CN104259193B - A kind of method repairing atrazine pesticide contaminated soil - Google Patents

A kind of method repairing atrazine pesticide contaminated soil Download PDF

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Publication number
CN104259193B
CN104259193B CN201410497863.4A CN201410497863A CN104259193B CN 104259193 B CN104259193 B CN 104259193B CN 201410497863 A CN201410497863 A CN 201410497863A CN 104259193 B CN104259193 B CN 104259193B
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China
Prior art keywords
atrazine
contaminated soil
pesticide contaminated
soil
metallurgical slag
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CN201410497863.4A
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CN104259193A (en
Inventor
程敏
曾光明
黄丹莲
赖萃
黄超
危臻
许飘
李宁杰
张辰
竺园
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Hunan University
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Hunan University
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Abstract

The invention discloses a kind of method repairing atrazine pesticide contaminated soil, comprise the following steps: metallurgical slag and atrazine pesticide contaminated soil are mixed to get mixture, in mixture, add H2O2Solution, carries out fenton-type reagent degraded and obtains catabolite;Catabolite is mixed with rice straw powder, whiterot fungi spore suspension, has been degraded the reparation to atrazine pesticide contaminated soil by biofermentation.The present invention uses the atrazine pesticide in metallurgical slag and whiterot fungi combined removal soil, has cost relatively low, and treatment effeciency is high, high treating effect, and the chemical drugs dosage added is few, it is possible to effectively improve the advantages such as soil property.

