CN106825026A - A kind of method that modified biomass charcoal and its resistance control heavy metal are accumulated in vegetables body - Google Patents

A kind of method that modified biomass charcoal and its resistance control heavy metal are accumulated in vegetables body Download PDF

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Publication number
CN106825026A
CN106825026A CN201710041203.9A CN201710041203A CN106825026A CN 106825026 A CN106825026 A CN 106825026A CN 201710041203 A CN201710041203 A CN 201710041203A CN 106825026 A CN106825026 A CN 106825026A
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China
Prior art keywords
biomass charcoal
vegetables
modified biomass
soil
heavy metal
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Pending
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CN201710041203.9A
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Chinese (zh)
Inventor
汪宜敏
徐兰
袁旭音
刘情
唐豆豆
张晓辉
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Hohai University HHU
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Hohai University HHU
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Priority to CN201710041203.9A priority Critical patent/CN106825026A/en
Publication of CN106825026A publication Critical patent/CN106825026A/en
Pending legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G22/00—Cultivation of specific crops or plants not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Abstract

The invention discloses a kind of method that modified biomass charcoal and its resistance control heavy metal are accumulated in vegetables body, a kind of to prepare the natural minerals modified biomass charcoal that pH value is 78 by dissolving concussion ultrasonic pyrolysis process, the wherein mass ratio of hydroxyapatite and biomass carbon is 0.5 5:1.It is on mild or moderate heavy-metal contaminated soil, this modified biomass charcoal is after-applied in rhizosphere soil for a period of time in vegetable growth by certain mass fraction, the enrichment of vegetables edible portion heavy metal can be effectively reduced, increase the content of N, P in blade.Environment-friendly, low cost of the invention, non-secondary pollution is workable, and can improve soil and vegetables quality while heavy metal plant interior accumulation is reduced.

