CN105903756A - Method for maintaining in-situ chemical improvement effect for acidic multi-metal contaminated soil - Google Patents
Method for maintaining in-situ chemical improvement effect for acidic multi-metal contaminated soil Download PDFInfo
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- CN105903756A CN105903756A CN201610234660.5A CN201610234660A CN105903756A CN 105903756 A CN105903756 A CN 105903756A CN 201610234660 A CN201610234660 A CN 201610234660A CN 105903756 A CN105903756 A CN 105903756A
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- soil
- zeolite
- lime stone
- modifying agent
- phosphate rock
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of improvement and restoration of heavy metal contaminated soil and discloses a method for in-situ restoring acidic multi-metal contaminated farmland soil by the utilization of a soil improvement agent and for maintaining soil improvement effect by the utilization of a calcium magnesium phosphate fertilizer during the restoring period. The method of the invention comprises the following specific steps: (1) crushing raw materials in the mixed improvement agent, sieving to prepare agricultural-grade powder, separately storing, uniformly mixing before application, and uniformly mixing the uniformly-mixed improvement agent and surface soil of 15 cm deep; and (2) applying the calcium magnesium phosphate fertilizer after the soil improvement agent has been applied for 300-540 d, and uniformly and fully mixing with the surface soil of 15 cm deep. According to the invention, action effects of the improvement agent are maintained by later application of the calcium magnesium phosphate fertilizer. In addition, sources of raw materials are wide, cost is low, and the method is simple and feasible and is suitable for large-area of farmland soil slightly and moderately contaminated with cadmium, lead, copper and zinc.
Description
Technical field
The invention belongs to improvement and the repairing and treating technical field of heavy-metal contaminated soil, particularly to a kind of profit
With soil conditioner in-situ immobilization acidic multimetallic polluted farmland soil, and during repairing, utilize calcium magnesium phosphate
The method maintaining the improved effect of soil.
Background technology
Along with Chinese Urbanization, industrialization and the quickening of intensive agriculture process, heavy metal pollution of soil is
Become one of important environmental problem of restriction China agricultural sustainable development." Chinese environmental situation in 2014
Publication " display, China's arable soil point position exceeding standard rate reaches 19.4%, the most slightly, slightly, moderate and
The pollution ratio of severe reaches 13.7%, 2.8%, 1.8%, 1.1% respectively, and cadmium, arsenic, mercury, lead, chromium etc. are
Major pollutants.Heavy metal-polluted soil is mainly derived from sewage irrigation, mud is used, mineral mining and smelting,
Wherein exploitation and the smelting of metalliferous mineral is one of major reason causing heavy metal pollution of soil.A soil huge sum of money
Belong to pollution there is the features such as chronicity, hysteresis quality, cumulative bad, by number of ways enter food chain accumulation and
Amplify, finally threaten human health.Such as, Pb is the unessential element in human body, Excess free enthalpy lead meeting
Human nerve, bone, circulation, endocrine and immune system are worked the mischief.Long Term Contact Cd, has
The harmful effects such as lung cancer, fracture, kidney disorder, hypertension.Therefore, the reparation of heavy-metal contaminated soil
It it is one of China's environmental problem the most urgently to be resolved hurrily.
Soil restoring technology includes physics, chemistry, plant and microorganism etc., but various recovery technique has respectively
From pluses and minuses.In-situ chemical improving technology is by adding different modifying agents to contaminated soil, by inhaling
Attached, precipitation, complex reaction, make heavy metal in soil transfer to solid phase of soil mutually by dissolving, change soil weight
Metal occurrence patterns, reduces its biological effectiveness, thus reaches to reduce bioavailability of heavy metals and toxicity
Effect.At present, conventional modifying agent have lime, bone black, zeolite, calcium phosphate, calcium carbonate, silicate and
Promote the organic substance etc. of reduction.Chemical modifying is little to soil environment destruction, expense is relatively low, be prone to behaviour
Make, be particularly suitable for we large-area in, the reparation of low heavy metal pollution agricultural land soil and improvement.
It is critical only that of chemical improvement agent technology selects modifying agent economic, the most effective.Mine Soil Surrounding
Tend to belong to Compound Heavy Metals, and the pH of soil is on the low side.Modifying agent can improve soil pH,
Heavy metal in stable soil.But it is undesirable generally to there is effect in the soil conditioner studied at present, persistently makees
By the problem such as the time is short.Such as, the field experiment of Wu Qi hall seminar of Agricultural University Of South China finds, lime
After effect can maintain 1 year about half.Therefore, the most not yet there is the heavy metal pollution of large-scale production and application
The modifying agent of soil.How to maintain the pH value of soil after improvement, it is ensured that the continual and steady effect of modifying agent,
The always difficult problem in soil in-situ chemical modifying technology.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of dimension
The method holding acidic multimetallic contaminated soil in-situ chemical improved effect.After the method can not only maintain improvement
The pH value of metal mine periphery contaminated soil, and modifying agent can be maintained Cadmium in Soil, lead, copper and zinc
Stablizing effect, it is ensured that the modifying agent continuous action to soil.
