CN108435785A - A method of with Persistent halogenated hydrocarbons in sustained release complex repairation chemicals treatment soil - Google Patents
A method of with Persistent halogenated hydrocarbons in sustained release complex repairation chemicals treatment soil Download PDFInfo
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- CN108435785A CN108435785A CN201810401554.0A CN201810401554A CN108435785A CN 108435785 A CN108435785 A CN 108435785A CN 201810401554 A CN201810401554 A CN 201810401554A CN 108435785 A CN108435785 A CN 108435785A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
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- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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Abstract
The invention discloses a kind of methods of Persistent halogenated hydrocarbons in complex repairation chemicals treatment soil with sustained release.Contaminated soil is turned in advance, a certain amount of sustained release complex repairation medicament is directly spread fertilizer over the fields in the soil after turning over, mixing of raking the soil level, and watering keeps certain water content, finally carries out anaerobic reduction dehalogenation reaction in soil surface protective mulch；0.05 1.5% that the medicament amount of spreading fertilizer over the fields is contaminated soil dry weight is repaired, Soil tillage depth is 25 40cm, repairs medicament and spreads fertilizer over the fields rear soil moisture content adjusting to the 50 80% of maximum field capacity, the repair process time is 30 350d.The restorative procedure utilizes the dissimilatory iron reduction dehalogenation ability of the good absorption property of black wood charcoal, the efficient electronation of nanoscale zero-valent metal and functional microorganism, it can reach and repairing effect is strengthened to the physics, chemistry and biological synergetic of Persistent halogenated hydrocarbons contaminated soil, there are action period length, stable structure, the of low cost and advantages such as environmental-friendly.
Description
Technical field
The invention belongs to contaminated soil remediation technical field, it is related to holding in a kind of complex repairation chemicals treatment soil with sustained release
The method of long property halogenated hydrocarbons.
Background technology
Persistent halogenated hydrocarbons (PHHs, such as organo-chlorine pesticide, Polychlorinated biphenyls, polybrominated diphenyl ethers) are widely used in machinery
During manufacture, electronic component cleaning, chemical and agricultural planting etc., there is " three cause " (carcinogenic, teratogenesis, mutagenesis) effect
It answers, refractory organics, property easy to migrate and bioconcentration can make the ecosystem and human health once entering soil environment
At serious harm.In view of the popularity and strong harmfulness, the control of the pollutant and treatment technology of Persistent halogenated hydrocarbons pollution
Have become the research hotspot of field of environmental improvement.
Currently, the technology for being usually used in Persistent halogenated hydrocarbons contaminated soil remediation has concrete dynamic modulus Jie added with adsorption capacity
Matter, the zero-valent metal with chemical reducing capability, physics, chemistry, the life such as organic carbon source for promoting indigenous microorganism reducing power
Object space formula, but these methods have its corresponding limitation.As pollutant is only simply enriched with and is moved by porous medium
It moves, can not thoroughly remove；The action effective of zero-valent metal is short, is also easy to produce secondary pollution and the oxidation that can reunite, leads to reactivity
Decline；The period for adding organic carbon source processing mode is long, and carbon source burst size is not easy to control, and treatment effect is unstable.
In recent years, some scholars began to focus on the technology of the many-sided Combined Treatment pollutant of physics, chemistry, biology, ground
The preparation for studying carefully various ingredients sustained release complex repairation medicament the problem of to make up monotechnics means, reaches collaboration and makees
With improving the treatment effect of pollutant.Generally there is the preparation method of composite drug in these researchs：By zero-valent metal, organic carbon
The active principles such as source, porous medium, dehalogenation bacterium are simply mixed, but the combination between active principle is weaker, and collaboration is strong
Change effect is not notable；Active principle physically trapping is fixed with embedding mediums such as polyvinyl alcohol, but common embedding medium has machinery by force
Degree is poor, sustained release control ability is weak, easily causes the shortcomings of secondary pollution, to reduce the stability, validity and reality of composite material
Border application.
Black wood charcoal is one kind of biomass carbon, with abundant pore structure, has very strong surface to inhale organic pollution
Attached effect can be used as a kind of environmental-friendly natural sorbing material, and be the effective carrier for loading bacterial strain.Locust bean gum is thorn
The sub- glue of plant that Chinese scholartree seed is process, internal carboxyl structure can pass through bivalent cation (such as Ca2+、Mg2+) electrostatic
Effect crosslinking aggregation forms gel micro-ball, and strong, environmental-friendly, the antiacid alkali of its high mechanical strength, mass-transfer performance and enzyme decompose, valence
Lattice are cheap, are a kind of ideal newtype drug sustained release embedding mediums.Shewanella bacterium (Shewanella) are a kind of wide in nature
General existing dissimilatory iron reduction bacterium, can be with Fe (III) for terminal electron acceptor, by enzymatic reaction extracellularly by Fe (III)
It is reduced to Fe (II), microorganism obtains energy promotion cell growth in the process.Meanwhile it is nearest researches show that
Shewanella bacterium can also further halogenated hydrocarbons such as dealuminated USY cataluyst carbon tetrachloride during reduced iron.But currently with black wood charcoal
As adsorbent and carrier, the microorganism with dissimilatory iron reduction dehalogenation ability is loaded, and using locust bean gum as embedding medium, system
The standby long-acting slow-release complex repairation medicament suitable for Persistent halogenated hydrocarbons contaminated soil has not been reported.
