CN102950146A - Improvement method for acid heavy metal lead contaminated soil of tropical zone - Google Patents
Improvement method for acid heavy metal lead contaminated soil of tropical zone Download PDFInfo
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- CN102950146A CN102950146A CN2012103953096A CN201210395309A CN102950146A CN 102950146 A CN102950146 A CN 102950146A CN 2012103953096 A CN2012103953096 A CN 2012103953096A CN 201210395309 A CN201210395309 A CN 201210395309A CN 102950146 A CN102950146 A CN 102950146A
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Abstract
The invention relates to an improvement method of acid heavy metal lead contaminated soil of the tropical zone, which is characterized in that sepiolite powder, lime powder, industrial waste coal ash and agricultural waste coconut shell are mixed in the contaminated soil, and the optimal proportion scope of the mass percentage of the materials are as follows: 12.5-57.13% of coconut shell, 12.5-22.22% of sepiolite, 14.29-50% of coal ash, and 11.11-25% of lime powder. According to the method, iron and manganese oxide combined state lead and residual state lead in the contaminated soil are respectively increased by 8.12-85.4% and 15.87-89.32%, thereby having the passivation function. The improvement characteristics of the invention are that lead ion is fixed by chelation, adsorption and other reactions, the biotoxicity is reduced, and the contaminated soil is improved. The preparation method is simple, effectively utilizes waste, is low in input cost, can remarkably improve the PH value of the laterite, and reduce the content of soil exchange state lead.
Description
Technical field
The present invention relates to the soil improvement method field, be specifically related to the modification method of a kind of torrid areas acid heavy metal lead-contaminated soil.
Background technology
Lead is to animals and plants and human one of the strongest heavy metal element that endangers in the environment, in 320 emphasis contaminated areas in the very fast area of the economic developments such as 24 provinces of China (city) outskirts of a town, sewage irrigation district, industrial and mineral, the agricultural output that content of beary metal exceeds standard and area account for pollutant more than 80% of agricultural product total amount and the gross area that exceeds standard, and wherein lead is one of the most serious pollution element.Plumbous in soil the holdup time long, can not be degraded by microorganisms, and precipitable, move, be enriched in the plant, thereby enter human body with food chain, health is produced greatly harm, also can occur when serious poisoning and dead.Therefore, control and remediating heavy metal lead-contaminated soil are extremely urgent.
The method of administering at present heavy-metal contaminated soil mainly contains Physical, chemical method and bioanalysis.In chemical method, original position fixedly repairing method is research and uses more recovery technique, it is by adding fixative in soil, regulate and the physicochemical properties of change heavy metal in soil, make it produce the series reaction such as precipitation, absorption, ion-exchange, humification, redox, reduce its biological effectiveness and transportable property in soil environment.The soil heavy metal passivants such as alkaline species material, organic materials and composite passivant such as plant slag have been begun to take shape at present, in soil, there is form by changing heavy metal, make the activated state of heavy metal change stable state into, thereby reduce its toxic action, reach the purpose that passivation is repaired with this.
Coconut husk is the endocarp of babassu coconut, contains ash content 0.61% (principal component is potassium hydroxide), lignin 36.51%, and cellulose 53.06%, pentosan 29.27% (total amount), cellulose contains pentosan 20.54%.Sepiolite is a kind of fibrous hydrous magnesium silicate mineral, has the performances such as extremely strong absorption and dispersion, SiO
2Generally between 54～60%, the MgO content range is many 21～25% for content.Flyash is the solid waste in thermal power plant, contains abundant CaO and MgO, and the pH value reaches 12, can play heavy metal in the passivation soil and the effect of kill pathogenic bacteria.The main component of quick lime is calcium oxide (CaO), uses quick lime and can improve soil pH value, reduces the lead amount that the validity higher part is divided in the soil, thereby suppresses plant to the absorption of lead.
The vast farmland that the heavy metal mild or moderate is polluted in repair process, must be considered and sustainable utilization combines; On reclamation activities, do not cause the secondary pollution in farmland as far as possible and reach effectively heavy metal-passivated purpose.Therefore, the research and development expense is low, implement easily agriculture chemistry measure, and the farmland of in-situ passivation repairing heavy metal pollution becomes one of inevitable choice of repairing in China heavy metal pollution farmland.
Summary of the invention
The object of the invention is to the technical deficiency that exists according in the existing heavy-metal contaminated soil modification method, problem such as improvement high cost etc., the method that provides the composite passivant of the reduction acid heavy metal Lead in Contaminated Soil activity that a kind of cost is low, improved effect is good that soil is improved.
