CN110280582A - The method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride - Google Patents
The method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride Download PDFInfo
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- B09C1/08—Reclamation of contaminated soil chemically
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Abstract
The invention discloses a kind of methods of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride.The invention firstly uses the chloro groups of the strong reducing action of micron Zero-valent Iron removing Organochlorine Pesticides In Soil, growth, breeding and metabolic degradation organo-chlorine pesticide that biological carbon source, electron donor, nitrogen and phosphorus promote indigenous microorganism in soil are added, the consumption of sulfate reduction inhibitor and the inhibition of methane phase inhibitor to electronics is added.Utilize Fe0Restore the Fe generated2+And Fe3+While promoting its growth to the enzymatic catalysis of indigenous microorganism, the organic acid of indigenous microorganism metabolic activity secretion influences the reduction dechlorination process of soil colloid interface organo-chlorine pesticide, soil pH is adjusted, accelerates the etching of Zero-valent Iron, promotes the reductive dechlorination of Zero-valent Iron.Compared with being restored using Zero-valent Iron merely or repairing the restorative procedure of organochlorine pesticide pollution soil using indigenous microorganism, this method has remediation efficiency height, short time limit, repairs the advantages such as thorough, without secondary pollution.
Description
Technical field
The invention belongs to soil pollution recovery technique fields, and in particular to a kind of Zero-valent Iron reduction joint indigenous microorganism is repaired
The method of multiple soil polluted by organic chloride.
Background technique
Organo-chlorine pesticide is a kind of typical environmental contaminants, their usual chemical stability (half-life period with higher
It is long), lipophilic hydrophobicity, bioconcentration, the features such as bio-toxicity.These pollutants are mainly derived from the useless raw material of pesticide producing,
Run, drip, leak etc. during chemical industry pesticide producing.China's " soil environment quality construction land soil pollution risk management and control mark
Quasi- (tentative) " (GB36600-2018) announcement 85 kinds of pollution projects in, organochlorine accounts for 46 kinds；China's " soil environment quality
Farming land soil pollution risk management and control standard (tentative) " (GB15618-2018) announce farming land soil pollution risk screening
In pollutant sundry item, the risk screening value of six six six total amount and DDT total amount is specified.Research shows that organo-chlorine pesticide
There is very strong carcinogenic, teratogenesis, mutagenesis to biology, most of organo-chlorine pesticide belongs to incretion interferent or potential
Incretion interferent.Since organo-chlorine pesticide is difficult to natural degradation, can exist steadily in the long term in the environment, if cannot effectively repair
Processing, it will the health or even existence of the mankind are posed a serious threat.
Currently, for organochlorine pesticide pollution soil restorative procedure mainly have physical method, thermal desorption method, advanced oxidation,
Electronation, bioanalysis, etc..Physical method mainly passes through the means such as soil moved in improve the original, landfill, and organochlorine pesticide pollution soil is shifted and is filled
To underground, pollutant can not be thoroughly eliminated, environmental risk still remains.Thermal desorption is by original position or dystopy heating pollution
Organo-chlorine pesticide in soil is desorbed out and regathers one kind of processing and repair by soil by being warming up to pollutant boiling point or more
Compound method；Its repairing effect is good, repairs thoroughly, but the capital construction investment of thermal desorption equipment is big, operation energy consumption is high, and rehabilitation cost is big,
It is difficult to carry out in some small-sized organochlorine pesticide pollution places.Advanced oxidation processes are by adding oxidizing drop into soil
Solve a kind of restorative procedure of pollutant；But there is strong electron-withdrawing ability due to containing cl radical on organo-chlorine pesticide, to organochlorine agriculture
The efficiency that the degradation of medicine directlys adopt advanced oxidization method is not high.Chemical reduction method be by adding reducing agent into soil,
Make a kind of restorative procedure of the removing containing cl radical in organo-chlorine pesticide by electronation effect.Zero-valent Iron be it is a kind of have compared with
The active material of strong reducing property matter can restore organo-chlorine pesticide, reduce the bio-toxicity of organochlorine pesticide pollution soil, generate
The higher intermediate product of biodegradable performance；And while Zero-valent Iron also parent pollutant, it itself can be oxidized to have
There is the ferriferous oxide of large specific surface area, these ferriferous oxides equally have certain reduction activation under anaerobic, and right
Organic pollutant has stronger suction-operated, and the organo-chlorine pesticide and its reduction intermediate product for being adsorbed on its surface can be by into one
Step is decomposed.Although electronation has preferable reductive dechlorination to organo-chlorine pesticide, can be by containing in organo-chlorine pesticide
