CN101733272A - Remediation method of decabromodiphenyl oxide contaminated soil - Google Patents
Remediation method of decabromodiphenyl oxide contaminated soil Download PDFInfo
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- CN101733272A CN101733272A CN201010103021A CN201010103021A CN101733272A CN 101733272 A CN101733272 A CN 101733272A CN 201010103021 A CN201010103021 A CN 201010103021A CN 201010103021 A CN201010103021 A CN 201010103021A CN 101733272 A CN101733272 A CN 101733272A
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Abstract
The invention discloses a remediation method of decabromodiphenyl oxide contaminated soil, which comprises the following steps: pore fungus is made into fungus pieces by using a puncher with the diameter of 10 mm, the pore fungus pieces and the decabromodiphenyl oxide contaminated soil are uniformly mixed at room temperature, and the degradation action of the pore fungus on the decabromodiphenyl oxide is utilized to realize the remediation of the decabromodiphenyl oxide contaminated soil. The remediation method of the invention has the advantages of low cost and simple operation, and has favorable effect on degrading decabromodiphenyl oxide in the soil. Some parameters in the remediation method are optimized, so that the pore fungus can be directly added to the soil to be remediated and can not be affected by complex ingredients in the soil, thereby effectively degrading the decabromodiphenyl oxide in the soil.
Description
Technical field
The present invention relates to soil pollution bioremediation technology field, be specifically related to a kind of restorative procedure of decabromodiphenyl oxide contaminated soil.
Background technology
Decabromodiphenyl oxide (BDE-209 or DeBDE) is a class PBDE that has the call on the market, be common be applied to the fire retardant industrial goods one of, be widely used in industries such as rubber, weaving, electronics, plastics.After decabromodiphenyl oxide is discharged in the environment, through processes such as photodissociation, pyrolytic, biology and microbial degradations, can be converted into the biphenyl ether of many bromines dibenzodioxin English, many bromines dibenzofurans and low bromo, enter organism easilier, also cause stronger toxic action.Decabromodiphenyl oxide itself is also tested to be gone out according to potential carcinogenicity is arranged, and the immunologic function of filial generation is exerted an influence.
The restorative procedure of contaminated soil generally includes physical chemistry repairing method and biological restoration method.Wherein the physics method usually by large-arealy dig, method such as soil removal and replacement realizes that it is huge that the method input expends fund.Chemical method has usually and destroys soil physico-chemical property and cause defective such as secondary pollution.
Bioremediation technology is that grow up over nearly 20 years a kind of effectively is used for the method that contaminated soil is administered, and cost is low because of having, non-secondary pollution, do not destroy characteristics such as soil environment and come into one's own day by day.
Biological restoration for decabromodiphenyl oxide contaminated soil, that has reported now has a He Jianzhong (He Jiangzhong, Robrock Kristinr, Lisa Alvarez-Cohen.Microbia reductive debromination of polybrominated diphenyl ethers (PBDEs) [J] .Environmental Science and Technology, 2006,40:4429-4434.) etc. by the effect of the single bag of vacation bacteria microorganism PBDE has been carried out reduction dechlorination, thereby noxious material is converted into innocuous substance.
Bracket fungus is a big monoid that has important economic worth in the fungi and receive much concern, and extensively distributes on earth.Most of kinds in the bracket fungus are timber saprophytic bacterias, cause timber white rot or brown rot, and usually said bracket fungus is actually an aggregate.
Microorganism in the soil is a lot, and this just makes mushroom is used for can facing a lot of technical difficulties when soil pollution is repaired that the certain micro-organisms in the soil can cause the activity of mushroom to reduce or disappear, thereby can't realize the reparation to soil pollution.
Do not have as yet at present bracket fungus is directly used in the decabromodiphenyl oxide contaminated soil reparation, and the relevant report that the various parameters in repairing are studied.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of cost low, efficient and safe, bracket fungus is directly used in the method for the reparation of decabromodiphenyl oxide contaminated soil.
