CN104259193A - Method for restoring atrazine pesticide polluted soil - Google Patents
Method for restoring atrazine pesticide polluted soil Download PDFInfo
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- CN104259193A CN104259193A CN201410497863.4A CN201410497863A CN104259193A CN 104259193 A CN104259193 A CN 104259193A CN 201410497863 A CN201410497863 A CN 201410497863A CN 104259193 A CN104259193 A CN 104259193A
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- atrazine
- contaminated soil
- pesticide contaminated
- soil
- spore suspension
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Abstract
The invention discloses a method for restoring atrazine pesticide polluted soil. The method comprises the following steps: mixing metallurgical slag with atrazine pesticide polluted soil to obtain a mixture, adding H2O2 solution into the mixture, and performing Fenton-like oxidization degradation to obtain a degraded product; and mixing the degraded product with straw powder and white-rot fungus spore suspension liquid, and restoring the atrazine pesticide polluted soil by virtue of biological fermentation and degradation. The atrazine pesticide in the soil is collectively removed by adopting the metallurgical slag and the white rot fungi. The method has advantages of low cost, high processing efficiency, good processing effect, little use amount of chemicals, capability of effectively improving the soil nature, and the like.
Description
Technical field
The present invention relates to field of environmental improvement, particularly relate to a kind of method of repairing atrazine pesticide contaminated soil.
Background technology
Agricultural chemicals, since invention, at control corps diseases, insect pest, crop smothering, has ensured crops normal growth, ensures higher yield of crops good harvest, solves mankind's food problem aspect and has played very important effect.Atrazine has another name called Atrazine, English name atrazine, and chemical name is the chloro-4-ethylamino-of 2--6-isopropylamine base-1,3,5-tri-pyridine, drops into commodity production, within about 1980 years, start to use in China in nineteen fifty-nine.Atrazine low price and have good herbicidal effect, becomes one of global the most widely used herbicide so far.But atrazine stable in properties is not easily degraded, and has bioconcentration, have serious harm to the mankind and animals and plants, while extensive Long-Time Service again, the residues of pesticides of accumulation have become large public hazards.Therefore, can suppress the diffusion of pollution by pesticides from source to the reparation of contaminated soil, in addition, the contaminated site stayed after the resettlement such as pesticide producing base, warehousing storage also needs to repair.
Chemical oxidation method can remove the organic pollution in soil effectively, but will reach higher clearance, often needs to add a large amount of chemicals, not only can damage the character of soil and also financial cost higher.Bioremediation technology is the new technology that environmental area develops rapidly in recent years, and it is with the pollutant in various organism degrades or absorption environment.Wherein, Phanerochaete chrysosporium (Phanerochaete chrysosporium), can carry out growth and breeding using lignocellulosic as nutrients at occurring in nature, its extracellular enzyme produced can non-specifically be degraded a series of pollutant in environment.Compared with conventional method, biological method has the advantages such as energy consumption is low, simple to operate, viable economically, but also has the shortcomings such as objective microbe and indigenous microbes are competed, length consuming time.Therefore, the advantages of biologic treating technique and chemical oxidation techniques is applied in the reparation of atrazine-containing pesticide contaminated soil has great importance.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides that a kind for the treatment of effeciency is high, treatment effect good, cost is lower and the reparation atrazine-containing pesticide contaminated soil method of environmental protection.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Provide a kind of method of repairing atrazine pesticide contaminated soil, comprise the following steps:
S1, metallurgical slag and atrazine pesticide contaminated soil are mixed to get mixture, in aforementioned mixture, add H
2o
2solution, carries out fenton-type reagent degraded and obtains catabolite;
S2, the catabolite prepared by abovementioned steps S1 mix with rice straw powder, whiterot fungi spore suspension, have been degraded to the reparation of atrazine pesticide contaminated soil by biofermentation.
Further, aforementioned H in aforementioned S1 step
2o
2solution divides and joins in aforementioned mixture 3 times, and each interval time is 4h.
Further, in aforementioned S1 step, aforementioned metallurgical slag comprises the CaO of 26 ~ 40wt%, the SiO of 22 ~ 37wt%
2, 3 ~ 18wt% Fe
2o
3, the FeO of 1 ~ 13wt%, the MgO of 0.3 ~ 8wt%, the Al of 0.1 ~ 5wt%
2o
3, 0.1 ~ 3wt% P
2o
5, 0.1 ~ 1.4wt% MnO.