Cl radical removing, is effectively reduced the bio-toxicity of soil, but the intermediate after dechlorination still remains in the soil, repairs not thorough
Bottom.Bioanalysis refers to a kind of restorative procedure using microbial degradation organo-chlorine pesticide；Under aerobic conditions, microorganism is to have
Machine chloro pesticide is electron donor, by electronics transfer to electron acceptors such as oxygen, and organo-chlorine pesticide is resolved into carbon dioxide, water
And chlorine；Under anaerobic, microorganism is using some food sources as electron donor, using organo-chlorine pesticide as electron acceptor, starts
Hydrogen replaces the reduction process of chlorine, by gradually removing in organo-chlorine pesticide containing cl radical, generates the environmental sounds such as alkene, alkane
Substance.But bioanalysis is repaired organochlorine pesticide pollution soil and is had certain problems, under anaerobic, with organochlorine agriculture
Being replaced one by one containing cl radical by hydrogen in medicine, reaction rate can reduce, and the intermediate product of low chloro can be accumulated in the environment, to ring
The harm in border is growing on and on；Under aerobic condition, only low organo-chlorine pollutant can be straight as electron donor by microorganism
Metabolic breakdown Cheng Shui and carbon dioxide are connect, polychlorinated organic pollutants can only gradually be degraded by microorganism Co metabolism, but micro- life
The Co metabolism of object will consume a large amount of electron donor, and metabolic rate is extremely slow.
Based on this, the present invention by electronation and it is biological prosthetic combine, selective reduction activity is high, environmental-friendly zeroth order
Iron is used for the reduction dechlorination of organo-chlorine pesticide, makes full use of the reduction characteristic of zeroth order iron and its oxi, accelerates organic in soil
The deoxidization, degradation of chloro pesticide converts；Meanwhile Zero-valent Iron reduction organo-chlorine pesticide is oxidized the Fe of generation2+And Fe3+To the micro- life of original inhabitants
The production of object has enzymatic catalysis, can promote the growth of indigenous microorganism.This no external source of selection activation indigenous microorganism is raw
Object adds, the method for risk without secondary pollution is used for the thorough degradation of low organo-chlorine pollutant after dechlorination, utilizes the micro- life of original inhabitants
Object is broken down into carbon dioxide and water；In addition, in soil indigenous microorganism metabolic activity secretion organic acid can directly or
The reduction dechlorination process of soil colloid interface organo-chlorine pesticide is influenced indirectly, while organic acid can also effectively adjust soil pH, add
The etching of fast Zero-valent Iron promotes the reductive dechlorination of Zero-valent Iron.Therefore, the present invention is outstanding using zeroth order iron and its oxi
Reductive dechlorination generates the activity of organic acid in conjunction with the metabolism of indigenous microorganism and metabolism, gives full play to electronation
With the advantage of indigenous microorganism degradation organo-chlorine pesticide, the advantages of the two, is combined together, is established a kind of economical, efficient, clear
The restorative procedure of clean, green organochlorine pesticide pollution soil.
Summary of the invention
It is an object of the invention to break through technical bottleneck existing for soil remediation field, organochlorine pesticide pollution soil is solved
Hardly possible is repaired chemically to problem up to standard, and it is organic to provide a kind of Zero-valent Iron reduction joint indigenous microorganism reparation
The method of chlorine pollution soil.In the chloro group of the reduction removing Organochlorine Pesticides In Soil using micron Zero-valent Iron, drop
On the basis of low geobiont toxicity, the life that biological carbon source, electron donor, nitrogen and phosphorus promote indigenous microorganism in soil is added
Long, breeding and metabolic degradation organo-chlorine pesticide are added sulfate reduction inhibitor and inhibit consumption of the sulfate to electronics in soil,
Methane phase inhibitor is added and inhibits consumption of the methane bacteria metabolism hydrocarbon methane phase process to electronics.Zero-valent Iron is also original
Machine chloro pesticide is oxidized the Fe of generation2+And Fe3+There is enzymatic catalysis to the production of indigenous microorganism, the micro- life of original inhabitants can be promoted
The growth of object.Low organo-chlorine pollutant after dechlorination can be thoroughly degraded to carbon dioxide and water by indigenous microorganism；Meanwhile
The organic acid of the metabolic activity secretion of indigenous microorganism can directly or indirectly influence the reduction of soil colloid interface organo-chlorine pesticide
Dechlorination process, organic acid can also effectively adjust soil pH, accelerate the etching of Zero-valent Iron, and the reduction dechlorination of Zero-valent Iron is promoted to make
With.Compared with being restored using Zero-valent Iron merely or repairing the restorative procedure of organochlorine pesticide pollution soil using indigenous microorganism,
This method has remediation efficiency height, short time limit, small investment, repairs the advantages such as thorough, without secondary pollution.