Above-mentioned purpose of the present invention is achieved by following scheme:
The modification method of a kind of torrid areas acid heavy metal lead-contaminated soil is characterized in that comprising the steps:
(1) with the pH value in below 6.0, slight pollution soil as the improvement object, simulate artificial farmland ecological environment, soil is carried out three grades of soiling values of lead (500mg/kg) artificial contamination;
(2) in the heavy metal lead contaminated soil, add soil conditioner (the interpolation level is 20g/100g), add simultaneously urea, calcium superphosphate, potassium chloride as base fertilizer;
(3) mix after, adding deionized water, to regulate soil moisture content be about 70% of maxmun field capacity, balance 1 month.
The composite passivated modifying agent of the soil that adds in the modification method of the present invention is made according to the certain mass mark by sepiolite powder, pulverized limestone, trade waste flyash and agricultural wastes coconut husk.
In the modification method of the present invention, the described method that soil is carried out the artificial contamination of step (1) is for analytically pure Pb (NO
3)
2Obtain solution adds it in the examination soil to, makes P in soil b concentration reach 500mg/kg, is prepared into the simulation heavy-metal contaminated soil.
In the modification method of the present invention, provide a kind of composite passivated modifying agent that reduces acid heavy metal Lead in Contaminated Soil activity, adopted technical measures as follows:
A kind of composite passivated modifying agent that reduces acid heavy metal Lead in Contaminated Soil activity, it is comprised of the mass fraction of following three kinds of raw materials:
A kind of composite passivated modifying agent that reduces acid heavy metal Lead in Contaminated Soil activity, it forms (preferable range) by the mass fraction of following three kinds of raw materials:
A kind of composite passivated modifying agent that reduces acid heavy metal Lead in Contaminated Soil activity, it forms (preferred plan) by the mass fraction of following three kinds of raw materials:
But the present invention finds the acid in the modifying agent efficient neutralization laterites such as employing sepiolite, pulverized limestone, flyash and coconut husk through lot of experiments, soil pH value is improved rapidly, but contents of many kinds of heavy metal ion such as chelating, complexing Pb, Cd, Cr also, reduce its available state content in soil, alleviate its toxicity.Simultaneously, some upgrade materials (such as flyash, coconut husk) itself is exactly solid waste, and the cyclic utilization of waste has the good value of environmental protection and economic benefit.Therefore, the present invention uses above-mentioned substance as soil passivation modifying agent.
The preparation method of composite passivated modifying agent of the present invention the steps include:
(1) preparation of sepiolite breeze: the sepiolite raw ore is crossed 100 mesh sieves through ball milling, for subsequent use.Described sepiolite silica content is (with SiO
2Meter) be 55～60%, magnesia (in MgO) 20～25%, heavy metal Pb content≤5mg/kg.
(2) preparation of coconut husk: the endocarp of coconut is dried, pulverized 100 mesh sieves, for subsequent use.Described coconut husk contains ash content 0.61% (principal component is potassium hydroxide), lignin 36.51%, and cellulose 53.06%, pentosan 29.27% (total amount), cellulose contains pentosan 20.54%.
(3) raw material and flyash, the pulverized limestone with step (1,2) preparation proportionally mixes, and is the composite passivated modifying agent of Heavy Metals in Soil Contaminated.
Passivation modifying agent of the present invention also can according to the characteristics of this regional soil, be used in conjunction with humic acid, fertilizer etc. when using.
After using by above-mentioned preferable range consumption, effect to the validity that reduces Lead In Soil is better, it makes in the soil that exchangeable species is plumbous, carbonate is plumbous and organically combine attitude lead content descended respectively 98.21-99.19%, 77.27-94.0% and 12.05-65.57% in conjunction with attitude, iron and manganese oxides has increased respectively 8.12-85.4% and 15.87-89.32% in conjunction with attitude, residual form lead, also makes simultaneously soil pH value improve 2.65-4.01.
Compared with prior art, the present invention has following advantage and effect:
(1) selected the sepiolite that the contents of many kinds of heavy metal ion such as Cd, Pb, Cr is had stronger passivation ability in the soil improvement method of the present invention, can improve rapidly the pulverized limestone of soil pH, and existing trade waste flyash, four kinds of raw materials of agricultural wastes coconut husk.Result of the test shows: product of the present invention makes in the soil that exchangeable species is plumbous, carbonate is plumbous and organically combine attitude lead content descended respectively 98.21-99.19%, 77.27-94.0% and 12.05-65.57% in conjunction with attitude, and iron and manganese oxides has increased respectively 8.12-85.4% and 15.87-89.32% in conjunction with attitude, residual form lead.
