CN114940907B - Heavy metal contaminated soil restoration agent and restoration method thereof - Google Patents
Heavy metal contaminated soil restoration agent and restoration method thereof Download PDFInfo
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- CN114940907B CN114940907B CN202210002488.6A CN202210002488A CN114940907B CN 114940907 B CN114940907 B CN 114940907B CN 202210002488 A CN202210002488 A CN 202210002488A CN 114940907 B CN114940907 B CN 114940907B
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- 239000002689 soil Substances 0.000 title claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 69
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 38
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 34
- 235000009566 rice Nutrition 0.000 claims abstract description 34
- 239000010902 straw Substances 0.000 claims abstract description 34
- 230000001580 bacterial effect Effects 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000001963 growth medium Substances 0.000 claims abstract description 22
- 235000015097 nutrients Nutrition 0.000 claims abstract description 12
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000001954 sterilising effect Effects 0.000 claims abstract description 8
- 238000012258 culturing Methods 0.000 claims abstract description 7
- NIILUHXNOXKZAE-UHFFFAOYSA-N NC(C(O)(O)O)C1=CC=CC=C1 Chemical compound NC(C(O)(O)O)C1=CC=CC=C1 NIILUHXNOXKZAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 6
- 229940041514 candida albicans extract Drugs 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 6
- 239000012138 yeast extract Substances 0.000 claims abstract description 6
- 238000007605 air drying Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000011081 inoculation Methods 0.000 claims abstract description 3
- 241000209094 Oryza Species 0.000 claims description 32
- 230000008439 repair process Effects 0.000 claims description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 230000031700 light absorption Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 abstract description 19
- 238000005516 engineering process Methods 0.000 abstract description 11
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 230000006641 stabilisation Effects 0.000 abstract description 4
- 238000011105 stabilization Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 240000007594 Oryza sativa Species 0.000 abstract 2
- 101000965313 Legionella pneumophila subsp. pneumophila (strain Philadelphia 1 / ATCC 33152 / DSM 7513) Aconitate hydratase A Proteins 0.000 abstract 1
- 238000009630 liquid culture Methods 0.000 abstract 1
- 238000006213 oxygenation reaction Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- 238000010257 thawing Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005067 remediation Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000194110 Bacillus sp. (in: Bacteria) Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000193395 Sporosarcina pasteurii Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 108010046334 Urease Proteins 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005370 electroosmosis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000010151 yanghe Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/22—Improving land use; Improving water use or availability; Controlling erosion
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Mycology (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a heavy metal contaminated soil restoration agent and a restoration method thereof, wherein the restoration agent is mixed with contaminated soil according to a proportion, and consists of porous silicon and rice straw biochar; preparing a bacterial liquid culture medium consisting of yeast extract powder, ammonium sulfate and trihydroxymethyl aminotoluene, and sequentially carrying out high-temperature sterilization, bacterial liquid inoculation and constant-temperature shake culture; inoculating the cultured bacterial liquid into an optimized culture medium and culturing at constant temperature; mixing the repairing agent with polluted soil, drying to obtain a soil sample, mixing the soil sample with the bacterial liquid, preparing a cylindrical sample, fully soaking the cylindrical sample in the cementing nutrient solution, and carrying out oxygenation to carry out mineralization reaction; and taking out the sample after the mineralization reaction time is reached, and naturally air-drying. The invention has the advantages that: the restoration agent is prepared by using MICP technology and porous silicon and rice straw biochar as raw materials, so that the zinc-lead polluted soil is restored, the leaching concentration of heavy metals in the polluted soil is reduced, and the solidification/stabilization of the polluted soil is realized.
Description
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to a heavy metal contaminated soil remediation agent and a remediation method thereof.
Background
Heavy metals are rich in biological environment due to the fact that the heavy metals are changeable in form in soil, have the characteristics of strong toxicity concealment, difficult removal from the environment and the like, and cause serious injury to plants, animals and even human beings. Thus, heavy metal pollution in soil has become one of the most serious environmental problems worldwide, which repair the impending need.