Invention content：
It is an object of the invention to：It is seriously polluted for Persistent halogenated hydrocarbons in current soil, existing reparation medicament and
Restorative procedure removal effect is bad, action effective is short, stability is poor, easily causes secondary pollution problems to environment, provides one kind
With the long-acting method with Persistent halogenated hydrocarbons in sustained release complex repairation chemicals treatment soil for strengthening repairing effect.
The method of Persistent halogenated hydrocarbons is as follows in a kind of complex repairation chemicals treatment soil with sustained release of the present invention：
Using sustained release complex repairation medicament, broadcast application is turned over using topsoil in situ, handles the persistence halogen in soil
For hydrocarbon；The topsoil turns over broadcast application in situ：Contaminated soil is turned in advance, and compound repair is sustained by a certain amount of
Multiple medicament is directly spread fertilizer over the fields in the soil after turning over, mixing of raking the soil level, and is watered and kept certain water content, is finally covered in soil surface
After lid protective layer, anaerobic reduction dehalogenation reaction is carried out, achievees the purpose that long-acting removal topsoil Persistent halogenated hydrocarbons in situ；
The sustained release complex repairation medicament, by the following method step be prepared：
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor：The dosage for adding 0.1-1.0g microorganism freeze-dried powders by every liter of physiological saline, by microorganism
Freeze-dried powder, which is added in the physiological saline that mass concentration is 0.8-1.0%, to be dissolved, and it is 0.1- that bacterial concentration, which is made,
The bacterium seed liquor of 1.0mg/mL；The microorganism freeze-dried powder is the freeze-dried powder of dissimilatory iron reduction bacterium.
Black wood charcoal pre-processes：The HCl solution that black wood charcoal is first 1.0-5.0% with mass concentration impregnates 12-24h, deionization washing
Only；12-24h is impregnated with the NaOH of a concentration of 10-20g/L again, deionized water is cleaned；It is finally 0.8-1.0% with mass concentration
Physiological saline impregnate 12-24h after, be placed in 120-125 DEG C of moist heat sterilization pot the 15-30min that sterilizes, be dried for standby.
Nanoscale zero-valent metal pre-processes：It is 0.1-2.0% that the zero-valent metal powder of 10-100nm, which is placed in mass concentration,
HCl solution in, be acidified 5-15min, it is 7-8 to be rinsed to pH value with deionized water after taking-up, be placed in anaerobic box air-dry it is standby
With.
(2) it is sustained the preparation of complex repairation medicament：
1) it prepares bacterium solution and is saturated black wood charcoal：The dosage for adding 10.0-1000.0g black wood charcoals by every liter of bacterium seed liquor, will pre-process
Good black wood charcoal is added in the bacterium seed liquor that the bacterial concentration prepared is 0.1-1.0mg/mL, by above-mentioned mixing suspension
It is placed in 100-200r/min in shaken cultivation case and vibrates 6-12h, air-dry 25-35 DEG C of anaerobic of solid matter after filtering off solution, most
Required bacterium solution is made eventually and is saturated black wood charcoal；
2) the colloidal solution A containing locust bean gum and organic carbon source is prepared：By every 100mL water add 0.5-4.5g locust bean gums and
Locust bean gum and organic carbon source are added in deoxygenation deionized water, are placed on heater by the dosage of 1.5-3.5g organic carbon sources
It is heated to 60-80 DEG C, machine mixer 100-250r/min is used in combination persistently to stir, until locust bean gum is completely dissolved and mixing,
It is cooled to 25-50 DEG C, obtains the colloidal solution A containing locust bean gum and organic carbon source；
3) the gluey suspension B that black wood charcoal is saturated containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is prepared：
Add 0.5-2.0g nanoscale zero-valent metals and 2.0-8.0g bacterium solutions to be saturated the dosage of black wood charcoal by every 100mL water, is obtained to step 2)
Colloidal solution A in bacterium solution made from the nanoscale zero-valent metal powder that pre-process and step 1) be added be saturated black wood charcoal, be used in combination
Machine mixer 100-250r/min is persistently stirred, until nanoscale zero-valent metal powder is saturated the complete mixing of black wood charcoal with bacterium solution,
The gluey suspension B for obtaining being saturated black wood charcoal containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is for use；
4) cross-linking reaction：Using peristaltic pump, pump discharge hose connects 2-8 Medical injection needles, will be obtained in step 3
Gluey suspension B the CaCl of the mass content containing 1.5-4.5% is added dropwise to the speed of 3-7mL/min2Saturation boric acid solution
In, it is placed in mechanical agitator room temperature 150-250r/min stirring crosslinkings reaction 2-6h, crosslinked fluid is then positioned over 2-6 DEG C of ice
6-24h is reinforced in case；
5) be delayed cross-linking reaction：Crosslinked fluid filtering after being reinforced in step 4), obtained gel micro-ball are transferred to quality
The Na of a concentration of 0.5-1.0%2SO4Be delayed cross-linking reaction 2-6h in solution, filters off Na2SO4Solution, thus obtained microsphere quality are dense
The physiological saline that degree is 0.8-1.0% cleans 2-3 times, room temperature natural air drying, obtains a kind of for handling persistence halogen in soil
For the sustained release complex repairation medicament of hydrocarbon, it is placed in anaerobic environment and saves backup.
