal, mix, bank up after 20～30 days, inoculate iron-reducing bacterium agent, mix, reparation continues to bank up.
Preferably, contaminated soil, through mesh screen air-dry, that mistake aperture is less than or equal to 5mm, then adds charcoal.
The invention has the beneficial effects as follows:
(1) iron-reducing bacterium can be reduced to by the high valence state of toxicity the valence state that toxicity is lower by heavy metal (Cu, Cr etc.), can also utilize the interaction of microorganism-soil mineral to make heavy metal (Pb, Cd, Zn etc.) aging, reach the object of passivation, fixing heavy metal; In heavy-metal contaminated soil, combine and apply charcoal and iron-reducing bacterium agent, except bringing into play the absorption of charcoal and the redox of iron-reducing bacterium, applying of charcoal can also maintain and improve soil physico-chemical property, adsorb the each heavy metal species in fixing soil, simultaneously for iron-reducing bacterium provides favourable place and a large amount of electron transfer mediators of perching, for the iron-reducing bacterium isoreactivity microorganism in soil provides advantage, the two synergy has greatly been accelerated 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 iron-reducing bacterium agent is simple, and its anaerobic metabolism ability also makes not need additional aeration facility in soil remediation process, 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 recovery technique, and heavy metal is fixed, passivation and aging remarkably productive, has a good application prospect.
The specific embodiment
Below in conjunction with embodiment, further set forth content of the present invention.
Charcoal is prepared from by agricultural wastes stalk: by quality, be that the air-dry rice straw of 5000g is placed in carbonizing apparatus, inflated with nitrogen deaeration, at 600 ℃ of temperature, make afterwards its complete charing, after being cooled to room temperature, take out, mix grinding, the charcoal quality obtaining is that 2269g(productive rate is 45.4%), its physicochemical property is as follows: pH 7.98, ash content 4.57wt%, organic carbon 66.52wt%.
Iron-reducing bacterium agent by Corynebacterium humireducens (
corynebacterium humireducenscGMCC 2452), comamonas (
comamonas guangdongensiscCTCC AB 2011133) and iron reduction spring bacillus (
fontibacter ferrireducenscCTCC M 2011498) 3 strain bacterial strain Mixed culture make, and exemplary, bacterial classification cultural method is as follows: LB culture medium, 7.0,30 ℃ of aerobic cultivation 48～72h of pH; LB culture medium consists of: peptone 10g/L, yeast extract 5g/L, sodium chloride 10g/L.
In embodiment, contaminated soil is taken from Dong Tang town, Renhua County, Guangdong Province demonstration pilot project.Soil is removed after the impurity such as stone, tree root, and natural air drying is standby.This soil types is sand loam, and concrete physicochemical property is as follows: pH 6.2, 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 the Zn of bioavailable state, Pb and Cd is respectively 774.5,309.8 and 3.4mg/kg; Medium Zn, the Pb of state and the concentration of Cd utilized is respectively 1535.5,524.3 and 10.4mg/kg; Difficulty utilizes Zn, the Pb of state and the concentration of Cd to be respectively 268.3,108.5 and 1.9mg/kg.
embodiment 1
In contaminated soil, only add charcoal:
Contaminated soil is crossed to 2.36mm mesh screen, get 2000g, the straw biological charcoal (crossing 4.0mm mesh screen) that adds 200g to prepare, evenly mixes; By deionized water, regulating soil moisture is afterwards 60% of field saturation moisture capacity, under room temperature, naturally bank up after 60d (by deionized water, regulating soil moisture content to initial value) in good time, measure in soil can biological utilisation state, medium utilize state utilize Zn, the Pb of form and the concentration value of Cd with difficulty.