The method is characterized in that MICP (Microbially induced calcite precipitation) technology is utilized to fix and remove heavy metals in polluted soil, and the method is a novel technology for restoring soil by combining microorganism in-situ restoration with chemical stationary phase. For the research of solidifying/stabilizing heavy metal contaminated soil by MICP technology, there has been studied to fix heavy metal ions by MICP technology, mineralize and solidify exchangeable heavy metal ions, and seal them in a carbonate bonding state. In the literature, "CHENG Yan, ZHAO Xingqing Study on the consolidation andmineralization of Pb 2+ by carbonate-mineralization bacteria "(Research ofEnvironmental Sciences, 2016, 29 (10): 1513-1520), literature Wang Xinhua, zhao Chenxi, pan Xiangliang. Lead-contaminated bioremediation based on microbial-induced calcium carbonate precipitation (MICP) (Earth and environment, 2015,43 (1): 80-85.), and literature" Muthusamy Govarthanan et al Significanceof autochthonous Bacillus sp, KK1 on biomineralization of lead in mine tailings "(chemsphere, 2013, 90 (8): 2267-2272), numerous domestic and foreign scholars such as gorgeous, wang Xinhua and Muthusamy Govarthanan have selected indigenous bacteria from the tailingsSeed and use for remediation of Pb contaminated soil, so that a steady state Pb-containing carbonate and Pb-containing CaCO is formed 3 To remove heavy metals in the soil. In the literature "Wang Ruixing, qian Chunxiang, wu Miao, cheng Liang. Investigation of heavy metals in microorganism mineralized consolidated soil" (functional material, 09): 1523-1526+1530.) and the literature "Wang Mingming, qian Chunxiang. Investigation of phosphate mineralizing bacteria mineralized heavy metal ions Zn (2") (functional material, 2013,44 (03): 393-395.), qian Chunxiang et al selected fixed strains to mineralize heavy metal ions in Zn contaminated soil and studied microorganism mineralized consolidated Zn under different contaminated conditions 2+ Is a mechanism of action of (a). The research progress of biochar repair of heavy metal contaminated soil "(engineering geology report, 2018, 26 (04): 1064-1077.)," Cang Junchao "research of electroosmosis reinforcement and electrokinetic repair theory and experiment research of contaminated foundation soil" (Hangzhou university: zhejiang, 2020.) and "Yang He" research of stability and environmental effect of microbial-induced carbonate deposition repair of heavy and chromium contaminated soil "(Yangzhou university: 2019.)," Li Li "research of spatial distribution and pollution evaluation of silver-all mining area soil based on GIS" (Beijing university of geology, 2018.). Shows that the research of singly using various adsorbing materials or biological methods for repairing heavy metal contaminated soil has more results, but the physical repair method, chemical repair method or biological repair method alone has certain limitations and the obtained effect is poor, so that the use of MICP technology and adsorbing materials in combination for repairing contaminated soil realizes the reduction of heavy metal concentration and improvement of the stability of the contaminated soil becomes the important research of the cured material.
Disclosure of Invention
According to the defects of the prior art, the invention provides the heavy metal contaminated soil repairing agent and the repairing method thereof, and the repairing method is used for repairing zinc-lead contaminated soil by using the repairing agent which is developed by taking MICP technology, porous silicon and rice straw biochar as raw materials, so that the problem of solidification/stabilization of the contaminated soil is effectively solved.
The invention is realized by the following technical scheme:
the heavy metal polluted soil repairing agent is characterized by being formed by combining porous silicon and rice straw biochar, wherein the mass ratio of the porous silicon to the rice straw biochar is 1:1-9:1.
The particle size of the porous silicon and the rice straw biochar is less than or equal to 1mm.
The mass ratio of the porous silicon to the rice straw biochar is 1:1.
The mass ratio of the porous silicon to the rice straw biochar is 1.5:1.
The mass ratio of the porous silicon to the rice straw biochar is 7:3.
The mass ratio of the porous silicon to the rice straw biochar is 4:1.
The mass ratio of the porous silicon to the rice straw biochar is 9:1.