The dissimilatory iron reduction bacterium is a kind of bacterium with dissimilatory iron reduction dehalogenation ability；It is described that there is dissimilatory iron reduction
The bacterium of dehalogenation ability, that is, dissimilatory iron reduction bacterium be Shewanella putrefaciens CN32,
Shewanellapiezotolerans WP3, Shewanella oneidensis MR-1 etc. belong to Shewanella (Xi Washi
Bacterium) Pseudomonas bacterium.
The organic carbon source is that the low molecular organic acids and xylose, fructose, maltose etc. such as acetic acid, oxalic acid, malic acid are single
Sugar or biglycan.
The nanoscale zero-valent metal is that nano zero valence iron, nano zero-valence zinc, nano zero-valence aluminium etc. are de- with electronation
The nanoscale zero-valent metal of halogen ability.
In the step 1), black wood charcoal is 2.0 × 10 to the saturated extent of adsorption of bacterium solution6-4.0×109cfu/g。
In gluey suspension B made from the step 3), the mass percentage that bacterium solution is saturated black wood charcoal is preferably 2.0-
8.0%, the mass percentage of locust bean gum is preferably 0.5-4.5%, and the mass percentage of nanoscale zero-valent metal is preferred
Mass percentage for 0.5-2.0%, organic carbon source is preferably 1.5-3.5%.
The grain size of the sustained release complex repairation medicament is preferably 0.5-2.0mm.
The Persistent halogenated hydrocarbons are in organo-chlorine pesticide, Polychlorinated biphenyls, polybrominated diphenyl ethers etc. and their degradation
Between product.
In the topsoil turns over broadcast application in situ, the sustained release complex repairation medicament amount of spreading fertilizer over the fields is contaminated soil dry weight
0.05-1.5%, the ploughed depth of soil is generally 25-40cm, and sustained release complex repairation medicament spreads fertilizer over the fields rear soil moisture content and adjusts
To the 50-80% of maximum field capacity, soil surface protective layer is PVC film or HDPE film, is repaiied with sustained release complex repairation medicament
The time handled again is preferably 30-350d.
Beneficial effects of the present invention：
Mass transfer is used in combination using strong microorganism of the black wood charcoal load with dissimilatory iron reduction dehalogenation ability of adsorption capacity in the present invention
Performance is high, had good sustained release effect locust bean gum is by the black wood charcoal of loading microorganisms and chemical reducing agent nanoscale zero-valent metal and micro- life
Object electron donor organic carbon source is coated, and is cross-linked to form that mechanical strength is big, microsphere particle of stable structure.The reparation medicament energy
Utilize the good absorption property of black wood charcoal, the dissimilatory iron reduction of nanoscale zero-valent metal efficient electronation and functional microorganism
Dehalogenation ability reaches and strengthens repairing effect to the physics, chemistry and biological synergetic of Persistent halogenated hydrocarbons contaminated soil, and with work
With period length, stable structure, the of low cost and advantages such as environmental-friendly.
Compared with prior art, the present invention has the following advantages：
(1) the dissimilatory iron reduction bacterium being sustained in complex repairation medicament has the energy of reductive dehalogenation degradation Persistent halogenated hydrocarbons
Power, and the bacterium is easy to survive to the adaptable of environment, and it is halogenated to persistence to help to improve sustained release complex repairation medicament
The biodegradable efficiency of hydrocarbon, meanwhile, which is facultative anaerobic bacteria, to the of less demanding of medicament preparation condition；Nanoscale zero-valent gold
The specific surface area and reactivity of category are much larger than micron order zero-valent metal, are imitated to the electronation dealuminated USY cataluyst of Persistent halogenated hydrocarbons
Rate higher；Organic carbon source as microorganism electron donor, can promotion functions bacterium (dissimilatory iron reduction bacterium) reductive dehalogenation activity.It will
After above-mentioned active principle is combined by embedding medium (locust bean gum), physics, the chemistry of Persistent halogenated hydrocarbons contaminated soil can be realized
Strengthen with biological synergetic and repair, makes the removal effect of target contaminant more preferably.
(2) compared with traditional microorganism immobilization method, the suction-operated of black wood charcoal, organic carbon source supplied for electronic act on
And the coating function of locust bean gum, suitable growing environment is provided for functional microorganism (dissimilatory iron reduction bacterium), enhances it
Activity and external interference resistance help to improve the ability of its Persistent halogenated hydrocarbons of degrading.
(3) compared with common biomass carbon, black wood charcoal have higher mechanical strength and smaller grain size, using black wood charcoal as
Basis material can mitigate gel-type and repair the swelling level of breakage of medicament in water, enhance its structural stability, help to carry
Height repairs the long-term effect of medicament.
(4) compared with traditional embedding medium, the mass-transfer performance of locust bean gum is strong, high mechanical strength, antiacid alkali and enzyme decompose,
Active principle slow release in medicament can be controlled, and it is made to be come into full contact with pollutant, while can further improve reparation medicine
The structural stability of agent.In addition, the coating function of locust bean gum, solves the agglomeration of nanoscale zero-valent metal, and slow down
Its oxidation rate is degraded the efficiency of Persistent halogenated hydrocarbons to improve zero-valent metal electronation.