Further, metallurgical slag comprises the CaO of 38.2wt%, the SiO of 26.4wt%
2, the Fe of 16.3wt%
2o
3, the Al of the MgO of the FeO of 8.2wt%, 6.1wt%, 2.7wt%
2o
3, the P of 1.4wt%
2o
5, the MnO of 0.4wt%.
Further, aforementioned whiterot fungi spore suspension is preferably the spore suspension of Phanerochaete chrysosporium, and every mL spore suspension is containing spore 2.0 × 10
6individual.
Further, in aforementioned S1 step, the mass ratio of metallurgical slag and atrazine pesticide contaminated soil is 0.05: 1 ~ 0.1: 1, H
2o
2the volume mass of solution and atrazine pesticide contaminated soil than 0.05 ~ 0.15L: 1kg, aforementioned H
2o
2the mass fraction of solution is 30%.
Further, the mass ratio 0.05: 1 of aforementioned rice straw powder and aforementioned atrazine pesticide contaminated soil in aforementioned S2 step.
Further, in aforementioned S2 step the volume mass of aforementioned whiterot fungi spore suspension and aforementioned atrazine pesticide contaminated soil than 20mL ~ 50mL: 1kg.
Further, in aforementioned atrazine pesticide contaminated soil, the concentration of atrazine is 0 ~ 600mg/kg, and preferred concentration is 0 ~ 300mg/kg.
Further, the time of aforementioned biological fermentative degradation is 12 ~ 30d, and preferred degradation time is 26 ~ 30d.
Creativeness of the present invention is:
The present invention adopts metallurgical slag and whiterot fungi synergy to repair atrazine pesticide contaminated soil, because metallurgical slag molysite content is higher, add hydrogenperoxide steam generator the hydroxyl radical free radical (OH) that Fenton or embryonic stem-like cells produce oxidisability extremely strong can occur be oxidized organic matter, its concrete reaction equation is:
Fe
3++H
2O
2→Fe
2++H
++HO
2·，
In the atrazine pesticide contaminated soil through embryonic stem-like cells, add whiterot fungi, whiterot fungi can be secreted ectoenzyme and degrade further to atrazine pesticide contaminated soil; Meanwhile, the Ca contained by slag, the elements such as Mg, Mn also can promote the growth and breeding of whiterot fungi, further increase the removal ability of whiterot fungi to atrazine-contaminated soil.
Compared with prior art, the invention has the advantages that:
1, the present invention adopts chemical oxidation to repair atrazine-contaminated soil in conjunction with bioremediation technology, there is the advantages such as chemical agent less investment, environmental protection, between metallurgical slag and whiterot fungi, there is complementary effect simultaneously, compared to adopting chemical oxidation treatment or bioremediation technology separately, method of the present invention is higher to the clearance of atrazine in contaminated soil.
2, the rice straw powder added in restorative procedure of the present invention both can provide growth substrate for Phanerochaete chrysosporium, the character of contaminated soil can be improved again, as increased hole between soil particle, the humus formed after Phanerochaete chrysosporium degraded also improves the fertility of soil.
3, restorative procedure of the present invention achieves the refuse reclamation of metallurgical slag, lower relative to traditional chemical cost of drugs, and treatment effeciency is high, treatment effect good, and the chemical drugs dosage added is few, effectively can improve soil property.
Detailed description of the invention
Below in conjunction with concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
The raw material adopted in following examples and instrument are commercially available.Wherein metallurgical slag is purchased from zhuzhou,hunan smeltery, and it is the CaO of 26 ~ 40wt%, the SiO of 22 ~ 37wt% that its main component comprises
2, 3 ~ 18wt% Fe
2o
3, the FeO of 1 ~ 13wt%, the MgO of 0.3 ~ 8wt%, the Al of 0.1 ~ 5wt%
2o
3, 0.1 ~ 3wt% P
2o
5, 0.1 ~ 1.4wt% MnO.The metallurgical slag comprising mentioned component all can be applied in method of the present invention, and in the embodiment of the present invention, preferred metallurgical slag contains the CaO of 38.2wt%, the SiO of 26.4wt%
2, the Fe of 16.3wt%
2o
3, the Al of the MgO of the FeO of 8.2wt%, 6.1wt%, 2.7wt%
2o
3, the P of 1.4wt%
2o
5, the MnO of 0.4wt%.
Before the above-mentioned metallurgical slag of use, first by being broken into the particle of diameter about 1mm after metallurgical slag drying, then for the process of atrazine pesticide contaminated soil.