(2) but the present invention's passivation heavy metal-polluted soil not only also can improve soil pH value greatly, repair acidified soil, improve the functions such as the soil texture.Result of the test shows: product of the present invention makes soil pH value improve 2.65-4.01 than contrast.
(3) raw material sources of the present invention not only extensively, cost is low, uses conveniently, realized the cycling and reutilization of existing industry, agricultural wastes, and can effectively reduce validity plumbous in the acid lead-contaminated soil.To control torrid areas acid ground heavy metal pollution, ensure food safety significant.
Description of drawings
Fig. 1 is that the composite passivant of different quality mark proportioning when carrying out potted plant the application in the embodiment of the invention is to the impact effect figure of soil pH value.
Fig. 2 is that the composite passivant of different quality mark proportioning when carrying out potted plant the application in the embodiment of the invention is to the impact effect figure of each form content of P in soil b.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but embodiment does not do any type of restriction to the present invention.
Embodiment
The modification method of a kind of torrid areas of the present invention acid heavy metal lead-contaminated soil, the composite passivated modifying agent in the method comprises sepiolite powder, pulverized limestone, flyash and coconut husk.Wherein sepiolite powder is bought the grand sharp sepiolite cashmere Co., Ltd in Hebei; Pulverized limestone is bought in Hainan pulverized limestone Group Plc; Flyash is the trade waste that produces in Danzhou City, Hainan Province artistic skill environmental protection brick field production process, is rich in CaO and MgO, and the pH value reaches 12; Coconut husk is the endocarp of babassu coconut, is the common agricultural wastes in torrid areas.
The preparation method of composite passivated modifying agent of the present invention the steps include:
(1) preparation of sepiolite breeze: the sepiolite raw ore is crossed 100 mesh sieves through ball milling, for subsequent use.Described sepiolite silica content is (with SiO
2Meter) be 55～60%, magnesia (in MgO) 20～25%, heavy metal Pb content≤5mg/kg.
(2) preparation of coconut husk: the endocarp of coconut is dried, pulverized 100 mesh sieves, for subsequent use.Described coconut husk contains ash content 0.61% (principal component is potassium hydroxide), lignin 36.51%, and cellulose 53.06%, pentosan 29.27% (total amount), cellulose contains pentosan 20.54%.
(3) raw material and flyash, the pulverized limestone with step (1,2) preparation proportionally mixes, and is the composite passivated modifying agent of Heavy Metals in Soil Contaminated.
Indoor pot is used:
Simulate artificial farmland ecological environment, adopt potted plant method to investigate composite passivated modifying agent of the present invention and modification method to the passivation effect of the plumbous validity of torrid areas acid ground (laterite).The confession examination soil of potted plant application is laterite, and its physicochemical property is as shown in table 1.
Table 1 is for the examination soil physico-chemical property
Whole application process arranges ten processing:
(1) control group does not apply the composite passivated modifying agent of soil of the present invention;
(2) apply the composite passivated modifying agent of soil (concentration level is 20g/100g), it is made according to the different quality mark by four kinds of raw materials of the present invention, and composition and consumption are as shown in table 2.
The compound improved formulations of 9 kinds in table 2 (unit: %)
Above-mentioned each processing repeats 3 times, and the air-dry 2mm of mistake sieves for examination soil, and according to the standard of soil environment quality value, plumbous three grades of soiling value 500mg/kg carry out the artificial contamination.Every kilogram of soil interpolation (solution form) 32mg urea, 15mg calcium superphosphate, 17mg potassium chloride are base fertilizer simultaneously.The plumbous matter soil that stirs is put basin, every basin 1kg, adding deionized water adjusting soil moisture content is about 70% of maxmun field capacity.
Soil pH adopts Potentiometric Determination; The full dose of heavy metal Pb adopts nitric acid-sulfuric acid-perchloric acid to disappear and boils atomic absorption spectrophotometry and hydride generation aas determination; The exchangeable species of Pb, carbonate adopt the Tessier continuous extraction to measure in conjunction with attitude, iron and manganese oxides in conjunction with the content of attitude, combination attitude and residual form in the soil.Test result is as shown in table 3.
Table 3: to the improved effect (unit: mg) of each form of Pb in Soil
The result of upper table 3 shows, uses composite modifying agent of the present invention (coconut husk+flyash+sepiolite+pulverized limestone) and modification method remarkable to the activity influence of each form heavy metal lead in the soil and lead.Use composite passivated modifying agent of the present invention and can significantly reduce the soil available lead amount.Compared with the control, when in the mass fraction preferable range, processing, plumbous, the carbonate of exchangeable species is plumbous and organically combine attitude lead content descended respectively 98.21-99.19%, 77.27-94.0% and 12.05-65.57% in conjunction with attitude in the soil, and iron and manganese oxides has increased respectively 8.12-85.4% and 15.87-89.32% in conjunction with attitude, residual form lead.