Result shows: soil pH value rises to 7.4; Zn, the Pb of bioavailable state and the concentration of Cd are respectively 469.8,207.5 and 2.1mg/kg, have declined respectively 39.3,33.1 and 37.0%; Medium Zn, the Pb of state and the concentration of Cd utilized is respectively 1767.3,456.5 and 7.4mg/kg, wherein Zn 15.1 % that risen, and the concentration of Pb and Cd has declined respectively 13.2 and 28.6%; Difficulty utilizes Zn, the Pb of state and the concentration of Cd to be respectively 274.3,287.5 and 5.5mg/kg, has risen respectively 2.2,164.9 and 183.1%.
embodiment 2
In contaminated soil, only add iron-reducing bacterium agent:
Contaminated soil is crossed to 2.36mm mesh screen, get 2000g, (living bacteria count is 1.75 × 10 to the agent of inoculation 80mL iron-reducing bacterium
10wherein, the living bacteria count ratio of Corynebacterium humireducens, comamonas and iron reduction spring bacillus is 0.8:1.3:1), then by deionized water, regulating soil moisture is 60% of field saturation moisture capacity, under room temperature, naturally bank up after 60d (by deionized water, regulating soil moisture content to initial value) in good time, measure in soil can biological utilisation state, medium utilize state utilize Zn, the Pb of form and the concentration value of Cd with difficulty.
Result shows: soil pH value rises to 6.5; Zn, the Pb of bioavailable state and the concentration of Cd are respectively 643.3,247.8 and 2.9mg/kg, have declined respectively 16.9,20.2 and 41.0%; Medium Zn, the Pb of state and the concentration of Cd utilized is respectively 1502.8,506.3 and 9.8mg/kg, and the concentration of Zn, Pb and Cd has declined respectively 2.1,3.4 and 6.2%; Difficulty utilizes Zn, the Pb of state and the concentration of Cd to be respectively 354.0,188.8 and 2.9 mg/kg, has risen respectively 31.9,73.9 and 51.9%.
embodiment 3
In contaminated soil, apply charcoal and iron-reducing bacterium agent simultaneously:
Contaminated soil is crossed to 2.36mm mesh screen, get 2000g, the straw biological charcoal (crossing 4.0mm mesh screen) that adds 200g to prepare, evenly mixes; Add again afterwards 80mL iron-reducing bacterium agent (with embodiment 2), by deionized water, regulating soil moisture is 60% of field saturation moisture capacity, under room temperature, naturally bank up after 60d (by deionized water, regulating soil moisture content to initial value) in good time, measure in soil can biological utilisation state, medium utilize state utilize Zn, the Pb of form and the concentration value of Cd with difficulty.
Result shows: soil pH value rises to 7.0; Zn, the Pb of bioavailable state and the concentration of Cd are respectively 408.8,185.9 and 1.2mg/kg, have declined respectively 47.2,40.0 and 65.9%; Medium Zn, the Pb of state and the concentration of Cd utilized is respectively 1732.3,430.0 and 8.7mg/kg, and wherein the risen concentration of 12.8%, Pb and Cd of Zn has declined respectively 17.9 and 16.8%; Difficulty utilizes Zn, the Pb of state and the concentration of Cd to be respectively 397.5,338.8 and 5.6mg/kg, has risen respectively 48.1,212.2 and 192.2%.
For verifying the repairing effect of this implementation method to heavy metal, after the soil remediation process of 60d finishes, respectively not transplanting pakchoi seedling in rehabilitating soil and rehabilitating soil, pakchoi growth period of growing seedlings is 20 days.By detecting the heavy metal concentration of pakchoi overground part and underground root, in rehabilitating soil, the concentration of pakchoi overground part and root Zn is respectively 256.8 and 177.6mg/kg, than not 613.2 and 255.2mg/kg of rehabilitating soil, declined respectively 58.1 and 30.4%; The concentration of overground part and root Pb is respectively 13.9 and 46.0mg/kg, than not 22.9 and 77.6mg/kg of rehabilitating soil, has declined respectively 39.3 and 40.7%; The concentration of overground part and root Cd is respectively 3.4 and 9.9mg/kg, than not 7.1 and 24.8mg/kg of rehabilitating soil, has declined respectively 52.1 and 60.1%.
embodiment 4
In contaminated soil, substep applies biological carbon and iron-reducing bacterium agent:
Contaminated soil is crossed to 2.36mm mesh screen, get 2000g, first add straw biological charcoal prepared by 200g (crossing 4.0mm mesh screen), evenly mix with soil, and by deionized water, to regulate soil moisture be 60% of field saturation moisture capacity, 30d banks up under room temperature; Afterwards, to adding the 30d that banks up again after 80mL iron-reducing bacterium agent (with embodiment 2) in soil, during banking up, by deionized water, regulate soil moisture content to initial value in good time, measure in soil can biological utilisation state, medium utilize state utilize Zn, the Pb of form and the concentration value of Cd with difficulty.