(6) present invention in repair medicament preparation method it is easy to operate, raw material economics is easy to get, can mass production, without secondary
Pollution has huge application potential, the Persistent halogenated hydrocarbons poor especially suitable for high concentration or dehalogenation functional microorganism dirty
Contaminate soil remediation.
Description of the drawings
Fig. 1 is the influence relational graph for repairing medicament applied amount to DDT treatment effects in soil；
Fig. 2 is the influence relational graph for loading different function strain to repairing heptachlor effect in chemicals treatment topsoil；
Fig. 3 is influence relational graph of the different DDT concentration to DDT effects in reparation chemicals treatment topsoil.
Specific implementation mode
Present disclosure is described further with reference to specific embodiment, makes the objects and effects of the present invention more
Obviously, and is not intended to limit the present invention.The scope of the present invention should be defined by the claims.
It is mass percentage or mass concentration in following embodiment.
Embodiment 1：
A kind of preparation method for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil, steps are as follows：
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor：The physiological saline solution 0.5g for being 0.9% with 5L mass concentrations
Shewanellaputrefaciens CN32 Shewanella freeze-dried powders, it is 0.1mg/mL's that bacterial concentration, which is made,
Shewanellaputrefaciens CN32 bacterium seed liquors.
Black wood charcoal pre-processes：Black wood charcoal first uses the HCl solution that mass concentration is 1.0% to impregnate 12h, and deionized water is cleaned；It uses again
The NaOH of a concentration of 10g/L impregnates 12h, and deionized water is cleaned；The physiological saline that mass concentration is 0.9% is finally used to impregnate 12h
Afterwards, it is placed in 121 DEG C of moist heat sterilization pots the 15-30min that sterilizes, is dried for standby.
Nano zero valence iron pre-processes：The zeroth order iron powder of 10nm is placed in the HCl solution that mass concentration is 0.1%, acid
Change 5min, it is 7 to be rinsed to pH value with deionized water after taking-up, is placed in anaerobic box air-dried spare.
(2) it is sustained the preparation of complex repairation medicament：
1) prepared by bacterium solution saturation black wood charcoal：The 1L made from step (1) is added in the black wood charcoal that 10g step (1) has been pre-processed
In bacterium seed liquor (bacterial concentration 0.1mg/mL), above-mentioned mixing suspension is placed in 100r/min in shaken cultivation case and is vibrated
6h air-dries 25 DEG C of anaerobics of solid matter after filtering off solution, and finally obtained saturated extent of adsorption is 2.0 × 106The bacterium solution of cfu/g is full
And black wood charcoal；
2) it weighs the locust bean gum of 0.5g and 1.5g malic acid is added in 100mL deoxygenation deionized waters, be placed in heater
On be heated to 60 DEG C, be used in combination machine mixer 100r/min persistently to stir, until locust bean gum is completely dissolved and mixing, be cooled to
25 DEG C of colloidal solution A obtained containing locust bean gum and malic acid；
3) it is added into colloidal solution A made from the nano zero valence iron and 2.0g steps 1) that 0.5g step (1) has pre-processed
Bacterium solution is saturated black wood charcoal, and machine mixer 100r/min is used in combination persistently to stir, until nano zero valence iron and bacterium solution saturation black wood charcoal are complete
Mixing, obtain containing 0.5% locust bean gum, 1.5% malic acid, 0.5% nano zero valence iron and 2.0% bacterium solution saturation black wood charcoal (be
Mass percentage) gluey suspension B it is for use；
4) utilize peristaltic pump (pump discharge hose connects No. 2 Medical injection needles) by gluey suspension B with 3mL/min's
Speed is added dropwise to the CaCl containing 1.5% mass content2Saturation boric acid solution in, be placed in mechanical agitator room temperature 150r/min
Then crosslinked fluid is positioned in 2 DEG C of refrigerators and reinforces 6h by stirring crosslinking 2h；
5) crosslinked fluid after reinforcing is filtered, obtained gel micro-ball is transferred to the Na that mass concentration is 0.5%2SO4Solution
Middle delay is crosslinked 2h, filters off Na2SO4Solution, thus obtained microsphere are cleaned 3 times with the physiological saline that mass concentration is 0.9%, and room temperature is certainly
It so air-dries, obtains the sustained release complex repairation medicament OZBB-1 of grain size 0.5mm.
Embodiment 2：
A kind of preparation method for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil, steps are as follows：
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor：With the Shewanella for the physiological saline solution 2.5g that 5L mass concentrations are 0.8%
The Shewanella that bacterial concentration is 0.5mg/mL is made in piezotolerans WP3 Shewanella freeze-dried powders
Piezotolerans WP3 bacterium seed liquors.
Black wood charcoal pre-processes：Black wood charcoal first uses the HCl solution that mass concentration is 3.0% to impregnate 16h, and deionized water is cleaned；It uses again
The NaOH of a concentration of 15g/L impregnates 16h, and deionized water is cleaned；The physiological saline that mass concentration is 0.8% is finally used to impregnate 16h
Afterwards, it is placed in 125 DEG C of moist heat sterilization pots the 20min that sterilizes, is dried for standby.
