WO1993016797A1 - Adsorbent, sealing layer and use of the adsorbent for immobilising heavy metals - Google Patents

Adsorbent, sealing layer and use of the adsorbent for immobilising heavy metals Download PDF

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Publication number
WO1993016797A1
WO1993016797A1 PCT/NL1993/000036 NL9300036W WO9316797A1 WO 1993016797 A1 WO1993016797 A1 WO 1993016797A1 NL 9300036 W NL9300036 W NL 9300036W WO 9316797 A1 WO9316797 A1 WO 9316797A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
smectite
sealing layer
aluminium
heavy metals
Prior art date
Application number
PCT/NL1993/000036
Other languages
French (fr)
Inventor
Mathias Gerardus Maria Bruggenwert
Egbertus Mattheus Wittich
Original Assignee
Agriton Van Den Ham & Co.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agriton Van Den Ham & Co. filed Critical Agriton Van Den Ham & Co.
Publication of WO1993016797A1 publication Critical patent/WO1993016797A1/en

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/10—Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step

Definitions

  • the present invention relates to an adsorbent whic binds large quantities of heavy metals in a manner that i independent of the presence of high concentrations of othe ions. It is possible with this adsorbent to bind substantial ly irreversible heavy metals in the form of ions.
  • This adsorbent can be used for a large number of dif ferent applications.
  • a first application comprises preventin emission of heavy metal ions from large compartments such a refuse tips and vehicle scrap yards.
  • a second applicatio relates to the removal of heavy metal ions from water, where in the heavy metal ions are concentrated in the relativel small adsorbent volume.
  • Another use of the adsorbent relate to the addition of the adsorbent to soil contaminated wit heavy metal ions, whereby the heavy metal ions are bound b the adsorbent and are substantially no longer available fo absorption by plant and animal. In principle the soil is thu cleaned and can better be made re-available for agricultur and market gardening, recreative and building purposes.
  • the adsorbent according to the invention for i mobi using heavy metals in the form of their ions is charac terized in that it contains a complex of smectite, aluminiu hydroxide and phosphate.
  • This complex can bind large quan tities of heavy metal ions in a manner that is independent o the presence of markedly higher concentrations of other ion such as ions of calcium, potassium, magnesium, chlorine, nitrate and sulphate.
  • Smectite, aluminium hydroxide and phosphate can b present in the complex in mutually changing ratios, thi being dependent among other factors on the strength an intended binding capacity of the complex.
  • hydroxide as aluminium
  • This ratio preferably amounts to 2-4 mol aluminium per kg smectite.
  • the molar ratio of phosphate to aluminium amounts to 0.1 to 1. In preference however this molar ratio amounts to 0.2-0.8.
  • the smectite comprises a group of clay minerals.
  • Belon ⁇ ging to this group of clay minerals are mont- morillonite, beidellite, nontronite, saponite, sauconite and hectorite. They are swelling clay minerals which can take up relatively large amounts of watery or organic liquid between layers of smectite particles.
  • An optimal action of the com ⁇ plex is obtained if the smectite is a homoionogenic alkali or earth alkali metal smectite such as sodium smectite and calcium smectite.
  • As preferred smectite use is made of a homoionogenic montmorillonite clay.
  • the adsorbent is used mainly for immobilising relati ⁇ vely large quantities of heavy metal ions present in watery liquid
  • the adsorbent according to the invention contains a mixture of the complex of smectite, aluminium hydroxide and phosphate in addition to a filter aid.
  • the relative quan ⁇ tities of the complex and the filter aid are chosen subject to the desired physical properties, such as stability and filterability of the filter in which the adsorbent is emplo ⁇ yed.
  • filter aid can be used fibre-like materials such as mineral wool and/or particle-like materials such as sand.
  • a sealing layer is used at storage sites such as refuse tips and vehicle scrap yards in order to limit the spread of heavy metal ions out of the storage sites with percolating rain ⁇ water.
