CN104673778A - Method for purifying highly-cyclic PAHs contaminated soil - Google Patents
Method for purifying highly-cyclic PAHs contaminated soil Download PDFInfo
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- CN104673778A CN104673778A CN201510108454.5A CN201510108454A CN104673778A CN 104673778 A CN104673778 A CN 104673778A CN 201510108454 A CN201510108454 A CN 201510108454A CN 104673778 A CN104673778 A CN 104673778A
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- pahs
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Abstract
The invention aims to provide a method for purifying highly-cyclic PAHs contaminated soil and microorganism immobilization particles used for purifying highly-cyclic PAHs. A microorganism bacterium solution capable of degrading the highly-cyclic PAHs is uniformly mixed with a gel solution to obtain particles, the particles are chemically cross-linked through a cross-linking agent and are soaked by sterile water, and microorganisms are subjected to multiplication culture in a multiplication culture medium to obtain the microorganism immobilization particles. The invention also provides the method for purifying the highly-cyclic PAHs contaminated soil. The microorganism immobilization particles are added into the soil, and a plant is planted on the soil. The highly-cyclic PAHs contaminated soil is purified by using the method, so that the highly-cyclic PAHs in the soil can be efficiently degraded, the environmental friendliness is achieved, and the secondary pollution is avoided.
Description
Technical field
The invention belongs to environment pollutant biological treatment technical field, be specifically related to a kind of method purifying epipodium PAHs contaminated soil.
Background technology
PAHs is the aromatic hydrocarbon that a class contains two or more phenyl ring, and they have three and cause effect-carcinogenic, teratogenesis, mutagenesis, and not easily degrade under field conditions (factors), easily high by biological accumulation, environmental risk.Usually the PAHs of more than 4 and 4 phenyl ring will be contained as epipodium PAHs.Epipodium PAHs chemical structure is complicated, not soluble in water, thermostability is strong, it is oxidized to be difficult to, be difficult to be biodegradable, and causes the extensive concern of Chinese scholars.
The purifying method that PAHs pollutes has Physical, chemical method, biological process.Biological process becomes the prefered method of PAHs contaminated soil purification because its non-secondary pollution, expense are few, especially utilize microorganism to the PAHs that degrades.But microbiological deterioration PAHs also to have in unit volume effectively degradation bacteria concentration low, compete with indigenous bacterium be in a disadvantageous position, toxin immunity encroaches on ability, to envrionment conditions sensitivity, react and start the defects such as slow, can not be applied to the in-situ immobilization of contaminated soil preferably.
Summary of the invention
The object of the invention is the defect overcoming prior art, a kind of method purifying epipodium PAHs contaminated soil is provided.
First the present invention provides a kind of microbe immobilized particles for purifying epipodium PAHs, its preparation method is as follows: the microbial inoculum of the epipodium PAHs that can degrade and coagulant liquid mix makes particle, again after linking agent chemically crosslinked, after being soaked with sterilized water by particle, after multiplication culture being carried out to microorganism in proliferated culture medium, make microbe immobilized particles.
Wherein coagulant liquid includes modification organic binder bond (modified PVA) and zeolite;
As preferably, the volume mass per-cent of modification organic binder bond and zeolite is 5 ~ 10% (mL:g);
Described modified PVA, its preparation method is as follows: be dissolved in deionized water by pulverous 1799 type polyvinyl alcohol under 85 DEG C of water bath condition, succinic acid is added after dissolving, be cooled to room temperature after reaction to be dissolved and namely obtain modification organic binder bond, wherein the proportioning of deionized water, polyvinyl alcohol, succinic acid is 80:5.6:1 (mL:g:g).
Described microorganism is the microorganism of the epipodium PAHs that can effectively degrade;
Described linking agent is CaCl
2the aqueous solution;
Described proliferated culture medium composed as follows: glucose 4%, yeast extract paste 0.3%, KH
2pO
40.05%, MgSO
47H
2o 0.025%, NH
4cl 0.2%, pH 7.0.
Above-mentioned microbe immobilized particles is in for purifying epipodium PAHs contaminated soil.
The present invention also provides a kind of method purifying epipodium PAHs contaminated soil, is in soil, add microbe immobilized particles and planting plants.
Wherein said plant is reed.
Immobilized microorganism placement position is the reed rhizosphere region apart from soil surface 10cm place.
With method purification epipodium PAHs contaminated soil of the present invention, the epipodium PAHs that can not only degrade efficiently in soil, and environmental friendliness, non-secondary pollution.