Result shows: soil pH value rises to 7.2; Zn, the Pb of bioavailable state and the concentration of Cd are respectively 390.1,147.1 and 0.9mg/kg, have declined respectively 49.6,52.5 and 74.7%; Medium Zn, the Pb of state and the concentration of Cd utilized is respectively 1738.5,481.3 and 8.6mg/kg, and wherein the risen concentration of 13.2%, Pb and Cd of Zn has declined respectively 8.2 and 17.1%; Difficulty utilizes Zn, the Pb of state and the concentration of Cd to be respectively 385.3,368.3 and 6.1mg/kg, and 45.6,239.8 and 216.9 % have risen respectively.
For verifying the repairing effect of this implementation method to heavy metal, after repair process finishes, respectively not transplanting pakchoi seedling in rehabilitating soil and rehabilitating soil, pakchoi growth period of growing seedlings is 20 days.By detecting the concentration of heavy metal of pakchoi overground part and underground root, the overground part of Zn and root concentration are respectively 270.9 and 118.4mg/kg, than not 613.2 and 255.2mg/kg of rehabilitating soil, have declined respectively 55.8 and 53.6%; The overground part of Pb and root concentration are respectively 10.9 and 37.8mg/kg, than not 22.9 and 77.6mg/kg of rehabilitating soil, have declined respectively 52.4 and 51.3%; The overground part of Cd and root concentration are respectively 2.6 and 6.9mg/kg, than not 7.1 and 24.8mg/kg of rehabilitating soil, have declined respectively 63.4 and 72.2%.
Comparative example 1～4 reparation result is known, compared to applying separately charcoal or inoculation iron-reducing bacterium, in heavy-metal contaminated soil charcoal and iron-reducing bacterium agent combined remediation method can more effective reduction soil in the heavy metal such as Zn, Pb and Cd can biological utilisation state concentration, and reduce the uptake of cultivated plant to heavy metal in soil, thereby reach the object of biological prosthetic heavy-metal contaminated soil.And, apply and add again iron-reducing bacterium agent after charcoal 30d and there is more significant repairing effect.
embodiment 5
Contaminated soil is crossed after 4.0mm mesh screen, got 2000g, first add straw biological charcoal prepared by 100g (crossing 4.75mm mesh screen), evenly mix with soil, and by deionized water, to regulate soil moisture be 50% of field saturation moisture capacity, 30d banks up under room temperature; Afterwards, to adding iron-reducing bacterium agent in soil, (living bacteria count is 1.64 × 10
10wherein, the living bacteria count ratio of Corynebacterium humireducens, comamonas and iron reduction spring bacillus is 0.5:0.5:1) after the 70d that banks up again, during banking up, by deionized water, regulate soil moisture content to initial value in good time, measure in soil can biological utilisation state, medium utilize state utilize Zn, the Pb of form and the concentration value of Cd with difficulty.
Result shows: soil pH value rises to 7.1; Zn, the Pb of bioavailable state and the concentration of Cd have declined respectively 45.8,49.5 and 71.1%; The risen concentration of 15.3%, Pb and Cd of the medium Zn that utilizes state has declined respectively 7.4 and 15.4%; Difficulty utilizes Zn, the Pb of state and the concentration of Cd to rise respectively 39.8,198.7 and 186.4%.
embodiment 6
Contaminated soil is crossed to 4.75mm mesh screen, get 2000g, first add straw biological charcoal prepared by 400g (crossing 4.75mm mesh screen), evenly mix with soil, and by deionized water, to regulate soil moisture be 70% of field saturation moisture capacity, 20d banks up under room temperature; Afterwards, to adding iron-reducing bacterium agent in soil, (living bacteria count is 1.3 × 10
10wherein, the living bacteria count ratio of Corynebacterium humireducens, comamonas and iron reduction spring bacillus is 1.0:1.2:1) after the 100d that banks up again, during banking up, by deionized water, regulate soil moisture content to initial value in good time, measure in soil can biological utilisation state, medium utilize state utilize Zn, the Pb of form and the concentration value of Cd with difficulty.