Above-mentioned purpose of the present invention is achieved by following scheme:
A kind of restorative procedure of decabromodiphenyl oxide contaminated soil, this method is to adopt bracket fungus, bracket fungus is directly added by in the decabromodiphenyl oxide contaminated soil, utilize the degradation of bracket fungus, thereby realize reparation decabromodiphenyl oxide contaminated soil to decabromodiphenyl oxide.
Above-mentioned restorative procedure, be that earlier bracket fungus to be adopted diameter be the become one with bacterium sheet of sheet of the card punch of 10mm, add the adding proportion of 3～9 bracket fungus again according to every 10g soil, bracket fungus bacterium sheet is directly at room temperature evenly mixed with the soil that contains decabromodiphenyl oxide, by the degradation of bracket fungus to decabromodiphenyl oxide, thereby realization is to the reparation of decabromodiphenyl oxide contaminated soil.
In the above-mentioned restorative procedure, used bracket fungus is any one bracket fungus fungi.
In the above-mentioned restorative procedure, after bracket fungus and soil to be repaired at room temperature mixed, can pass through gas phase-GC-MS, at set intervals disposition is carried out analyzing and testing, by testing result as can be seen, when not adding bracket fungus, the natural degradation rate of decabromodiphenyl oxide slowly increases in time, and degradation process is not remarkable; After adding bracket fungus, the decabromodiphenyl oxide degradation speed significantly increases, and along with the increase that adds the bacterium amount, degradation rate is faster, and along with the increase that adds the bacterium amount, the degradation rate of decabromodiphenyl oxide is also more and more higher, just can keep a higher degradation rate when adding when bacterium amount is 6, therefore of the present inventionly adds bacterium and measures 6 bracket fungus of preferred every 10g soil interpolation.
Detect by gas phase-mass spectrometry repair process, after the inventor also finds contaminated soil to be detected carried out sterilization treatment, on the contrary not as for sterile soil, analysis may be that some microorganisms in the soil have facilitation to the degradation effect of bracket fungus to bracket fungus to the degradation effect of decabromodiphenyl oxide.
Restorative procedure of the present invention all can play good degrading decabromodiphenyl ether effect to polytype soil.
Compared with prior art, the present invention has following beneficial effect:
1. restorative procedure of the present invention, it is with low cost, simple to operate, and the effect of decabromodiphenyl oxide is fine in the degraded soil;
2. the present invention passes through some parameter optimizations in the restorative procedure, thereby makes bracket fungus can directly add in the soil to be repaired, can not be subjected to the influence of complicated component in the soil, thereby effectively the decabromodiphenyl oxide in the soil be degraded.
Description of drawings
Fig. 1 be among the embodiment 3 different soil samples to the broken line graph that influences of bracket fungus degrading decabromodiphenyl ether.
The specific embodiment
Below in conjunction with specific embodiment the present invention is done description further, but specific embodiment is not done any qualification to the present invention.
Embodiment 1 bracket fungus is repaired decabromodiphenyl oxide contaminated soil and adds the research of bacterium amount
Gather Guangzhou Agricultural University Of South China arboretum red earth, be placed on the laboratory natural air drying after soil sample is returned, it is standby to cross 60 mesh sieves.
Decabromodiphenyl oxide is at room temperature evenly mixed with above-mentioned processing pedotheque later, be put in shady place, preparation decabromodiphenyl ether content is the decabromodiphenyl oxide contaminated red earth of 2.5mg/kg.
Present embodiment is provided with four experimental group:
The blank group: not add bacterial classification in decabromodiphenyl oxide contaminated red earth is blank;
Add 1 group of bacterium: add bracket fungus bacterium sheet and evenly mixing in decabromodiphenyl oxide contaminated red earth, adding the bacterium ratio is 3/10g soil;
Add 2 groups of bacterium: add bracket fungus bacterium sheet and evenly mixing in decabromodiphenyl oxide contaminated red earth, adding the bacterium ratio is 6/10g soil;
Add 3 groups of bacterium: add bracket fungus bacterium sheet and evenly mixing in decabromodiphenyl oxide contaminated red earth, adding the bacterium ratio is 9/10g soil.