Accompanying drawing explanation
Fig. 1 is immobilized microorganism-plant combined purification system schematic diagram;
Wherein, 1 water dispensing apparatus; 2 indigenous microorganisms; 3 reed ponds; 4 rhizosphere soils; 5 degradation bacteria immobilization particles; 6 reeds.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail
Embodiment 1 (comparative example)
1, choosing of the microorganism of epipodium PAHs is purified
Efficient degrading bacteria used by immobilization is mixed strains (Methylobacterium sp.lxb-3, Methylobacter, deposit number is CGMCC NO.3713 and Rhodococcus sp.lxb-6, Rhod, and deposit number is CGMCC NO.3715); But the microorganism of the purification epipodium PAHs that other also can be used known.
2, epipodium PAHs efficient degrading bacteria is fixing
To the degradation bacteria suspension centrifugal concentrating of logarithmic phase be cultivated to OD
600=1.0, by the method for embedding, the degradation bacteria strains of mixing is fixed on zeolite ball.Detailed process is: with the zeolite through milled 100 mesh sieve for solid support material, and modified PVA is that gelifying agent obtains coagulant liquid; Finally according to the ratio of weight 10%, the coagulant liquid of turbid for bacterium liquid and sterilizing is mixed; at ambient temperature; by the nodulizer of 4-10mm; being fixed particle; again through linking agent 12h chemically crosslinked; soak 4d, multiplication culture 3d with sterilized water, namely obtain the immobilization particle of epipodium PAHs degradation bacteria.
3, the simulation of epipodium PAHs device in immobilized microorganism-plant combined purification soil
The construction process of combined purifying system of the present invention: for the practical situation of Liaohe Estuary seashore wetland water inlet, in conjunction with the growing state of wetland soil and Root of Wetland Plants, PVC plastic flitch is utilized to develop wetland simulation test device, this device is made up of water dispensing apparatus 1, reed pond 3, degradation bacteria immobilization particle 5, reed 6, rhizosphere soil 4 and indigenous microorganism 2, in reed pond with water dispensing apparatus can meet wetland simulator water inlet controllability, the Liaohe Estuary seashore wetland plant reed 16 plant heights being about 15cm is transplanted in this device.When reed grows into height about 50cm, in the reed rhizosphere soil at distance upper soll layer 10cm place, (bacterium amount is 0.6 × 10 to add degradation bacteria immobilization particle 300g
9-1.2 × 10
9cells) wherein, the length in reed pond is 1.0m, and wide is 0.5m, high 0.5m, soil floor height 0.4m.
For checking this combined purifying system to the removal effect of epipodium PAHs, not add immobilization degradation bacteria or not plant the soil of reed for contrast, gather pedotheque when 0,2,4,6,10,20,30,40d.First soil by 2mm mesh sieve, remove larger plant tissue and stone, then rejects macroscopic radicula manual on ice.Natural air drying under low-temperature dark condition, crosses 100 mesh sieve, for the analysis of PAHs after pulverizing grinding.All samples process completes in 6h after sampling.
PAHs is extracted by ultrasonic extraction, detailed process is as follows: take 2.0g pedotheque and 2.0g anhydrous sodium sulphate in centrifuge tube, and mixing, adds the mixed solution (volume ratio is 1:1) of 20mL normal hexane and methylene dichloride wherein, after covering tightly bottle stopper, ultrasonic extraction 20min.After leaving standstill 30min, transfer supernatant liquor, to Florence flask, repeats aforesaid operations 2 times.Supernatant liquor being merged, revolves and steam to 2mL, with the liquid in glue head dropper absorption Florence flask to loading in complete chromatography column (3cm aluminum oxide, 6cm silica gel, 0.5cm anhydrous sodium sulphate), with appropriate normal hexane drip washing alkane, discarding the liquid eluted.With mixed solution (volume ratio is 7:3) the elution chromatography post of 30mL normal hexane and methylene dichloride.Finally revolved by solution and steam to 1mL, nitrogen blows and is settled to 1mL, treats that machine measures.
The content of epipodium PAHs in each pedotheque is analyzed by gas-chromatography-GC-MS (GC-MS).GC-MS instrument condition is as follows: injector temperature 290 DEG C, and sample size 1 μ L, without splitting ratio; Initial column temperature 50 DEG C, keeps 2min; With 8 DEG C of min
-1speed be warming up to 230 DEG C; Again with 3.5 DEG C of min
-1speed be warming up to 300 DEG C, keep 7min.
According to above step, this method be applied in the purification of epipodium PAHs, testing soil used is that PAHs pollutes more serious soil.Wherein the starting point concentration of epipodium PAHs is 284.5ng/g.
Compared with control group (A group) and the soil that only adds immobilization degradation bacteria (B group) or only plant reed (C group), with the addition of immobilization degradation bacteria and planted epipodium PAHs content in the soil of reed (D group) and significantly reduce, after 40d, the concentration of epipodium PAHs decreases 78.4%; But, only add epipodium PAHs in the soil of immobilization degradation bacteria particle and a plantation reed and eliminate 62.8% and 59.1% respectively; In control group soil, epipodium PAHs decreases 29.4%.Illustrate that immobilized microorganism-plant combined can significantly improve decontamination effect improving.