Specific technical solution of the present invention is as follows:
A kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride, its step are as follows:
(1) organochlorine pesticide pollution soil to be repaired is dug clearly to earth's surface, and be transported in closed disposition greenhouse；
(2) organochlorine pesticide pollution soil is subjected to sieving approach, forms the fine grained soil that partial size is less than 50mm；
(3) will add on Tu Duo by sieving approach treated fine grained organochlorine pesticide pollution soil code at Tu Duo
Add a micron zeroth order iron powder, is turned over turner and throw Tu Duo mixing；And throwing is turned in the process successively toward sprinkling on Tu Duo biological carbon source, electronics
Donor, sulfate reduction inhibitor, methane phase inhibitor, nitrogenous fertilizer and phosphate fertilizer, it is ensured that the reagent and contaminated soil of sprinkling are sufficiently mixed
It closes；
(4) a micron Zero-valent Iron, biological carbon source, electron donor, sulfate reduction inhibitor, methane phase suppression are uniformly being mixed with
The native pile Surface mulch waterproof cloth of preparation, nitrogenous fertilizer and phosphate fertilizer builds anaerobic reduction condition, stands maintenance, and in maintenance processes
Middle holding soil moisture content is substantially at saturation state, using the degradation of micron Zero-valent Iron reduction dechlorination and indigenous microorganism,
The final thorough degradation for realizing organo-chlorine pesticide.
Preferably, closed disposition greenhouse described in step (1) is furnished with extractor fan and exhaust gas processing device, ventilation frequency
Rate is 2~6h/ times.
Preferably, the specification of Tu Duo described in step (3) be trapezoidal long pile, lower bottom width 4~8m, upper 2~5m of bottom width,
Long 30m~50m, high 1m~2m, 1.5~2m of pile spacing.
Preferably, the micron Zero-valent Iron partial size used in step (3) must be less than 74 microns (200 mesh), there is reproducibility
Iron powder mass ratio >=80%, the addition mass ratio of micron zeroth order iron powder is 1.0~3.0% in native pile.Micron zeroth order iron powder
Addition mass ratio can specifically be determined according to Organochlorine Pesticides In Soil and other oxidizing substance contents.
Preferably, biological carbon source described in step (3) and electron donor are sodium acetate solution, sulfate reduction inhibits
Agent is sodium molybdate solution, and methane phase inhibitor is BES solution, the sodium acetate solution of sprinkling, sodium molybdate solution and BES solution it is dense
Degree is 20~40mMol/L.
Further, the sodium acetate solution, sodium molybdate solution of sprinkling and the concentration of BES solution are in step (3)
20mMol/L, and the volume ratio sprayed is sodium acetate solution: sodium molybdate solution: BES solution=1:1:1, sodium acetate solution, molybdic acid
The sprinkling total amount of sodium solution and BES solution is the 0.1%~1.0% of soil quality.The total amount of sprinkling specifically can be according in soil
The classification and concentration of organo-chlorine pesticide determine.
Preferably, the nitrogenous fertilizer sprayed in step (3) is preferably sodium nitrate solution or potassium nitrate solution, solution concentration is
0.25g~0.5g/L；Phosphate fertilizer is preferably sodium radio-phosphate,P-32 solution or potassium phosphate solution, and solution concentration is 0.1g~0.2g/L；Sprinkling
The volume ratio of nitrogenous fertilizer and phosphate fertilizer is 1:1, and the sprinkling total amount of nitrogenous fertilizer and phosphate fertilizer is the 0.1%~1.0% of soil quality.That sprays is total
The content measured with specific reference to N, P original in contaminated soil determines, need to guarantee the indigenous microorganism in organochlorine pesticide pollution soil
It can stablize, quickly grow, developing the biological prosthetic effect of performance.
