CN100493744C - Method for harnessing arsenic contaminated soil - Google Patents
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- CN100493744C CN100493744C CNB2006100383019A CN200610038301A CN100493744C CN 100493744 C CN100493744 C CN 100493744C CN B2006100383019 A CNB2006100383019 A CN B2006100383019A CN 200610038301 A CN200610038301 A CN 200610038301A CN 100493744 C CN100493744 C CN 100493744C
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- 239000002689 soil Substances 0.000 title claims abstract description 81
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 80
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 31
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims abstract description 10
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 4
- 239000003895 organic fertilizer Substances 0.000 claims description 17
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- 235000013922 glutamic acid Nutrition 0.000 claims description 9
- 239000004220 glutamic acid Substances 0.000 claims description 9
- 229930182817 methionine Natural products 0.000 claims description 9
- 238000011109 contamination Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims 1
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- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
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- RVIXKDRPFPUUOO-UHFFFAOYSA-N dimethylselenide Chemical compound C[Se]C RVIXKDRPFPUUOO-UHFFFAOYSA-N 0.000 description 2
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- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
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- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
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- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
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- DVUATXGAAOINPS-UHFFFAOYSA-N dimethoxyarsinic acid Chemical compound CO[As](O)(=O)OC DVUATXGAAOINPS-UHFFFAOYSA-N 0.000 description 1
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- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FRLCRPUWDUKNGO-UHFFFAOYSA-N methoxyarsonic acid Chemical compound CO[As](O)(O)=O FRLCRPUWDUKNGO-UHFFFAOYSA-N 0.000 description 1
- IDDBICIFODFKQO-UHFFFAOYSA-N methylarsane Chemical compound [AsH2]C IDDBICIFODFKQO-UHFFFAOYSA-N 0.000 description 1
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- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 1
- JWOWJQPAYGEFFK-UHFFFAOYSA-N trimethylarsine oxide Chemical compound C[As](C)(C)=O JWOWJQPAYGEFFK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses the treatment method of arsenic pollution soil, comprising the following steps: 1 adding biology fertilizer into the soil polluted by arsenic; 2 adding methilanin and aminoglutaric acid; 3 adjusting the soil moisture percentage; 4 adjusting the pH between 5.3 and 8; 5 making the anaerobic environment. The traditional method can only reduce the arsenic content in soil, not remove it. Utilizing the vaporization of edaphon, the method can remove the arsenic. The accumulator plant method needs plant and harvest plants, but the biology volatilization technique needn't plant and harvest plants.
Description
One, technical field
The present invention designs the improvement method that a kind of soil is subjected to the improvement method, particularly a kind of As polluted soil of metallic pollution.
Two, background technology
In many industries, arsenic compound once was widely used, as being used as Insecticides (tech) ﹠ Herbicides (tech), anticorrisive agent and additive etc.Also have a large amount of arsenic residual in soil in the exploitation process of mineral products, therefore, worldwide arsenic in soil pollutes ubiquity.Because the residual and toxic and side effect serious threat of arsenic contamination thing in soil human beings'health, cause arsenic in soil to pollute influence to environment and be subjected to people and pay close attention to greatly.Detection that arsenic in soil pollutes and control just are one of hot issues of academia's research always.
As polluted soil restorative procedure commonly used at present comprises soil conditioner method, molten local method, casting method, chemical douche and bioremediation technology.Bioremediation technology is the form of utilizing biological (mainly being microorganism, plant) to be used for subduing, purifies arsenic in the soil or changing arsenic, and quilt generally believes it is the technology of tool application prospect in the arsenic contamination improvement.The phytoremediation technology that wherein utilizes hyperaccumulative plant to remove arsenic in soil has been obtained breakthrough progress in nearest several years, Ma and Chen Tongbin etc. have been found the plant ciliate desert-grass (Brakefern of the tired arsenic of ultraproduct first, Pteris vitta), can in the soil of height arsenic contamination, grow, arsenic content can be up to the 20g/kg biomass in the plant, and mainly concentrates on aerial part.Chen Tongbin and Wei Chaoyang etc. further investigate the mechanism and the environmental condition thereof of tired arsenic plant Da Ye rough brake herb (Pteris nervosa) the absorption and transport arsenic of ultraproduct of ciliate desert-grass and discovery subsequently, and set up the phytoremediation demonstration project of first As polluted soil in the world in Chenzhou, Hunan, for the popularization and the practicability of this technology are laid a good foundation.