Description

A kind of method that modified biomass charcoal and its resistance control heavy metal are accumulated in vegetables body
Technical field
The present invention relates to a kind of modified biomass charcoal, and in particular to a kind of modified biomass charcoal and its resistance control heavy metal are in vegetable The method of accumulation in dish body.
Background technology
2014《National Soil Pollution Investigation publication》It has been shown that, the total super punctuation bit of China's soil pollution is 16.1%, the point position exceeding standard rate of wherein arable soil is up to 19.4%, and major pollutants type is cadmium (Cd), nickel (Ni), copper (Cu), arsenic (As), mercury (Hg), lead (Pb) etc..In recent years, vegetable field soil is because for a long time by sewage irrigation, sludge and containing heavy metal Agrochemical fertilizer the influence such as apply, have become in arable soil that to receive heavy metal contaminants type and quantity more and more collect In soil types.Found when the content of beary metal in the scattered vegetable field soil of In The Suburbs of Nanjing and vegetables is detected, Cd in vegetables, The content of Zn, Pb is higher, and especially the content of Pb, Cd greatly exceed national food hygienic standard.Red Soils in Southern China ground Area's hydrothermal resources is sufficient, and the yield of its grain and vegetables has all accounted for the larger market share.In order to fully ensure the city of vegetables Field supply, the long-term a large amount of fertilizer and pesticides of applying in these areas have had resulted in serious soil heavy metal combined pollution problem.Together When, because red soil rate of decay is high, nutrient content is low, and in highly acid (pH ≈ 4.5), heavy metal contaminants especially have After the Cd of stronger bioconcentration and toxicity enters red soil, its heavy metal activity is higher, and this will increase vegetable plant strain to a huge sum of money The absorption of category and the risk into food chain.Display is calculated according to the per day food consumption result of China resident, in these vegetables Heavy metal element can bring health risk, the health risk that Cd causes more to be up to 42.17% to eater.As can be seen here, We are necessary to carry out the repairing and treating work of heavy metal on red soil vegetable plot, and then reduce its Ecological Environment Risk.
At present, China's arable soil heavy metals exceeding standard point position is mainly based on middle low heavy metal pollution.Therefore, it is real The double goal that existing agriculture normal production and heavy metal-polluted soil are repaired, we should be taken to addition modifying agent in soil (also known as blunt Agent) by heavy metal to low dissolving, by fixed, low toxicity Forms Transformation, reduce enrichment of the heavy metal in plant body, reach guarantor While barrier agricultural production, the purpose of polluted heavy metals environmental risk is reduced.
At present, widely used soil passivation renovation agent mainly includes inorganic passivant and the major class of organic passivation agent two.Its In, phosphate compound such as hydroxyapatite (hydroxyapatite, abbreviation HAP) is the relatively broad passivation of current application Renovation agent.Hu Tiantian (repairing research [D] the Anhui agricultures of Hu Tiantian nanometer hydroxyapatites heavy metal coppers and lead-contaminated soil Sparetime university is learned, and 2012.) confirm that micron order HAP can effectively reduce exchangeable species and carbonate in soil by cell field test With reference to the content of state Cu, the Ecological Environment Risk of Cu is reduced.And outside inorganic passivant, numerous studies find organic passivation agent Such as the agricultural land soil of charcoal centering minuent heavy metal pollution, it may have good ecological passivation repairing effect；Ensureing agricultural production While product yield and quality, the utilization of the resource recyclings such as a large amount of forest and agricultural biomass, livestock waste is realized.Can especially drop The biological effectiveness of heavy metal on low acid red soil of south China.Additionally, the biological substantial amounts of inorganic ions of carbon surface such as Na, Ca, Mg, P Etc. the important sources for being charcoal alkalescence and nutrient.
Although increasing research and patent have begun to pay close attention to the reparation of HAP and charcoal to heavy metal pollution of soil Ability, but less someone studies the repair ability and a huge sum of money in reduction vegetables body after two kinds of optimization of material are combined to heavy metal-polluted soil Category enrichment, the ability for improving quality of vegetable.
The content of the invention
To solve the deficiencies in the prior art, it is an object of the invention to provide a kind of modified biomass charcoal and its a resistance control huge sum of money Belong to the method accumulated in vegetables body.
In order to realize above-mentioned target, the present invention is adopted the following technical scheme that：
A kind of modified biomass charcoal, including mass ratio is 0.5-5:1 hydroxyapatite and biomass carbon.
Above-mentioned hydroxyapatite is micron order.
Above-mentioned biomass carbon is cornstalk biological matter charcoal or pine needle biomass carbon.
A kind of preparation method of above-mentioned modified biomass charcoal, comprises the following steps：
A1, dissolving：It is soluble in water after mixing biomass charcoal and hydroxyapatite by certain mass ratio；
A2, concussion：The above-mentioned aqueous solution is put into after shaking a period of time in isothermal vibration case, adjusts pH value；
A3, ultrasound：After being continuing with microwave ultrasound for a period of time, dry, grind sieving, modified biomass charcoal is obtained.
The method accumulated in vegetables body using a kind of above-mentioned modified biomass charcoal resistance control heavy metal, will germinate one section when Between after vegetable seedling be planted in flowerpot with including the training method of the root bag of heavy-metal contaminated soil, in one section of vegetable growth Modified biomass charcoal is mixed with soil in certain mass percent and root bag after time, vegetable is harvested after a period of time is cultivated Dish.
Above-mentioned modified biomass charcoal is the 2-8% of the quality of soil in root bag.
Above-mentioned vegetable seedling germinating time is 5d, and growth time is 10d, and incubation time is 40d.
Above-mentioned bag is cylinder, diameter d=8.3cm, height h=10cm；The diameter d=31cm, h=high of flowerpot 11cm。
Above-mentioned vegetables include Lettuce, spinach.
The present invention is advantageous in that：The modified biomass carbon material of natural minerals can significantly improve Cd pollution red soil The pH value and the content of organic matter of upper plant rhizosphere soil, reduce the bioavailability of Cd in rhizosphere soil, reduce Cd in vegetables Accumulation in the edible portion of ground, increases N, the content of P element in vegetable leaf, ensures the security of vegetables, improves vegetables Quality, cost is relatively low and is not likely to produce secondary pollution.