Preferably, sprinkling tap water or sodium acetate solution, molybdic acid need to be passed through in standing maintenance processes in step (4)
Sodium solution, BES solution keep soil moisture content to be substantially at saturation state.
Further, the saturated aqueous rate of soil is different and different according to soil property, and generally 30%~60%.
Preferably, standing curing cycle in step (4) is 14~28 days.
Compared with the existing technology, the invention has the following advantages:
(1) environmental-friendly: present invention utilizes the high reproducibility of zeroth order iron and its oxi, environment friendly, enzymatics to make
With the indigenous microorganism with advantage in soil to the metabolism of organochlorine pesticide pollution, the high reproducibility of micron Zero-valent Iron is utilized
The chloro group for removing Organochlorine Pesticides In Soil, substantially reduces the bio-toxicity of soil, be added biological carbon source, electron donor,
The nutritional agents such as nitrogen phosphorus promote indigenous microorganism growth, breeding and the metabolic degradation organo-chlorine pesticide of advantage in soil and its metabolism to produce
Raw intermediate product containing chlorine, final product are carbon dioxide and water, the final thorough degradation for realizing organo-chlorine pesticide.It repaired
The introducing of Cheng Zhongwu xenobiotic pollutants and microorganism repairs overall process and cleans, is safe, environmental-friendly, without secondary pollution.
(2) expense is low: micron Zero-valent Iron of the present invention can be by by cheap bushel iron bits, iron wire, iron powder, iron plate
Equal industrial wastes are made as the processing of raw material ball milling, from a wealth of sources；Promote sodium acetate and the nitrogen phosphorus battalion of indigenous microorganism production
Supporting substance is common chemical raw material and the common repair materials of agricultural fertilizer and soil remediation field.Also by Zero-valent Iron
The reparation investment of original joint indigenous microorganism showering soil polluted by organic chloride is can be controlled within 1000 yuan/ton of soil, relatively
For the native reparation cost of investment of 2000 yuan/ton of currently used thermal desorption recovery technique, investment cost at least reduces by 50%.
(3) it is extensive to repair object: most of organo-chlorine pesticide can effectively be degraded in soil.
Detailed description of the invention
Fig. 1 is a kind of operation of the method for Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride of the present invention
Flow diagram.
Fig. 2 is six six six content and degradation rate schematic diagram in soil.
Specific embodiment
The present invention is further elaborated and is illustrated with reference to the accompanying drawings and detailed description.
Degradable organo-chlorine pesticide containing suitable kind in organochlorine pesticide pollution soil to be repaired of the present invention
Advantage original inhabitants anaerobe；The usual bacterium of advantage indigenous microorganism, fungi, actinomyces and part in invention is primary dynamic
Object, after the bio-toxicity for reducing soil by Zero-valent Iron dechlorination, advantage indigenous microorganism can directly drop under anaerobic environment
Intermediate product after solving part organo-chlorine pesticide and some dechlorinations is carbon dioxide and water, so that realizing has in thoroughly degradation soil
The purpose of machine chloro pesticide.Restorative procedure process of the invention is as shown in Figure 1.
The present invention using indigenous microorganism for a long time by organochlorine pesticide pollution environment have stronger vitality, adaptation
The characteristic of property and degradation capability, makes full use of the anaerobism indigenous microorganism in organochlorine pesticide pollution soil, builds and suitable detests
Oxygen environment adds biological carbon source, electron donor, nitrogen and phosphorus after reducing geobiont toxicity using Zero-valent Iron reduction dechlorination
It stimulates indigenous microorganism to grow, breeding, while organo-chlorine pesticide of degrading, greatly shortens repairing for organochlorine pesticide pollution soil
Multiple time, the removal rate of the organo-chlorine pesticide after reparation largely reduced organochlorine pesticide pollution soil bring close to 80%
Harm.
Embodiment 1
In the present embodiment, selection by organochlorine pesticide pollution contaminated site to be repaired, site investigation the result shows that: pollution
Object is mainly six six six, and α-six six six, β-six six six, γ-six six six total concentration are 500~10000mg/kg, pollution depth
For underground 1m to underground 6m.