The purpose of the present invention is realized by following proposal:
A kind of method maintaining acidic multimetallic contaminated soil in-situ chemical improved effect, specifically includes following step
Rapid:
(1) applying of soil conditioner: the raw material in mixing modifying agent is pulverized, sieved, is prepared as agriculture
The powder of industry level, separately deposits, and is sufficiently mixed uniformly, the modifying agent after then mixing before using
Mix with the topsoil of top layer 15cm；
(2) after soil conditioner applies 300～540d, calcium magnesium phosphate is applied, with the soil of top layer 15cm
Earth is sufficiently mixed uniformly.
The mixture that modifying agent is lime stone, zeolite, ground phosphate rock described in step (1), or be lime
The mixture of stone, zeolite, ground phosphate rock and mushroom residue.
The amount of application of modifying agent used is 1100～1700kg/ mus.
Preferably, when the mixture that described modifying agent is lime stone, zeolite and ground phosphate rock, lime stone,
The mass ratio of zeolite and ground phosphate rock is (20～30): (30～40): (30～50)；When described modifying agent
During for the mixture of lime stone, zeolite, ground phosphate rock and mushroom residue, lime stone, zeolite, ground phosphate rock and mushroom
Slag mass ratio is (15～20): (25～35): (20～25): (25～35).
Without heavy metal in described lime stone and zeolite.
Sieving described in step (1) referred to the hole sizer of 100 mesh.
The applied amount of calcium magnesium phosphate used in step (2) is 260kg/ mu.
The mechanism of the present invention is: calcium magnesium phosphate can effectively maintain mixing modifying agent to acidic multimetallic contaminated soil
Improved effect.Its reaction mechanism is more complicated, is broadly divided into three classes: phosphate radical that (1) dissolves and heavy metal
Generate precipitation；(2) the direct Adsorption of Heavy Metals in surface；(3) phosphate radical induction heavy metal adsorption.Meanwhile, calcium and magnesium
Phosphate fertilizer can keep the soil pH value after improvement, suppression soil to be again acidified.Therefore, the present invention uses mixed
Close modifying agent improvement acid ground, after improving soil pH value and tentatively reaching improved effect, use the later stage single
The method solely applying calcium magnesium phosphate maintains the action effect of modifying agent.
The present invention, relative to prior art, has such advantages as and beneficial effect:
(1) later stage of calcium magnesium phosphate applies effectively to maintain the improved effect of acid ground heavy metal pollution.
Calcium magnesium phosphate can by directly adsorbing, replacing, the effect such as precipitation carry out heavy metal in further stable soil, protect
Hold soil pH, effectively maintain the action effect of modifying agent, the phosphorus needed for plant growth and Mg are provided simultaneously2+,
Promote plant growth.
(2) raw material sources of the present invention is extensive, with low cost, method is simple, it is adaptable to big face
Long-pending by light moderate cadmium, lead, copper, the acid agricultural land soil of zinc pollution.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
The raw material sources that embodiment uses are as follows: zeolite (Shuan Long Yuhang, Ningbo branch company), and lime stone is (wide
Zhou Zhen prestige Chemical Industry Science Co., Ltd), ground phosphate rock (Yunnan Yi Pu biological fertilizer Co., Ltd), mushroom residue is (wide
Dong Xuneng bio tech ltd)；Calcium magnesium phosphate (Xijiang River, Guangxi Chemical Co., Ltd., available phosphorus content
>=14%).
Comparative example 1
The test of comparative example 1 is carried out in solarium of Environmental Science and Engineering system of Agricultural University Of South China, pot experiment soil
Earth takes from 0～20cm agricultural land soil, the wherein heavy metal in new Jiang Zhen Shang Ba village, Wengyuan County, Shaoguan City of Guangdong Province
Pb, Cd, Cu and Zn exceed country's standard of soil environment quality (GB15618-1995).Every basin dress soil
2.8kg, applying the mixing modifying agent of 25.2g, i.e. amount of application is 9g/kg soil, is converted into field rate and (takes
Soil weight 1.30g/cm3, top layer height 0.15m): 1.30*0.15*667*9=1170kg/ mu, Qi Zhongshi
The mass ratio of lime stone, zeolite and ground phosphate rock is 2:4:3.Non-nitrogen fertilizer application in whole improved, process.
Measure the soil pH value after applying modifying agent.In the case of finding to apply fertilizer, apply modifying agent
Rear 80d and 200d, soil pH is respectively 6.00 and 6.01, without significant change.Illustrate not apply any
During fertilizer, the improved effect of soil is not significantly altered in short-term (200d).