Description

A kind of method repairing atrazine pesticide contaminated soil
Technical field
The present invention relates to field of environmental improvement, particularly relate to a kind of method repairing atrazine pesticide contaminated soil.
Background technology
Pesticide, since invention, at preventing and treating corps diseases, insect pest, crop smothering, it is ensured that crops normal growth, has ensured farming Thing high yield and bumper harvest, solves mankind's food problem aspect and has played highly important effect.Atrazine has another name called G-30027, English name Claiming atrazine, chemical name is 2-chloro-4-ethylamino--6-isopropylamine base-1,3,5-tri-pyridines, puts into business in nineteen fifty-nine raw Produce, within about 1980, start to use in China.Atrazine low price and have good herbicidal effect, becomes the most complete One of the most widely used herbicide of ball.But atrazine stable in properties is the most degradable, and has bioconcentration, to people Class and animals and plants have serious harm, and while life-time service the most again, the pesticide residues of accumulation have become as a grand duke Evil.Therefore, the reparation of contaminated soil can be suppressed from source the diffusion of pollution by pesticides, it addition, pesticide producing base, storage The contaminated site stayed after the resettlement such as warehouse is also required to repair.
Chemical oxidation method can remove the organic pollution in soil effectively, but is intended to reach higher clearance, Generally require and add substantial amounts of chemical drugs, not only the character of soil can be damaged but also Financial cost is higher.Biology is repaiied Recovering technology is the new technique that environmental area develops rapidly in recent years, and it is with the dirt in the degraded of various organisms or absorption environment Dye thing.Wherein, Phanerochaete chrysosporium (Phanerochaete chrysosporium), can be with wooden fibre in nature Dimension element carries out growth and breeding as nutrient, and its extracellular enzyme produced can non-specifically be degraded a series of dirt in environment Dye thing.Compared with traditional method, biological method has the advantages such as energy consumption is low, simple to operate, viable economically, but also has target The shortcomings such as microorganism and indigenous microbes are competed, time-consuming length.Therefore, by biologic treating technique and the advantage of chemical oxidation techniques Connected applications has great importance in atrazine-containing pesticide contaminated soil reparation.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind for the treatment of effeciency is high, process effect The best, cost is relatively low and the reparation atrazine-containing pesticide contaminated soil method of environmental protection.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
Provide a kind of method 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 H2O2 Solution, carries out fenton-type reagent degraded and obtains catabolite;
S2, catabolite abovementioned steps S1 prepared mix with rice straw powder, whiterot fungi spore suspension, logical Cross biofermentation to have degraded the reparation to atrazine pesticide contaminated soil.
Further, aforementioned H in aforementioned S1 step2O2Solution divides 3 times and joins in aforementioned mixture, each interval time For 4h.
Further, in aforementioned S1 step, aforementioned metallurgical slag includes CaO, 22~the 37wt%'s of 26~40wt% SiO2, 3~the Fe of 18wt%2O3, 1~the Al of the MgO of the FeO of 13wt%, 0.3~8wt%, 0.1~5wt%2O3, 0.1~ The P of 3wt%2O5, 0.1~the MnO of 1.4wt%.
Further, metallurgical slag includes the CaO of 38.2wt%, the SiO of 26.4wt%2, the Fe of 16.3wt%2O3, The Al of the MgO of the FeO of 8.2wt%, 6.1wt%, 2.7wt%2O3, the P of 1.4wt%2O5, the MnO of 0.4wt%.
Further, aforementioned whiterot fungi spore suspension is preferably the spore suspension of Phanerochaete chrysosporium, every mL spore Fullness over the chest during pregnancy supernatant liquid contains spore 2.0 × 106Individual.
Further, in aforementioned S1 step the mass ratio of metallurgical slag and atrazine pesticide contaminated soil be 0.05: 1~ 0.1: 1, H2O2The volume mass ratio 0.05~0.15L: 1kg of solution and atrazine pesticide contaminated soil, aforementioned H2O2The matter of solution Amount mark is 30%.
Further, aforementioned rice straw powder and the mass ratio 0.05 of aforementioned atrazine pesticide contaminated soil in aforementioned S2 step: 1。
Further, aforementioned whiterot fungi spore suspension and the body of aforementioned atrazine pesticide contaminated soil in aforementioned S2 step Long-pending mass ratio 20mL~50mL: 1kg.
Further, in aforementioned atrazine pesticide contaminated soil, the concentration of atrazine is 0~600mg/kg, preferred concentration It is 0~300mg/kg.
Further, the time of aforementioned biological fermentative degradation is 12~30d, and preferred degradation time is 26~30d.
The creativeness of the present invention is:
The present invention uses metallurgical slag and whiterot fungi synergy to repair atrazine pesticide contaminated soil, due to metallurgical slag Iron salt content is higher, adds hydrogenperoxide steam generator and Fenton or embryonic stem-like cells can be occurred to produce the hydroxyl that oxidisability is extremely strong Organic substance is aoxidized by free radical (OH), and its concrete reaction equation is:
Fe3++H2O2→Fe2++H++HO2,
Adding whiterot fungi in the atrazine pesticide contaminated soil of embryonic stem-like cells, whiterot fungi can secrete exoenzyme Atrazine pesticide contaminated soil is degraded further;Meanwhile, the Ca contained by slag, the element such as Mg, Mn also can promote white rot The growth and breeding of bacterium, further increases the whiterot fungi removal ability to atrazine-contaminated soil.
Compared with prior art, it is an advantage of the current invention that:
