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WO1998008991A1 - Procede de phytoextraction de nickel, cobalt et autres metaux presents dans le sol - Google Patents

Procede de phytoextraction de nickel, cobalt et autres metaux presents dans le sol Download PDF

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Publication number
WO1998008991A1
WO1998008991A1 PCT/US1997/015109 US9715109W WO9808991A1 WO 1998008991 A1 WO1998008991 A1 WO 1998008991A1 US 9715109 W US9715109 W US 9715109W WO 9808991 A1 WO9808991 A1 WO 9808991A1
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WO
WIPO (PCT)
Prior art keywords
soil
solution
concentration
nickel
alyssum
Prior art date
Application number
PCT/US1997/015109
Other languages
English (en)
Inventor
Rufus L. Chaney
Jay Scott Angle
Yin-Ming Li
Original Assignee
University Of Maryland College Park
United States As Represented By The Secretary Of Agriculture
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 University Of Maryland College Park, United States As Represented By The Secretary Of Agriculture filed Critical University Of Maryland College Park
Priority to US09/147,721 priority Critical patent/US6786948B1/en
Priority to AU42380/97A priority patent/AU4238097A/en
Priority to CA2272849A priority patent/CA2272849C/fr
Publication of WO1998008991A1 publication Critical patent/WO1998008991A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • This invention pertains to a method of extracting nickel, cobalt and other metals, including the platinum and palladium metal families, from soil by cultivation of the soil with hyperaccumulating plants that concentrate these metals in above-ground portions of the plants, which can be harvested, dried and smelted to recover the metal (metal phytomining).
  • U.S. Patent 5,364,451 Raskin et al.. is directed to a method of removing metals from metal-rich soil by growing genetically altered plants of the family Brassicaceae in these soils, so as to remediate polluted soils at a reduced cost.
  • Suitable parents for the mutants that are the subject of the Raskin patent include B. juncea. While the patent generally describes a large number of metals that may be recovered, specific artificial examples are directed to recovery of chromium and lead.
  • the entire disclosure of U.S. Patent 5,364,451 is incorporated herein by reference.
  • Nickel is a natural constituent in all soils, being particularly high in concentration in serpentine, lateritic serpentine, ultramafic and meteor-derived soils. Cobalt, which has chemical and geological characteristics very similar to nickel, can similarly be found in these soils, and is another valuable metal.
  • Other metals that are also subjects for phytomining within the scope of the invention including those of the platinum and palladium families, including palladium, rhodium, ruthenium, platinum, iridium, osmium and rhenium which commonly co-occur with Ni and Co.
  • Cultivation of plants which are hyperaccumulators of these metals, in metal-rich soils, or "phytomining" is a desirable alternative as a means for recovering metals from soil.
  • Ordinary cultivation methods without adequate preparation and maintenance of soil conditions, does not lead to adequate hyperaccumulation of metals in the plants economically interesting. Additionally, specific methods for recovery of the metals remain to be explored.
  • a ratio recognized as important in maintaining the health of various plants endemic to serpentine soils is the exchangeable Ca/Mg ratio.
  • Prior art reports set a ratio of about 0.67 recommended as a fertility index. Alexander et aL, Soil Sci. 149: 138-143 (1990).
  • exchangeable Ca/Mg ratios in serpentine soils are at much lower values of about 0.2.
  • the general teaching of the art is that to preserve fertility, a substantial increase in available calcium is required, which can be expected to decrease nickel uptake.
  • the inventors By screening a wide variety of plants from the Brassicaceae family, the inventors have identified plants in the Alyssum genus which may be hyperaccumulators of nickel and which accumulate valuable amounts of cobalt.
  • hyperaccumulator plants accumulate over 1000 mg Ni or Co/kg dry weight growing in the soils where they evolved. Because cobalt occurs at about 3- 10% of the level of Ni in the listed soils, Ni is the dominant toxic metal which induced evolutionary selection of the Ni hyperaccumulator plants and Co is accumulated to economically useful levels but Ni hyperaccumulation is the dominant economic benefit of the phytomining technology.
  • Evidence suggests members of the section Odontarrhena of the genus Alyssum are likely candidates as nickel hyperaccumulators.
  • the plant may also concentrate, in the above-ground plant tissues, metal from the platinum and palladium families, including Pd, Rh, Ru, Pt, Ir, Os and Re, in significant amounts. Accumulation of nickel in plant tissues in excess of 2.5 percent is practicable.
  • the metals listed accumulate in biomass by growing nickel hyperaccumulating Alyssum species in the target soils.
  • Some 48 taxa within the section Odontarrhena of the genus Alyssum are known to be hyperaccumulators of nickel. These include the following species already evaluated: A. murale, and A. pintodasilvae (A. serpyllifolium ssp.), A. malacitanum, A. lesbiacum, and A. fallacinum.