In the bioremediation technology of metallic pollution soil, absorb the enriched in metals except using hyperaccumulative plant, utilize plant, microorganism that metal is converted into the lower thing that organises of boiling point and evaporate in the atmosphere and go, metal has also caused people's attention gradually in the soil thereby remove.Utilize the effect of microorganism and plant as Terry etc., the Se in the environment be converted into the lower gaseous form of bio-toxicity (dimethyl-selenide and dimethyl diselenide), directly or the tissue by plant evaporate in the atmosphere.After Meagher etc. changed the Mercuryreductase gene in the bacterial body over to mustard seed section plant Arabidopsis, the genetically modified plants that obtain can tolerate, absorb the mercury in the soil environment, and with Hg
2+Be reduced into Hg
0The back volatilization enters atmosphere.
One piece of " research of Biovolatilization of Arsenic from Contaminated Soil " article that " Research of Environmental Sciences " magazine the 18th volume the 1st periodical is stepped on disclose the volatilization of microorganism to arsenic in the soil, but its effect is not high.
Three, summary of the invention
1, goal of the invention: the purpose of this invention is to provide a kind of improvement method of utilizing microorganism the volatilization of arsenic to be realized removing arsenic in the height As polluted soil.
2, technical scheme: the improvement method of As polluted soil of the present invention is characterized in that this method may further comprise the steps:
(1) in by the soil of arsenic contamination, adds biological organic fertilizer, contain nutritive salt and abundant organic matters such as a large amount of nitrogen phosphorus in the biological organic fertilizer, can promote the growth of arsenic volatilization bacterial classification in the soil, improve biomass;
Biological organic fertilizer is that the organic waste that produces with feces of livestock and poultry, agricultural crop straw, agricultural byproducts and food processing is a raw material, is equipped with the organic fertilizer that contains a certain amount of functional microbial that multi-functional fermented bacterium agent processes.The addition of biological organic fertilizer can obviously promote the arsenic volatilization of soil when being 5-20% (mass ratio of soil relatively).The used biological organic fertilizer of the present invention is available from Luhe super large biological organic fertilizer company.
(2) add methionine and glutamic acid as methyl donor.Methionine and glutamic acid are the arsenic important methyl donors in the process that methylates, and add methyl donor and can promote the inorganic arsenic in the soil to be converted into organic arsenic acid, and microorganism is easier organic arsenic acid are converted into the gaseous state organo-arsenic.
The methionine addition is 0.05%-1% among the present invention, and the glutamic acid addition is 0.1%-5% (mass ratio of soil relatively), can obviously promote the arsenic volatilization of soil.
(3) regulate soil moisture content.The moisture of soil has influenced the oxidation-reduction potential of soil greatly, and higher moisture content can stop the circulation of air, thereby forms the anaerobism anaerobic environment, and anaerobism and anoxic environment relatively help the biology volatilization of arsenic.On the other hand, soil moisture content has also directly determined composition and the abundance of edaphon, crosses to hang down with too high moisture content to be unfavorable for microbial growth.
Soil moisture content relatively helps the volatilization of arsenic between 5%-30% (mass ratio of soil relatively).
(4) regulate the pH value.There is one in the microorganism volatilization of arsenic and adapts to the pH scope most, it is generally acknowledged that the pH value of neutrality or meta-acid helps the volatilization of arsenic.The used soil pH of this experiment is 7.8, reaches reduction pH value by add HCL solution in soil, improves the purpose of arsenic volatile quantity.
Soil pH all has arsenic volatilization, the volatile quantity maximum of arsenic between pH6-7 between 5.3-8.
(5) regulate oxidation-reduction potential, create anaerobic environment.There are a balance in methylate and the demethylation of arsenic in soil, under the aerobic condition, the demethylation of arsenic is occupied an leading position, and under the anaerobic condition, balance more tends to methylate.Regulate soil to the slant acidity environment, improve moisture content, add measure such as fertilizer and can reduce oxidation-reduction potential, hinder circulation of air and consume oxygen in the soil, the soil that makes deep layer and press close to the top layer is all with the lower oxidation-reduction potential of acquisition, thus the volatilization of promotion arsenic.In addition, cover agricultural film at upper soll layer, the blocking-up circulation of air can be so that soil be in anaerobic state.And the arsenic that evaporates can be reclaimed by adsorbents such as active carbons.