Result shows: soil pH value rises to 7.4; Zn, the Pb of bioavailable state and the concentration of Cd have declined respectively 58.3,65.4 and 91.2%; The risen concentration of 7.5%, Pb and Cd of the medium Zn that utilizes state has declined respectively 14.3 and 27.6%; Difficulty utilizes Zn, the Pb of state and the concentration of Cd to rise respectively 58.1,289.4 and 257.6%.
embodiment 7
Contaminated soil is crossed to 4.0mm mesh screen, get 2000g, first add straw biological charcoal prepared by 300g (crossing 2.8mm mesh screen), evenly mix with soil, and by deionized water, to regulate soil moisture be 60% of field saturation moisture capacity, 20d banks up under room temperature; Afterwards, to adding iron-reducing bacterium agent in soil, (living bacteria count is 1.82 × 10
10wherein, the living bacteria count ratio of Corynebacterium humireducens, comamonas and iron reduction spring bacillus is 0.8:1.5:1) after the 80d that banks up again, during banking up, by deionized water, regulate soil moisture content to initial value in good time, measure in soil can biological utilisation state, medium utilize state utilize Zn, the Pb of form and the concentration value of Cd with difficulty.
Result shows: soil pH value rises to 7.3; Zn, the Pb of bioavailable state and the concentration of Cd have declined respectively 53.6,57.9 and 82.4%; The risen concentration of 9.1%, Pb and Cd of the medium Zn that utilizes state has declined respectively 9.6 and 22.4%; Difficulty utilizes Zn, the Pb of state and the concentration of Cd to rise respectively 52.7,254.1 and 239.8%.
Claims (8)
1. a method for charcoal and iron-reducing bacterium agent renovation of heavy metal polluted soil with combined, is characterized in that: in every 1kg contaminated soil, add 50～200g charcoal and living bacteria count>=6 × 10
9iron-reducing bacterium agent, mix, bank up, repair.
2. method according to claim 1, is characterized in that: iron-reducing bacterium agent contains Corynebacterium humireducens (CGMCC 2452), comamonas (CCTCC AB 2011133) and iron reduction spring bacillus (CCTCC M 2011498).
3. method according to claim 2, is characterized in that: in iron-reducing bacterium agent, the living bacteria count ratio of Corynebacterium humireducens, comamonas and iron reduction spring bacillus is (0.5～1.0): (0.5～1.5): 1.
4. method according to claim 1, is characterized in that: the particle diameter of charcoal is less than or equal to 5mm.
5. method according to claim 1, is characterized in that: in repair process, maintaining soil moisture is 50～70% of field saturation moisture capacity.
6. method according to claim 1, is characterized in that: repairing efficiency is 60～120 days.
7. according to the method described in claim 1～6 any one, it is characterized in that: in contaminated soil, add charcoal, mix, bank up after 20～30 days, inoculate iron-reducing bacterium agent, mix, reparation continues to bank up.
8. method according to claim 1, is characterized in that: contaminated soil, through mesh screen air-dry, that mistake aperture is less than or equal to 5mm, then adds charcoal.
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| CN105170641A (en) * | 2015-09-30 | 2015-12-23 | 河南行知专利服务有限公司 | Combined remediation method for heavy metal contaminated soil |
| CN105385451A (en) * | 2015-12-10 | 2016-03-09 | 湖南美鑫隆生态环保科技有限公司 | Iron humate-microbe composite soil pollution repairing agent and preparation method thereof |
| CN105670640A (en) * | 2016-01-07 | 2016-06-15 | 湖南美鑫隆生态环保科技有限公司 | Composite soil conditioner for treating Cd pollution, and preparation and use methods thereof |
| CN105950164A (en) * | 2016-04-30 | 2016-09-21 | 安徽农业大学 | Heavy metal polluted soil repairing agent and repairing method thereof |
| CN106008051A (en) * | 2014-10-21 | 2016-10-12 | 苗庆龄 | Complex improver for restoring heavy metal contaminated soil |
| CN107597826A (en) * | 2017-10-27 | 2018-01-19 | 中国环境科学研究院 | The preparation method and applications of charcoal base compost fulvic acid composite |
| CN109626771A (en) * | 2018-12-13 | 2019-04-16 | 广东省生态环境技术研究所 | A method of promote anaerobically digested sludge heavy metal stable |
| CN110257272A (en) * | 2019-04-04 | 2019-09-20 | 华中农业大学 | Comamonas and the efficiently fixed cadmium of the composite bacteria agent of enterobacteria and the application in cadmium pollution reparation |
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