The repairing method related to any one of the heavy metal contaminated soil repairing agents is characterized by comprising the following steps of:
(1) Mixing the repairing agent and polluted soil according to the mass ratio of 1:10, and passing through a sieve with the aperture of 1mm together, and screening out fine particles with the particle size of less than 1mm for later use; the repairing agent is formed by combining porous silicon and rice straw biochar, and the mass ratio of the porous silicon to the rice straw biochar is 1:1-9:1;
(2) Preparing a bacterial culture medium, wherein the culture medium is prepared from yeast extract powder, ammonium sulfate and trihydroxymethyl aminotoluene; sterilizing the culture medium at high temperature; inoculating 2% of bacterial liquid into the culture medium, wherein the bacterial liquid is bacillus pasteurizus, and the strain number is ATCC11859; then shake culturing for 48h in a constant temperature incubator; inoculating the cultured bacterial liquid into the optimized culture medium according to an inoculation proportion of 5%, culturing at a constant temperature for 12 hours during expansion culture, and enabling a light absorption value OD600 = 1.2 at a wavelength of 600 nm;
(3) Weighing 150g of the repairing agent, mixing the repairing agent with the polluted soil, and mixing the soil sample with the bacterial liquid with the concentration of OD600 = 1.2 and the volume of 40 ml;
(4) Uniformly stirring the bacterial liquid and the soil sample, and then filling the bacterial liquid and the soil sample into a cylindrical flexible mold with the diameter of 40mm and the height of 80mm to form a cylindrical sample;
(5) Fully soaking the cylindrical sample with the cylindrical flexible die in 1L of cementing nutrient solution, and inserting an oxygen pump for oxygen injection so as to fully generate mineralization reaction; the cementing liquid consists of NH4Cl, nutrient broth, naHCO3, urea and CaCl2.2H2O;
(6) And taking out the cylindrical sample after the mineralization reaction time of 10 days is reached, removing the cylindrical flexible mold, and performing natural air drying.
The culture medium is formed by combining 20g/L of yeast extract powder, 10g/L of ammonium sulfate and 15.748g/L of trihydroxymethyl aminotoluene; the high-temperature sterilization of the culture medium means that the culture medium is sterilized in a high-temperature sterilization pot at 121 ℃ for 20 minutes; the temperature in the incubator was set at 30℃and 200rpm.
The cementing liquid comprises the following components in concentration: NH4Cl 10g/L, nutrient broth 3.0g/L, naHCO 3.2.12 g/L, urea 42.0.42.0 g/L, caCl 2.2H2O 88.42g/L.
The invention has the advantages that: the restoration agent is prepared by using MICP technology and porous silicon and rice straw biochar as raw materials, so that the zinc-lead polluted soil is restored, the leaching concentration of heavy metals in the polluted soil is reduced, the solidification/stabilization of the polluted soil is realized, and the polluted site is secondarily developed and utilized.
Drawings
FIG. 1 is a graph showing the relationship between the leaching concentration of zinc and lead and the repairing agent in different proportions;
FIG. 2 is a graph showing the relationship between unconfined compressive strength and restorative in accordance with the present invention;
FIG. 3 is a plot of zinc leach concentration versus freeze-thaw cycles in accordance with the present invention;
FIG. 4 is a graph of lead leaching concentration versus freeze-thaw cycle in accordance with the present invention;
FIG. 5 is a graph showing the relationship between unconfined compressive strength and freeze-thaw cycles in accordance with the present invention.
Detailed Description
The features of the present invention and other related features are described in further detail below by way of example in conjunction with the following drawings, to facilitate understanding by those skilled in the art:
examples: as shown in fig. 1-5, the embodiment specifically relates to a repairing agent for heavy metal contaminated soil and a repairing method thereof, and the repairing method is used for repairing zinc-lead contaminated soil by using a repairing agent which is developed by using MICP technology and porous silicon and rice straw biochar as raw materials, so that the problem of solidification/stabilization of the contaminated soil is effectively solved; the repairing agent is formed by combining porous silicon (DKG) and rice straw biochar (SDT), wherein the mass ratio of the porous silicon to the rice straw biochar is 1:1-9:1; .
The porous silicon material is mainly composed of C, ca, O, si, mg and Al, and exists in the form of stable metal oxides such as magnesium oxide and aluminum oxide. The porous silicon contains bound water inside, the surface contains abundant mesopores, and a large number of silica bonds and hydroxyl groups are distributed on the mesopores, so that the porous silicon has large specific surface area and pore volume. The surface of the porous silicon has a large number of cellular mesoporous structures, and silicon oxygen bonds and hydroxyl groups are distributed in the mesopores, so that the porous silicon has good adsorption performance and can provide adsorption sites for heavy metal ions.
The pH value of the rice straw biochar is 10, the specific surface area is 21.42m2/g, the average pore diameter is 9.35nm, and the proportion of C and H, N, O is 44.5, 1.89, 1.35 and 10.35 respectively.
MICP (Microbially induced calcite precipitation) is a process in which microorganisms induce calcium carbonate to precipitate, i.e. the urease which can decompose urea is produced by bacillus pasteurizer in its own metabolism, and carbonate ions produced after urea decomposition combine with free metal cations in the cementing liquid to produce carbonate.