  • a sealing layer contains a mixture of sand and clay, which mixture can in principle prevent water transport throu ⁇ gh the sealing layer. Diffusion transport is not however prevented by the sealing layer. In the course of time the heavy metal ions will therefore leak out of the storage site through the sealing layer.
  • a seal ⁇ ing layer results with which the diffusion of heavy metal ions through the sealing layer is almost completely preven- ted.
  • the advantage is moreover achieved that if a crac occurs in the sealing layer due to drying, the adsorbent wil immobilise heavy metal ions from the liquid passing along th crack through the sealing layer.
  • the mixture for use in th sealing layer preferably contains the adsorbent according t the invention, sand and clay in a weight ratio of 0.5-5:5- 10:0.2-5. More preferably this weight ratio amounts to 1-3:6- 8:0.5-2.
  • Another application of the adsorbent according to th invention is the cleaning of soil contaminated with heav metal ions. This cleaning can take place in situ.
  • the adsorbent according to the invention is mixed wit the contaminated soil, whereafter the heavy metal ions pre ⁇ sent therein are immobilised in the adsorbent and are n longer available for plants and animals present on and in th soil.
  • the bio-availability of the heavy metal ions present is thus reduced enormously, whereby in principle the soil is cleaned.
  • the adsorbent for immobilising heavy metal ions such as of the heavy metals lead, mercury, cadmium, nickel, zinc, copper and chromium, and the application thereof will b further elucidated on the basis of a number of embodiments, without the invention being limited thereto.
  • Example 1 preparation of the complex of the adsorben according to the invention
  • Sodium montmorillonite clay is mixed with an aqueou solution of aluminium chloride or aluminium nitrate. Th amount of aluminium salt is such that the ratio aluminium sodium montmorillonite varies between 2-4 mol aluminium pe kg sodium montmorillonite.
  • a base such as sodium hyd ⁇ roxide and potassium oxide the pH is increased to a pH > 5, preferably a pH within the range pH 6-7.
  • Phosphate in the form of sodium di-hydrogen phosphate/ sodium mono hydrogen phosphate is subsequently added in quantity such that the molar ratio of phosphate to aluminiu amounts to 0.5.
  • the suspension is dried in air at a tempera ⁇ ture preferably no higher than 40°C.
  • the binding of the heavy metal ions of cadmium, lead, zinc and copper to the adsorbent was subsequently tested. From an equilibrium solution of 1 mM of the respective heavy metal ions and at a very high salt concentration (0.01 molar Ca(N0 3 ) 2 ) the binding amounted to 0.05 mol cadmium, 0.1 mol lead, 0.3 mol zinc and 0.4 mol copper per kg adsorbent.
  • the adsorption of zinc ions to the adsorbent A according to the invention was moreover compared to the adsorption to an adsorbent B not containing any phosphate.
  • Adsorbent A (according to the invention) 1400 400 200
  • Adsorbent B (not according to invention) 1400 0 200
  • a sealing layer for preventing emission of heavy metal ions from a refuse tip was prepared by mixing of the adsor ⁇ bent prepared in example 1 with sand and sodium montmoril ⁇ lonite. The ratio adsorbent:sand:clay amounted to 2:7:1. This sealing layer adequately prevented emission of heavy metal ions by both convection flux and diffusion.
  • Contaminated soil contained 500 ppm copper (0.5 k copper per ton of soil) .
  • 35-50 kg of adsorbent prepared i example 1 was mixed with the soil (pH 5-6) .
  • a coppe concentration of 10 "e mol a minimum of 10-15 grams of coppe can be immobilised. The contamination in the form of coppe is thus immobilised and no longer available to plant an animal growing on and in the grotind. This manner of cleanin is very economic.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Dispersion Chemistry (AREA)
  • Soil Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to an adsorbent for immobilising heavy metals, containing a complex of smectite, aluminium hydroxide and phosphate, to a sealing layer containing a mixture of this adsorbent, sand and clay, and to the use of this adsorbent for cleaning soil contaminated with heavy metals.