The method of Zero-valent Iron provided in this embodiment reduction joint indigenous microorganism remedying soil polluted by organic chloride, by with
Lower step is implemented:
(1) six six six contaminated soil is dug clearly with excavator to earth's surface from underground, samples inspection third party testing laboratory
Testing result shows that the contaminated soil six six six total concentration is 1296.495mg/kg.Six six six contaminated soil is turned with loading machine
It is transported in closed greenhouse and keeps in, greenhouse is the closed greenhouse of steel construction, and greenhouse is furnished with extractor fan and exhaust gas processing device, ventilation frequency
Rate is to take a breath 1 time every 4h.
(2) it is equipped with sieving approach and sifts out the stone in organochlorine pesticide pollution soil, bulk is consolidated into organochlorine agriculture
After chemicals contamination soil breaking is at fine grained soil of the partial size less than 50mm, for mound at pile, Tu Duo is trapezoidal long pile, lower bottom width
4m, upper bottom width 2m, long 30m, high 1m, pile spacing 1.5m.
(3) according to mass ratio 1.64% (the 1.64% of soil quality in i.e. native pile) addition micron Zero-valent Iron, micron zeroth order
325 mesh of abrasive grit diameter, effective content >=90%.Turning over throwing 3~5 times with turner is uniformly mixed contaminated soil and micron Zero-valent Iron,
Turning over throwing, successively the sprinkling sodium acetate solution of 20mMol/L, the sodium molybdate solution of 20mMol/L, the BES of 20mMol/L are molten in the process
Liquid, the sodium nitrate solution of 0.25g/L, 0.1g/L sodium radio-phosphate,P-32 solution, wherein the sodium acetate solution sprayed, sodium molybdate solution and
The volume ratio V of BES solutionSodium acetate solution:VSodium molybdate solution:VBESSolution=1:1:1, sodium acetate solution, sodium molybdate solution and BES solution
Spray 0.1% that total amount is soil quality；The sodium nitrate solution of sprinkling and the volume ratio V of sodium radio-phosphate,P-32 solutionSodium nitrate solution:VSodium radio-phosphate,P-32 solution=
1:1, and the sprinkling total amount of sodium nitrate solution and sodium radio-phosphate,P-32 solution is the 0.1% of soil quality.
In this step, sodium acetate is as biological carbon source and electron donor, and sodium molybdate is as sulfate reduction inhibitor, BES
Solution is methane phase inhibitor, and sodium nitrate solution is as nitrogenous fertilizer (N nutritive solution), and sodium phosphate is as phosphate fertilizer (P nutritive solution).
(4) tap water is sprayed on the surface layer Tu Duo and persistently turn over throwing, it is ensured that the close saturation of contaminated soil moisture content.Turning over throwing makes to repair
Multiple medicament, nutritional agents and contaminated soil after evenly mixing, in native pile Surface mulch waterproof cloth and are compacted closed, construction anaerobic reduction
Environment stands maintenance, maintenance six six six content into sample detection soil after 8 days, 16 days.Testing result is as shown in Figure 2.
Testing result shows maintenance into 16 days samples, and six six six total amount is down to from 1296.495mg/kg
278.1424mg/kg, degradation efficiency reach 78.547%, greatly reduce the bio-toxicity of soil.
In above-mentioned repair process, Zero-valent Iron and indigenous microorganism play the effect of coupling, and micron Zero-valent Iron is logical first
On the basis of reducing geobiont toxicity, biological carbon is added in the chloro group for crossing reduction removing Organochlorine Pesticides In Soil
Source, electron donor, nitrogen and phosphorus promote soil in indigenous microorganism growth, breeding and metabolic degradation organo-chlorine pesticide, be added
Sulfate reduction inhibitor inhibits consumption of the sulfate to electronics in soil, and methane phase inhibitor is added and inhibits methane bacteria metabolism
Consumption of the hydrocarbon methane phase process to electronics.Zero-valent Iron reduction organo-chlorine pesticide is oxidized the Fe of generation2+And Fe3+It is right
The production of indigenous microorganism has enzymatic catalysis, can promote the growth of indigenous microorganism.Indigenous microorganism can will be after dechlorination
Low organo-chlorine pollutant be thoroughly degraded to carbon dioxide and water；Meanwhile the metabolic activity secretion of indigenous microorganism is organic
Acid can directly or indirectly influence the reduction dechlorination process of soil colloid interface organo-chlorine pesticide, and organic acid can also effectively adjust soil
Earth pH accelerates the etching of Zero-valent Iron, promotes the reductive dechlorination of Zero-valent Iron.It is indigenous with being restored or being utilized using Zero-valent Iron merely
The restorative procedure of microorganism remediation organochlorine pesticide pollution soil is compared, and the integrated processes remediation efficiency of this method significantly improves.