1, the present invention uses chemical oxidation to combine bioremediation technology and repairs atrazine-contaminated soil, has chemical agent and throws Enter less, the advantage such as environmental protection, there is complementary effect simultaneously, compared to individually using chemistry between metallurgical slag and whiterot fungi Oxidation processes or bioremediation technology, the method for the present invention is higher to the clearance of atrazine in contaminated soil.
2, the rice straw powder added in the restorative procedure of the present invention both can be that Phanerochaete chrysosporium provides growth substrate, again The character of contaminated soil can be improved, as increased hole between soil particle, the humus formed after Phanerochaete chrysosporium is degraded Also improve the fertility of soil.
3, the restorative procedure of the present invention achieves the refuse reclamation of metallurgical slag, relative to traditional chemical cost of drugs relatively Low, treatment effeciency is high, high treating effect, and the chemical drugs dosage added is few, it is possible to effectively improve soil property.
Detailed description of the invention
Below in conjunction with concrete preferred embodiment, the invention will be further described, but not thereby limiting the invention Protection domain.
Raw material and instrument employed in following example are commercially available.Wherein metallurgical slag is purchased from zhuzhou,hunan smelting Factory, its main component includes being the SiO of CaO, 22~the 37wt% of 26~40wt%2, 3~the Fe of 18wt%2O3, 1~13wt% The Al of the MgO of FeO, 0.3~8wt%, 0.1~5wt%2O3, 0.1~the P of 3wt%2O5, 0.1~the MnO of 1.4wt%.Bag Metallurgical slag containing mentioned component all can apply in the method for the present invention, and in the embodiment of the present invention, preferred metallurgical slag contains The SiO of the CaO of 38.2wt%, 26.4wt%2, the Fe of 16.3wt%2O3, the MgO of the FeO of 8.2wt%, 6.1wt%, 2.7wt% Al2O3, the P of 1.4wt%2O5, the MnO of 0.4wt%.
Before using above-mentioned metallurgical slag, first metallurgical slag is broken into after drying the granule of diameter about 1mm, then Process for atrazine pesticide contaminated soil.
The whiterot fungi spore suspension of the present invention refers to Phanerochaete chrysosporium (Phanerochaete Chrysosporium, CCTCC AF96007) spore suspension, but the present invention is not limited in Phanerochaete chrysosporium spore Suspension.This suspension is to be prepared by the following method: the Rhizoma Solani tuber osi glucose training being placed in by strain in the biochemical cultivation case of 37 DEG C Supporting and cultivate on base, after 6d, the preferable strain of growth selection situation carries out preservation in being placed on the refrigerator of 4 DEG C;At sterilizing platform In, dissolve in sterilized water with aseptic cotton carrier viscous spore taking object bacteria from culture medium, make spore uniform by stirring and vibrations Dispersion, forms spore suspension.Measuring the turbidity of solution, when turbidity is about 60%, the yellow archespore hair used by the present invention is put down The spore suspension of lead fungi.Described Rhizoma Solani tuber osi dextrose culture-medium consists of: Rhizoma Solani tuber osi 40g, glucose 4g, water 200mL.
The preparation method of Caulis et Folium Oryzae granule is: cleaned by the Caulis et Folium Oryzae Radix Platycodonis clear water collected from field, after natural air drying, uses Mill passes through 5mm nylon sieve after grinding, and collects standby.
Atrazine-contaminated soil of the present invention takes from Yue Lu mountain, Changsha, Hunan, one provided by the present invention The method repairing atrazine pesticide contaminated soil can be applicable to the atrazine pesticide contaminated soil of any character, all can reach preferable Technique effect.
Embodiment 1
Take atrazine content and be respectively 100, the contaminated soil of 200,300,400,500,600mg/kg, use following steps Process:
(1) metallurgical slag the mix homogeneously that add 0.05kg in the atrazine pesticide contaminated soil of 1kg are mixed Thing;Adding 0.05L mass fraction every 4h in mixture is the H of 30%2O2Solution, adds 3 times altogether, by interpolation go from It is about 30% that sub-water adjusts system moisture content, carries out fenton-type reagent reaction 24h.
(2) add in the atrazine pesticide contaminated soil of fenton-type reagent the Caulis et Folium Oryzae granule of 0.05kg with (every mL spore suspension contains spore 2.0 × 10 to the Phanerochaete chrysosporium spore suspension of 0.05L6Individual) and mix homogeneously, Gu State fermentation 30d, completes the reparation to pesticide contaminated soil.
Detected by extraction-high performance liquid chromatography from the sampling of each individual system after oxidation 24h and microorganism remediation 30d The content of atrazine in soil, measurement result is shown 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 to the pesticide contaminated soil that atrazine content is 100mg/kg~600mg/kg Repairing effect is notable, wherein atrazine content be 100mg/kg~300mg/kg pesticide contaminated soil clearance all 95% with On.Visible, utilize the method for the present invention to repair the pesticide contaminated soil of atrazine-containing concentration≤300mg/kg, effect is best.
Embodiment 2
(1) 1kg atrazine pesticide contaminated soil (in atrazine pesticide contaminated soil, atrazine content is 300mg/kg) In be separately added into the metallurgical slag of 0.05kg and mix homogeneously obtains mixture;0.05L mass is added every 4h in mixture Mark is the H of 30%2O2Solution, adds 3 times altogether, being about 30% by add deionized water adjusting system moisture content, carrying out Fenton-type reagent reaction 24h;
(2) take 5 parts of atrazine pesticide contaminated soils through fenton-type reagent, add the Caulis et Folium Oryzae granule of 0.05kg respectively (every mL spore suspension contains spore 2.0 × 10 with the Phanerochaete chrysosporium spore suspension of 0.05L6Individual) and mix homogeneously, Solid fermentation 30d, completes the reparation to pesticide contaminated soil.