Description

ADSORBENT, SEALING LAYER AND USE OF THE ADSORBENT FOR IMMOBILISING HEAVY METALS
The present invention relates to an adsorbent whic binds large quantities of heavy metals in a manner that i independent of the presence of high concentrations of othe ions. It is possible with this adsorbent to bind substantial ly irreversible heavy metals in the form of ions.
This adsorbent can be used for a large number of dif ferent applications. A first application comprises preventin emission of heavy metal ions from large compartments such a refuse tips and vehicle scrap yards. A second applicatio relates to the removal of heavy metal ions from water, where in the heavy metal ions are concentrated in the relativel small adsorbent volume. Another use of the adsorbent relate to the addition of the adsorbent to soil contaminated wit heavy metal ions, whereby the heavy metal ions are bound b the adsorbent and are substantially no longer available fo absorption by plant and animal. In principle the soil is thu cleaned and can better be made re-available for agricultur and market gardening, recreative and building purposes.
The adsorbent according to the invention for i mobi using heavy metals in the form of their ions is charac terized in that it contains a complex of smectite, aluminiu hydroxide and phosphate. This complex can bind large quan tities of heavy metal ions in a manner that is independent o the presence of markedly higher concentrations of other ion such as ions of calcium, potassium, magnesium, chlorine, nitrate and sulphate. If phosphate is omitted from the com plex, heavy metal ions are bound but, during this bindin process, the properties of the adsorbent change such that further binding of heavy metal ions is greatly inhibited This inhibiting action is decreased by the presence of phos phate in the complex.
Smectite, aluminium hydroxide and phosphate can b present in the complex in mutually changing ratios, thi being dependent among other factors on the strength an intended binding capacity of the complex. In general th ratio of smectite to aluminium, hydroxide (as aluminium) amounts to 1-6 mol. This ratio preferably amounts to 2-4 mol aluminium per kg smectite. In general the molar ratio of phosphate to aluminium amounts to 0.1 to 1. In preference however this molar ratio amounts to 0.2-0.8.
The smectite comprises a group of clay minerals. Belon¬ ging to this group of clay minerals, among others, are mont- morillonite, beidellite, nontronite, saponite, sauconite and hectorite. They are swelling clay minerals which can take up relatively large amounts of watery or organic liquid between layers of smectite particles. An optimal action of the com¬ plex is obtained if the smectite is a homoionogenic alkali or earth alkali metal smectite such as sodium smectite and calcium smectite. As preferred smectite use is made of a homoionogenic montmorillonite clay.
If the adsorbent is used mainly for immobilising relati¬ vely large quantities of heavy metal ions present in watery liquid the adsorbent according to the invention contains a mixture of the complex of smectite, aluminium hydroxide and phosphate in addition to a filter aid. The relative quan¬ tities of the complex and the filter aid are chosen subject to the desired physical properties, such as stability and filterability of the filter in which the adsorbent is emplo¬ yed. As filter aid can be used fibre-like materials such as mineral wool and/or particle-like materials such as sand.
Another application of the adsorbent according to the invention is the use of the adsorbent in a sealing layer. A sealing layer is used at storage sites such as refuse tips and vehicle scrap yards in order to limit the spread of heavy metal ions out of the storage sites with percolating rain¬ water. A sealing layer contains a mixture of sand and clay, which mixture can in principle prevent water transport throu¬ gh the sealing layer. Diffusion transport is not however prevented by the sealing layer. In the course of time the heavy metal ions will therefore leak out of the storage site through the sealing layer. By making of use of a mixture of the adsorbent according to the invention in addition to sand and clay as sealing layer according to the invention a seal¬ ing layer results with which the diffusion of heavy metal ions through the sealing layer is almost completely preven- ted. The advantage is moreover achieved that if a crac occurs in the sealing layer due to drying, the adsorbent wil immobilise heavy metal ions from the liquid passing along th crack through the sealing layer. The mixture for use in th sealing layer preferably contains the adsorbent according t the invention, sand and clay in a weight ratio of 0.5-5:5- 10:0.2-5. More preferably this weight ratio amounts to 1-3:6- 8:0.5-2.
Another application of the adsorbent according to th invention is the cleaning of soil contaminated with heav metal ions. This cleaning can take place in situ. This means that the adsorbent according to the invention is mixed wit the contaminated soil, whereafter the heavy metal ions pre¬ sent therein are immobilised in the adsorbent and are n longer available for plants and animals present on and in th soil. The bio-availability of the heavy metal ions present is thus reduced enormously, whereby in principle the soil is cleaned.
The adsorbent for immobilising heavy metal ions such as of the heavy metals lead, mercury, cadmium, nickel, zinc, copper and chromium, and the application thereof will b further elucidated on the basis of a number of embodiments, without the invention being limited thereto.
Example 1: preparation of the complex of the adsorben according to the invention
Sodium montmorillonite clay is mixed with an aqueou solution of aluminium chloride or aluminium nitrate. Th amount of aluminium salt is such that the ratio aluminium sodium montmorillonite varies between 2-4 mol aluminium pe kg sodium montmorillonite. Using a base such as sodium hyd¬ roxide and potassium oxide the pH is increased to a pH > 5, preferably a pH within the range pH 6-7.
Phosphate in the form of sodium di-hydrogen phosphate/ sodium mono hydrogen phosphate is subsequently added in quantity such that the molar ratio of phosphate to aluminiu amounts to 0.5. The suspension is dried in air at a tempera¬ ture preferably no higher than 40°C. The binding of the heavy metal ions of cadmium, lead, zinc and copper to the adsorbent was subsequently tested. From an equilibrium solution of 1 mM of the respective heavy metal ions and at a very high salt concentration (0.01 molar Ca(N03)2) the binding amounted to 0.05 mol cadmium, 0.1 mol lead, 0.3 mol zinc and 0.4 mol copper per kg adsorbent.
The adsorption of zinc ions to the adsorbent A according to the invention was moreover compared to the adsorption to an adsorbent B not containing any phosphate.
Al phosphate ( mol) Zn
Adsorbent A (according to the invention) 1400 400 200
Adsorbent B (not according to invention) 1400 0 200
Adsorbent A immobilised 82% and adsorbent B immobilised 74% of the zinc ions present in the system.
Example 2
A sealing layer for preventing emission of heavy metal ions from a refuse tip was prepared by mixing of the adsor¬ bent prepared in example 1 with sand and sodium montmoril¬ lonite. The ratio adsorbent:sand:clay amounted to 2:7:1. This sealing layer adequately prevented emission of heavy metal ions by both convection flux and diffusion.
Example 3
Contaminated soil contained 500 ppm copper (0.5 k copper per ton of soil) . 35-50 kg of adsorbent prepared i example 1 was mixed with the soil (pH 5-6) . At a coppe concentration of 10"e mol a minimum of 10-15 grams of coppe can be immobilised. The contamination in the form of coppe is thus immobilised and no longer available to plant an animal growing on and in the grotind. This manner of cleanin is very economic.