Embodiment 2
In the present embodiment, selection is same as Example 1 by the contaminated site to be repaired of organochlorine pesticide pollution.
The method of Zero-valent Iron provided in this embodiment reduction joint indigenous microorganism remedying soil polluted by organic chloride, by with
Lower step is implemented:
(1) six six six contaminated soil is dug clearly from underground to earth's surface with excavator, with loading machine by six six six contaminated soil
It is transported in closed greenhouse and keeps in, greenhouse is the closed greenhouse of steel construction, and greenhouse is furnished with extractor fan and exhaust gas processing device, ventilation
Frequency is to take a breath 1 time every 6h.
(2) it is equipped with sieving approach and sifts out the stone in organochlorine pesticide pollution soil, bulk is consolidated into organochlorine agriculture
After chemicals contamination soil breaking is at fine grained soil of the partial size less than 50mm, for mound at pile, Tu Duo is trapezoidal long pile, lower bottom width
8m, upper bottom width 5m, long 50m, high 2m, pile spacing 2m.
(3) according to mass ratio 3% (the 3% of soil quality in i.e. native pile) addition micron Zero-valent Iron, micron Zero-valent Iron partial size
325 mesh, effective content >=80%.Turning over throwing 3~5 times with turner is uniformly mixed contaminated soil and micron Zero-valent Iron, turns over and threw
BES solution, the 0.5g/ of the sodium acetate solution of 40mMol/L, the sodium molybdate solution of 40mMol/L, 40mMol/L are successively sprayed in journey
The potassium phosphate solution of the potassium nitrate solution of L, 0.2g/L, wherein the body of the sodium acetate solution sprayed, sodium molybdate solution and BES solution
Product compares VSodium acetate solution:VSodium molybdate solution:VBESSolution=1:1:1, the sprinkling total amount of sodium acetate solution, sodium molybdate solution and BES solution are soil
The 1% of loamy texture amount；The potassium nitrate solution of sprinkling and the volume ratio V of potassium phosphate solutionPotassium nitrate solution:VPotassium phosphate solution=1:1, and potassium nitrate is molten
The sprinkling total amount of liquid and potassium phosphate solution is the 1% of soil quality.
In this step, sodium acetate is as biological carbon source and electron donor, and sodium molybdate is as sulfate reduction inhibitor, BES
Solution is methane phase inhibitor, and potassium nitrate solution is as nitrogenous fertilizer (N nutritive solution), and potassium phosphate is as phosphate fertilizer (P nutritive solution).
(4) tap water is sprayed on the surface layer Tu Duo and persistently turn over throwing, it is ensured that the close saturation of contaminated soil moisture content.Turning over throwing makes to repair
Multiple medicament, nutritional agents and contaminated soil after evenly mixing, in native pile Surface mulch waterproof cloth and are compacted closed, construction anaerobic reduction
Environment stands maintenance, stands in maintenance processes, continues through sprinkling tap water or sodium acetate solution, sodium molybdate solution, BES are molten
Liquid keeps soil moisture content to be substantially at saturation state.Maintenance six six six content, six six six into sample detection soil after 14 days
Degradation efficiency reaches 71.235%, greatly reduces the bio-toxicity of soil.
Above-mentioned embodiment is only a preferred solution of the present invention, so it is not intended to limiting the invention.Have
The those of ordinary skill for closing technical field can also make various changes without departing from the spirit and scope of the present invention
Change and modification.For example, the shape of Tu Duo, size can be adjusted according to place.The various techniques of soil during processing
Parameter can also be adjusted according to the degradation situation of pollutant in soil.In addition, be based on the repair mechanisms it is contemplated that, though
The pollutant being directed in right embodiment is six six six, but this method has contamination with chlorinated organics most of in soil
Effect.Therefore all mode technical solutions obtained for taking equivalent substitution or equivalent transformation, all fall within protection scope of the present invention
It is interior.
