CN108031706A - For rehabilitating soil Cd contaminated soils modifying agent and its application - Google Patents
For rehabilitating soil Cd contaminated soils modifying agent and its application Download PDFInfo
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- CN108031706A CN108031706A CN201711093771.XA CN201711093771A CN108031706A CN 108031706 A CN108031706 A CN 108031706A CN 201711093771 A CN201711093771 A CN 201711093771A CN 108031706 A CN108031706 A CN 108031706A
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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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- 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
- C09K17/06—Calcium compounds, e.g. lime
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The present invention relates to soil pollution improvement and the technical field of repairing and treating, and specifically, the invention discloses one kind to be used for rehabilitating soil Cd contaminated soil modifying agents, it is made of the component of following weight content:45~49% lime, 45~49% zeolite, 4~6% perphosphate and 0.8~1.2% biomass carbon.The present invention further simultaneously discloses the above-mentioned application process for rehabilitating soil Cd contaminated soil modifying agents:Uniformly it is manured into soil, additive amount 1.25kgm‑2~5kgm‑2.In heavy Cd contamination soil, the bio-available Zn concentration of Cd in soil can be effectively reduced using the modifying agent, reduces the content of cadmium in Brown Rice, while rice yield can be improved, reaches the grain sanitary standard of national regulation.
Description
Technical field
The present invention relates to the improvement of soil pollution and the technical field of repairing and treating, and in particular in heavy metal pollution of soil
Cd pollution improvement and repairing and treating.
Background technology
With the progress of modern society, cadmium is used widely in nuclear industry, battery industry, Electroplating Operations, Plastics Industry etc., is led to
Cross atmospheric sedimentation and human production activity enter soil so that Cd Pollution in Soil increasingly become one it is serious the problem of.Cadmium at the same time
It is the extremely strong pollution element of kind of toxicity, serious harm is respectively provided with to human body and animals and plants, it is with stronger mobility and biology
Enriching.China's Cd Pollution in Soil situation allows of no optimist, 2014《National Soil Pollution Investigation publication》Show cadmium pollution
Object point position exceeding standard rate reaches 7.0%.From Japan's the 1980s Itai-itai diseases caused by cadmium wastewater irrigated farmland, to 2013
Hunan " cadmium rice " event in year, the cadmium pollution event occurred again and again, sounds the alarm for food-safety problem.
For the improvement of cadmium pollution soil, soil conditioner is considered as a kind of relatively inexpensive, convenient soil remediation side
Method.Soil conditioner is generally divided into natural amendments, synthesis modifying agent, natural-synthetic copolymer modifying agent, life by raw material sources
Four major class of thing modifying agent, the utilization of wherein natural amendments are relatively broad.Common natural amendments have lime, zeolite, biology
Matter charcoal, bentonite, vermiculite, peat etc..Finding fertilising at the same time, there are certain influence, numerous studies to show calcium to plant absorption cadmium
Magnesium phosphorus, calcium monohydrogen phosphate and potassium dihydrogen phosphate add soil, raise soil pH value, so as to reduce the biological effectiveness of cadmium;It is and right
The report that the validity of heavy metal-polluted soil is reduced in perphosphate is less.Because easily there is soil quality using single soil conditioner
The situation of degeneration, present soil conditioner is more using two or more modifying agent hybrid combining use or modifying agent and fertilizer
Material is used cooperatively.Have been reported that using the conversion of natural zeolite and lime research to soil Cd species, find lime (Ca (OH)2)
The combined effect of 2g/kg soil and zeolite (70% clinoptilolite) 60g/kg soil is best, can decline exchange state cadmium content in soil
34.68%.
The content of the invention
It is used for rehabilitating soil Cd contaminated soils modifying agent the technical problem to be solved in the present invention is to provide one kind and its answers
With.
In order to solve the above technical problem, the present invention provides one kind to be used for rehabilitating soil Cd contaminated soil modifying agents, its
It is made of the component of following weight content:45~49% lime, 45~49% zeolite, 4~6% perphosphate and 0.8
~1.2% biomass carbon.
As the present invention the improvement for rehabilitating soil Cd contaminated soil modifying agents, its by following weight content into
It is grouped into:47% lime, 47% zeolite, 5% perphosphate and 1% biomass carbon.
The improvement for rehabilitating soil Cd contaminated soil modifying agents as the present invention:The perphosphate is particulate form
Calcium superphosphate, lime are powdered calcium oxide, and zeolite is powdered artificial zeolite, and biomass carbon is bamboo in anaerobic closed container
In be heated to 600 ± 50 DEG C heat treatment 2 it is small when prepare gained.
The present invention also provides the above-mentioned application process for rehabilitating soil Cd contaminated soil modifying agents at the same time:Uniformly apply
Enter soil (making modifying agent be uniformly mixed with soil by farming technique), additive amount 1.25kgm-2~5kgm-2(by soil
Earth weight ratio is equivalent to 0.5%~2%).