Know-why of the present invention is: occurring in nature exists a circulation of the Biogeochemistry between inorganic arsenic and the organo-arsenic in soil, water and atmosphere.Arsenic in the soil can escape in the atmosphere with the form of volatile compound owing to the methylation of microorganism.Challenger in 1945 confirmed microorganism can by a series of biological methylations reactions with inorganic arsenic finally be converted into volatile Gosio gas-arsenic trimethide (trimethylarsine, TMA).Along with deepening continuously of research, microorganism that more and more can volatilized arsenic is found, comprise methagen (Methanobacterium), desulfovibrio (Desulfovibrio), Candida (Candida), aspergillus (Aspergillus), reaping hook mould (Fusarium), broom mould (Sxopulariopsis), Paecilomyces varioti (Paecilomyces).Under microbial action, inorganic arsenic can be converted into lower monomethyl arsenic acid (the monomethylarsonic acid of toxicity, MMAA), dimethyl arsenate (dimethylarsinic acid, DMAA) and arsenic trimethide oxygen (trimethylarsine oxide, TMAO) and nontoxic aromatic compound arsenocholine (AsC) and arsenobetaine (AsB).Methylarsonic acid can under the effect of certain micro-organisms, be separately converted to arsenic hydride the derivative monomethyl arsenic that methylates (monomethylarsine, MMA), dimethyl arsenic (dimethylarsine, DMA) and arsenic trimethide (trimethylarsine, TMA).The boiling point of methyl arsenic is lower, is easy to volatilization and enters into atmosphere.In atmosphere, methyl arsenic is oxidized into methylarsonic acid again gradually, along with the precipitation process is got back in the soil, finishes the circulation of arsenic in soil and atmosphere.Utilize biological volatilization technology can repair the soil of arsenic contamination, the gaseous state organo-arsenic is emitted from the High Concentration of Arsenic IA,, be deposited to ground by factors such as precipitation at last and be converted into inorganic arsenic again to other areas through Atmospheric Diffusion, this will become the new method that As polluted soil is repaired.Because the gaseous state organo-arsenic character that evaporates is more stable, very limited through the atmospheric dilution of long period to the raising of arsenic content near the soil, be deposited to ground as the organic selenium of gaseous state from atmospheric environment, can newly not pollute environment structure.
3, beneficial effect: traditional physics and chemical repair method can only reduce the bioavailability of arsenic in the soil by additive, arsenic in can not substantial removal soil, the present invention utilizes the arsenic of the volatilization of edaphon in can substantial removal soil, cost is low, non-secondary pollution.The hyperaccumulative plant method needs the establishing in large scale plant and in time gathers in plant, and how disposing harvested plant also is a difficult problem, and then there are not these problems in biological volatilization technology, and is time saving and energy saving relatively.
Four, description of drawings
Fig. 1 is the biological evaporation curve of fertilizer content.
Fig. 2 is the biological evaporation curve of different moisture content.
Fig. 3 is an anaerobism oxygen consumption environment to the arsenic influence curve that volatilizees.
Five, specific implementation method
Embodiment 1: the present invention reaches the purpose that reduces arsenic in soil content by microorganism volatilization principle, organic by adding to the High Concentration of Arsenic contaminated soil, add methyl donor, regulate comprehensive means such as soil moisture content, pH value and oxidation-reduction potential, promote arsenic volatilization microbial growth, construction helps the environmental condition of arsenic volatilization, thereby reaches the purpose that improves the arsenic volatile quantity.
At the biological organic fertilizer addition is 15%, moisture content 25%, the methionine of interpolation 0.2% and 1% glutamic acid are under the anaerobic environment of pH7, the volatile quantity of arsenic can reach 2.64mg/kg soil in five weeks, and the volatile quantity of soil then only is a 2.4ug/kg soil under the natural conditions.Wherein biological organic fertilizer is that the organic waste that produces with feces of livestock and poultry, agricultural crop straw, agricultural byproducts and food processing is a raw material, is equipped with the organic fertilizer that contains a certain amount of functional microbial that multi-functional fermented bacterium agent processes.As seen biological volatilization technology can improve the rate of volatilization of arsenic in soil nearly 1,000 times, becomes a kind of feasible arsenic in soil and pollutes the biological restoration means.From great deal of experiment data, can learn (referring to accompanying drawing):
1, fertilizer content is to the influence of arsenic volatile quantity.Add the efficient that biological organic fertilizer can improve the arsenic volatilization in the soil, biological organic fertilizer content is high more, and the biological rate of volatilization of arsenic is fast more.
