CN109913233A - A kind of water paddy soil heavy metal passivation modifying agent - Google Patents
A kind of water paddy soil heavy metal passivation modifying agent Download PDFInfo
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- CN109913233A CN109913233A CN201910347164.4A CN201910347164A CN109913233A CN 109913233 A CN109913233 A CN 109913233A CN 201910347164 A CN201910347164 A CN 201910347164A CN 109913233 A CN109913233 A CN 109913233A
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- 239000002689 soil Substances 0.000 title claims abstract description 135
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002161 passivation Methods 0.000 title abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 37
- 239000010457 zeolite Substances 0.000 claims abstract description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000019738 Limestone Nutrition 0.000 claims abstract description 19
- 239000006028 limestone Substances 0.000 claims abstract description 19
- 239000002671 adjuvant Substances 0.000 claims abstract description 18
- 239000003337 fertilizer Substances 0.000 claims abstract description 17
- 239000010455 vermiculite Substances 0.000 claims abstract description 11
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 11
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000001103 potassium chloride Substances 0.000 claims abstract description 7
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 7
- 239000010828 animal waste Substances 0.000 claims abstract description 5
- 210000003608 fece Anatomy 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 241001494479 Pecora Species 0.000 claims description 5
- 241001465754 Metazoa Species 0.000 claims description 2
- 239000010871 livestock manure Substances 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 57
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 47
- 229910052785 arsenic Inorganic materials 0.000 abstract description 38
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011574 phosphorus Substances 0.000 abstract description 12
- 239000011669 selenium Substances 0.000 abstract description 11
- 238000009825 accumulation Methods 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 7
- 229910052711 selenium Inorganic materials 0.000 abstract description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 5
- 241000209094 Oryza Species 0.000 description 58
- 235000007164 Oryza sativa Nutrition 0.000 description 58
- 235000009566 rice Nutrition 0.000 description 58
- 230000000694 effects Effects 0.000 description 22
- 238000012545 processing Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 15
- 235000019796 monopotassium phosphate Nutrition 0.000 description 14
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000011651 chromium Substances 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
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- 239000002585 base Substances 0.000 description 4
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- 229910000278 bentonite Inorganic materials 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 235000021329 brown rice Nutrition 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
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- 235000013312 flour Nutrition 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
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- 230000007774 longterm Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
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- 238000000034 method Methods 0.000 description 3
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- 238000005067 remediation Methods 0.000 description 3
- 229910052624 sepiolite Inorganic materials 0.000 description 3
- 235000019355 sepiolite Nutrition 0.000 description 3
- -1 silicon (aluminium) oxygen Chemical compound 0.000 description 3
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- 241000196324 Embryophyta Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- APAWRDGVSNYWSL-UHFFFAOYSA-N arsenic cadmium Chemical compound [As].[Cd] APAWRDGVSNYWSL-UHFFFAOYSA-N 0.000 description 2
- 229960002594 arsenic trioxide Drugs 0.000 description 2
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000011049 filling Methods 0.000 description 2
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- 239000004615 ingredient Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
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- 230000035772 mutation Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 201000009030 Carcinoma Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 206010010144 Completed suicide Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000005577 Gastroenteritis Diseases 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 208000012641 Pigmentation disease Diseases 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WDVOGFKLHTXRJS-UHFFFAOYSA-N [Mg].[Si].[K].[P] Chemical compound [Mg].[Si].[K].[P] WDVOGFKLHTXRJS-UHFFFAOYSA-N 0.000 description 1
- RDXARWSSOJYNLI-UHFFFAOYSA-N [P].[K] Chemical compound [P].[K] RDXARWSSOJYNLI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 208000012873 acute gastroenteritis Diseases 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
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- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
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- 229940000489 arsenate Drugs 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
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- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of water paddy soil heavy metals to be passivated modifying agent comprising host agent and adjuvant；Host agent is made of natural zeolite, natural limestone and biphosphate sylvite；Adjuvant includes animal wastes, vermiculite, decomposing agent and siliceous fertilizer.Water paddy soil heavy metal passivation modifying agent can effectively improve soil pH value and reduces its change rate, reduce activated state cadmium in soil, in arsenic content and crops cadmium and arsenic enriching quantity, and improve in soil available phosphorus content and crops to the accumulation ability of Selenium in Soil.