  • Other Ni-hyperaccumulating species which may be employed include: A. argenteum, A. bertolonii, A. tenium, A. heldreichii. About 250 other plant taxa have been shown to hyperaccumulate nickel, but many of these do not exceed 10,000 mg Ni/kg d.w., and the majority are of tropical origin.
  • the identified metal species are accumulated by growing the Alyssum in nickel-rich soil, under specific soil conditions.
  • the conditions include: (1) lowering the soil pH, which increases the phytoavailability of nickel; (2) maintaining moderate levels of Ca in the soil by appropriate treatments and by use of Ca, Mg- rich soil amendments adjusted to maintain Ca levels at levels corresponding to solution values between 0.128 mM and 5.0 mM; (3) using ammonium constraining or ammonium-generating nitrogen fertilizers to improve plant growth and to increase Ni hyperaccumulation due to rhizosphere acidification; and (4) applying chelating agents to the soil to improve nickel uptake by the roots of the hyperaccumulating Alyssum species.
  • suitable chelating agents include nitrilotriacetic acid (NT A) .
  • chelating agents commonly used in connection with increasing soil metal mobility for plant uptake include ethylenediaminetetraacetic acid, and ethylene glycol-bis-( ⁇ -aminoethylethehr)-N, N- tetraacetic acid. Maintenance of these soil-conditioning factors will improve nickel hyperaccumulation in Alyssum, in excess of a 2.5 percent concentration in above- ground portions of the plant, particularly leaves and stems or shoots, which make for easy cultivation and metal recovery. This is preferable to concentration in the roots, discussed in Raskin et al.. which may be an aid in soil rededication if non- leachable therefrom, but does not offer convenience for phytomining.
  • FIGS. 1 -10 are graph illustrations of experimental data obtained and discussed below.
  • Figures 1-3 reflect shoot yield for given levels of Ni as a function of Ca concentration for Cabbage, A.murale and A. pintodasilvae, respectively.
  • Figures 4-6 reflect Ni levels in shoots for given levels of Ni as a function of Ca concentration for Cabbage, A.murale and A. pintodasilvae, respectively.
  • Figures 7-8 reflect the ratio of Ni in shoots/roots for A.murale and A. pintodasilvae, respectively.
  • Figures 9-10 reflect shoot Ni content at five given Ni concentration values as a function of Ca concentration for A.murale and A. pintodasilvae, respectively.
  • Applicants have screened a large wild-type collection of germplasm to identify hyperaccumulating plants.
  • plants of the Brassicaceae family particularly naturally occurring plants as opposed to those with induced mutations, such as those employed in the Raskin patent, are known to be Ni + Co accumulators.
  • Ni + Co accumulators Within the family, and even with the various genera, however, wide variations in metal accumulation, to the extent it occurs, do appear.
  • Alyssum species that are preferred candidates for use in the claimed invention concentrate and hyperaccumulate nickel, shown enhanced uptake of cobalt and may be useful in accumulating other metals.
  • Preferred species have a preference for, and a high toxicity resistance to these metallic elements. This appears to be due to evolutionary driving forces, which permit the plant to benefit from the ecological niche presented.
  • Thlaspi caerulescens which accumulates very high levels of zinc and cadmium. While Alyssum exhibits a higher uptake rate at low nickel and cobalt concentrations than other species, Thlaspi actually grow well on soils with much higher Zn and Cd concentrations. Thus, while Alyssum concentrates nickel and cobalt over a range of concentrations, Thlaspi hyperaccumulates very high levels of Zn and Cd, some strains accumulating Ni and Co. Rather than relying on the unpredictable process of mutagenesis, the applicants in screening a large library of wild-type germplasm, have identified several Alyssum species including A. murale, A.
  • pintodasilvae A. serpyllifolium ssp.
  • A. malacitanum A. lesbiacum
  • A. tenium A. fallacinum
  • Pd, Rh, Ru, Pt, Ir, Os and Re accumualte
  • the soil in which they are grown is preferentially conditioned taking advantage of different factors.
  • pH of soil is altered or modified so as to maintain it within a near neutral range of about 6.0-7.5.
  • soil near a limestone foundation or other building may be treated with acidifying soil amendments so as to reduce an alkaline pH.
  • Soil with a naturally low pH may instead be treated with limestone or similar amendment, so as to increase the soil pH.
  • a reduced pH increases the phytoavailability of nickel and cobalt.
  • a reduced pH increases solubility and optimizes the release of these metals for absorption by the roots, and translocation to the above-ground tissues of the plant.
  • Soil pH can be maintained in any of a variety of established methods, and the methods themselves do not constitute an aspect of this invention.
  • soil pH is managed at a low value by addition of sulfur and use of ammonium - N fertilizers.
  • An optimum pH range for phytomining using Alyssum is a pH of 4.5 to 6.2, preferably 5.2-6.2. After extraction of economically phytominable Ni and Co from the soil, limestone application can raise soil to pH levels required by more traditional farm crops.