2, moisture content is to the influence of arsenic volatile quantity.Add the biology volatilization that moisture can promote arsenic, and water content is too high unfavorable to the biology volatilization.The biological rate of volatilization of sample that adds 20ml water has reached 0.9ug/ (kgweek), far above adding 100ml water and not adding the control group of water.
3, anaerobism oxygen consumption environment is to the influence of arsenic volatilization.Arsenic volatile quantity under anaerobic is higher than the oxygen consumption condition far away, and the week that volatile quantity is the highest reaches 1mg/kg soil, has only 3-8ug/kg soil and aerobic condition is next.
Embodiment 2: as embodiment 1, other is constant, and changing the biological organic fertilizer addition is 5%, and moisture content is 30%, methionine be 1% and glutamic acid be 0.1%, pH8 under the anaerobic environment, reaches a large amount of volatilizations of arsenic in the soil equally.
Embodiment 3: as embodiment 1, other is constant, and changing the biological organic fertilizer addition is 20%, and moisture content is 5%, methionine be 0.05% and glutamic acid be 5%, pH5.3 under the anaerobic environment, reaches a large amount of volatilizations of arsenic in the soil too.
Embodiment 4: as embodiment 1, other is constant, and changing the biological organic fertilizer addition is 10%, and moisture content is 10%, methionine be 0.6% and glutamic acid be 3%, pH6 under the anaerobic environment, reaches a large amount of volatilizations of arsenic in the soil equally.
Claims (5)
1, a kind of improvement method of As polluted soil is characterized in that this method may further comprise the steps:
(1) in by the soil of arsenic contamination, adds biological organic fertilizer;
(2) add methionine and glutamic acid as methyl donor;
(3) regulate soil moisture content;
(4) regulating the pH value is 5.3-8;
(5) create anaerobic environment.
2, the improvement method of As polluted soil according to claim 1 is characterized in that in step (1), the addition of biological organic fertilizer is soil quality 5-20%.
3, the improvement method of As polluted soil according to claim 1 is characterized in that in step (2), the methionine addition is the 0.05%-1% of soil quality, and the glutamic acid addition is 0.1%-5%.
4, the improvement method of As polluted soil according to claim 1 is characterized in that in step (3), soil moisture content is the 5%-30% of soil quality.
5, the improvement method of As polluted soil according to claim 1 is characterized in that in step (4), pH is 6-7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102233354A (en) * | 2010-05-06 | 2011-11-09 | 中国科学院生态环境研究中心 | Remediation method of arsenic (As)-contaminated soil |
| CN101879521A (en) * | 2010-06-11 | 2010-11-10 | 中国地质大学（北京） | Method for remedying arsenic polluted soil |
| CN103962369B (en) * | 2014-04-30 | 2016-01-20 | 中南林业科技大学 | A kind of method utilizing energy-source plant configuration mode restoration of soil polluted by heavy metal |
| CN104475436A (en) * | 2014-12-03 | 2015-04-01 | 山水园林股份有限公司 | Method for repairing mine discarded polluted soil layer |
| CN109604326A (en) * | 2018-12-07 | 2019-04-12 | 佛山科学技术学院 | A method of reducing the accumulation of rice grain arsenic |
| CN114713625B (en) * | 2022-04-18 | 2022-09-20 | 广东省科学院生态环境与土壤研究所 | Method for synchronous heavy/metalloid conversion and greenhouse gas emission reduction through targeted regulation and control of soil microorganisms and application |
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| CN1397390A (en) * | 2001-07-18 | 2003-02-19 | 中国科学院地理科学与资源研究所 | Method for treating As polluted soil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397390A (en) * | 2001-07-18 | 2003-02-19 | 中国科学院地理科学与资源研究所 | Method for treating As polluted soil |
| CN1217753C (en) * | 2002-11-27 | 2005-09-07 | 中国科学院地理科学与资源研究所 | Method for repairing arsenium contaminated environment |
Non-Patent Citations (4)
| Title |
|---|
| 土壤环境中的砷及其生态效应. 张国祥等.土壤，第2期. 1996 |
| 土壤环境中的砷及其生态效应. 张国祥等.土壤，第2期. 1996 * |
| 砷污染土壤生物挥发的研究. 宋红波等.环境科学研究，第18卷第1期. 2005 |
| 砷污染土壤生物挥发的研究. 宋红波等.环境科学研究，第18卷第1期. 2005 * |
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| CN1806952A (en) | 2006-07-26 |
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