The further of the application process for rehabilitating soil Cd contaminated soil modifying agents as the present invention is improved:It is preferred that
Additive amount is 1.25kgm-2、2.5kg·m-2(by soil weight ratio equivalent to 0.5%, 1%).
The present invention in actual use, applies in Cd contaminated soils by each component of modifying agent after mixing, abundant with soil
Mixing.In the present invention, lime, zeolite and perphosphate etc. can be obtained by conventional form purchased in market.
In the present invention:Lime component can improve soil pH in modifying agent of the present invention, improve acid soil, reduce heavy metal
The validity of Cd;Zeolite, which has, preserves moisture, adsorbs the ability of heavy metal in soil.Biomass carbon equally has in reduction soil
The ability of the available state of heavy metal.Perphosphate in modifying agent is a kind of fertilizer at the same time, is reducing the effective of heavy metal-polluted soil
While state, P can be provided for plant, improve the biomass of plant.Modifying agent low in raw material price in the present invention is suitable wide
General popularization.The present invention can effectively reduce the bio-available Zn concentration of Cd in soil using the modifying agent in heavy Cd contamination soil, drop
The content of cadmium in low Brown Rice, while rice yield can be improved, reach the grain sanitary standard of national regulation.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the change comparison diagram of water-saving irrigntion soil pH during 90 days;
Fig. 2 is the change comparison diagram of water-saving irrigntion soil exchange state Cd during 90 days;
Fig. 3 is influence comparison diagram of the modifying agent to exchange state Cd in soil during paddy growth;
Fig. 4 is the full cadmium content comparison diagram in each position of rice.
Embodiment
Below in conjunction with specific embodiment, the present invention is furture elucidated.Involved method in following embodiments, such as without especially
Explanation is conventional method, and set raw material is marketable material unless otherwise instructed.
Embodiment 1, it is a kind of be used for rehabilitating soil Cd contaminated soil modifying agents, it is by following weight content into packet
Into:47% lime, 47% zeolite, 5% perphosphate and 1% biomass carbon.
The perphosphate is particulate form calcium superphosphate;Lime is powdered calcium oxide;Zeolite is powdered artificial zeolite;
The preparation method of biomass carbon is:Bamboo is put into anaerobic closed container be heated to 600 DEG C heat treatment 2 it is small when, obtain biomass
Charcoal.
Experiment 1, a kind of modifying agent are used for the water-saving irrigntion of Cd Pollution in Soil
Improved experimental and in June, 2016~2016 year November are in area of Zijingang Campus of Zhejiang of Hangzhou, Zhejiang province city laboratory
Carry out.For examination soil to be derived from Hangzhou, Zhejiang province city West Zone of Zijingang Campus of Zhejiang University rice terrace, which is 6.52,
Full cadmium 0.02mgkg-1.Using culture experiment, often cultivate bucket and air-dry rice soil 0.5kg, with CdSO4The form addition Cd of solution
20mg·kg-1Soil, is uniformly mixed, and adjusts soil moisture content to 60% field capacity, stabilizes one week.0 is set (not add respectively
Add soil conditioner, CK), 0.5%, 1%, 2%, 4%, 10% modifying agent additive amount it is horizontal.Modifying agent is added, is uniformly mixed
Afterwards, enough deionized waters are added in each Duplicate Samples to be made water submerged soil surface and surface water layer is reached 1-2cm, room temperature training
Support, weight method moisturizing is used in incubation.
Note:By arable layer 20cm, soil weight 1.25t/m3Calculate, above-mentioned 0.5%, 1%, 2%, 4%, 10% adds
Dosage is respectively 1.25kgm-2、2.5kg·m-2、5kg·m-2、10kg·m-2And 25kgm-2。
Experimental result:Modifying agent of the present invention adds Cd contaminated soils, significantly raises soil pH value, and the amount of modifying agent addition
Bigger, the value that soil pH value rises is bigger (Fig. 1).Water-saving irrigntion the 1st day, modifying agent additive amount are 10% and 4% processing pH value
12.22 and 11.96 are risen to respectively, compared with CK, when improvement dosage is added to 10%, 4%, 2%, 1% and 0.5%, soil
PH value rises 5.24,4.98,4.22,2.49 and 1.51 successively.After culture 90 days, each pH value that handles has slow decline, changes
Good dose of additive amount declines maximum for 2%, have dropped 1.18, secondly modifying agent additive amount is 4%, have dropped 0.97.