  • Alyssum species which hyperaccumulate Ni and Co evolved in Ni-rich ultramafic and serpentine soils which simultaneously have low soil calcium.
  • the presence of extremely low and extremely high calcium concentrations in soil inhibits nickel/cobalt hyperaccumulation by Alyssum.
  • Acceptable calcium concentrations in soil ranges from 0.128 mM to 5.0 mM, as set forth in the examples below.
  • Calcium concentrations may be maintained by any of a variety of known methods. One method involves acidification of the soil with sulfur, sulfuric acid, or other amendments and leaching, followed by use of Ca soil amendments. Whatever method is selected to adjust calcium concentration in soil, it should be selected so as to be consistent with the objective of soil phytomining.
  • Metal chelates are commonly used in agriculture, and occur naturally is living cells.
  • the addition of chelating agents, such a NTA, or any of a variety of amino-acetic acids known to those of ordinary skill in the art as chelating agents, to the soil to be phytomined for Ni/Co and Pt, Pd metals improves the movement of soil metals to root surfaces for uptake and translocation of these materials into the above-ground plant tissues.
  • Any of a variety of known chelating agents of commerce may be used.
  • a preferred chelating agent is NTA or EDTA.
  • chelating agents will be added at 5-100 kg/ha after the plants are established. As with the use of fertilizers, optimum additions of chelating agents can be determined on an empirical basis. Chelating compounds which chelate Ni int eh presence of high soil levels of Fe, Mg, and Ca selectively increase Ni uptake by the hyperaccumulator plants. Metal Recovery
  • a principal object of this invention is the recovery of the metal sequestered by the hyperaccumulating plant.
  • plants are identified which accumulate the metals in the roots. Recovery of metals from roots poses substantial mechanical problems, including the recovery of the root itself, as well as recovery of the metal from the root-tissue.
  • Alyssum genotypes as contemplated in the claimed invention, a very high degree of the nickel/cobalt absorbed by the roots is translocated to above-ground tissues, such as stems, leaves, flowers and other leaf and stem tissues. This feature facilitates recovery of the metal extracted from the soil.
  • the Alyssum can be harvested in conventional fashion, that is, cutting of the plant at soil level.
  • the harvested materials are left to dry, in much the same fashion that alfalfa is dried, so as to remove most of the water present in the plant tissues.
  • the plant material is collected from the field by normal agricultural practices of hay-making, incinerated and reduced to an ash with or without energy recovery.
  • This organic material may alternatively be further treated by roasting, sintering, or smelting methods which allow the metals in an ash or ore to be recovered according to conventional metal refining methods such as acid dissolution and electrowinning. With metal concentrations as high as 2.5 to 5.0% in the above-ground plant tissues, particularly leaves or shoots, metal recovery becomes economical, thus satisfying the primary objective of the invention.
  • a nutrient solution study was conducted to define the effects of Ca and Mg on Ni uptake by two know Ni hyperaccumulator species, Alyssum murale and Alyssum pintodasilvae, compared to the normal non-tolerant crop species, cabbage (Brassia oleracea var. capitata) cultivar Danish Roundhead.
  • a varying solution concentrations of Ni (3 levels) and Ca (5 levels) were used in a factorial experimental design for Alyssum, while 2 levels of Ni and 5 levels of Ca were used in a factorial experimental design for cabbage. All solutions contained a high concentration of Mg to simulate serpentine soils where phytomining plants might be grown. Seeds for Alyssum murale and Alyssum pintodasilvae were collected from plants growing in Panorama, Thessaloniki, N. Greece and Braganca, NE Portugal.
  • the study was conducted in an environmental growth chamber; temperature in the chamber was maintained at 25 °C day and 19°C night, and relative humidity was set at 70% .
  • the day period was maintained for 16 hours periods with >400 ⁇ Em "2 sec " ' photosynthetically active radiation at plant height from a combination of cool -white fluorescent and incandescent lamps.
  • Alyssum seeds were treated with ethanolic Arasan for 45 seconds and germinated by placing seeds in company germination bags with a macronutrient solution (1 mM Mg as MgSO 4 ; 2.5 mM CaNO 3 and KNO 3 ; 0.1 mM K j HPO ⁇ . The bags were kept moist all the time.
  • Alyssum seedlings were transferred into 8 L buckets containing a 0.5 strength Hoagland solution (1 mM Mg as MgSO 4 ; 2.5 mM CaNO 3 and KNO 3 ; 0.1 mM K 2 HPO 4 ; 20 ⁇ M Fe as FeHBED; 75 ⁇ M KC1; 25 ⁇ M HC1; 10 ⁇ M H,BO 3 ; 2 ⁇ M Mn as MnCl 2 ; 05 ⁇ M Cu as CuSO 4 ; and 0.2 ⁇ M Mo as NajMoO,; 1.0 mM Zn as ZnSO 4 ). Seedlings were maintained in these buckets for an additional 2 weeks to grow to larger or reasonable handling before transplanting to treatment solutions.