As shown in fig. 1 to 5, the method for repairing the heavy metal contaminated soil by using the repairing agent in the embodiment comprises the following steps:
(1) Preparing a repairing agent, wherein the repairing agent is formed by combining porous silicon and rice straw biochar, and 5 groups of repairing agent formulas are selected in the embodiment, wherein the repairing agent is shown in the following table:
the repairing agent (75 g) and heavy metal polluted soil (750 g) are mixed according to the mass ratio of 1:10 and pass through a sieve with the aperture of 1mm together, and fine particles with the particle size of less than 1mm are screened out for standby, specifically:
in the case of the No. 1 repairing agent, 37.5g of porous silicon (DKG) and 37.5g of rice straw biochar (SDT) are taken;
in the case of the No. 2 repairing agent, 45g of porous silicon (DKG) and 30g of rice straw biochar (SDT) are taken;
in the case of the No. 3 repairing agent, 52g of porous silicon (DKG) and 22.5g of rice straw biochar (SDT) are taken;
in the case of the No. 4 repairing agent, 60g of porous silicon (DKG) and 15g of rice straw biochar (SDT) are taken;
in the case of No. 5 restoration agent, 67.5g of porous silicon (DKG) and 7.5g of rice straw biochar (SDT) are taken.
(2) Preparing a bacterial culture medium, wherein the culture medium is prepared from a formula of 20g/L yeast extract powder, 10g/L ammonium sulfate and 15.748g/L trihydroxymethyl aminotoluene (Tris); after complete dissolution, the medium was sterilized in a high temperature sterilization pot at 121 ℃ for 20min.
Inoculating 2% of bacterial liquid into a culture medium, wherein the bacterial liquid is bacillus pasteurizus (Sporosarcina pasteurii), and the bacterial liquid is of a strain number: ATCC11859, a bacterium which is nonpathogenic and which hydrolyzes urea, is commercially available. The optical density of the bacterial liquid is measured by a spectrophotometer (ultraviolet (UV) -1700 ultraviolet-visible spectrophotometer) and is expressed as OD600, and the light absorption value is 600 nm.
Then shake culturing in a constant temperature incubator at 30deg.C and 200rpm for 48h, inoculating the cultured bacterial liquid into optimized culture medium according to 5% inoculating ratio, and culturing at constant temperature for 12h during expansion culture to maintain optimal optical density, i.e. OD600 = 1.2.
(3) The soil sample obtained by mixing and drying the repairing agent with the polluted soil was weighed 150g, and mixed with a bacterial liquid having a concentration of od600=1.2 and a volume of 40 ml.
(4) And (3) uniformly stirring the bacterial liquid and the soil sample, and then filling the bacterial liquid and the soil sample into a cylindrical flexible mold with the diameter of 40mm and the height of 80mm to form a cylindrical sample.
(5) Fully soaking a cylindrical sample with a cylindrical flexible die in 1L of cementing nutrient solution, and inserting an oxygen pump to perform oxygen injection so as to fully perform mineralization reaction; the concentration of each substance in the cementing nutrient solution is as follows: NH4Cl 10g/L, nutrient broth 3.0g/L, naHCO 3.2.12 g/L, urea 42.0.42.0 g/L, caCl 2.2H2O 88.42g/L.
(6) And taking out the cylindrical sample after the mineralization reaction time of 10 days is reached, removing the cylindrical flexible mold, and naturally air-drying.
(7) As shown in fig. 1-5, air-dried 5-group formulation samples were subjected to an unconfined compressive strength test, a freeze-thaw cycle test, and a toxic leaching test, wherein the heavy metal content in the toxic leaching test was determined using a flame atomic absorption method.
As shown in FIG. 1, in this example, the relationship between the leaching concentration of zinc and lead and the restoratives (restoratives 1, 2, 3,4 and 5) in different proportions is schematically shown, and the heavy metal concentration of the polluted soil in the mining area is measured after the polluted soil is retrieved, so that the leaching concentration of lead in the field soil is measured to be 7.61mg/L, and the leaching concentration of zinc is measured to be 8.01mg/L. After the above-mentioned restoration agent and restoration method are used in combination, the leaching concentration of zinc and lead is shown in fig. 1. According to the image, in the polluted soil treated by 5 groups of different repairing agents, the degradation effect of zinc is best when the No. 1 repairing agent is adopted, the degradation rate is as high as 91%, the degradation effect of lead ions is also best, and the degradation rate is as high as 96%.