Modifying agent of the present invention adds Cd contaminated soils, can significantly reduce exchange state Cd contents (Fig. 2) in soil.Culture 90
My god, compared with CK, modifying agent additive amount in turn reduces 98.77% for 10%, 4%, 2%, 1% and 0.5% exchange state Cd,
98.03%th, 98.13%, 89.49% and 75.55%.During culture 90 days, modifying agent additive amount reduces width for 1% exchange state Cd
Degree is maximum, reduces 80.25%, secondly 0.5%, reduce 80.25%.
From the above results, modifying agent additive amount can significantly reduce exchangeability Cd contents in soil for 10% and 4%, but
It, which easily increases soil pH value, makes plant be not easy to survive, and is unsuitable for actual popularization and application.
To find modifying agent additive amount, i.e. the most appropriate bioavailability for not only having reduced soil Cd but also ensure crops
The additive amount of normal growth, inventor have carried out the rice pot experiment described in following experiment 2.
Experiment 2, application of the modifying agent of the present invention on Cd contaminated soils
1st, experimental conditions
Improved experimental in March, 2017~2017 year July Hangzhou, Zhejiang province city area of Zijingang Campus of Zhejiang greenhouse into
OK.It is the rice soil that is derived from Ningbo City, Zhejiang Province Heng Xi towns for examination soil, experimental planting crop:Rice (kind name:Mound two is excellent
7717)。
Table 1, the physicochemical character for trying soil
Using potted plant experiment.Per basin, dress soil 3kg, artificially adds cadmium sulfate solution, adjusts to soil Cd 10mgkg-1Soil,
It is uniformly mixed, stablizes 2 weeks.Add modifying agent dosage and be used as experimental group for 0 (CK), 0.5%, 1%, 2%, while one group of setting is complete
Full blank (CK0) is not added with Cd pollutions and modifying agent.It is repeated 3 times.After adding modifying agent by Different adding amount, it is uniformly mixed, adds
Enter deionized water to flooding soil surface and reach water layer 1cm or so, water-saving irrigntion transplanted paddy rice seedling after 1 month.Rice transplantation
Base manure is applied within first 7 days, base manure dosage is that urea (N 46%) 0.77g, calcium superphosphate (P are added per basin2O512%) 1.84g and chlorine
Change potassium (K2O 60%) 0.31g.Per the rice seedlings of the seedling age 30 days of pot transplanting 4 or so.Apply urine per basin in rice tillering early period
Plain 0.39g, and panicle primordium dif ferentiation stage apply urea 0.39g and potassium chloride 0.31g top dressings per basin.Rice whole growth period keeps water layer
1-2cm, deionized water are poured.Throughout the growing season other management are consistent with field.
2nd, result and analysis
2.1st, the influence of growth and development and yield of the different disposal to rice
Rice was transplanted in basin on April 24th, 2017, and the rice of 2% processing and other processing is found during paddy growth
Seedling is short and small, thin and weak compared to plant.Rice transplantation harvests after 93 days.
Table 2 is the Biomass and yield of rice after rice harves, and compared with CK0 and CK, modifying agent additive amount reduces for 2%
Plant height, stalk dry weight, yield and the mass of 1000 kernel of rice, modifying agent additive amount for 0.5% and 1% increase rice stalk dry weight and
Yield.
The Biomass and yield of table 2, different disposal rice
Note:The different letter of same row represents between managing everywhere the significant difference under 5% level.
Influence of 2.2 different disposals to the full cadmium content of soil exchange state cadmium and each position of rice
As shown in figure 3, compared with CK, modifying agent is added, the exchangeability Cd contents in soil significantly reduce, and in rice
Throughout the growing season, the content of exchange state Cd is below 0.1mgkg in soil-1。
Found by the measure (Fig. 4) of full cadmium content in the root, stalk, brown rice to rice, the full cadmium in each position of rice contains
Amount is followed successively by:Root>Stalk>Brown rice.The additive amount of different modifying agents is to full Cd content sequences in rice straw and brown rice:CK>
0.5%>1%>2%.According to《GB2762-2012 pollutants in food is limited the quantity》Middle regulation, the limitation of Cd is 0.2mg in brown rice
kg-1, full cadmium content is all higher than national standard in the Brown Rice of this experiment addition modifying agent, but compared with CK, present invention improvement
Agent additive amount is that full Cd reduces by 78.61%, 82.63% and 89.25% successively in 0.5%, 1% and 2% Brown Rice, the present invention
It is significant that modifying agent, which reduces Cd content effects in Brown Rice,.
In summary understand, when modifying agent additive amount of the present invention is 0.5% and 1%, Cd in brown rice can be significantly reduced and contained
Amount, and the yield of rice can be increased.Test at the same time has good passivation using modifying agent of the present invention to exchangeability Cd in soil
Effect, significantly reduces Cd contents in Brown Rice, can reduce the risk of the food security of farming Cd contaminated soils.
Comparative example 1-1, the use for cancelling biomass carbon, i.e. soil conditioner is made of the component of following weight content:
47% lime, 47% zeolite, 6% perphosphate, remaining is equal to embodiment 1.