Above-mentioned four experimental group are provided with 3 repetitions respectively.
It is that the card punch of 10mm is got that the bracket fungus bacterium sheet of present embodiment all adopts diameter.
Above-mentioned four experimental group will all will be tested before test for the decabromodiphenyl oxide initial concentration in the examination soil, and each experimental group in sampling in the 3rd, 6,9,12,15 day of bracket fungus processing, detects each sample respectively then.
The detection method of sample is: acetone/n-hexane mixed solvent (volume ratio is 1: 1) is carried out rope chamber extracting 48h to the pedotheque that takes out, and add an amount of copper sheet at end bottle and be used for desulfurization, the extract rotary evaporation is concentrated into 1～2ml, add the 10ml n-hexane and carry out solvent switch, rotary evaporation to 1～2ml again, cross multilayer silica gel aluminium oxide combined column then: use the n-hexane of 30ml successively, the equal-volume of 70ml is than the n-hexane-dichloromethane solution drip washing that mixes.The leacheate rotary evaporation is concentrated into 1ml, changes in the bottle of 1.8ml soft N over to
2Blow to 200 μ l in n-hexane, utilize gas phase-GC-MS to carry out sample analysis at last.
The chromatographic condition that gas phase-the GC-MS operation is adopted: DB-5MS (15m * 0.25mm.id., 0.1 μ m) capillary column; Carrier gas is He, constant current, and the post flow is 1mL/min, no split sampling, sample size are 1 μ L; 280 ℃ of injector temperatures, 110 ℃ of post beginning temperature, 10 ℃/min rises to 300 ℃ (5min), NCI ion gun; Methane is reaction gas; 230 ℃ of ion source temperatures.The scan ion m/z of decabromodiphenyl oxide is 79,81,486.7 and 488.7.
Table 1 provides bracket fungus and adds the influence result of the difference of bacterium amount to the decabromodiphenyl oxide degradation rate.
Table 1 adds the influence of bacterium amount to the decabromodiphenyl oxide degradation rate
As can be seen from Table 1, when not adding bracket fungus, the natural degradation rate of decabromodiphenyl oxide slowly increases in time, and degradation process is not remarkable; After adding bracket fungus, the decabromodiphenyl oxide degradation speed significantly increases, and along with the increase that adds the bacterium amount, degradation rate is faster, when adding bacterium amount and be 3,6,9, after 15 days, the degradation rate of decabromodiphenyl oxide has all reached more than 50%, after this explanation adds bracket fungus, the bracket fungus decabromodiphenyl oxide in the soil of degrading significantly, this provides assurance for adopting bracket fungus directly to repair decabromodiphenyl oxide contaminated soil.
In addition, it can also be seen that from table 1, when the bacterium amount that adds of bracket fungus is 3～9/10g soil, all can obtain good decabromodiphenyl oxide degradation effect, reach a higher degradation effect when adding when the bacterium amount is 6, add bacterium this moment and measure when being increased to 9, then effect can not be significantly improved yet, therefore for cost consideration, the preferred bracket fungus of restorative procedure of the present invention to add the bacterium amount be 6/10g soil.
The condition optimizing of embodiment 2 soil to be detected
The processing method that is primarily aimed at soil to be detected of present embodiment is optimized, and pedotheque adopts the decabromodiphenyl oxide contaminated red earth of the 2.5mg/kg of embodiment 1 preparation, is divided into two experimental group:
(1) non-sterilization group: this group does not adopt sterilization treatment to the decabromodiphenyl oxide contaminated red earth of the 2.5mg/kg of embodiment 1 preparation, directly according to the dosage ratio of 6/10g soil, bracket fungus is added in the decabromodiphenyl oxide contaminated red earth, evenly mixes;
(2) sterilization group: after this group is carried out conventional sterilization treatment to the decabromodiphenyl oxide contaminated red earth of the 2.5mg/kg of embodiment 1 preparation earlier, again according to the dosage ratio of 6/10g soil, bracket fungus is added in the decabromodiphenyl oxide contaminated red earth after the sterilization, evenly mix.