As shown in fig. 2, the relationship between the unconfined compressive strength and the restoratives (restoratives 1, 2, 3,4 and 5) in different proportions in this embodiment is schematically shown, and after the restoratives and the restoration method are matched, it can be seen from the image that the unconfined compressive strength in the restorative agent 3 is the highest in the polluted soil treated by 5 groups of different restoratives, and is 506KPa.
As shown in fig. 3, the relationship between the leaching concentration of zinc and the freeze thawing cycle in this embodiment is shown, the contaminated soil repaired by 5 repairing agents with different proportions has a rising trend in the leaching concentration of zinc after freeze thawing damage, but has a small fluctuation, and compared with the concentration of heavy metals in the contaminated soil when untreated, the degradation effect is still remarkable, and the degradation rate of the repairing agent No. 2 on zinc after the 7 th freeze thawing cycle is the lowest and is 69%; the repair agent 1 has the best degradation effect, and the minimum degradation rate is as high as 80% even after 7 freeze thawing cycles. Therefore, from the aspect of degradation degree of zinc, the best degradation is the No. 1 repairing agent, and the worst is the No. 2 repairing agent, so the No. 1 repairing agent is the best option.
As shown in fig. 4, the relationship between the leaching concentration of lead and the freeze thawing cycle in this embodiment is shown, the contaminated soil repaired by 5 repairing agents with different proportions has a rising trend in the leaching concentration of lead after freeze thawing damage, but has a small fluctuation, and the degradation effect is still remarkable compared with the concentration of heavy metals in the contaminated soil when untreated, and the degradation rate of the repairing agent No. 5 to zinc after the 7 th freeze thawing cycle is 57% as the lowest; the repair agent 1 has the best degradation effect, and the minimum degradation rate is as high as 87% even after 7 freeze thawing cycles. Therefore, from the aspect of degradation degree of zinc, the best degradation is the No. 1 repairing agent, and the worst is the No. 5 repairing agent, so the No. 1 repairing agent is the best option.
As shown in fig. 5, in this embodiment, the relationship between unconfined compressive strength and freeze thawing cycle is shown, and the strength of the test piece is wholly decreased after the contaminated soil is repaired by 5 repairing agents with different proportions and is damaged by freeze thawing. The compressive strength of the sample repaired by the No. 3 repairing agent is best, and the highest compressive strength of the sample can reach 514KPa. After 7 days of freeze-thawing cycle, its unconfined compressive strength was reduced to 371KPa. Meets the minimum strength 350KPa of solid waste after curing/stabilizing and repairing of refuse landfill specified by the United states environmental protection agency.
The repair agent 1 and the repair agent 3 are compared in terms of unconfined compressive strength, and although the strength of a test piece repaired by the repair agent 1 is 477KPa and is reduced to 321KPa after 7 freeze thawing cycles, the repair effect of the repair agent 1 is most ideal from the standpoint of the leaching concentration of zinc and lead of the repair agent 3.
In this embodiment, each test was performed in the following manner:
the unconfined compressive strength test was performed using a fully automatic testing machine from Shandong Dai test instruments, inc., and loaded at a loading rate of 0.5 KN/s.
And (3) a freeze-thawing cycle test is carried out, wherein the maintained test piece is placed into a freeze-thawing test machine with the temperature set to minus 20 ℃ and plus 20 ℃, the control time of each temperature is 12 hours, and the freeze-thawing cycle of one cycle is completed for 24 hours.
Toxicity leaching experiments leached metal concentrations in leachate were determined using the 1311-toxicity characterization leaching method (TCLP: toxicity Characteristic Leaching Procedure) specified by the United states Environmental Protection Agency (EPA). 5.7ml of glacial acetic acid are dissolved in 500ml of deionized water, 64.3ml of 1mol/L sodium hydroxide are added and the volume is set to 1L. The pH of the solution was adjusted to within 4.93.+ -. 0.05 with 1mol/L HNO3 or NaON. The prepared solution is TCLP extract. The test sample was ground and sieved by a 2mm sieve, 10ml of the extract and 0.5g of sediment were added into a 50ml centrifuge tube, the bottle cap was closed, the mixture was fixed on a shaker for shaking for 18 hours, the supernatant was taken after standing and passed through a 0.45 μm filter membrane, and the leaching concentration of heavy metals was tested by flame atomic absorption.