Description
Technical field
The present invention relates to a kind of soil conditioners, in particular to a kind of to be used in farmland cadmium arsenic combined pollution/acid soil
It is passivated modifying agent, belongs to agricultural land soil environment remediation technical field.
Background technique
Soil certainly will pollute periphery as human being's production, the foundation of life, the production of industrial and mineral smeltery and waste stacking
Soil, food-safety problem certainly will be formed by carrying out Agricultural Activities on contaminated soil；With " national soil pollution shape
Condition investigate bulletin " and " Soil Pollution Control action plan " publication, remediation contaminated soil become research hotspot.Currently, being directed to
Heavy metal pollution of soil river harnessing ideas carries out the strategy based on risk control by completely removing heavy metal to be changed into.
With a large amount of development and utilization of resource, industrialized fast-developing and various chemical products, pesticide and chemical fertilizer it is wide
General use, the pollutant containing heavy metal enter environment through a variety of ways, and soil, especially farmland soil heavy metals is caused to pollute
It gets worse.It is shown according to " national Soil Pollution Investigation bulletin ", the total point exceeding standard rate of national soil is 16.1%, from soil
Ground type sees that arable soil point exceeding standard rate is 19.4%；In terms of pollution type, exceeded digit of inorganic pollution accounts for all super
The 82.8% of punctuation bit, wherein cadmium, arsenic pollution object point position exceeding standard rate are respectively 7.0%, 2.7%.Cadmium, arsenic are in environment to plant
Object and human body poison biggish heavy metal element.Excessive cadmium can inhibit the normal growth of plant in soil, and pass through food
Chain enters human body, other than the acute and chronic poisoning that can cause human body, also has carcinogenesis.According to Ministry of Agriculture's rice and product
Quality surveillance detection department shows that the cadmium exceeding standard rate of rice has been more than 25%, some contaminated areas to rice safety findings of the survey
Rice in cadmium content be up to 1.3mg/kg, be seriously more than the highest permissible levels 0.3mg/kg of cadmium in China's cereal.Simple substance
Arsyl sheet is nontoxic, but arsenic chemical property is more active, easily aoxidizes, and arsenic oxide and arsenate are more toxic, trivalent arsenic toxicity compared with
Pentavalent arsenic is strong, and arsenic can inhibit cellular oxidation process in conjunction with the enzyme in cell containing sulfydryl；Vasomotor center can also be benumbed, is made
Capillary paralysis, expansion and permeability increase.Arsenide contaminated food products or drinking-water are more common in the poisoning of acute arsenide, wrongly take or
Suicide.Clinical manifestation is more common with " acute gastroenteritis type ".Severe may occur in which shock, liver damage, or even die of the Poisoning heart
Flesh damage.Arsenic minerals smelt and arsenic trioxide direct labor and because atmosphere, drinking-water for a long time by arsenic pollution or take for a long time arsenical
Deng arsenicalism can occur.Outstanding behaviours is cutaneous pigmentation, hyperkeratinization or verrucous hyperplasia, also shows leucocyte and subtracts
Less or anaemia.Cutaneum carcinoma and lung cancer can be caused by having been accepted as Long Term Contact arsenide.Soil arsenic pollution in China's is more serious at present, this is
Since soil has the ability of absorption, accumulation arsenic.Cadmium in soil, arsenic element total content be known as full dose, can be by plant in full dose
The part being absorbed and utilized is referred to as activated state or bound residue.At present, farmland soil heavy metals pollution is mostly combined pollution,
It, can be with other after often reducing certain heavy metal species bound residue ion concentration and due to interionic collaboration or antagonism
Heavy metal ion or inorganic ion content increase, and are unable to reach the mesh for thoroughly reducing bound residue contents of heavy metal elements in soil
's.
Existing farmland soil heavy metals pollution in-situ passivation technology is with physical absorption, raising soil pH value, change soil
Redox Condition or the low accumulation crops of choosing training heavy metal are mainstream, but physical absorption stability is poor, at any time may be again
Activation；It improves pH value to spill based on lime stone largely to apply, southern area polyacid rain need to be applied for a long time and spill lime, will lead to soil plate
The problems such as knot；The second is changing redox of soil condition, the long-term waterflooding in field is kept, soil environment reducing environment is made, dropped
The heavy metal activities such as low cadmium, but this mode is unfavorable for the good growth of rice, and the Cr under reducing condition in soil3+It may
It is reduced to Cr6+, high degree raising pollution of chromium risk；The low accumulation variety of crops of choosing training heavy metal is better method, but mesh
It is preceding still in breed of variety experimental stage.