Nano zero-valence aluminium pre-processes：The nano zero-valence aluminium powder of 50nm is placed in the HCl solution that mass concentration is 1.0%
In, it is acidified 10min, it is 7.5 to be rinsed to pH value with deionized water after taking-up, is placed in anaerobic box air-dried spare.
(2) prepared by sustained release complex repairation medicament：
1) prepared by bacterium solution saturation black wood charcoal：The black wood charcoal that 100.0g step (1) has been pre-processed is added made from step (1)
In 1L bacterium seed liquors (bacterial concentration 0.5mg/mL), above-mentioned mixing suspension is placed in 150r/min in shaken cultivation case and is shaken
8h is swung, air-dries 30 DEG C of anaerobics of solid matter after filtering off solution, finally obtained saturated extent of adsorption is 5.0 × 108The bacterium solution of cfu/g
It is saturated black wood charcoal；
2) 3.0g locust bean gums are weighed and 2.5g acetic acid is added in 100mL deoxygenation deionized waters, is placed on heater and adds
Heat is used in combination machine mixer 150r/min persistently to stir to 70 DEG C, until locust bean gum is completely dissolved and mixing, is cooled to 35 DEG C
Obtain the colloidal solution A containing locust bean gum and acetic acid；
3) it is added into colloidal solution A made from the nano zero-valence aluminium and 4.0g steps 1) that 1.0g step (1) has pre-processed
Bacterium solution is saturated black wood charcoal, and machine mixer 150r/min is used in combination persistently to stir, until nano zero-valence aluminium and bacterium solution saturation black wood charcoal are complete
Mixing obtains containing 3.0% locust bean gum, 2.5% acetic acid, 1.0% nano zero-valence aluminium and 4.0% bacterium solution saturation black wood charcoal (being matter
Measure percentage composition) gluey suspension B it is for use；
4) utilize peristaltic pump (pump discharge hose connects No. 4 Medical injection needles) by gluey suspension B with 5mL/min's
Speed is added dropwise to the CaCl containing 2.5% mass content2Saturation boric acid solution in, be placed in mechanical agitator room temperature 200r/min
Then crosslinked fluid is positioned in 4 DEG C of refrigerators and reinforces 12h by stirring crosslinking 4h；
5) crosslinked fluid after reinforcing is filtered, obtained gel micro-ball is transferred to the Na that mass concentration is 0.7%2SO4Solution
Middle delay is crosslinked 4h, filters off Na2SO4Solution, thus obtained microsphere are cleaned 2 times with the physiological saline that mass concentration is 0.8%, and room temperature is certainly
It so air-dries, obtains the sustained release complex repairation medicament OZBB-2 of grain size 1.0mm.
Embodiment 3：
A kind of preparation method for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil, steps are as follows：
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor：With the Shewanella for the physiological saline solution 5.0g that 5L mass concentrations are 1.0%
The Shewanella oneidensis that bacterial concentration is 1.0mg/mL are made in oneidensis MR-1 Shewanella freeze-dried powders
MR-1 bacterium seed liquors.
Black wood charcoal pre-processes：Black wood charcoal first uses the HCl solution that mass concentration is 5.0% to impregnate for 24 hours, and deionized water is cleaned；It uses again
The NaOH of a concentration of 20g/L impregnates for 24 hours, and deionized water is cleaned；The physiological saline that mass concentration is 1.0% is finally used to impregnate for 24 hours
Afterwards, it is placed in 120 DEG C of moist heat sterilization pots the 30min that sterilizes, is dried for standby.
Nano zero-valence zinc pre-processes：The nano zero-valence zinc powder of 100nm is placed in the HCl solution that mass concentration is 2.0%
In, it is acidified 15min, it is 8 to be rinsed to pH value with deionized water after taking-up, is placed in anaerobic box air-dried spare.
(2) it is sustained the preparation of complex repairation medicament：
1) prepared by bacterium solution saturation black wood charcoal：The black wood charcoal that 1000.0g step (1) has pre-processed is added and is made by step (1)
1L bacterium seed liquors in (bacterial concentration 1.0mg/mL), above-mentioned mixing suspension is placed in 200r/min in shaken cultivation case
12h is vibrated, air-dries 35 DEG C of anaerobics of solid matter after filtering off solution, finally obtained saturated extent of adsorption is 4.0 × 109Cfu/g's
Bacterium solution is saturated black wood charcoal；
2) 4.5g locust bean gums are weighed and 3.5g fructose is added in 100mL deoxygenation deionized waters, is placed on heater and adds
Heat is used in combination machine mixer 250r/min persistently to stir to 80 DEG C, until locust bean gum is completely dissolved and mixing, is cooled to 50 DEG C
Obtain the colloidal solution A containing locust bean gum and fructose；
3) it is added into colloidal solution A made from the nano zero-valence zinc and 8.0g steps 1) that 2.0g step (1) has pre-processed
Bacterium solution is saturated black wood charcoal, and machine mixer 250r/min is used in combination persistently to stir, until nano zero-valence zinc and bacterium solution saturation black wood charcoal are complete
Mixing obtains containing 4.5% locust bean gum, 3.5% fructose, 2.0% nano zero-valence zinc and 8.0% bacterium solution saturation black wood charcoal (being matter
Measure percentage composition) gluey suspension B it is for use；
4) utilize peristaltic pump (pump discharge hose connects No. 8 Medical injection needles) by gluey suspension B with 7mL/min's
Speed is added dropwise to the CaCl containing 4.5% mass content2Saturation boric acid solution in, be placed in mechanical agitator room temperature 250r/min
Then crosslinked fluid is positioned in 6 DEG C of refrigerators and reinforces for 24 hours by stirring crosslinking 6h；
5) crosslinked fluid after reinforcing is filtered, obtained gel micro-ball is transferred to the Na that mass concentration is 1.0%2SO4Solution
Middle delay is crosslinked 6h, filters off Na2SO4Solution, thus obtained microsphere are cleaned 3 times with the physiological saline that mass concentration is 1.0%, and room temperature is certainly
It so air-dries, obtains the sustained release complex repairation medicament OZBB-3 of grain size 2.0mm.