Claims (10)
1. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride, it is characterised in that step is such as
Under:
(1) organochlorine pesticide pollution soil to be repaired is dug clearly to earth's surface, and be transported in closed disposition greenhouse；
(2) organochlorine pesticide pollution soil is subjected to sieving approach, forms the fine grained soil that partial size is less than 50mm；
(3) it will be added on Tu Duo micro- by sieving approach treated fine grained organochlorine pesticide pollution soil code at Tu Duo
Rice zeroth order iron powder is turned over turner and throws Tu Duo mixing；And it turns over throwing and is successively supplied in the process toward the biological carbon source of sprinkling on Tu Duo, electronics
Body, sulfate reduction inhibitor, methane phase inhibitor, nitrogenous fertilizer and phosphate fertilizer, it is ensured that the reagent of sprinkling is sufficiently mixed with contaminated soil；
(4) a micron Zero-valent Iron, biological carbon source, electron donor, sulfate reduction inhibitor, methane phase inhibition are uniformly being mixed with
Agent, nitrogenous fertilizer and phosphate fertilizer native pile Surface mulch waterproof cloth, build anaerobic reduction condition, maintenance stood, and in maintenance processes
Soil moisture content is kept to be substantially at saturation state, using the degradation of micron Zero-valent Iron reduction dechlorination and indigenous microorganism, most
The thorough degradation of organo-chlorine pesticide is realized eventually.
2. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as described in claim 1,
It is characterized by: closed disposition greenhouse described in step (1) is furnished with extractor fan and exhaust gas processing device, ventilation frequency is 2
~6h/ times.
3. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as described in claim 1,
It is characterized by: the specification of Tu Duo described in step (3) is trapezoidal long pile, lower bottom width 4~8m, upper 2~5m of bottom width, long 30m
~50m, high 1m~2m, 1.5~2m of pile spacing.
4. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as described in claim 1,
It is characterized by: the micron Zero-valent Iron partial size used in step (3) must be less than 74 microns, the iron powder mass ratio with reproducibility
>=80%, the addition mass ratio of micron zeroth order iron powder is 1.0~3.0% in native pile.
5. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as described in claim 1,
It is characterized by: biological carbon source described in step (3) and electron donor are sodium acetate solution, sulfate reduction inhibitor is molybdenum
Acid sodium solution, methane phase inhibitor are BES solution, and the concentration of the sodium acetate solution of sprinkling, sodium molybdate solution and BES solution is 20
~40mMol/L.
6. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as claimed in claim 5,
It is characterized by: the concentration of the sodium acetate solution sprayed in step (3), sodium molybdate solution and BES solution is 20mMol/L, and
The volume ratio of sprinkling is sodium acetate solution: sodium molybdate solution: BES solution=1:1:1, sodium acetate solution, sodium molybdate solution and BES
The sprinkling total amount of solution is the 0.1%~1.0% of soil quality.
7. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as described in claim 1,
It is characterized by: the nitrogenous fertilizer sprayed in step (3) is preferably sodium nitrate solution or potassium nitrate solution, solution concentration be 0.25g~
0.5g/L；Phosphate fertilizer is preferably sodium radio-phosphate,P-32 solution or potassium phosphate solution, and solution concentration is 0.1g~0.2g/L；The nitrogenous fertilizer and phosphorus of sprinkling
The volume ratio of fertilizer is 1:1, and the sprinkling total amount of nitrogenous fertilizer and phosphate fertilizer is the 0.1%~1.0% of soil quality.
8. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as described in claim 1,
It is characterized by: in standing maintenance processes in step (4), need to by sprinkling tap water or sodium acetate solution, sodium molybdate solution,
BES solution keeps soil moisture content to be substantially at saturation state.
9. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as claimed in claim 8,
It is characterized by: the saturated aqueous rate of soil is different and different according to soil property, generally 30%~60%.
10. a kind of method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride as described in claim 1,
It is characterized by: standing curing cycle in step (4) is 14~28 days.
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| CN113711723A (en) * | 2020-05-24 | 2021-11-30 | 中国环境科学研究院 | Microbial remediation method for organic pesticide in soil layer of agricultural activity area |
| CN115124384A (en) * | 2022-06-28 | 2022-09-30 | 张珈毓 | Pesticide-contaminated soil remediation agent, preparation method and application thereof, and method for remediating pesticide-contaminated soil |
| CN117772778A (en) * | 2024-01-25 | 2024-03-29 | 北京市生态环境保护科学研究院 | Method for restoring hexachlorobenzene-polluted soil by ferric salt-reinforced indigenous bacteria |
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