Summary of the invention
Existing defect, the purpose of the present invention are repaired for the most common cadmium arsenic combined pollution agricultural land soil in the prior art
Be be to provide one kind can effectively improve soil pH value and reduce its change rate, reduce activated state cadmium in soil, arsenic content and
The enriching quantity of cadmium and arsenic in crops, and available phosphorus content and crops are improved in soil to the rice of the accumulation ability of Selenium in Soil
Field heavy metal-polluted soil is passivated modifying agent.
In order to achieve the above technical purposes, the present invention provides a kind of water paddy soil heavy metals to be passivated modifying agent, packet
Include host agent and adjuvant；The host agent is made of natural zeolite, natural limestone and biphosphate sylvite；The adjuvant includes animal
Excrement, vermiculite, decomposing agent and siliceous fertilizer；
Preferred scheme, the host agent are made of following content of component: 65~70 parts of natural zeolite, natural limestone 25
~28 parts, 2~5 parts of biphosphate sylvite.
Preferred scheme, the adjuvant include following content of component: 52~61 parts of animal wastes, 26~32 parts of vermiculite,
0.5~0.7 part of decomposing agent, 6~8 parts of siliceous fertilizer.
Preferred scheme, the animal wastes include at least one of cow dung, sheep dung and pig manure.
Preferred scheme, the mass ratio between the host agent and adjuvant are 1.8~2.2:0.9~1.1.
Water paddy soil heavy metal passivation modifying agent host agent of the invention is mainly used for adsorbing the Active Heavy Metals in soil
Ion cadmium and arsenic.Natural zeolite (the main component A used(x/q)[(AlO2)x(SiO2)y]n(H2O)) not only there is porous knot
Structure, but also contain a large amount of activity Ca2+、Na+、K+, because property is more active, easily with Cd in soil and its solution2+And As3+Occur
Ion exchange makes Cd2+And As3+It is formed with silicon (aluminium) oxygen tetrahedron screen work of zeolite compared with resistant mineral, reduces activated state in soil
Cadmium and arsenic content.Potassium dihydrogen phosphate (KH2PO4) it is used for Zeolite modifying, by Ca original in zeolite2+It is substituted for the K of small volume+,
To increase the pore volume of zeolite, while the electrical property of the replacement change zeolite crystal layer end face by ion, make its enhancing to a huge sum of money
Belong to the adsorption capacity of cation, and because containing H2PO4 -, the increase of soil pH can be caused by exchanging desorption, further increases zeolite
Physical and chemical adsorption effect.And natural limestone can be with the water and H in the soil liquid+Reaction reduces H in soil+Content, the side of body
Compel Cd2+、As3+With Ca in zeolite2+、Na+、K+Displacement, to strengthen the chemisorption effect of divalent cadmium ion, trivalent arsenic ion.
Three's synergistic effect increases zeolite specific surface area, improves cadmium in the soil liquid, arsenic plasma is handed over by increasing zeolite pore volume
Efficiency is changed, with H2PO4 -And CaCO3With H in the soil liquid+Reaction reduces H in soil+Content, while improving Ca in soil2+It is dense
Degree, with higher concentration, the stronger Ca of activity2+And K+Coerce Cd in soil2+、As3+In the zeolite that entrance aperture increases, and simultaneously
With the Ca in silicon (aluminium) oxygen tetrahedron screen work2+、K+Equal alkaline-earth metal or alkali metal ion carry out ion exchange, with silicon (aluminium) oxygen four
Face physique frame is formed compared with resistant mineral, to reduce Mobile Forms Cd in soil2+And As3+Content, the host agent of three's synthesis are exchanges
Adsorb effective natural mineral matter passivator of active cadmium and arsenic in soil.Adjuvant include mainly include ox (sheep) excrement, it is vermiculite, decomposed
Agent, siliceous fertilizer etc., wherein cow dung (sheep) is mainly used for improving organic matter and nitrogen, phosphorus, potassium content and chesson, and vermiculite is mainly used
In slowing down pH value mutation, keep the passivation effect of host agent steady in a long-term, water-retaining effect, and the crop growths such as K, Mg, Ca, Fe are provided
Necessary microelement, siliceous fertilizer improve rice yield and lodging tolerance, compound adjuvant mixes auxiliary for supplementing instant capacity silicon
Agent is mainly used for slowing down pH mutation efficiency, while it is micro to enhance the necessary organic matter of crop growth and nitrogen, phosphorus, potassium, calcium, magnesium etc.