Comparative example 1-2, soil conditioner are made of the component of following weight content:45% lime, 45% zeolite,
5% perphosphate and 5% biomass carbon, remaining is equal to embodiment 1.
Comparative example 2, soil conditioner are made of the component of following weight content:42% lime, 52% zeolite, 5%
Perphosphate and 1% biomass carbon, remaining is equal to embodiment 1.
Comparative example 3-1, make perphosphate into calcium monohydrogen phosphate;Content is constant;Remaining is equal to embodiment 1.
Comparative example 3-2, make perphosphate into potassium dihydrogen phosphate;Content is constant;Remaining is equal to embodiment 1.
Contrast experiment:Above-mentioned all comparative examples are detected according to above-mentioned 2 the method for experiment, soil conditioner adds
Dosage is 0.5%;Result during rice harves is described in table 3 below.
Table 3, each comparative example than rice Biomass and yield
Finally, it should also be noted that it is listed above be only the present invention several specific embodiments.Obviously, this hair
It is bright to be not limited to above example, there can also be many deformations.Those of ordinary skill in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (5)
1. it is used for rehabilitating soil Cd contaminated soil modifying agents, it is characterised in that be made of the component of following weight content:45~
49% lime, 45~49% zeolite, 4~6% perphosphate and 0.8~1.2% biomass carbon.
2. according to claim 1 be used for rehabilitating soil Cd contaminated soil modifying agents, it is characterised in that by following weight
The component composition of content:47% lime, 47% zeolite, 5% perphosphate and 1% biomass carbon.
3. according to claim 1 or 2 be used for rehabilitating soil Cd contaminated soil modifying agents, it is characterised in that:
The perphosphate is particulate form calcium superphosphate, and lime is powdered calcium oxide, and zeolite is powdered artificial zeolite, biology
Matter charcoal is heated to preparing gained when 600 ± 50 DEG C of heat treatments 2 are small for bamboo in anaerobic closed container.
4. the application process for rehabilitating soil Cd contaminated soil modifying agents as described in claims 1 to 3 is any, its feature
It is:Uniformly it is manured into soil, additive amount 1.25kgm-2~5kgm-2。
5. the application process according to claim 4 for rehabilitating soil Cd contaminated soil modifying agents, it is characterised in that:
Additive amount is 1.25kgm-2、2.5kg·m-2。
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Cited By (8)
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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 |
CN110157447A (en) * | 2019-05-22 | 2019-08-23 | 辽宁工程技术大学 | A kind of dust storm soil conditioner and preparation method thereof and application method |
CN111303893A (en) * | 2020-03-27 | 2020-06-19 | 重庆市环境保护工程设计研究院有限公司 | Composite passivator for reducing soil available cadmium and compound optimization method |
CN111518567A (en) * | 2020-04-25 | 2020-08-11 | 浙江大学 | Cadmium-enriched microbial strengthening method for hyperaccumulator plants and composite suspension used in method |
CN111778039A (en) * | 2020-08-12 | 2020-10-16 | 浙江省地质调查院 | Preparation of calcined biochar type conditioner and application method of conditioner |
CN112266792A (en) * | 2020-10-22 | 2021-01-26 | 江西省地质工程(集团)公司 | Heavy metal contaminated soil composite passivator and preparation method thereof |
US10918024B2 (en) * | 2018-07-24 | 2021-02-16 | Guangdong Institute Of Eco-Environmental China Science & Technology | Method for safe production of rice soil mildly and moderately polluted by heavy metals |
CN112980453A (en) * | 2021-02-27 | 2021-06-18 | 广州绿邦环境技术有限公司 | Soil restoration and improvement agent and production process |
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US10918024B2 (en) * | 2018-07-24 | 2021-02-16 | Guangdong Institute Of Eco-Environmental China Science & Technology | Method for safe production of rice soil mildly and moderately polluted by heavy metals |
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CN110157447A (en) * | 2019-05-22 | 2019-08-23 | 辽宁工程技术大学 | A kind of dust storm soil conditioner and preparation method thereof and application method |
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CN111518567B (en) * | 2020-04-25 | 2021-02-09 | 浙江大学 | Cadmium-enriched microbial strengthening method for hyperaccumulator plants and composite suspension used in method |
CN111778039A (en) * | 2020-08-12 | 2020-10-16 | 浙江省地质调查院 | Preparation of calcined biochar type conditioner and application method of conditioner |
CN112266792A (en) * | 2020-10-22 | 2021-01-26 | 江西省地质工程(集团)公司 | Heavy metal contaminated soil composite passivator and preparation method thereof |
CN112980453A (en) * | 2021-02-27 | 2021-06-18 | 广州绿邦环境技术有限公司 | Soil restoration and improvement agent and production process |
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