Whiterot fungi spore suspension of the present invention refers to the spore suspension of Phanerochaete chrysosporium (Phanerochaete chrysosporium, CCTCC AF96007), but the present invention is not limited in Phanerochaete chrysosporium spore suspension.This suspension prepares by the following method: potato dextrose culture-medium bacterial classification being placed in the biochemical cultivation case of 37 DEG C is cultivated, and carries out preservation in the refrigerator that after 6d, the good bacterial classification of growth selection situation is placed on 4 DEG C; In sterilizing platform, dissolve in sterilized water with aseptic cotton carrier from the sticky spore getting object bacteria of culture medium, by stir and vibrations make spore dispersed, form spore suspension.Measuring the turbidity of solution, when turbidity is about 60%, is the spore suspension of the present invention Phanerochaete chrysosporium used.Described potato dextrose culture-medium consists of: potato 40g, glucose 4g, water 200mL.
The preparation method of straw particle is: cleaned by the straw balloonflower root clear water collected from field, after natural air drying, by 5mm nylon sieve after grinding, collects for subsequent use with grinding mill.
Atrazine-contaminated soil of the present invention takes from Yue Lu mountain, Changsha, Hunan, and a kind of method of repairing atrazine pesticide contaminated soil provided by the present invention can be applicable to the atrazine pesticide contaminated soil of any character, all can reach good technique effect.
Embodiment 1
Get the contaminated soil that atrazine content is respectively 100,200,300,400,500,600mg/kg, adopt following steps to process:
(1) in the atrazine pesticide contaminated soil of 1kg, add the metallurgical slag of 0.05kg and mix and obtain mixture; Add every 4h the H that 0.05L mass fraction is 30% in mixture
2o
2solution, altogether interpolation 3 times, being about 30% by adding deionized water adjustment system moisture content, carrying out fenton-type reagent reaction 24h.
(2) in the atrazine pesticide contaminated soil through fenton-type reagent, adding the Phanerochaete chrysosporium spore suspension of the straw particle of 0.05kg and 0.05L, (every mL spore suspension is containing spore 2.0 × 10
6individual) and mix, solid state fermentation 30d, complete the reparation to pesticide contaminated soil.
After oxidation 24h and microorganism remediation 30d, detected the content of atrazine soil from each individual system sampling by extraction-high performance liquid chromatography, measurement result is in table 1.
Table 1: atrazine clearance testing result table in atrazine pesticide contaminated soil
| Atrazine content (mg/kg) | 100 | 200 | 300 | 400 | 500 | 600 |
| 24h clearance (%) | 91.25 | 88.16 | 61.74 | 47.22 | 39.67 | 33.41 |
| 30d clearance (%) | 97.48 | 97.12 | 96.15 | 82.63 | 71.21 | 59.29 |
As shown in Table 1, this restorative procedure is that the repairing effect of the pesticide contaminated soil of 100mg/kg ~ 600mg/kg is remarkable to atrazine content, and wherein atrazine content is that the pesticide contaminated soil clearance of 100mg/kg ~ 300mg/kg is all more than 95%.Visible, utilize method of the present invention to repair the pesticide contaminated soil of atrazine-containing concentration≤300mg/kg, effect is best.
Embodiment 2
(1) in 1kg atrazine pesticide contaminated soil (in atrazine pesticide contaminated soil, atrazine content is 300mg/kg), add the metallurgical slag of 0.05kg respectively and mix and obtain mixture; Add every 4h the H that 0.05L mass fraction is 30% in mixture
2o
2solution, altogether interpolation 3 times, being about 30% by adding deionized water adjustment system moisture content, carrying out fenton-type reagent reaction 24h;
(2) get 5 parts of atrazine pesticide contaminated soils through fenton-type reagent, (every mL spore suspension is containing spore 2.0 × 10 to add the Phanerochaete chrysosporium spore suspension of the straw particle of 0.05kg and 0.05L respectively
6individual) and mix, solid state fermentation 30d, complete the reparation to pesticide contaminated soil.
In microorganism remediation process, sample the content being detected atrazine in soil by extraction-high performance liquid chromatography, measurement result is in table 2.
The clearance testing result table of atrazine in table 2 microorganism remediation process
| Time (d) | 12 | 14 | 16 | 18 | 20 | 22 | 24 | 26 | 28 | 30 |
| Clearance (%) | 79.45 | 84.45 | 88.04 | 91.39 | 93.03 | 93.87 | 94.41 | 95.04 | 95.12 | 95.18 |
As shown in Table 2, at 26d, in soil, the removal efficiency of atrazine is more than 95%.Due to little with 24d treatment effect difference after 26d, so from the viewpoint of saving time, the biological prosthetic time that the inventive method repairs the best of atrazine-contaminated soil is 26d.