Element, and siliceous fertilizer content is improved, improve plant growth quality.Entire water paddy soil heavy metal passivation modifying agent is not endangering agriculture
Under the premise of the ecological environment of field, can cadmium ion and arsenic ion effectively in displacement sorption displacement soil, while reducing H in soil+Content simultaneously reduces it and changes efficiency, reduces activated state cadmium in soil, cadmium and arsenic content in arsenic content and crops, and improves soil
Available phosphorus content in earth improves crops to the accumulation ability of Selenium in Soil.
Cadmium, lead, arsenic, mercury, copper, nickel, zinc etc. in natural zeolite of the invention, natural limestone, natural dolomite and vermiculite
There is the heavy metal element total amount of larger impact allowing in content range crops or human body, these ingredients are essentially natural mine
Object, stable components, heavy metal element activity are relatively low.The potassium dihydrogen phosphate used is efficient phosphorus potassium complex fertilizer raw material, vermiculite
For common plant growth substrate, siliceous fertilizer be secondary nutrients, ox (sheep) excrement is nature organic fertilizer.Host agent and the equal day of adjuvant ingredient
Right or useful material, and it is low in cost.
The preparation method of water paddy soil heavy metal passivation modifying agent of the invention: natural zeolite is smashed to pieces little to partial size
In the little particle of 1mm, then biphosphate sylvite is configured to the solution of 20g/L concentration, the natural zeolite particle after smashing to pieces is set
In configured potassium dihydrogen phosphate, 2 days are stood after concussion, is added and is ground into the natural stone that partial size is not more than 0.85 millimeter
Limestone flour oscillation stirs and evenly mixs, and stands 1 day, obtains host agent after sufficiently air-drying；Stirring is crushed to partial size after cow dung is dry in adjuvant
No more than 1 millimeter, then the mixture that moisture content is 40~50% is made in a small amount of distilled water, is sequentially added into said mixture
After decomposing agent, vermiculite, siliceous fertilizer, mixing dope is made in 1~1.5h of ultrasonic disperse, and it is 3 millimeters that dope, which is pressed through aperture,
Mesh screen；The host agent mixed will be held under mesh screen, shake host agent bucket when making adjuvant particle, fall into adjuvant particle
After host agent bucket, surface wraps one layer of host agent powder, after molding.
Compared with the prior art, water paddy soil heavy metal of the invention is passivated modifying agent bring advantageous effects:
1. water paddy soil heavy metal passivation modifying agent of the invention can slightly improve soil pH value, while reduce soil
The change rate of pH reduces bound residue cadmium content in soil, reduces the enriching quantity of cadmium and arsenic in crops；It improves in soil effectively
Phosphorus and potassium, content of calcium and magnesium improve crops to the accumulation ability of Selenium in Soil；Lodging resistance in rice ability is improved, and is mentioned to a certain degree
High rice per mu yield provides a passivation effect of fertilizer, improves the beneficial elements contents such as potassium phosphorus silicon magnesium, improves production
The synthesis of amount is effectively passivated modifying agent.
2. the synergistic effect between heavy metal-polluted soil passivation modifying agent each component of the invention is obvious, relatively single zeolite,
Lime stone etc. is compared as heavy metal deactivator, more significant to the passivation effect of Cd and As, in this season rice yield and soil
It is also more significant that available phosphorus content promotes effect.
3. heavy metal-polluted soil passivation modifying agent raw material sources of the invention are wide, preparation method is simple, advantageously reduces use
Cost.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits scope of protection of the claims.