  • Hoagland solution 1 mM Mg as MgSO 4 ; 2.5 mM CaNO 3 and KNO 3 ; 0.1 mM K 2 HPO 4 ; 20 ⁇ M Fe as FeHBED; 75 ⁇ M KC1; 25 ⁇ M HC1; 10
  • Cabbage seeds germination was begun 10 days before transplanting to treatment solutions. Cabbage seeds were placed in standard seed germination papers with the same germination macronutrient solution and showed good germination within six days.
  • one plant of each species was transferred to separate 1 L polyethylene beakers containing a modified 0.5 strength Hoagland solution (2 mM MG as MgSO 4 ; 2.5 mM KNO 3 ; 0.1 mM K 2 HPO 4 ; 20 ⁇ M Fe as FeHBED; 75 ⁇ M KC1; 25 ⁇ M HC1; 15 ⁇ M H 3 BO 3 ; 2 ⁇ M Mn as MnCI 2 ; 0.5 ⁇ M Cu as CuSO 4 ; 0.2 ⁇ M MO as NaMoO 4 ; and 1.0 mM Zn as ZnSO 4 ) with 2 mM MES to maintain solution pH at 6.2, high Mg level (2 mM) and Ca and Ni treatments.
  • FeHBED was used because even high levels of Ni or micronutrients do not displace Fe from this chelate, and dicots easily obtain the Fe by reduction.
  • a randomized complete block design with three replications was used.
  • the plants were placed into polyurethane foam plant supports and inserted into a slot and hole in a black plexiglass cover.
  • the beakers were covered with black polyethylene to minimize light exposure. Each beaker was continuously aerated.
  • Plants were harvested six weeks after treatment initiation. At harvest, plants were separated into roots and shoots. Plants were rinsed with deionized water. Roots were rinsed with 2.5 mM Ca(NO 3 ) 2 to remove extracellular metals prior to rinsing with deionized water. All samples were dried at 65 °C in a forced draft oven.
  • Ni was supplied as NiSO 4 6H 2 O. Three high concentrations Ni treatments were established for the Alyssum spp. (31.6 ⁇ M, 316 ⁇ M, and 1000 ⁇ M), and two Ni treatments were established for cabbage (1.0 ⁇ M and 10.0 ⁇ M) based on preliminary studies of Ni tolerance by these species.
  • Ca was supplied as Ca(NO 3 ) 2 4H 2 0 with NH 4 NO 3 to adjust nitrogen concentration to 10 mM for all treatments.
  • Necessary dilutions were made in IN HC1 to maintain constant viscosity. Blanks were prepared for every 10 samples and NBS#1575 pine needles standard reference materials were digested for every 20 samples for quality assurance. Plant analysis was performed in duplicate when there was sufficient sample. Ni concentration of plants were determined using a flame atomic absorption spectrometer (AA). Zn, P, Cu, Mn, Fe, Mg, Ca, and K concentrations were analyzed by using an ICP-ES (emission spectrometer), and all results were corrected by use of the internal standard. Statistical Analysis
  • Alyssum species translocated a greater percentage of Ni to shoot tissue.
  • Shoot contained was 84% to 98% of total plant Ni acrose all Ni and Ca treatments.
  • Shoot Ni/root Ni concentration ratio values ranged from 1 to 10 (Figs. 7,8), far higher than found in cabbage or in tomato (Chaney et al. 1997).
  • the best treatment to get maximum Ni content in shoots was 316 ⁇ M Ni with 5 mM Ca for Alyssum murale (50 mg/plant) and 1000 ⁇ M Ni with 2 mM Ca for Alyssum pintodasilvae (40 mg/plant) in 6 weeks growth period.
  • Cabbage shoots contained only less than 1.5 mg Ni/plant in all conditions.
  • Table 1A Mean squares (MS) for the combined analyses over species, Ni treaiments, Ca treatments, and blocks on shoot yield (log g) of 2 Alyssum spp. and 1 cabbage reference species.
  • TablelB M-.ean squares (MS) for the combined analyses ov:er species, Ni treatm ents, Ca tr.eatm.tnts, and blocks on shoot Ni concentration 1 of 2 Alyssum spp. and 1 cabbage r.efc er.ence sp:eci-.es.
  • Type I MS for Sp.ec s x Ni trt x Ca trt was us:ed as tb:e .error Ue ⁇ n to test for hypoth:es.es. t Ni concentration is log mg L '1 .
  • Table IC Mean squares (MS) for the combined analyses by species, Ni treatments, Ca treatments, and blocks on shoot yield t of 2 Alyssum spp. and 1 cabbage reference species.
  • Type III MS for Species x Ni trt x Ca trt was used as the error term to test for hypotheses.
  • t shoot yield is log g. Table ID. Mean squares (MS) for the combined analyses by species, Ni treatments, Ca treatments, and blocks on shoot Ni concentration 1 of 2 Alyssum spp. and 1 cabbage reference species.
  • Type III MS for Species x Ni trt x Ca trt was used as the error term to test for hypotheses.
  • t Ni concentration is log mg L l .
  • Table 2 Nickel concentration for Ni treatment* additions to 0.5 strength Hoagland solution with 2.0 mM MgSO 4 , respectively.
  • t NiSO was used as nickel treatments. Due to the death of cabbage before nickel ⁇ eatment reaching 31.6 mM in pre-experiment, cabbage was only applied 2 lower nickel levels.
  • t Alyssum spp. are Alyssum murale and Alyssum pintodasilvae Table 3. Mean squares from analysis of variance of shoot, root, and whole plant dry matter yield, Ni concentration, and Ca concentration for A. murale, A. pintodasilvae, and cabbage across Ca and Ni treatments, respectively.
  • Table4B Matrix of correlation coefficient (r) of interelemental relationships in Ni hyperaccumulator, Alyssum pintodasilvae , grown in 0.5 strength Hoagland solution with nickel and calcium treatments.
  • Tabll ⁇ C ilvatrix of correlation coefficient (r) of interelemental relationships in cabbage grown in 0.5 strength Hoagland solution with nickel and calcium treatments.