Environment-friendly, low cost of the invention, non-secondary pollution is workable, and can reduce heavy metal plant While interior accumulation, improve soil and vegetables quality, with very strong practicality and wide applicability.
Brief description of the drawings
Fig. 1 is the structural representation of vegetable cultivation of the invention.
Fig. 2 is the SEM scanning figures of modified corn biomass carbon of the invention.
Fig. 3 is that modified biomass charcoal of the invention applies to Cd fractionation Software quality in rhizosphere red soil.
Fig. 4 is influence figure of the modified biomass charcoal of the invention to Accumulation of heavy metals in Lettuce on cadmium pollution red soil.
The implication marked in accompanying drawing is as follows：1st, vegetables, 2, root bag, 3, flowerpot.
Specific embodiment
Make specific introduction to the present invention below in conjunction with the drawings and specific embodiments.
Biomass carbon raw material is maize straw, is prepared in Liyang City Desheng activated carbon factory, 350-500 DEG C under anoxic conditions After pyrolysis 4-6h, ground after natural cooling stand-by.Use the mesh sieve of preceding mistake 100 (particle diameter is less than 0.15mm).The basic reason of charcoal Changing property is：PH=10.45, organic carbon content is 500.67g/kg, and the mass fraction of charcoal C, H, O element is respectively 64.77%th, 1.05% and 15.9%, after tested total cadmium content be below detection line.
Hydroxyapatite is purchased from Nanjing Ai Purui companies, and micron order is spherical, particle diameter<12μm.
Contaminated soil picks up from Anhui, is cadmium pollution red soil, and sample level is top layer 0-20cm.Pedotheque through natural air drying, Ground 60 mesh sieve is standby, and the soil is mainly strongly acidic soil, and pH is 4.45 ± 0.122 (mean+SDs)；It is organic Carbon content scope is in 1.69gkg-1Left and right；Cation exchange capacity (CEC) CEC is 15.9cmolkg-1；Cd pollution concentrations are respectively 0, 1、2.5、5mg/kg。
A kind of preparation method of modified biomass charcoal, comprises the following steps：
A1, by 2.5:1 mass ratio, it is soluble in water after hydroxyapatite is mixed with biomass carbon；
A2, the above-mentioned aqueous solution is put into isothermal vibration case, with 300rpm/min, 12-24h is shaken under 25 DEG C of constant temperature, Adjust pH value of solution to 7-8；
A3, be continuing with microwave ultrasound 1h after, drying, milled 60 mesh sieve at 250 DEG C are obtained modified biomass charcoal.
The method accumulated in the body of vegetables 1 using a kind of above-mentioned modified biomass charcoal resistance control heavy metal, will germinate 5d's Lettuce seedling is put into the flowerpot 3 equipped with gross weight 2.5kg heavy-metal contaminated soils, and the centre position of flowerpot 3 is placed with a circle Cylindricality root bag 2 simultaneously fills the contaminated soil of 0.2kg, and seedling grows in root bag 2, by modification biological after Lettuce growth 10d Matter charcoal is mixed with soil in 3% mass percent and root bag 2, is further cultured for the underground and aboveground of results Lettuce after 40d. Each treatment is lower to set three repetitions.
The diameter d=8.3cm, height h=10cm of root bag 2；The diameter d=31cm, h=11cm high of flowerpot 3.
Before vegetables 1 are cultivated, to adding 0.4gkg in basin-1Urea and 0.2gkg-1Dipotassium hydrogen phosphate, there is provided vegetable Nutrient needed for dish 1, regulation soil moisture content is maintained at 60% of field capacity or so.
Interpretation of result：
After vegetables 1 are partly rinsed well through running water above and below the ground, the 10mmol/L of certain volume is respectively put into After soaking 15min in EDTA solution, then rinsed well with deionized water, the dry for standby under the conditions of 75 DEG C.
By the method for BCR grading extractions, the metamorphosis of cadmium in rhizosphere soil is evaluated.Determine the enrichment of Cd in vegetables 1 Amount, the content of N, P in blade.
Modified corn biomass carbon SEM scanning figures as shown in Figure 2.
Micron order hydroxyapatite is combined in the form of particle attachment or chemical bonds with biomass carbon, can be effective Increase biomass carbon surface area and the binding sites with cadmium, the restoring cadmium polluted effect of enhancing biomass carbon material.
Table 1 below is influence of modified biomass carbon particle (BP) applying to the main physical and chemical index of rhizosphere red soil：
Table 1
From table 1, the addition of BP can effectively improve the pH value of red soil rhizosphere soil, the incrementss of pH wherein on red soil It is 2.73 units, can effectively reduces mobility and biological effectiveness of the Cd on red soil.The alkalescence of biomass carbon is main next From the oxygen-containing functional group (such as-COO- ,-OH etc.) and carbonate material that are enriched in its surface, so that the CEC contents of soil are improved, It is especially relatively low in the content of organic matter, become the excellent material of acid soil improvement.At the same time, compared to traditional alkali Property improved materials for, loaded the biomass carbon of hydroxyapatite also containing abundant phosphate, by increasing capacitance it is possible to increase Ca in soil, P content.
Fig. 3 is the influence that modified biomass charcoal applies to change Cd fractionation in rhizosphere red soil, and Fig. 3 (a) does not apply the root of BP Cd is mainly and exists in the form of weak acid extractable and reducible state on the soil of border, has accounted for the 70%- of total Cd contents in soil 80%.The properties such as this and pH value relatively low on red soil, the less content of organic matter are related, so as to cause the biology of Cd on red soil to have Effect property is higher.With addition such as Fig. 3 (b) of 3%BP repair materials, the content of weak acid extractable Cd is significantly reduced in soil, can The content of oxidation state and residual form Cd increases, and shows that the administration of BP reduces the mobility and biological effectiveness of Cd in soil, more The organic matter and phosphate that many Cd are brought into by BP are combined, and are generated the precipitation of Cd or are entered into and are fixed in residual form lattice.
Fig. 4 is influence of the modified biomass charcoal to Accumulation of heavy metals in Lettuce on cadmium pollution red soil, and emphasis shows BP Repair materials apply the influence to cadmium content in Lettuce root and edible portion.
From fig. 4, it can be seen that when soil cadmium concentration is 1.0mgkg-1When, Lettuce edible part in 3%BP repair process groups The content of cadmium is less than《Pollutants in food limitation GB2762-2005》The limit value 0.2mgkg of regulation-1Requirement.All places In reason group, the addition of BP can effectively reduce the Cd accumulation that Lettuce root neutralizes edible portion.
The basic principles, principal features and advantages of the present invention have been shown and described above.The technical staff of the industry should Understand, the invention is not limited in any way for above-described embodiment, it is all to be obtained by the way of equivalent or equivalent transformation Technical scheme, all falls within protection scope of the present invention.