Sample by the content of atrazine in extraction-high performance liquid chromatography detection soil during microorganism remediation, Measurement result is shown in Table 2.
The clearance testing result table of atrazine during table 2 microorganism remediation
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, in 26d, soil the removal efficiency of atrazine more than 95%.Owing to processing effect with 24d after 26d Really difference is little, so from the standpoint of time-consuming, the inventive method is repaired the optimal biology of atrazine-contaminated soil and repaiied The multiple time is 26d.
Embodiment 3
Take 5kg atrazine pesticide contaminated soil (in atrazine pesticide contaminated soil, atrazine content is 300mg/kg), will It is equally divided into 5 parts, every part of 1kg:
(1) in the contaminated soil of 5 parts of 1kg, be separately added into 0,0.05,0.1,0.15, the metallurgical slag of 0.2kg mixing Uniformly obtain mixture;
(2) adding 0.05L mass fraction every 4h in 5 parts of mixture is the H of 30%2O2Solution, adds 3 times altogether, logical Crossing interpolation deionized water and adjusting system moisture content is about 30%, carries out fenton-type reagent 24h;
(3) in 5 parts of treated contaminated soils, add the Caulis et Folium Oryzae granule of 0.05kg and yellow archespore Mao Pingge of 0.05L (every mL spore suspension contains spore 2.0 × 10 to bacterium spore suspension6Individual) and mix homogeneously, solid fermentation 30d, complete pesticide The reparation of contaminated soil.
Detected by extraction-high performance liquid chromatography from the sampling of each individual system after oxidation 24h and microorganism remediation 26d The content of atrazine in soil, measurement result is shown in Table 3.
Table 3: the clearance result table of atrazine under different slag additions
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 increases to 0.05kg/kg from 0kg/kg, the clearance of atrazine 24h from 26.23% increases to 62.18%, increases the addition of slag further, and the clearance of atrazine slightly improves, when adding of slag Dosage is when more than 0.15kg/kg, and the clearance of atrazine the most significantly drops to less than 50%.From going of atrazine 26d From the point of view of rate, when the addition of slag is 0.1kg/kg, the atrazine of 97.25% is had to be removed, it is seen that the suitable interpolation of slag Amount is 0.05kg/kg~0.1kg/kg, and optimum addition is 0.1kg/kg.It is unnecessary that the metallurgical slag of excess not only can occur Consumption of chemical reaction H2O2, the pH simultaneously also resulting in soil is too high, is unfavorable for the growth of microorganism.Therefore the adding of metallurgical slag The clearance of atrazine pesticide contaminated soil is affected notable by dosage.
Embodiment 4
Take 4kg atrazine pesticide contaminated soil (in atrazine pesticide contaminated soil, atrazine content is 400mg/kg), will Atrazine pesticide contaminated soil is equally divided into 4 parts, every part of 1kg:
(1) in the contaminated soil of 4 parts of 1kg, each metallurgical slag adding 0.1kg mix homogeneously obtain mixture;
(2) in 4 parts of mixture, be separately added into 0.05 every 4h, 0.075,0.1,0.0125,0.15L mass fraction be The H of 30%2O2Solution, adds 3 times altogether, being about 30% by add deionized water adjusting system moisture content, carrying out class Fenton oxidation is angry answers 24h;
(3) in 4 parts of treated contaminated soils, add the Caulis et Folium Oryzae granule of 0.05kg and yellow archespore Mao Pingge of 0.05L Bacterium spore suspension mix homogeneously, solid fermentation 26d, complete the reparation to pesticide contaminated soil.
Detected by extraction-high performance liquid chromatography from the sampling of each individual system after oxidation 24h and microorganism remediation 26d The content of atrazine in soil, measurement result is shown in Table 4.
The different H of table 42O2The clearance of atrazine under solution addition
H2O2Solution (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 H2O2Each addition of solution is 0.05~0.15L/kg, and the clearance of atrazine is higher, when When addition is 0.1L/kg, atrazine 26d clearance reaches 95.35%, illustrates by increasing H2O2The addition of solution, this Bright method can apply to repair the contaminated soil of higher atrazine content.
Therefore, the repairing effect utilizing the method reparation atrazine-containing soil of the present invention is good, adds at metallurgical slag Amount is 0.1kg/kg, H2O2Solution addition be each 0.05L/kg, under conditions of microorganism remediation 26d, the inventive method The clearance of the atrazine that content in soil is 300mg/kg be can reach 96.52%.By increasing H2O2Solution interpolation Amount, the inventive method can repair the atrazine contaminated soil of higher amount.
In the embodiment above, the addition of Phanerochaete chrysosporium spore suspension all can reach at 0.02L~0.05L Same or analogous technique effect.
The above, be only presently preferred embodiments of the present invention, and the present invention not makees any pro forma restriction.Though So the present invention discloses as above with preferred embodiment, but is not limited to the present invention.Any it is familiar with those skilled in the art Member, in the case of without departing from the spirit of the present invention and technical scheme, may utilize in method and the technology of the disclosure above Hold and technical solution of the present invention is made many possible variations and modification, or be revised as the Equivalent embodiments of equivalent variations.Therefore, Every content without departing from technical solution of the present invention, according to the present invention technical spirit to made for any of the above embodiments any simply Amendment, equivalent, equivalence change and modification, all still fall within the range of technical solution of the present invention protection.