Embodiment 1
According to previous research and appraisal achievement, surface layer 0~20cm thick soil stratum is taken in the farmland of Xiangjiang River basin alluvial plain,
Loamy texture rice soil is glued for lark, base is transported back and does indoor culture experiment, stirred and evenly mixed repeatedly after water filling, standing is air-dried to humidity
18.5%, 24 parts are divided into, pH, Cd, As, Cr, Cu, Pb, Zn are tested in every part of soil sample, each part soil testing analysis after mixing
As a result almost the same, pH mean value 5.82,2865 μ g/kg of Cd mean value 3.72mg/kg, As mean value 23.57mg/kg, Hg mean value, Pb are equal
Value 53.76mg/kg, Cu mean value 42.39mg/kg, Cr mean value 83.17mg/kg.Soil entirety slant acidity, existing soil environment
Problem is that Cd total amount is exceeded.
Setting natural zeolite powder (Z), natural limestone powder (CA), natural zeolite powder mixed with natural limestone powder (ZCA),
Natural zeolite powder and potassium dihydrogen phosphate (ZP), natural limestone powder and potassium dihydrogen phosphate (CAP), potassium dihydrogen phosphate (P), natural boiling
Mountain flour and 7 kinds of potassium dihydrogen phosphate and agstone (ZPCA) processing, while 1 blank control group (CK) is set, every kind of processing is set
Set and repeat three times, each reagent dosage distinguishes zeolite powder 68g/kg, agstone 26g/kg, potassium dihydrogen phosphate 4g/kg, zeolite powder and
Agstone granularity is 100 mesh, applies and stirs and evenly mixs after spilling, potassium dihydrogen phosphate be made aqueous solution apply spill after mix, ZPCA processing
Potassium dihydrogen phosphate immersion zeolite powder is blended into after agstone to apply in liquid and spills mixing, blank control group (CK) without
Any processing.After treatment measures, after the soil under each processing is placed at room temperature for 30 days, then by rice cultivating requirement late rice (day is sowed
Two excellent 682) cultivations, acquire the soil and Rice Samples test analysis under each processing respectively after rice is mature.The pH of soil is analyzed,
Cd, effective cadmium content simultaneously do five step morphological analyses to cadmium, analyze Cd, Hg, As, Pb, Cr, Cu content of rice.
Test result is shown:
1. relative to CK group, six kinds of Z, CA, ZCA, CAP and ZPCA handle lower soil pH value and have different degrees of raising,
In it is best with ZPCA effect, pH value rises to that 6.35, Z treatment effect is relatively poor, and pH is only promoted to 5.91.It is each to handle lower soil
PH value sequence are as follows: ZPCA > ZCA > CA > Z > CAP > CK ≈ ZP ≈ P.
2. Cd content interval is 1.17~1.42mg/kg in CK rice (brown rice), Cd limit standard in remote super brown rice
(0.2mg/kg), other five content of beary metal are in brown rice pollutant limitation range.Cd, As in the treatment measures rice of part
Content significantly reduces, and wherein CA, which handles Cd content in rice, reduces by 19.39%；Z, which handles Cd content in rice, reduces by 31.27%,
Rice As content reduces by 17.24%；ZCA, which handles Cd content in rice, which reduces by 39.71%, As content, reduces by 18.12%；ZP processing
Cd content, which reduces by 41.26%, As content, in rice reduces by 23.47%；ZPCA, which handles Cd content in rice, reduces by 63.29%, As
Content reduces by 27.68%.
3. Z handles effectively 58.92%, ZP of cadmium content reduction in soil and handles the effective cadmium content drop of soil relative to CK group
The effective cadmium of low 67.17%, CA processing soil, which reduces the effective cadmium of 53.41%, CAP processing soil, reduces by 52.69%, ZCA processing soil
The effective cadmium of earth, which reduces the effective cadmium content of 63.84%, ZPCA processing soil, reduces by 81.76%.
4. the residual form cadmium accounting that the residual form cadmium accounting of Z processing increases by 52.75%, ZP processing increases relative to CK group
79.31%, P handle soil residual form cadmium accounting and increase residual form cadmium accounting increase by 18.37% in 12.92%, CA processing soil,
CAP handles residual form cadmium accounting in soil and increases by 21.32%, ZCA processing soil residual form cadmium accounting increase, 53.66%, ZPCA
It handles residual form cadmium accounting in soil and increases by 89.87%.