The sterilization process of above-mentioned sterilization group carries out in autoclave.
Non-sterilization group and sterilization group will all will be tested earlier before test for the decabromodiphenyl oxide initial concentration in the examination soil, and so latter two experimental group was carried out sample analysis, analytical method such as embodiment 1 respectively at the 3rd, 6,9,12,15 day.
Table 2 is the influence of the difference of agent, soil treatment method to be detected to the bracket fungus degrading decabromodiphenyl ether.
The different soil sample processing methods of table 2 are to the influence of bracket fungus degrading decabromodiphenyl ether
As shown in Table 2, to before and after decabromodiphenyl oxide contaminated red earth sterilizes, the usefulness generation marked change of bracket fungus degrading decabromodiphenyl ether, in two kinds of different soil samples, increase along with the time, the decabromodiphenyl oxide degradation rate all also increases gradually, but in a period of time, the degradation rate of decabromodiphenyl oxide is 38.14% in the sterilization soil, be lower than non-sterilization soil, be the degradation rate 52.59% of decabromodiphenyl oxide in the red earth of collection in worksite, this illustrates that the usefulness that adopts the bracket fungus degrading decabromodiphenyl ether in the non-sterilization soil is better than sterilization soil.
The repairing effect of embodiment 3 different soils samples detects
Present embodiment has been gathered red earth, red soil, laterite, rice soil and field of vegetables soil totally 5 kinds of soil samples respectively, and wherein red earth derives from magnificent agricultural arboretum, and rice soil and vegetable garden soil derive from magnificent rural area, and red soil comes from Zhanjiang, the bad Shaoguan that derives from of laterite.
Be placed on the laboratory natural stype after soil sample is returned, it is standby to cross 60 mesh sieves.Prepare the decabromodiphenyl oxide contaminated red earth of the 2.5mg/kg of above-mentioned five kinds of soil respectively, the preparation method is with embodiment 1.
Native 10g is used in each processing, and 3 repetitions are set, and it is 6/10g soil that bracket fungus adds the bacterium amount.
The test Pretesting is for the decabromodiphenyl oxide initial concentration of examination soil, and sample analysis is carried out in 3,6,9,12,15 days after test is carried out respectively, analytical method such as example 1.Finally obtain decabromodiphenyl oxide residual content in each soil sample.
The different soil samples of Fig. 1 are to the broken line graph that influences of bracket fungus degrading decabromodiphenyl ether, 5 broken lines among the figure are respectively red earth, red soil, laterite, the testing result of rice soil and these 5 kinds of soil samples of field of vegetables soil, as can be seen from the figure, for these 5 kinds of different soil samples, after adding bracket fungus, bracket fungus all has degradation to the decabromodiphenyl oxide in the soil, increase along with the time, degradation rate also increases gradually, after about 15 days, degradation rate tends to balance, the degradation rate of 5 kinds of soil samples has all reached more than 50%, this explanation bracket fungus all has good degradation effect to above-mentioned 5 kinds of decabromodiphenyl oxide contaminated soil samples, illustrates that also bracket fungus degrading decabromodiphenyl ether effect in multiple soil sample has universality simultaneously.
Claims (5)
1. the restorative procedure of a decabromodiphenyl oxide contaminated soil, this method are that bracket fungus is directly added in the decabromodiphenyl oxide contaminated soil, utilize the degradation of bracket fungus to decabromodiphenyl oxide, thereby realize the reparation to decabromodiphenyl oxide contaminated soil.