When using the preferred plan processing (coconut husk 22.22%+ flyash 44.45%+ sepiolite 22.22%+ pulverized limestone 11.11%) of composite passivated modifying agent of the present invention, exchangeable species lead, carbonate have descended respectively 99.19%, 94.0% and 65.57% in conjunction with attitude lead and combination attitude lead content in the soil, and iron and manganese oxides has increased respectively 85.4% and 89.32% in conjunction with attitude, residual form lead.This shows, the method of soil heavy metal combined passivation modifying agent of the present invention and improvement soil has obvious passivation effect to torrid areas acid heavy metal lead-contaminated soil, use in right amount the available state content that can significantly reduce Pb in Soil, reduce plant to the absorption of Pb in Soil.
Claims (7)
1. the modification method of a torrid areas acid heavy metal lead-contaminated soil is characterized in that comprising the steps:
(1) with the pH value in below 6.0, slight pollution soil as the improvement object, simulate artificial farmland ecological environment, soil is carried out three grades of soiling values of lead (500mg/kg) artificial contamination;
(2) in the heavy metal lead contaminated soil, add soil conditioner, add simultaneously urea, calcium superphosphate, potassium chloride as base fertilizer;
(3) mix after, adding deionized water, to regulate soil moisture content be about 70% of maxmun field capacity, balance 1 month.
2. the modification method of a kind of torrid areas according to claim 1 acid heavy metal lead-contaminated soil, it is characterized in that: the composite passivated modifying agent of the soil of interpolation comprises sepiolite powder, pulverized limestone, trade waste flyash and agricultural wastes coconut husk.
3. the modification method of a kind of torrid areas according to claim 1 acid heavy metal lead-contaminated soil is characterized in that: the method for described in the step (1) soil being carried out the artificial contamination is for analytically pure Pb (NO
3)
2Obtain solution adds it in the examination soil to, makes P in soil b concentration reach 500mg/kg, is prepared into the simulation heavy-metal contaminated soil.
4. the modification method of a kind of torrid areas according to claim 2 acid heavy metal lead-contaminated soil, it is characterized in that: the mass fraction that adds sepiolite is 11.11%～50%.
5. the modification method of a kind of torrid areas according to claim 2 acid heavy metal lead-contaminated soil is characterized in that: add the mass fraction of pulverized limestone 11.11%～50%.
6. the modification method of a kind of torrid areas according to claim 2 acid heavy metal lead-contaminated soil is characterized in that: add the mass fraction of flyash 11.11%～50%.
7. the modification method of a kind of torrid areas according to claim 2 acid heavy metal lead-contaminated soil is characterized in that: add the mass fraction of coconut husk 12.5%～57.13%.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333031A (en) * | 2013-07-10 | 2013-10-02 | 丹阳市淸云农业发展有限公司 | Modifier for acidic soil |
| CN103433273A (en) * | 2013-08-12 | 2013-12-11 | 四川农业大学 | Application of willow herb to remediation of heavy metal lead pollution in soil |
| CN103495600A (en) * | 2013-09-30 | 2014-01-08 | 桂林理工大学 | Method for repairing acid heavy metal contaminated soil |
| CN104117529A (en) * | 2014-07-09 | 2014-10-29 | 华南师范大学 | In-situ remediation method of acidic soil containing heavy metals |
| CN104722573A (en) * | 2015-02-02 | 2015-06-24 | 中国科学院沈阳应用生态研究所 | Method for rapidly improving pH value of acidified soil |
| CN104726104A (en) * | 2015-03-27 | 2015-06-24 | 盱眙欧佰特粘土材料有限公司 | Preparation method of modification mineral composition for improving heavy metal polluted soil |
| CN107032931A (en) * | 2017-05-31 | 2017-08-11 | 中国农业科学院农业资源与农业区划研究所 | One kind changes sour auxotype composite soil conditioner and its application |