Embodiment 4：
Influence of the medicament applied amount to chemicals treatment topsoil Persistent halogenated hydrocarbons effect is repaired in research, and specific steps are such as
Under：
Substantially sustained release complex repairation medicament OZBB-4 is prepared by the step of embodiment 1, the difference is that：Step
(2) quality hundred of locust bean gum, malic acid, nano zero valence iron and bacterium solution saturation black wood charcoal in gluey suspension B obtained by step 3)
Point content is respectively 4.0%, 3.0%, 2.0% and 6.0%.
DDT (DDT) contaminated soil 5g is weighed respectively to be placed in four 150mL tool plug glass culture bottles (in contaminated soil
A concentration of 1.5mg/kg of DDT), it is added by the 0.05% of soil dry weight, 0.2%, 0.8%, 1.5% repair medicament OZBB- respectively
4.Medicament will be repaired to mix well with contaminated soil, mixed system cultivates 50d in 25 DEG C of growth cabinets, during which maintains soil
Moisture content soil sampling after 70% maximum field capacity, culture measures the wherein residual concentration of DDT, and calculates removal
Rate, the results are shown in Figure 1.As shown in Figure 1, with the increase for repairing medicament applied amount, the removal rate of DDT constantly increases in soil
Add, removal rate reaches 81.7% when applied amount is 1.5%, but at the scene during use should in conjunction with prepare and use cost etc. because
Element determines the best applied amount for repairing medicament.
Embodiment 5：
Study influence of the black wood charcoal load different function strain to Persistent halogenated hydrocarbons effect in chemicals treatment topsoil, tool
Steps are as follows for body：
Substantially by preparation sustained release complex repairation medicament the step of embodiment 3, the difference is that：The function that black wood charcoal is loaded
Strain be respectively Shewanella putrefaciens CN32, Shewanella piezotolerans WP3 and
Shewanella oneidensis MR-1 respectively obtain sustained release complex repairation medicament OZBB-C, OZBB-W and OZBB-M.
Heptachlor contaminated soil 10g is weighed respectively is placed in four 250mL tool plug glass culture bottles that (heptachlor is dense in contaminated soil
Degree is 5.0mg/kg), medicament OZBB-C, OZBB-W and OZBB-M will be repaired respectively by the 1.0% of soil dry weight, and Polluted Soil is added
In earth.Medicament will be repaired to mix well with soil, mixed system cultivates 60d in 25 DEG C of growth cabinets, during which maintains soil
Moisture content soil sampling after 80% maximum field capacity, culture measures the residual concentration of wherein heptachlor, and calculates removal
Rate, the results are shown in Figure 2.As shown in Figure 2, the OZBB-C of load Shewanella putrefaciens CN32 bacterium is to heptachlor
Removal effect is best, and removal rate reaches 89.6% when 60d, loads the OZBB-W of Shewanella piezotolerans WP3 bacterium
Effect is taken second place (83.6%), and the OZBB-M effects for loading Shewanella oneidensis MR-1 bacterium are poor (76.1%).
Embodiment 6：
Study influence of the different concentrations of contaminants to Persistent halogenated hydrocarbons effect in chemicals treatment topsoil, specific steps
It is as follows：
Sustained release complex repairation medicament OZBB-3 is made by the preparation method of embodiment 3.
Weigh respectively containing 0.5,2.0,6.0, the contaminated soil 20g of 15.0mg/kg DDT be placed in four 100mL tool plug glass
In culture bottle, applies respectively according to the 1.5% of contaminated soil dry weight and repair medicament OZBB-3.It is fully mixed with soil that medicament will be repaired
Even, mixed system cultivates 90d in 25 DEG C of growth cabinets, during which maintains soil moisture content in 70% maximum field capacity,
Soil sampling measures the wherein residual concentration of DDT after culture, and calculates removal rate, and the results are shown in Figure 3.From the figure 3, it may be seen that place
Repair medicament after reason 90d has apparent removal effect (89.6-90.5%) to the DDT of various concentration in soil, and in soil
The removal rate of various concentration DDT is not significantly different, and illustrates the complex repairation medicament to low, medium and high concentration DDT contaminated soils
The applicability of improvement is ideal.