Claims (8)

1. the method repairing atrazine pesticide contaminated soil, it is characterised in that comprise the following steps:
S1, metallurgical slag and atrazine pesticide contaminated soil are mixed to get mixture, in described mixture, add H2O2Molten Liquid, carries out fenton-type reagent degraded and obtains catabolite;Described metallurgical slag includes CaO, 22~the 37wt% of 16~40wt% SiO2, 3~the Fe of 18wt%2O3, 1~the Al of the MgO of the FeO of 13wt%, 0.3~8wt%, 0.1~5wt%2O3, 0.1~3wt% P2O5, 0.1~the MnO of 1.4wt%;
S2, the catabolite described step S1 prepared mix with rice straw powder, whiterot fungi spore suspension, by life Thing fermentative degradation completes the reparation to atrazine pesticide contaminated soil;Metallurgical slag described in described step S1, atrazine pesticide Contaminated soil and H2O2The mass volume ratio of solution is (0.05~0.1 kg): 1 kg: (0.05~0.15L).
Method the most according to claim 1, it is characterised in that H described in described S1 step2O2Solution divides 3 times and joins institute Stating in mixture, each interval time is 4h.
Method the most according to claim 1, it is characterised in that described metallurgical slag includes the CaO of 38.2wt%, 26.4wt% SiO2, the Fe of 16.3wt%2O3, the Al of the MgO of the FeO of 8.2wt%, 6.1wt%, 2.7wt%2O3, the P of 1.4wt%2O5, The MnO of 0.4wt%.
Method the most according to claim 1, it is characterised in that described whiterot fungi spore suspension is Phanerochaete chrysosporium Spore suspension, every mL spore suspension contain spore 2.0 × 106Individual.
Method the most according to any one of claim 1 to 4, it is characterised in that atrazine agriculture described in described step S1 In chemicals contamination soil, the concentration of atrazine is 0~600mg/kg.
Method the most according to any one of claim 1 to 4, it is characterised in that rice straw powder described in described step S2 with The mass ratio 0.05: 1 of described atrazine pesticide contaminated soil.
Method the most according to any one of claim 1 to 4, it is characterised in that whiterot fungi spore described in described step S2 The volume mass of fullness over the chest during pregnancy supernatant liquid and described atrazine pesticide contaminated soil is than 20mL~50mL: 1kg.
Method the most according to any one of claim 1 to 4, it is characterised in that biofermentation degraded in described step S2 Time be 12~30d.
CN201410497863.4A 2014-09-25 A kind of method repairing atrazine pesticide contaminated soil Expired - Fee Related CN104259193B (en)

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Publication number Priority date Publication date Assignee Title
US6423531B1 (en) * 1999-11-17 2002-07-23 Geovation Technologies, Inc. Advanced organic-inorganic solid-chemical composition and methods for anaerobic bioremediation
CN101306427A (en) * 2007-05-17 2008-11-19 中国科学院生态环境研究中心 Method for increasing organic pollutant degradation efficiency in soil
CN103240267A (en) * 2013-04-28 2013-08-14 华中师范大学 Soil restoration method based on oxygen activation of iron powder and polyphosphoric acid molecules
CN103882003A (en) * 2014-03-11 2014-06-25 东北农业大学 Bacterial strain composite carrier material for restoration of atrazine polluted soil as well as preparation method and application thereof

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