When test result shows to carry out culture experiment using cadmium pollution soil, potassium dihydrogen phosphate, lime stone and the equal energy of zeolite
Cd contaminated soil is repaired, but Cd contaminated soil remediation is imitated with the combination combination of natural zeolite powder, potassium dihydrogen phosphate and agstone
Fruit more preferably, while can significantly reduce total As content in rice, and reduced rate highest.It is found that natural zeolite powder, potassium dihydrogen phosphate and
Agstone combination combination can effectively reduce the Mobile Forms content of Cadmium in Soil, arsenic, while reduce cadmium in rice, arsenic content, and its
Effect is much better than zeolite powder, lime stone, potassium dihydrogen phosphate three individually or any the two is administered in combination, and reflects three to a certain extent
Person's combination has obvious cooperative synergism effect.
Embodiment 2
Using the test method of plot experiment and field demonstration, ten plots of model fields and two pieces of field trial fields are arranged in scheme,
Every piece of model field is arranged a kind of processing, actual effect of each scheme to soil and crops under the conditions of observation of nature；Experimental plot is total
Five kinds for the treatment of measures are set, and each treatment measures are set to be repeated and a control three times, compares almost the same natural farm environment
Under each treatment measures superiority and inferiority.The experimental plot selected is the test of Hunan Province, the town Xin Xu, the Xintian County village Tong Muwo proving ground TM17
Field, field area are 0.95 mu.The experimental plot soil is ecru rice soil, and quality is configured as tight type, and the soil texture is
Clay loam, topsoil thickness about 27cm.Soil pH average value is 8.0, belongs to alkaline soil, and soil organic matter content 6.01% is main to support
Divide element to show as potassium slightly to lack, effective potassium content is 74.4mg/kg；Main soil environment problem shows as Cd, Hg total amount
Exceeded, wherein Cd average content is 2.18mg/kg, and effective cadmium average content is 1.04mg/kg, and Hg average content is 3.14mg/
kg；Experimental field Cd, Hg, As, Pb, Cr equal size reach agricultural product quality standard in Rice Seed.It is experimental field tobacco leaf-rice
Crop rotation, spring drought kind of tobacco leaf, autumn water kind rice, because the heavy metals exceeding standards situation such as late rice seed cadmium is relatively tight under normal circumstances
Weight, the passivation effect that main experimental heavy metal-polluted soil passivation modifying agent is planted in late rice, for studying object as the hybridization of excellent 996 type in emblem two
Rice, the field management such as routine fertilization application are passivated by peasant household's voluntarily decision with testing heavy metal-polluted soil under nature tillage condition
The actual effectiveness of modifying agent.
Testing program sets modified meerschaum, calcium-base bentonite, natural zeolite powder, natural limestone powder, organic fertilizer and Ben Fa
Bright heavy metal-polluted soil is passivated modifying agent (mass ratio=2:1 of host agent and adjuvant；Host agent composition: 68 parts of natural zeolite, natural stone
27 parts of lime stone, 5 parts of biphosphate sylvite；Adjuvant composition: 54 parts of cow dung, 30 parts of vermiculite, 0.6 part of decomposing agent, 8 parts of siliceous fertilizer), totally six
Kind processing, every kind of processing set primary blank control and repeat three times, and the amount of application of various passivator is 200kg/ mus.It uses
The substrate content of each heavy metal element of heavy metal-polluted soil passivation modifying agent of the invention is below soil environment quality second level mark
Standard, all kinds of heavy metal element total amounts 3~4 orders of magnitude lower than soil contents of heavy metal elements itself.Five kinds of passivation modifying agents
It is shed when plowing, crop field rotary tillage when shedding mixes, and it is small that test is newly built in experimental plot after rotary tillage of plowing, with soil in field
Area and mating filling drainage ditch and overlay film water proof, then passivation modifying agent and mixing of manually raking the soil level manually are shed, it applies after spilling mixing operation
Beginning rice transplanting in 3~5 days is staticly settled, periodic monitoring records growing state and pours water, drainage situation during rice is raw.Rice is received
When obtaining, Rice Seed sample and pedotheque are acquired respectively by cell, rice is gathered in by cell/crop field and packs, dries respectively,
It weighs after drying weighing, compares volume variance.