| CN107118058A (en) * | 2017-05-31 | 2017-09-01 | 中国农业科学院农业资源与农业区划研究所 | A kind of water conservation fertilizer changes the multi-functional red soil conditioner of acid type and its application |
| CN107311757A (en) * | 2017-07-06 | 2017-11-03 | 波普克国际生态科技（北京）有限公司 | Micropowders formula applied to the mineral humus mixture of arable land Heavy Metal Pollution Control |
| CN107384433A (en) * | 2017-08-23 | 2017-11-24 | 江苏省农业科学院 | A kind of soil heavy metal passivant |
| CN107879850A (en) * | 2017-11-28 | 2018-04-06 | 湖南本农环境科技有限公司 | A kind of acid heavy metal polluted soil of farmland conditioner and its preparation method and application |
| CN112334241A (en) * | 2018-06-01 | 2021-02-05 | 现代建筑工程有限公司 | Method for neutralizing acid-washed dredged soil |
| CN114739926A (en) * | 2022-04-08 | 2022-07-12 | 新疆维吾尔自治区产品质量监督检验研究院 | Method for measuring residual quantity of harmful heavy metals in printing ink |
| CN115404084A (en) * | 2022-09-20 | 2022-11-29 | 江西中江环保集团股份有限公司 | Green fertilizing and pollution-reducing matrix for improving polluted farmland soil |
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| CN103333031A (en) * | 2013-07-10 | 2013-10-02 | 丹阳市淸云农业发展有限公司 | Modifier for acidic soil |
| CN103433273A (en) * | 2013-08-12 | 2013-12-11 | 四川农业大学 | Application of willow herb to remediation of heavy metal lead pollution in soil |
| CN103433273B (en) * | 2013-08-12 | 2014-11-05 | 四川农业大学 | Application of willow herb to remediation of heavy metal lead pollution in soil |
| CN103495600A (en) * | 2013-09-30 | 2014-01-08 | 桂林理工大学 | Method for repairing acid heavy metal contaminated soil |
| CN104117529A (en) * | 2014-07-09 | 2014-10-29 | 华南师范大学 | In-situ remediation method of acidic soil containing heavy metals |
| CN104117529B (en) * | 2014-07-09 | 2016-03-23 | 华南师范大学 | A kind of in-situ remediation method containing heavy metal acid ground |
| CN104722573A (en) * | 2015-02-02 | 2015-06-24 | 中国科学院沈阳应用生态研究所 | Method for rapidly improving pH value of acidified soil |
| CN104726104B (en) * | 2015-03-27 | 2018-04-13 | 盱眙欧佰特粘土材料有限公司 | The preparation method of heavy-metal contaminated soil improvement modified mineral composition |
| CN104726104A (en) * | 2015-03-27 | 2015-06-24 | 盱眙欧佰特粘土材料有限公司 | Preparation method of modification mineral composition for improving heavy metal polluted soil |
| CN107032931A (en) * | 2017-05-31 | 2017-08-11 | 中国农业科学院农业资源与农业区划研究所 | One kind changes sour auxotype composite soil conditioner and its application |
| CN107118058A (en) * | 2017-05-31 | 2017-09-01 | 中国农业科学院农业资源与农业区划研究所 | A kind of water conservation fertilizer changes the multi-functional red soil conditioner of acid type and its application |
| CN107311757A (en) * | 2017-07-06 | 2017-11-03 | 波普克国际生态科技（北京）有限公司 | Micropowders formula applied to the mineral humus mixture of arable land Heavy Metal Pollution Control |
| CN107384433A (en) * | 2017-08-23 | 2017-11-24 | 江苏省农业科学院 | A kind of soil heavy metal passivant |
| CN107384433B (en) * | 2017-08-23 | 2020-03-31 | 江苏省农业科学院 | Soil heavy metal passivator |
| CN107879850A (en) * | 2017-11-28 | 2018-04-06 | 湖南本农环境科技有限公司 | A kind of acid heavy metal polluted soil of farmland conditioner and its preparation method and application |
| CN107879850B (en) * | 2017-11-28 | 2021-02-02 | 湖南本农环境科技有限公司 | Acidic farmland heavy metal polluted soil conditioner and preparation method and application thereof |
| CN112334241A (en) * | 2018-06-01 | 2021-02-05 | 现代建筑工程有限公司 | Method for neutralizing acid-washed dredged soil |
| CN114739926A (en) * | 2022-04-08 | 2022-07-12 | 新疆维吾尔自治区产品质量监督检验研究院 | Method for measuring residual quantity of harmful heavy metals in printing ink |
| CN114739926B (en) * | 2022-04-08 | 2022-11-22 | 新疆维吾尔自治区产品质量监督检验研究院 | Method for measuring residual quantity of harmful heavy metals in printing ink |
| CN115404084A (en) * | 2022-09-20 | 2022-11-29 | 江西中江环保集团股份有限公司 | Green fertilizing and pollution-reducing matrix for improving polluted farmland soil |
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