Comparative example 2
The test pre-treatment of this comparative example is with comparative example 1, but Nitrogen Top Dressing after applying modifying agent one-year age,
As the contrast test with calcium magnesium phosphate, nitrogenous fertilizer uses urea, and amount of application is 0.84g, by urea with 1:200
Ratio be dissolved in distilled water add potted plant in.Measure the soil pH value after applying modifying agent, and determine soil
The bio-available Zn concentration of copper, cadmium, lead, zinc in earth.It is provided with the comparison being not added with modifying agent and nitrogenous fertilizer simultaneously
(CK), result is as shown in table 1:
Table 1 applies soil pH value and heavy metal bio-available Zn concentration (mg/kg soil) after urea
From the result of the test of comparative example 2 it can be seen that after the long period (500d), even if adding
Nitrogenous fertilizer, soil pH value still significantly reduces, and heavy metal in soil bio-available Zn concentration significantly improves, and illustrates changing
After good dose, Nitrogen Top Dressing (urea) can not play the effect maintaining acidic multimetallic improvement of contaminated soil effect.
Embodiment 1
The present embodiment test is carried out in solarium of Environmental Science and Engineering system of Agricultural University Of South China, and potted plant soil is taken from
0～the 20cm agricultural land soil in new Jiang Zhen Shang Ba village, Wengyuan County, Shaoguan City of Guangdong Province, wherein heavy metal Pb, Cd,
Cu and Zn exceedes country's standard of soil environment quality (GB15618-1995).Every basin dress soil 2.8kg, executes
Adding 36.4g mixing modifying agent, i.e. amount of application is 13g/kg soil, is converted into field rate and (takes the soil weight
1.30g/cm3, top layer height 0.15m): 1.30*0.15*667*13=1690kg/ mu.The wherein group of modifying agent
Become lime stone, zeolite, ground phosphate rock and mushroom residue, the quality of lime stone, zeolite, ground phosphate rock and mushroom residue
Ratio is 2:4:3:4.After modifying agent and soil fully mix, add deionized water to the 60% of field capacity,
Fully balance under room temperature, and carry out potted plant experiment with Lettuce for test plant, with by measuring weight in plant
Tenor, verifies the improved effect of soil further.It is provided with simultaneously and is not added with modifying agent and fertilizer
Control group (CK).
Apply modifying agent on January 20th, 2015, after fully balancing, plant 2 batches of Lettuces.First
Stubble was sowed on March 12nd, 2015, gathered in the crops on May 18th, 2015.Fill basin after loosening the soil, and apply
Calcium magnesium phosphate (applies the after-applied calcium magnesium phosphate of modifying agent 300d), and amount of application is that 5.6g is (in i.e. actual application
Consumption 260kg/ mu, the same modifying agent of computational methods).Water water balance 3 weeks, move on December 14th, 2015
Seed plants second batch of Lettuce, gathers in the crops plant on January 20th, 2016.
During plant growth, add distilled water according to its growth needs from flowerpot bottom tray, to keep soil
Humidity.After plant maturation, results plant sample (edible portion) and pedotheque.Measure heavy metal in plant
Content, and apply the soil pH value of modifying agent 100d and 360d, heavy metal bio-available Zn concentration, result
As shown in table 2, table 3.
Table 2 applies Lettuce overground part content of beary metal change (mg/kg fresh weight meter) before and after calcium magnesium phosphate
Table 3 applies soil pH value and heavy metal bio-available Zn concentration (mg/kg soil) before and after calcium magnesium phosphate
Embodiment 2
The present embodiment test Dabaoshan Mine contaminant water in new Jiang Zhen Shang Ba village, Wengyuan County, Shaoguan City of Guangdong Province
The downstream area in territory is carried out, and wherein heavy metal Pb, Cd, Cu and Zn exceed country's soil environment quality mark
Accurate (GB15618-1995).Experiment field is divided into 6 district's groups, the field of each district 3 1m × 2m of component
Block, has 18 little fields, line-spacing 30cm between field.After digging in soil, dig the ditch between field
Gully, is piled into the field of 15cm thickness.On May 20th, 2014 applies modifying agent and carries out soil improvement.
Wherein modifying agent is provided with 3 process: zeolite+lime stone+ground phosphate rock (processing A) (executing of each field
Dosage is 3.51kg, i.e. amount of application 1170kg/ mu, and wherein the mass ratio of lime stone, zeolite and ground phosphate rock is
2:4:3), zeolite+lime stone+ground phosphate rock+mushroom residue (process B) (each field applied amount is 5.07kg,
I.e. amount of application 1690kg/ mu, wherein the mass ratio of lime stone, zeolite, ground phosphate rock and mushroom residue is 2:4:3:4),
Do not improve soil comparison (CK), process and carry out according to RANDOMIZED BLOCK DESIGN, 6 blocks of soils of each process group, with
The operation of sample, test result is averaged.