Claims

1. Adsorbent for immobilising heavy metals, containing complex of smectite, aluminium hydroxide and phosphate.
2. Adsorbent as claimed in claim 1, wherein the ratio o smectite to aluminium hydroxide (as aluminium) amounts to 1- mol, preferably 2-4 mol aluminium per kg smectite.
3. Adsorbent as claimed in claim 1 or 2, wherein th molar ratio of phosphate to aluminium amounts to 0.1 to 1 preferably 0.2-0.8.
4. Adsorbent as claimed in claims 1-3, wherein th smectite is a homoionogenic alkali or earth alkali meta smectite.
5. Adsorbent as claimed in claims 1-4, wherein th smectite is a montmorillonite clay.
6. Adsorbent as claimed in claims 1-5, containing mixture of the complex and a filter aid.
7. Adsorbent as claimed in claim 6, wherein the filte aid comprises fibre-like material such as mineral wool and/o particle-like material such as sand.
8. Sealing layer containing a mixture of an adsorbent a claimed in claims 1-5, sand and clay.
9. Sealing layer as claimed in claim 8, wherein the mixture contains adsorbent, sand and clay in a weigh ratio of 0.5-5:5-10:0.2-5.
10. Sealing layer as claimed in claim 9, wherein the weight ratio amounts to 1-3:6-8:0.5-2.
11. The use of the adsorbent as claimed in claims 1-5 for cleaning soil contaminated with heavy metals.
*****
PCT/NL1993/000036 1992-02-20 1993-02-18 Adsorbent, sealing layer and use of the adsorbent for immobilising heavy metals WO1993016797A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9200322A NL9200322A (en) 1992-02-20 1992-02-20 ADSORBENT, SEALING COAT AND USE OF THE ADSORBENT FOR IMMOBILIZING HEAVY METALS.
NL9200322 1992-02-20

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2277515A (en) * 1993-03-15 1994-11-02 Sevenson Environmental Service Treating metal-bearing waste
EP0765842A1 (en) * 1995-08-28 1997-04-02 Rheox International, Inc. Process for the removal of heavy metals from aqueous systems using organoclays
EP0845306A1 (en) * 1995-07-05 1998-06-03 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Wastes disposing material and method for disposing of wastes
WO1999034913A1 (en) * 1997-12-31 1999-07-15 METAL ADSORBENS PROMOTION COMPANY N.V. in het kort 'METAPRO' Composition of adsorbent
WO2000062949A1 (en) * 1999-04-15 2000-10-26 Upperforce Limited Treatment of polluted or contaminated substrates
CN103639194A (en) * 2013-12-26 2014-03-19 江苏盖亚环境工程有限公司 Method for repairing mercury polluted soil by sodium bentonite
CN105682813A (en) * 2013-10-28 2016-06-15 吉野石膏株式会社 Insolubilizing material for specific hazardous substance and method for insolubilizing specific hazardous substance with same
CN109122143A (en) * 2018-09-14 2019-01-04 国家地质实验测试中心 A kind of technique in the micro- geochemistry barrier technique repairing heavy metal pollution rice transplanting rice cultivation field of root system