In six kinds of passivator that this test uses, applies heavy metal-polluted soil of the invention and be passivated in the reduction paddy of modifying agent
Cd, As content effect are best, and relative to blank group rice sample, Cd content reduces by 19.85%, Cd concentration coefficient (rice cadmium
Content/Cadmium in Soil total amount) 25.19% is reduced, As content, which reduces by 13.13%, As concentration coefficient, in rice reduces by 34.18%；It applies
Reducing by 4.19%, concentration coefficient with Cd content in pulverized limestone rice reduces by 6.87%, As content without significant change (< 1%)；It applies
14.21% is reduced with the Cd concentration coefficient that Cd content in natural zeolite powder rice reduces by 11.27%, rice, rice As content drop
Low 7.24%, concentration coefficient reduces by 15.63%；Other the three kinds Cd contents for handling rice sample and its concentration coefficient are with respect to blank
For group, change rate is less than 5%, and variation is unobvious, and As is without significant changes.
Application modified meerschaum, natural zeolite powder, calcium-base bentonite and heavy metal-polluted soil of the present invention passivation modifying agent make soil
Effective cadmium and effective nickel content significantly reduce in earth, reduced rate 40%~50%, but difference is smaller between each treatment measures, apply stone
Limestone flour makes effective cadmium content in soil reduce by 32%, and effectively cadmium content reduces by 28% in application of organic fertilizers soil；Apply this hair
Bright heavy metal-polluted soil passivation modifying agent makes rice this season output increased 6.16%, and application of organic fertilizers makes rice this season output increased
4.79%, application zeolite powder makes rice this season output increased 2.74%, other several processing are to this season rice yield without obvious shadow
It rings；Applying heavy metal-polluted soil passivation modifying agent of the present invention makes Se content in rice improve 16.4%, concentration coefficient of the rice to Se
14.5% is improved, simple zeolite powder of applying makes Se content in rice improve 8.54%, concentration coefficient raising 9.02%, simple to apply
Agstone makes Se content in rice improve 4.32%, concentration coefficient raising 5.11%, Se content in other several processing rice
Substantially unchanged, in general, in contrast reagent of the invention, can most improve rice to the absorption efficiency of selenium；Apply this hair
Bright heavy metal-polluted soil passivation modifying agent makes available phosphorus content in soil improve 25.9%, and application calcium-base bentonite makes in soil effectively
Phosphorus content improves 22.5%, and application zeolite makes available phosphorus content in soil improve 16.18%, and application of organic fertilizers makes in soil effectively
Phosphorus content improves 16.16%, other treatment effects are unobvious.
This test result is shown: without other manual interventions, in the actual production of paddy planting rice, and this hair
Bright heavy metal-polluted soil passivation modifying agent can effectively reduce Cd, As content in rice, reduce rice to the absorption effect of Cd, As in soil
Rate reduces effective cadmium content in soil, improves available phosphorus content in soil, improves increasing production of rice, rice Se content.And compare mesh
The common passivator effect such as preceding sepiolite on the market, bentonite and organic fertilizer is more preferable.
Claims (5)
1. a kind of water paddy soil heavy metal is passivated modifying agent, it is characterised in that:
Including host agent and adjuvant；
The host agent is made of natural zeolite, natural limestone and biphosphate sylvite；
The adjuvant includes animal wastes, vermiculite, decomposing agent and siliceous fertilizer.
2. a kind of water paddy soil heavy metal according to claim 1 is passivated modifying agent, it is characterised in that: the host agent by
Following content of component composition: 65~70 parts of natural zeolite, 25~28 parts of natural limestone, 2~5 parts of biphosphate sylvite.
3. a kind of water paddy soil heavy metal according to claim 1 is passivated modifying agent, it is characterised in that: the adjuvant packet
Include following content of component: 52~61 parts of animal wastes, 26~32 parts of vermiculite, 0.5~0.7 part of decomposing agent, 6~8 parts of siliceous fertilizer.
4. a kind of water paddy soil heavy metal according to claim 3 is passivated modifying agent, it is characterised in that: the animal excreta
It just include at least one of cow dung, sheep dung and pig manure.
5. a kind of water paddy soil heavy metal according to any one of claims 1 to 4 is passivated modifying agent, it is characterised in that:
Mass ratio between the host agent and adjuvant is 1.8~2.2:0.9~1.1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111282985A (en) * | 2020-02-20 | 2020-06-16 | 广东省生态环境技术研究所 | Method for treating soil cadmium-arsenic combined pollution by using multifunctional manganese-based material |
| 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 |
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