Embodiment 3
Get 5kg atrazine pesticide contaminated soil (in atrazine pesticide contaminated soil, atrazine content is 300mg/kg), be equally divided into 5 parts, every part of 1kg:
(1) in the contaminated soil of 5 parts of 1kg, add 0 respectively, 0.05,0.1,0.15, the metallurgical slag of 0.2kg mix and obtain mixture;
(2) in 5 parts of mixtures, add every 4h the H that 0.05L mass fraction is 30%
2o
2solution, altogether interpolation 3 times, being about 30% by adding deionized water adjustment system moisture content, carrying out fenton-type reagent 24h;
(3) in 5 parts of treated contaminated soils, adding the Phanerochaete chrysosporium spore suspension of the straw particle of 0.05kg and 0.05L, (every mL spore suspension is containing spore 2.0 × 10
6individual) and mix, solid state fermentation 30d, complete the reparation to pesticide contaminated soil.
After oxidation 24h and microorganism remediation 26d, detected the content of atrazine soil from each individual system sampling by extraction-high performance liquid chromatography, measurement result is in table 3.
Table 3: the clearance result table of atrazine under different slag addition
| Slag (kg) | 0 | 0.05 | 0.1 | 0.15 | 0.2 |
| 24h clearance (%) | 26.23 | 62.18 | 65.73 | 47.24 | 45.61 |
| 26d clearance (%) | 57.49 | 96.06 | 97.25 | 73.41 | 53.78 |
From table 3, slag addition is increased to 0.05kg/kg from 0kg/kg, the clearance of atrazine 24h is increased to 62.18% from 26.23%, the addition of further increase slag, the clearance of atrazine slightly improves, when the addition of slag is at more than 0.15kg/kg, the clearance of atrazine drops to less than 50% on the contrary significantly.From the clearance of atrazine 26d, when the addition of slag is 0.1kg/kg, have the atrazine of 97.25% to be removed, the broiler diets of visible slag is 0.05kg/kg ~ 0.1kg/kg, and optimum addition is 0.1kg/kg.Not only can there is unnecessary consumption of chemical reaction H in excessive metallurgical slag
2o
2, the pH of soil also can be caused too high simultaneously, be unfavorable for microbial growth.Therefore the addition of metallurgical slag on the clearance impact of atrazine pesticide contaminated soil significantly.
Embodiment 4
Get 4kg atrazine pesticide contaminated soil (in atrazine pesticide contaminated soil, atrazine content is 400mg/kg), atrazine pesticide contaminated soil be equally divided into 4 parts, every part of 1kg:
(1) in the contaminated soil of 4 parts of 1kg, respectively add the metallurgical slag of 0.1kg and mix and obtain mixture;
(2) in 4 parts of mixtures, add 0.05 respectively every 4h, 0.075,0.1,0.0125,0.15L mass fraction is the H of 30%
2o
2solution, altogether interpolation 3 times are about 30% by adding deionized water adjustment system moisture content, carry out that fenton-type reagent is angry answers 24h;
(3) in 4 parts of treated contaminated soils, adding the straw particle of 0.05kg with the Phanerochaete chrysosporium spore suspension of 0.05L mixes, solid state fermentation 26d, completes the reparation to pesticide contaminated soil.
After oxidation 24h and microorganism remediation 26d, detected the content of atrazine soil from each individual system sampling by extraction-high performance liquid chromatography, measurement result is in table 4.
The different H of table 4
2o
2the clearance of atrazine under solution addition
| H 2O 2Solution (L) | 0.05 | 0.075 | 0.1 | 0.125 | 0.15 |
| 24h clearance (%) | 49.83 | 65.37 | 74.16 | 77.51 | 79.73 |
| 26d clearance (%) | 83.62 | 94.58 | 95.35 | 95.41 | 95.22 |
From table 4, at H
2o
2each addition of solution is 0.05 ~ 0.15L/kg, and the clearance of atrazine is higher, and when addition is 0.1L/kg, atrazine 26d clearance reaches 95.35%, illustrates by increasing H
2o
2the addition of solution, the inventive method can be applied to the contaminated soil of the higher atrazine content of reparation.
Therefore utilizing the repairing effect of method of the present invention reparation atrazine-containing soil good, is 0.1kg/kg, H at metallurgical slag addition
2o
2solution addition be under the condition of each 0.05L/kg, microorganism remediation 26d, the inventive method is that the clearance of the atrazine of 300mg/kg can reach 96.52% to content in soil.By increasing H
2o
2solution addition, the inventive method can repair the atrazine contaminated soil of more high-load.