Embodiment 2 (comparative example)
Difference from Example 1 is: be added in the lower soil of PAHs pollution level by obtained epipodium PAHs degradation bacteria immobilization particle, wherein the starting point concentration of epipodium PAHs is 186ng/g.
With the addition of immobilization degradation bacteria and planted in the soil of reed (D group), after 40d, the clearance of epipodium PAHs is 58.9%; In the soil only adding immobilization degradation bacteria (B group) or only plant reed (C group), the clearance of epipodium PAHs is 42-48%; By contrast, in control group (A group), the clearance of epipodium PAHs is negligible, less than 25%.Illustrate that immobilized microorganism-plant combined purification techniques can overcome single immobilized microorganism or the defect of plant purification thus, significantly improve purification efficiency and effect.
Claims (9)
1. one kind for purifying the microbe immobilized particles of epipodium PAHs, it is characterized in that, the preparation method of described microbe immobilized particles is as follows: the microbial inoculum of the epipodium PAHs that can degrade and coagulant liquid mix makes particle, again after linking agent chemically crosslinked, after being soaked with sterilized water by particle, after multiplication culture being carried out to microorganism in proliferated culture medium, make microbe immobilized particles.
2. microbe immobilized particles as claimed in claim 1, it is characterized in that, described coagulant liquid includes modification organic binder bond and zeolite.
3. microbe immobilized particles as claimed in claim 2, it is characterized in that, described modification organic binder bond and the volume mass per-cent of zeolite are 5 ~ 10%.
4. microbe immobilized particles as claimed in claim 1, it is characterized in that, described linking agent is CaCl
2the aqueous solution.
5. microbe immobilized particles as claimed in claim 1, is characterized in that, described proliferated culture medium composed as follows: glucose 4%, yeast extract paste 0.3%, KH
2pO
40.05%, MgSO
47H
2o 0.025%, NH
4cl 0.2%, pH 7.0.
6. the application of microbe immobilized particles according to claim 1 in purification epipodium PAHs contaminated soil.
7. purify a method for epipodium PAHs contaminated soil, it is characterized in that, described method is in soil, add microbe immobilized particles according to claim 1, and grown on soil plant.
8. method as claimed in claim 8, it is characterized in that, described plant is reed.
9. method as claimed in claim 8, it is characterized in that, described microbe immobilized particles placement position is reed rhizosphere region.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106085449A (en) * | 2016-06-17 | 2016-11-09 | 战锡林 | Organophosphorus pesticide pollution soil remediation material |
CN108480382A (en) * | 2018-02-06 | 2018-09-04 | 金华市飞凌生物科技有限公司 | A kind of organic polluted soil modifying agent |
CN109516649A (en) * | 2018-12-27 | 2019-03-26 | 中关村海绵城市工程研究院有限公司 | A kind of Wind energy storage formula artificial wetland purifying system |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102276124A (en) * | 2011-05-30 | 2011-12-14 | 昆山工研院华科生物高分子材料研究所有限公司 | Microbe dredging agent and preparation method thereof |
CN102718327A (en) * | 2012-07-05 | 2012-10-10 | 浙江皇冠科技有限公司 | Nano-biological water body remediation agent for aquaculture and preparation method thereof |
CN104313008A (en) * | 2014-10-15 | 2015-01-28 | 湖南大学 | Compound microbial preparation as well as preparation method and application thereof |
-
2015
- 2015-03-12 CN CN201510108454.5A patent/CN104673778A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102276124A (en) * | 2011-05-30 | 2011-12-14 | 昆山工研院华科生物高分子材料研究所有限公司 | Microbe dredging agent and preparation method thereof |
CN102718327A (en) * | 2012-07-05 | 2012-10-10 | 浙江皇冠科技有限公司 | Nano-biological water body remediation agent for aquaculture and preparation method thereof |
CN104313008A (en) * | 2014-10-15 | 2015-01-28 | 湖南大学 | Compound microbial preparation as well as preparation method and application thereof |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106085449A (en) * | 2016-06-17 | 2016-11-09 | 战锡林 | Organophosphorus pesticide pollution soil remediation material |
CN108480382A (en) * | 2018-02-06 | 2018-09-04 | 金华市飞凌生物科技有限公司 | A kind of organic polluted soil modifying agent |
CN108480382B (en) * | 2018-02-06 | 2020-07-24 | 金华市飞凌生物科技有限公司 | Organic contaminated soil conditioner |
CN109516649A (en) * | 2018-12-27 | 2019-03-26 | 中关村海绵城市工程研究院有限公司 | A kind of Wind energy storage formula artificial wetland purifying system |
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Application publication date: 20150603 |