Embodiment 7：
The sustained release complex repairation medicament OZBB-4 prepared in embodiment 4 is applied to the original position that six six six pollutes topsoil
It turns over and spreads fertilizer over the fields in reparation, be as follows：
Contaminated soil is turned in advance, ploughed depth 25cm, prepares to repair medicine by the 0.05% of contaminated soil dry weight
The applied amount of agent OZBB-4 spreads fertilizer over the fields ready reparation medicament OZBB-4 in turning in rear soil, and mixing of raking the soil level, watering is kept
Soil moisture content is the 50% of field capacity, and covers PVC film in soil surface, and different sampled point soil are measured after handling 30d
Pollutant concentration and removal rate is calculated in earth, the results showed that the removal rate of six six six is all higher than 79% in all sampled point soil,
And residual concentration be showed no it is exceeded, it is believed that will sustained release complex repairation medicament OZBB-4 be applied to six six six pollute topsoil
Original position turn over that spread fertilizer over the fields reparation be successful.
Embodiment 8：
The sustained release complex repairation medicament OZBB-W prepared in embodiment 5 is applied to the original that tetrachloro biphenyl pollutes topsoil
Position, which is turned over, spreads fertilizer over the fields in reparation, is as follows：
Contaminated soil is turned in advance, ploughed depth 30cm, prepares to repair medicament by the 0.7% of contaminated soil dry weight
The applied amount of OZBB-W spreads fertilizer over the fields ready reparation medicament OZBB-W in turning in rear soil, and mixing of raking the soil level, watering keeps soil
Earth moisture content is the 60% of field capacity, and covers HDPE film in soil surface, and different sampled point soil are measured after handling 180d
Pollutant concentration and removal rate is calculated in earth, the results showed that the removal rate of tetrachloro biphenyl is all higher than in all sampled point soil
88%, and residual concentration be showed no it is exceeded, it is believed that will sustained release complex repairation medicament OZBB-W be applied to tetrachloro biphenyl pollution
The original position of topsoil turns over that spread fertilizer over the fields reparation be successful.
Embodiment 9：
The sustained release complex repairation medicament OZBB-C prepared in embodiment 5 is applied to tetrabromo Biphenyl Ether and pollutes topsoil
Original position, which is turned over, spreads fertilizer over the fields in reparation, is as follows：
Contaminated soil is turned in advance, ploughed depth 40cm, prepares to repair medicament by the 1.5% of contaminated soil dry weight
The applied amount of OZBB-C spreads fertilizer over the fields ready reparation medicament OZBB-C in turning in rear soil, and mixing of raking the soil level, watering keeps soil
Earth moisture content is the 80% of field capacity, and covers HDPE film in soil surface, and different sampled point soil are measured after handling 350d
Pollutant concentration and removal rate is calculated in earth, the results showed that the removal rate of tetrachloro biphenyl is all higher than in all sampled point soil
95%, and residual concentration be showed no it is exceeded, it is believed that will sustained release complex repairation medicament OZBB-C to be applied to tetrabromo Biphenyl Ether dirty
The original position of dye topsoil turns over that spread fertilizer over the fields reparation be successful.
Claims (10)
1. a kind of method of Persistent halogenated hydrocarbons in complex repairation chemicals treatment soil with sustained release, which is characterized in that
Using sustained release complex repairation medicament, broadcast application is turned over using topsoil in situ, handles the Persistent halogenated hydrocarbons in soil；
The topsoil turns over broadcast application in situ：Contaminated soil is turned in advance, by a certain amount of sustained release complex repairation medicine
Agent is directly spread fertilizer over the fields in the soil after turning over, mixing of raking the soil level, and is watered and kept certain water content, is finally covered and is protected in soil surface
After sheath, anaerobic reduction dehalogenation reaction is carried out, achievees the purpose that long-acting removal topsoil Persistent halogenated hydrocarbons in situ；
Step is prepared the sustained release complex repairation medicament by the following method：
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor：The dosage for adding 0.1-1.0g microorganism freeze-dried powders by every liter of physiological saline, microorganism is lyophilized
Powder, which is added in the physiological saline that mass concentration is 0.8-1.0%, to be dissolved, and it is 0.1-1.0mg/mL that bacterial concentration, which is made,
Bacterium seed liquor；The microorganism freeze-dried powder is the freeze-dried powder of dissimilatory iron reduction bacterium；
Black wood charcoal pre-processes：The HCl solution that black wood charcoal is first 1.0-5.0% with mass concentration impregnates 12-24h, and deionized water is cleaned；Again
12-24h is impregnated with the NaOH of a concentration of 10-20g/L, deionized water is cleaned；The physiology for being finally 0.8-1.0% with mass concentration
After saline sook 12-24h, it is placed in 120-125 DEG C of moist heat sterilization pot the 15-30min that sterilizes, is dried for standby；
Nanoscale zero-valent metal pre-processes：The zero-valent metal powder of 10-100nm is placed in the HCl that mass concentration is 0.1-2.0%
In solution, it is acidified 5-15min, it is 7-8 to be rinsed to pH value with deionized water after taking-up, is placed in anaerobic box air-dried spare；
(2) it is sustained the preparation of complex repairation medicament：
1) it prepares bacterium solution and is saturated black wood charcoal：The dosage for adding 10.0-1000.0g black wood charcoals by every liter of bacterium seed liquor, by what is pre-processed