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH682810A5 (en) * 1992-09-04 1993-11-30 Industrieorientierte Forsch Methods for immobilizing organic and inorganic pollutants in a contaminated soil material of a remediation site.
CN115301713B (en) * 2022-08-09 2023-07-25 北京建工环境修复股份有限公司 Harmless treatment method for barium slag and compound thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
GB2162223A (en) * 1984-07-26 1986-01-29 Soletanche Process for leakproofing a storage space for wastes containing metal cations
EP0313016A2 (en) * 1987-10-21 1989-04-26 Förster, Fritz Inorganic, insoluble industrial raw material producible from waste, method for its production and use
EP0338438A1 (en) * 1988-04-16 1989-10-25 CPM Ceramic Patent Management, Inc. Process for treating or processing clay or clayey masses, process for disposing of harmful substances by clay or clayey masses, and dumping ground sealing or lining by clay or clayey masses

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2162223A (en) * 1984-07-26 1986-01-29 Soletanche Process for leakproofing a storage space for wastes containing metal cations
EP0313016A2 (en) * 1987-10-21 1989-04-26 Förster, Fritz Inorganic, insoluble industrial raw material producible from waste, method for its production and use
EP0338438A1 (en) * 1988-04-16 1989-10-25 CPM Ceramic Patent Management, Inc. Process for treating or processing clay or clayey masses, process for disposing of harmful substances by clay or clayey masses, and dumping ground sealing or lining by clay or clayey masses

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 115, no. 15, 14 October 1991, Columbus, Ohio, US; abstract no. 163326t, KEIZER P. 'ADSORPTION OF HEAVY METALS BY CLAY-ALUMINUM HYDROXIDE COMPLEXES' page 254 ; *
DATABASE WPI Week 7636, Derwent Publications Ltd., London, GB; AN 76-67472X *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2277515A (en) * 1993-03-15 1994-11-02 Sevenson Environmental Service Treating metal-bearing waste
GB2277515B (en) * 1993-03-15 1997-07-09 Sevenson Environmental Service Fixation and stabilization of metals in contaminated materials
EP0845306A1 (en) * 1995-07-05 1998-06-03 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Wastes disposing material and method for disposing of wastes
EP0845306A4 (en) * 1995-07-05 1998-07-08
EP0765842A1 (en) * 1995-08-28 1997-04-02 Rheox International, Inc. Process for the removal of heavy metals from aqueous systems using organoclays
US6339040B1 (en) 1997-12-31 2002-01-15 Metal Adsorbens Promotion Company N.V. Composition of adsorbent
BE1011691A4 (en) * 1997-12-31 1999-12-07 Boodt Marcel De COMPOSITION OF adsorbent.
WO1999034913A1 (en) * 1997-12-31 1999-07-15 METAL ADSORBENS PROMOTION COMPANY N.V. in het kort 'METAPRO' Composition of adsorbent
WO2000062949A1 (en) * 1999-04-15 2000-10-26 Upperforce Limited Treatment of polluted or contaminated substrates
CN105682813A (en) * 2013-10-28 2016-06-15 吉野石膏株式会社 Insolubilizing material for specific hazardous substance and method for insolubilizing specific hazardous substance with same
JPWO2015064522A1 (en) * 2013-10-28 2017-03-09 吉野石膏株式会社 Insolubilizing material for specified hazardous substances and method for insolubilizing specified hazardous substances using the same
EP3064286A4 (en) * 2013-10-28 2017-05-24 Yoshino Gypsum Co., Ltd. Insolubilizing material for specific hazardous substance and method for insolubilizing specific hazardous substance with same
US10125317B2 (en) 2013-10-28 2018-11-13 Yoshino Gypsum Co., Ltd. Insolubilizing material for specific hazardous substance and method for insolubilizing specific hazardous substance with same
CN105682813B (en) * 2013-10-28 2020-05-05 吉野石膏株式会社 Insolubilization material for specific harmful substance and insolubilization method using the same
CN103639194A (en) * 2013-12-26 2014-03-19 江苏盖亚环境工程有限公司 Method for repairing mercury polluted soil by sodium bentonite
CN109122143A (en) * 2018-09-14 2019-01-04 国家地质实验测试中心 A kind of technique in the micro- geochemistry barrier technique repairing heavy metal pollution rice transplanting rice cultivation field of root system
CN109122143B (en) * 2018-09-14 2021-02-05 国家地质实验测试中心 Process for repairing heavy metal pollution seedling-throwing planting paddy field by root system micro-geochemical barrier technology

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NL9200322A (en) 1993-09-16
AU3769093A (en) 1993-09-13

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