Claims (10)

1. a kind of modified biomass charcoal, it is characterised in that including mass ratio be 0.5-5:1 hydroxyapatite and biomass carbon.
2. a kind of modified biomass charcoal according to claim 1, it is characterised in that the hydroxyapatite is micron order.
3. a kind of modified biomass charcoal according to claim 1, it is characterised in that the biomass carbon is maize straw life Material charcoal or pine needle biomass carbon.
4. according to a kind of preparation method of any described modified biomass charcoals of claim 1-3, it is characterised in that including following Step：
A1, dissolving：It is soluble in water after mixing biomass charcoal and hydroxyapatite by certain mass ratio；
A2, concussion：The above-mentioned aqueous solution is put into after shaking a period of time in isothermal vibration case, adjusts pH value；
A3, ultrasound：After being continuing with microwave ultrasound for a period of time, dry, grind sieving, modified biomass charcoal is obtained.
5. the preparation method of a kind of modified biomass charcoal according to claim 4, it is characterised in that in the step A1 Hydroxyapatite is 0.5-5 with the mass ratio of biomass carbon:1；Concussion frequency in step A2 is 300rpm/min, shakes temperature It is 25 DEG C, the concussion time is 12-24h, and pH value is 7-8,；Ultrasonic time in step A3 is 1h, and drying temperature is 250 DEG C, sieve It is 60 mesh.
6. the side accumulated in vegetables body using a kind of any described modified biomass charcoal resistance control heavy metals of claim 1-3 Method, it is characterised in that by germinate a period of time after vegetable seedling with include heavy-metal contaminated soil root bag training method kind It is implanted in flowerpot, for a period of time afterwards mixes modified biomass charcoal with soil in root bag with certain mass percent in vegetable growth It is even, it is further cultured for harvested vegetable after a period of time.
7. the method that a kind of utilization modified biomass charcoal resistance control heavy metal according to claim 6 is accumulated in vegetables body, Characterized in that, the modified biomass charcoal is the 2-8% of the quality of soil in root bag.
8. the method that a kind of utilization modified biomass charcoal resistance control heavy metal according to claim 6 is accumulated in vegetables body, Characterized in that, the vegetable seedling germinating time is 5d, growth time is 10d, and incubation time is 40d.
9. the method that a kind of utilization modified biomass charcoal resistance control heavy metal according to claim 6 is accumulated in vegetables body, Characterized in that, described bag is cylinder, diameter d=8.3cm, height h=10cm；The diameter d=31cm, h=high of flowerpot 11cm。
10. the method that a kind of utilization modified biomass charcoal resistance control heavy metal according to claim 6 is accumulated in vegetables body, Characterized in that, the vegetables include Lettuce, spinach.
CN201710041203.9A 2017-01-20 2017-01-20 A kind of method that modified biomass charcoal and its resistance control heavy metal are accumulated in vegetables body Pending CN106825026A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109158079A (en) * 2018-08-07 2019-01-08 杭州师范大学 Earthworm excrement base resistance control agent and the preparation method and application thereof for vegetable field soil Cu/Zn pollution
CN109852567A (en) * 2019-01-30 2019-06-07 中国环境科学研究院 Accelerate the microbial bacterial agent and its preparation method and application of heavy metal pollution of soil reparation
CN110551504A (en) * 2019-05-13 2019-12-10 北京化工大学 Hydroxyapatite-modified biochar material and application thereof
CN112898978A (en) * 2021-01-12 2021-06-04 中国环境科学研究院 Repairing agent for lead-polluted alkaline soil and preparation and use methods thereof
CN113058985A (en) * 2020-01-03 2021-07-02 益壤（厦门）环保科技有限公司 Heavy metal contaminated soil degradation harmless treatment method
CN113145636A (en) * 2021-04-02 2021-07-23 中国科学院水生生物研究所 Biochar material for immobilizing soil heavy metal cadmium and method for repairing heavy metal contaminated soil by biochar material