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  • Engineering & Computer Science (AREA)
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  • Chemical & Material Sciences (AREA)
  • Mycology (AREA)
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Abstract

L'invention concerne un procédé de phytoextraction de nickel, cobalt et autres métaux. A cet effet, les plantes du genre Alyssum sont cultivées dans des sols riches en nickel. On peut favoriser l'absorption du nickel en maintenant le sol dans des conditions spécifiques, par ex. une concentration en calcium supérieure à 0,128 mM et inférieure à 5,0 mM et un pH acide. On peut accroître davantage l'absorption du nickel en maintenant un rapport Ca/Mg échangeable de 0,16-0,40. Cette absorption peut être encore accrue par addition d'agents chélateurs et d'engrais à base d'ammonium.
PCT/US1997/015109 1996-08-30 1997-08-29 Procede de phytoextraction de nickel, cobalt et autres metaux presents dans le sol WO1998008991A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US09/147,721 US6786948B1 (en) 1996-08-30 1997-08-29 Method for phytomining of nickel, cobalt and other metals from soil
AU42380/97A AU4238097A (en) 1996-08-30 1997-08-29 Method for phytomining of nickel, cobalt and other metals from soil
CA2272849A CA2272849C (fr) 1996-08-30 1997-08-29 Procede de phytoextraction de nickel, cobalt et autres metaux presents dans le sol