Test plant is Lettuce, sows on March 20th, 2015, on May 22nd, 2015 results the
One batch of Lettuce.After applying modifying agent 540d, imposing calcium magnesium phosphate, amount of application is 260kg/667m2,
Mix with the topsoil of top layer 15cm.Sow on November 27th, 2015, in 2016 3
The moon 1 gathered in the crops second batch of Lettuce.After crop grows up to, results plant sample and pedotheque, mensuration is planted
Content of beary metal and soil pH value, heavy metal bio-available Zn concentration in thing, result is as shown in table 4 below and table 5:
Table 4 applies soil pH value and heavy metal bio-available Zn concentration (mg/kg soil) after calcium magnesium phosphate
Table 5 applies Lettuce overground part content of beary metal change (mg/kg fresh weight meter) before and after calcium magnesium phosphate
In table, "-" represents Plant death, it is impossible to be measured.
It can be seen that apply calcium magnesium phosphate can make the pH value in soil from embodiment 1 and embodiment 2
Maintain a long-term stability state, and the heavy metal bio-available Zn concentration in soil is basically unchanged even lower, simultaneously can
Significantly decrease phytotoxicity and the plant availability of Cadmium in Soil, lead, copper and zinc for a long time.Illustrate to apply calcium
The method of magnesium-phosphorus fertilizer has remarkable effect to maintenance acidic multimetallic improvement of contaminated soil effect.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality
Execute the restriction of example, the change made under other any Spirit Essence without departing from the present invention and principle, modification,
Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (7)
1. the method maintaining acidic multimetallic contaminated soil in-situ chemical improved effect, it is characterised in that
Mainly comprise the steps that
(1) applying of soil conditioner: the raw material in soil conditioner is pulverized, sieved, is prepared as agriculture
The powder of industry level, separately deposits, and mixes before using, then the modifying agent after mixing and top layer
The topsoil of 15cm mixes；
(2) after soil conditioner applies 300～540d, calcium magnesium phosphate is applied, with the soil of top layer 15cm
Earth is sufficiently mixed uniformly.
Method the most according to claim 1, it is characterised in that: the modifying agent described in step (1)
For lime stone, zeolite, the mixture of ground phosphate rock, or it is lime stone, zeolite, ground phosphate rock and mushroom residue
Mixture.
Method the most according to claim 2, it is characterised in that: when the improvement described in step (1)
When agent is the mixture of lime stone, zeolite, ground phosphate rock, the quality of described lime stone, zeolite and ground phosphate rock
Ratio is 20～30:30～40:30～50.
Method the most according to claim 2, it is characterised in that: when the improvement described in step (1)
When agent is the mixture of lime stone, zeolite, ground phosphate rock and mushroom residue, described lime stone, zeolite, phosphorus ore
The mass ratio of powder and mushroom residue is 15～20:25～35:20～25:25～35.
Method the most according to claim 1, it is characterised in that: modifying agent used in step (1)
Consumption be 1100～1700kg/ mus.
Method the most according to claim 1, it is characterised in that: sieving described in step (1) is
Referred to the hole sizer of 100 mesh.
Method the most according to claim 1, it is characterised in that: calcium and magnesium phosphorus used in step (2)
Fertile applied amount is 260kg/ mu.
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Cited By (5)
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| CN108541522A (en) * | 2018-05-29 | 2018-09-18 | 华南农业大学 | A kind of acidity mining area refuse dump method for recovering vegetation |
| CN109702007A (en) * | 2018-12-27 | 2019-05-03 | 广东开源环境科技有限公司 | A kind of in-situ remediation method for heavy metals in farmland cadmium intermediate pollution |
| CN109913233A (en) * | 2019-04-28 | 2019-06-21 | 湖南省地球物理地球化学勘查院 | A kind of water paddy soil heavy metal passivation modifying agent |
| CN110423624A (en) * | 2019-09-03 | 2019-11-08 | 森特士兴集团股份有限公司 | A kind of stabilization renovation agent of soil pollution and preparation and application |
| CN116948654A (en) * | 2023-07-28 | 2023-10-27 | 中国农业大学 | Acid soil conditioner based on calcium-magnesium supplement and application thereof |
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| CN108541522A (en) * | 2018-05-29 | 2018-09-18 | 华南农业大学 | A kind of acidity mining area refuse dump method for recovering vegetation |
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| CN116948654A (en) * | 2023-07-28 | 2023-10-27 | 中国农业大学 | Acid soil conditioner based on calcium-magnesium supplement and application thereof |
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