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CN104178178A (en) * 2014-08-16 2014-12-03 中国科学院南京土壤研究所 Organic amendment capable of passivating Cu, Zn and Pb in soil of vegetable field
CN105131960A (en) * 2015-06-26 2015-12-09 华南师范大学 Preparation method and application of lead-polluted soil restoration material
CN105419805A (en) * 2015-11-27 2016-03-23 同济大学 Preparing method for complex function repairing agent for treatment of heavy metal contaminated soil
CN105689374A (en) * 2016-01-28 2016-06-22 中南大学 Application of phosphorus base charcoal material to remediation of lead contaminated soil
CN105772496A (en) * 2016-03-09 2016-07-20 浙江大学 Farmland soil heavy metal blocking and controlling method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104178178A (en) * 2014-08-16 2014-12-03 中国科学院南京土壤研究所 Organic amendment capable of passivating Cu, Zn and Pb in soil of vegetable field
CN105131960A (en) * 2015-06-26 2015-12-09 华南师范大学 Preparation method and application of lead-polluted soil restoration material
CN105419805A (en) * 2015-11-27 2016-03-23 同济大学 Preparing method for complex function repairing agent for treatment of heavy metal contaminated soil
CN105689374A (en) * 2016-01-28 2016-06-22 中南大学 Application of phosphorus base charcoal material to remediation of lead contaminated soil
CN105772496A (en) * 2016-03-09 2016-07-20 浙江大学 Farmland soil heavy metal blocking and controlling method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109158079A (en) * 2018-08-07 2019-01-08 杭州师范大学 Earthworm excrement base resistance control agent and the preparation method and application thereof for vegetable field soil Cu/Zn pollution
CN109852567A (en) * 2019-01-30 2019-06-07 中国环境科学研究院 Accelerate the microbial bacterial agent and its preparation method and application of heavy metal pollution of soil reparation
CN110551504A (en) * 2019-05-13 2019-12-10 北京化工大学 Hydroxyapatite-modified biochar material and application thereof
CN113058985A (en) * 2020-01-03 2021-07-02 益壤（厦门）环保科技有限公司 Heavy metal contaminated soil degradation harmless treatment method
CN112898978A (en) * 2021-01-12 2021-06-04 中国环境科学研究院 Repairing agent for lead-polluted alkaline soil and preparation and use methods thereof
CN112898978B (en) * 2021-01-12 2021-11-16 中国环境科学研究院 Repairing agent for lead-polluted alkaline soil and preparation and use methods thereof
CN113145636A (en) * 2021-04-02 2021-07-23 中国科学院水生生物研究所 Biochar material for immobilizing soil heavy metal cadmium and method for repairing heavy metal contaminated soil by biochar material

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Application publication date: 20170613