In the embodiment above, the addition of Phanerochaete chrysosporium spore suspension all can reach same or analogous technique effect at 0.02L ~ 0.05L.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Any those of ordinary skill in the art, when not departing from Spirit Essence of the present invention and technical scheme, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (10)
1. repair a method for atrazine pesticide contaminated soil, it is characterized in that, comprise the following steps:
S1, metallurgical slag and atrazine pesticide contaminated soil are mixed to get mixture, in described mixture, add H
2o
2solution, carries out fenton-type reagent degraded and obtains catabolite;
S2, the catabolite prepared by described step S1 mix with rice straw powder, whiterot fungi spore suspension, have been degraded to the reparation of atrazine pesticide contaminated soil by biofermentation.
2. method according to claim 1, is characterized in that, H described in described S1 step
2o
2solution divides and joins for 3 times in described mixture, and each interval time is 4h.
3. method according to claim 1, is characterized in that, described in described S1 step, metallurgical slag comprises the CaO of 16 ~ 40wt%, the SiO of 22 ~ 37wt%
2, 3 ~ 18wt% Fe
2o
3, the FeO of 1 ~ 13wt%, the MgO of 0.3 ~ 8wt%, the Al of 0.1 ~ 5wt%
2o
3, 0.1 ~ 3wt% P
2o
5, 0.1 ~ 1.4wt% MnO.
4. method according to claim 3, is characterized in that, described metallurgical slag comprises the CaO of 38.2wt%, the SiO of 26.4wt%
2, the Fe of 16.3wt%
2o
3, the Al of the MgO of the FeO of 8.2wt%, 6.1wt%, 2.7wt%
2o
3, the P of 1.4wt%
2o
5, the MnO of 0.4wt%.
5. method according to claim 1, is characterized in that, described whiterot fungi spore suspension is the spore suspension of Phanerochaete chrysosporium, and every mL spore suspension is containing spore 2.0 × 10
6individual.
6. method according to any one of claim 1 to 5, is characterized in that, metallurgical slag described in described step S1, atrazine pesticide contaminated soil and H
2o
2the mass volume ratio of solution is (0.05 ~ 0.1kg): 1kg: (0.05 ~ 0.15L).
7. method according to any one of claim 1 to 5, is characterized in that, in atrazine pesticide contaminated soil described in described step S1, the concentration of atrazine is 0 ~ 600mg/kg.
8. method according to any one of claim 1 to 5, is characterized in that, the mass ratio 0.05: 1 of rice straw powder described in described step S2 and described atrazine pesticide contaminated soil.
9. method according to any one of claim 1 to 5, is characterized in that, the volume mass of whiterot fungi spore suspension described in described step S2 and described atrazine pesticide contaminated soil is than 20mL ~ 50mL: 1kg.
10. method according to any one of claim 1 to 5, is characterized in that, in described step S2, the time of biofermentation degraded is 12 ~ 30d.
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|---|---|---|---|
| CN201410497863.4A CN104259193B (en) | 2014-09-25 | A kind of method repairing atrazine pesticide contaminated soil |
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|---|---|---|---|
| CN201410497863.4A CN104259193B (en) | 2014-09-25 | A kind of method repairing atrazine pesticide contaminated soil |
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| CN104259193B CN104259193B (en) | 2017-01-04 |
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| CN107470339A (en) * | 2017-09-30 | 2017-12-15 | 青岛农业大学 | The method and system of polycyclic aromatic hydrocarbon pollution is repaired in class Fenton and microorganism combination |
| CN107954509A (en) * | 2016-10-14 | 2018-04-24 | 湖南大学 | The method for removing alachlor in water body is reacted using Fenton |
| CN109365508A (en) * | 2018-10-26 | 2019-02-22 | 湖南理工学院 | A method of repairing pesticide contaminated soil |
| CN109759432A (en) * | 2019-01-25 | 2019-05-17 | 湖南新九方科技有限公司 | The restorative procedure of atrazine-contaminated soil |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107470339A (en) * | 2017-09-30 | 2017-12-15 | 青岛农业大学 | The method and system of polycyclic aromatic hydrocarbon pollution is repaired in class Fenton and microorganism combination |
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| CN109759432A (en) * | 2019-01-25 | 2019-05-17 | 湖南新九方科技有限公司 | The restorative procedure of atrazine-contaminated soil |
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