The beneficial effects of this embodiment lie in: compared with the method for stabilizing heavy metals in the composite polluted soil by using biochar alone and the method for stabilizing the composite polluted soil by using MICP technology alone, the method for repairing the heavy metal polluted soil has excellent effect, and the method for repairing the heavy metal polluted soil combines chemical fixation with long-term benefit by using a small amount of externally doped repairing agent and microorganism in-situ repairing technology, so that the heavy metals in the polluted soil can be greatly reduced, the strength of the polluted soil field is improved, and the secondary development and utilization of the polluted field are facilitated.
Claims (8)
1. The repairing method of the heavy metal polluted soil repairing agent is characterized in that the repairing agent is formed by combining porous silicon and rice straw biochar, and the mass ratio of the porous silicon to the rice straw biochar is 1:1-9:1;
the repairing method comprises the following steps:
(1) Mixing the repairing agent and polluted soil according to the mass ratio of 1:10, and passing through a sieve with the aperture of 1mm together, and screening out fine particles with the particle size of less than 1mm for later use; the repairing agent is formed by combining porous silicon and rice straw biochar, and the mass ratio of the porous silicon to the rice straw biochar is 1:1-9:1;
(2) Preparing a bacterial culture medium, wherein the culture medium is prepared from yeast extract powder, ammonium sulfate and trihydroxymethyl aminotoluene; sterilizing the culture medium at high temperature; inoculating 2% of bacterial liquid into the culture medium, wherein the bacterial liquid is bacillus pasteurizus, and the strain number is ATCC11859; then shake culturing for 48h in a constant temperature incubator; inoculating the cultured bacterial liquid into the optimized culture medium according to an inoculation proportion of 5%, culturing at a constant temperature for 12 hours during expansion culture, and enabling a light absorption value OD600 = 1.2 at a wavelength of 600 nm;
(3) Weighing 150g of the repairing agent, mixing the repairing agent with the polluted soil, and mixing the soil sample with the bacterial liquid with the concentration of OD600 = 1.2 and the volume of 40 ml;
(4) Uniformly stirring the bacterial liquid and the soil sample, and then filling the bacterial liquid and the soil sample into a cylindrical flexible mold to form a cylindrical sample;
(5) Fully soaking the cylindrical sample with the cylindrical flexible die in 1L of cementing nutrient solution, and inserting an oxygen pump for oxygen injection so as to fully generate mineralization reaction; the cementing nutrient solution is prepared from NH 4 Cl, nutrient broth, naHCO 3 、Urea、CaCl 2 ·2H 2 O is formed; the cementing nutrient solution comprises the following components in percentage by weight: NH (NH) 4 Cl 10g/L, nutrient broth 3.0g/L, naHCO 3 2.12g/L、Urea 42.0g/L、CaCl 2 ·2H 2 O 88.42g/L；
(6) And taking out the cylindrical sample after the mineralization reaction time of 10 days is reached, removing the cylindrical flexible mold, and performing natural air drying.
2. The method for repairing the heavy metal polluted soil repairing agent according to claim 1, wherein the particle size of the porous silicon and the particle size of the rice straw biochar are less than or equal to 1mm.
3. The repair method of the heavy metal contaminated soil repair agent according to claim 1, wherein the mass ratio of the porous silicon to the rice straw biochar is 1:1.
4. The repair method of the heavy metal contaminated soil repair agent according to claim 1, wherein the mass ratio of the porous silicon to the rice straw biochar is 1.5:1.
5. The repair method of the heavy metal contaminated soil repair agent according to claim 1, wherein the mass ratio of the porous silicon to the rice straw biochar is 7:3.
6. The repair method of the heavy metal contaminated soil repair agent according to claim 1, wherein the mass ratio of the porous silicon to the rice straw biochar is 4:1.
7. The repair method of the heavy metal contaminated soil repair agent according to claim 1, wherein the mass ratio of the porous silicon to the rice straw biochar is 9:1.
8. The method for repairing the heavy metal contaminated soil repairing agent according to claim 1, wherein the culture medium is formed by combining 20g/L of yeast extract powder, 10g/L of ammonium sulfate and 15.748g/L of trihydroxymethyl aminotoluene; the high-temperature sterilization of the culture medium means that the culture medium is sterilized in a high-temperature sterilization pot at 121 ℃ for 20 minutes; the temperature in the incubator was set at 30℃and 200rpm.
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