2. restorative procedure according to claim 1, it is characterized in that in the described soil that the direct adding of bracket fungus is decabromodiphenyl oxide contaminated, be that to adopt earlier diameter be that the card punch of 10mm breaks into the bacterium sheet with bracket fungus, again with bracket fungus bacterium sheet with at room temperature evenly mixed by decabromodiphenyl oxide contaminated soil.
3. restorative procedure according to claim 2, it is characterized in that described bracket fungus bacterium sheet at room temperature evenly being mixed with decabromodiphenyl oxide contaminated soil, wherein the mixed proportion of bracket fungus bacterium sheet and decabromodiphenyl oxide contaminated soil is that every 10g soil adds 3～9 bracket fungus.
4. restorative procedure according to claim 3, the mixed proportion that it is characterized in that described bracket fungus bacterium sheet and decabromodiphenyl oxide contaminated soil are that every 10g soil adds 6 bracket fungus.
5. restorative procedure according to claim 1 and 2 is characterized in that described decabromodiphenyl oxide contaminated soil adopts the soil of non-sterilization treatment.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642713A (en) * | 2013-11-11 | 2014-03-19 | 华南理工大学 | Dominant microflora for degrading deca-brominated diphenyl ether waste water and preparation method thereof |
| CN103691732A (en) * | 2013-12-08 | 2014-04-02 | 浙江大学 | Method for performing phytoremediation on decabromodiphenyl ether polluted soil by alternation of wetting and drying |
| CN103805205A (en) * | 2014-02-28 | 2014-05-21 | 浙江农林大学 | Granules for repairing poly brominated diphenyl ether contaminated soil and application for same |
| CN104307870A (en) * | 2014-02-28 | 2015-01-28 | 浙江农林大学 | Bioslurry repair method for poly brominated diphenyl ethers polluted soil, and special equipment |
| CN106424129A (en) * | 2016-10-13 | 2017-02-22 | 湖南大学 | Method for remedying soil contaminated with 2,2',4,4'-tetrabromodiphenyl ether |
| CN107081332A (en) * | 2017-04-28 | 2017-08-22 | 华南理工大学 | A kind of method that utilization composting technology removes decabromodiphenyl oxide in soil |
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2010
- 2010-01-26 CN CN201010103021A patent/CN101733272A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642713A (en) * | 2013-11-11 | 2014-03-19 | 华南理工大学 | Dominant microflora for degrading deca-brominated diphenyl ether waste water and preparation method thereof |
| CN103642713B (en) * | 2013-11-11 | 2015-12-02 | 华南理工大学 | A kind of dominant microflora for degrading decabromodiphenyl ether waste water and preparation method thereof |
| CN103691732A (en) * | 2013-12-08 | 2014-04-02 | 浙江大学 | Method for performing phytoremediation on decabromodiphenyl ether polluted soil by alternation of wetting and drying |
| CN103805205A (en) * | 2014-02-28 | 2014-05-21 | 浙江农林大学 | Granules for repairing poly brominated diphenyl ether contaminated soil and application for same |
| CN104307870A (en) * | 2014-02-28 | 2015-01-28 | 浙江农林大学 | Bioslurry repair method for poly brominated diphenyl ethers polluted soil, and special equipment |
| CN104307870B (en) * | 2014-02-28 | 2018-02-23 | 浙江农林大学 | The biological mud restorative procedure and special equipment of a kind of PBDE contaminated soil |
| CN106424129A (en) * | 2016-10-13 | 2017-02-22 | 湖南大学 | Method for remedying soil contaminated with 2,2',4,4'-tetrabromodiphenyl ether |
| CN106424129B (en) * | 2016-10-13 | 2019-12-06 | 湖南大学 | Method for repairing 2,2 ', 4, 4' -tetrabromobisphenol contaminated soil |
| CN107081332A (en) * | 2017-04-28 | 2017-08-22 | 华南理工大学 | A kind of method that utilization composting technology removes decabromodiphenyl oxide in soil |
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Application publication date: 20100616 |