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US2492896P 1996-08-30 1996-08-30
US60/024,928 1996-08-30
US3046296P 1996-11-06 1996-11-06
US60/030,462 1996-11-06

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2787143A1 (fr) 1998-12-14 2000-06-16 Magneti Marelli France Detection de l'encrassement d'un filtre a carburant d'un circuit d'alimentation d'un moteur a combustion interne
EP0993510A4 (fr) * 1997-06-20 2000-08-23 Univ Sheffield Procede de phytoextraction de nickel, de cobalt et d'autres metaux presents dans le sol
AU775573B2 (en) * 1997-06-20 2004-08-05 United States Of America, As Represented By The Secretary Of Agriculture, The Recovering metals from soil
US7049492B1 (en) 1998-11-23 2006-05-23 The United States Of America As Represented By The Secretary Of Agriculture Thlaspi caerulescens subspecies for cadmium and zinc recovery
US7268273B2 (en) 1995-06-06 2007-09-11 The University Of Maryland Recovering metals from soil

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102515939B (zh) * 2011-11-26 2013-05-29 湖南科技大学 一种将富集重金属植物转化为矿山植被恢复专用的含生物炭土杂肥的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364451A (en) * 1993-06-04 1994-11-15 Phytotech, Inc. Phytoremediation of metals

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364451A (en) * 1993-06-04 1994-11-15 Phytotech, Inc. Phytoremediation of metals

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7268273B2 (en) 1995-06-06 2007-09-11 The University Of Maryland Recovering metals from soil
EP0993510A4 (fr) * 1997-06-20 2000-08-23 Univ Sheffield Procede de phytoextraction de nickel, de cobalt et d'autres metaux presents dans le sol
AU775573B2 (en) * 1997-06-20 2004-08-05 United States Of America, As Represented By The Secretary Of Agriculture, The Recovering metals from soil
US7049492B1 (en) 1998-11-23 2006-05-23 The United States Of America As Represented By The Secretary Of Agriculture Thlaspi caerulescens subspecies for cadmium and zinc recovery
FR2787143A1 (fr) 1998-12-14 2000-06-16 Magneti Marelli France Detection de l'encrassement d'un filtre a carburant d'un circuit d'alimentation d'un moteur a combustion interne

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CA2272849C (fr) 2011-11-01
AU4238097A (en) 1998-03-19

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