Black wood charcoal is added in the bacterium seed liquor that the bacterial concentration prepared is 0.1-1.0mg/mL, and above-mentioned mixing suspension is placed in
100-200r/min vibrates 6-12h in shaken cultivation case, air-dries 25-35 DEG C of anaerobic of solid matter after filtering off solution, final to make
It obtains required bacterium solution and is saturated black wood charcoal；
2) the colloidal solution A containing locust bean gum and organic carbon source is prepared：Add 0.5-4.5g locust bean gums and 1.5- by every 100mL water
Locust bean gum and organic carbon source are added in deoxygenation deionized water by the dosage of 3.5g organic carbon sources, are placed on heater and are heated
To 60-80 DEG C, machine mixer 100-250r/min is used in combination persistently to stir, until locust bean gum is completely dissolved and mixing, it is cooling
To 25-50 DEG C, the colloidal solution A containing locust bean gum and organic carbon source is obtained；
3) the gluey suspension B that black wood charcoal is saturated containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is prepared：By every
100mL water adds 0.5-2.0g nanoscale zero-valent metals and 2.0-8.0g bacterium solutions to be saturated the dosage of black wood charcoal, the glue obtained to step 2)
Bacterium solution saturation black wood charcoal made from the nanoscale zero-valent metal powder pre-processed and step 1) is added in shape solution A, machinery is used in combination
Blender 100-250r/min is persistently stirred, until nanoscale zero-valent metal powder is saturated the complete mixing of black wood charcoal with bacterium solution, is obtained
The gluey suspension B that black wood charcoal is saturated containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is for use；
4) cross-linking reaction：Using peristaltic pump, pump discharge hose connects 2-8 Medical injection needles, the glue that will be obtained in step 3
Shape suspension B is added dropwise to the CaCl of the mass content containing 1.5-4.5% with the speed of 3-7mL/min2Saturation boric acid solution in, and
It is placed in mechanical agitator room temperature 150-250r/min stirring crosslinkings reaction 2-6h, then crosslinked fluid is positioned in 2-6 DEG C of refrigerator
Reinforce 6-24h；
5) be delayed cross-linking reaction：Crosslinked fluid filtering after being reinforced in step 4), obtained gel micro-ball are transferred to mass concentration
For the Na of 0.5-1.0%2SO4Be delayed cross-linking reaction 2-6h in solution, filters off Na2SO4Solution, thus obtained microsphere are with mass concentration
The physiological saline of 0.8-1.0% cleans 2-3 times, room temperature natural air drying, obtains a kind of for handling Persistent halogenated hydrocarbons in soil
Sustained release complex repairation medicament, be placed in anaerobic environment and save backup.
2. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as described in claim 1 with sustained release
It is, the dissimilatory iron reduction bacterium is a kind of bacterium with dissimilatory iron reduction dehalogenation ability；It is described de- with dissimilatory iron reduction
The bacterium of halogen ability, that is, dissimilatory iron reduction bacterium is Shewanella.
3. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as claimed in claim 2 with sustained release
It is, the Shewanella is Shewanella putrefaciens CN32, Shewanella piezotolerans WP3
Or Shewanella oneidensis MR-1.
4. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as described in claim 1 with sustained release
It is, the nanoscale zero-valent metal is nano zero valence iron, nano zero-valence zinc or nano zero-valence aluminium；The step 1) and the step
It is rapid 5) used in physiological saline be mass concentration be 0.9% physiological saline.
5. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as described in claim 1 with sustained release
Be, the organic carbon source is the low molecular organic acids including acetic acid, oxalic acid, malic acid, and including xylose, fructose,
Monosaccharide including maltose or biglycan.
6. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as described in claim 1 with sustained release
It is, the grain size of the sustained release complex repairation medicament is 0.5-2.0mm.
7. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as described in claim 1 with sustained release
It is, black wood charcoal is 2.0 × 10 to the saturated extent of adsorption of bacterium solution in the step 1)6-4.0×109cfu/g。
8. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as described in claim 1 with sustained release
It is, in gluey suspension B made from the step 3), the mass percentage that bacterium solution is saturated black wood charcoal is 2.0-8.0%, locust tree
The mass percentage of bean gum is 0.5-4.5%, and the mass percentage of nanoscale zero-valent metal is 0.5-2.0%, organic carbon
The mass percentage in source is 1.5-3.5%.
9. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as described in claim 1 with sustained release
It is, in the topsoil turns over broadcast application in situ, the sustained release complex repairation medicament amount of spreading fertilizer over the fields is contaminated soil dry weight
The ploughed depth of 0.05-1.5%, soil are 25-40cm, and sustained release complex repairation medicament spreads fertilizer over the fields rear soil moisture content and adjusts to maximum
The 50-80% of field capacity, soil surface protective layer is PVC film or HDPE film, with sustained release complex repairation medicament repair process
Time be 30-350d.
10. the method for Persistent halogenated hydrocarbons, feature in the complex repairation chemicals treatment soil as described in claim 1 with sustained release
It is, the Persistent halogenated hydrocarbons include among organo-chlorine pesticide, Polychlorinated biphenyls, polybrominated diphenyl ethers and their degradation
Product.
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