Patent Application
20080134364
1. Field of the Invention
This invention pertains to methods for recovering metals, such as nickel and cobalt, from metal-rich soil using phytoextracting or phytomining techniques. Metals can be selectively extracted from soil by cultivating certain metal hyperaccumulating plants, such as Alyssum plants, on soil treated to adjust the pH.
2. Related Art
Industrial practices such as mining, smelting and disposing of manufacturing wastes have increased the concentrations of toxic metals in the environment. For example, at many nickel mining and smelting sites, levels of nickel and cobalt in soil have become so high that few plants survive, resulting in severe disruption of local ecosystems. Once nickel and cobalt enter soil, their removal is difficult since they are relatively immobile and they do not degrade into less toxic substances. The size of the areas affected by smelter and mine wastes are usually so large that engineering methods of soil remediation, such as soil removal and replacement, are too expensive to be practical (Cunningham et al., “Phytoremediation of Contaminated Soils,” Trends Biotechnol. 13: 393-397 (1995)).
The ability of certain plants to grow in metal-containing or metal-contaminated soil, and to actively accumulate heavy metals in their tissues, has created an interest in using such plants to extract metals from soil. Growing plants, including crops, on contaminated soil to extract contaminants is referred to as phytoextraction. This method is particularly effective in arable contaminated soils because it causes little disruption or dispersal, while preserving soil fertility and landscapes.
Nickel is one of the most widely found, and technologically important metals. It is a natural constituent in all soils, being particularly high in concentration in certain types of soil and geological materials such as serpentine, lateritic serpentine, ultramafic and meteor-derived soils. Cobalt, another valuable metal, has chemical and geological characteristics very similar to nickel and is generally found in the same soils. Other metals that may be found in such soils include those of the platinum and palladium families such as palladium, rhodium, ruthenium, platinum, iridium, osmium and rhenium, and metals such as selenium, zinc and cadmium.
Sites containing serpentine, lateritic serpentine, ultramafic and meteor-derived soils and materials can be conventionally mined or cultivated with metal-accumulating plants. Using such plants to extract metals from mineralized (geogenic) soils is referred to as phytomining.
U.S. Pat. No. 5,364,451 to Raskin et al., is directed to a method of remediating polluted soils at a reduced cost. Raskin et al. remove metals from metal-rich soil by growing plants of the family Brassicaceae in the metal-rich soil. While Raskin et al. generally describe a variety of plants and a large number of metals that may be recovered, the examples mainly describe the recovery of chromium and lead from genetically altered plants. Thus, although promising, Raskin et al. offer little basis for an opportunity to proceed directly with soil phytomining or phytoextraction through plant growth or cultivation.
U.S. Pat. No. 5,785,735 to Raskin et al., is also directed to methods of remediating polluted soils. Raskin et al. remove metals from metal-rich soil by growing crop and crop-related members of the plant family Brassicaceae in the metal-rich soil. The methods require the formation of a complex between the metal and a chelating agent added to the soil, the application of an electric field to the soil or a reduction in the pH of the soil. While Raskin et al. generally describe a variety of plants, the specification mainly describes the recovery of metals from genetically altered plants. Thus, again, Raskin et al. offer little basis for an opportunity to proceed directly with soil phytomining or phytoextraction through plant growth or cultivation.
Scientists recognize that increasing the pH of soil decreases the ability of farm crops to take-up heavy metals. U.S. Pat. No. 5,711,784 to Chaney et al. reflects the belief in the art that reducing the pH of the soil “increases the phytoavailability of nickel and cobalt.” As disclosed by Chaney et al., 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.” However, reducing the pH of the soil also renders the metals more mobile and may allow for further contamination of the site. Therefore, cultivating plants which are hyperaccumulators of nickel, cobalt and other metals through phytoextraction or phytomining, is a desirable alternative as a means for recovering such metals.
Accordingly, this invention relates to improved systems for recovering metals by phytomining or phytoextracting soils rich in metals.
The invention further relates to increasing nickel uptake by plants used in phytomining and phytoextraction by elevating the soil pH. Nickel is ultimately recovered from plant tissues at economically acceptable levels without further contaminating the nickel-containing site.
The invention further relates to lowering the pH in soils prior or subsequent to nickel (or cobalt) recovery to collect, for example, cobalt (or nickel) or any other metal present in the metal-laden soil.
In a particular aspect of the invention, Alyssum plants are cultivated under favorable pH conditions to selectively accumulate certain metals relative to other metals.
The invention further relates to a method for selectively increasing the amount of at least one metal recovered from metal-containing soil comprising:
(a) elevating or lowering the pH of the soil;
(b) cultivating at least one metal-hyperaccumulator plant in the soil under conditions sufficient to permit said at least one plant to accumulate at least one metal from the soil in above-ground tissue;
(c) elevating the pH of the soil if the pH was lowered in step (a) or lowering the pH of the soil if the pH was elevated in step (a); and
(d) cultivating the at least one metal-hyperaccumulator plant in the soil under conditions sufficient to permit said at least one plant to accumulate at least one second metal from the soil in above-ground tissue.
The invention further relates to a method for recovering nickel from nickel-containing soil comprising:
(a) elevating the pH of the soil;
(b) cultivating at least one nickel-hyperaccumulator plant in the soil under conditions such that at least 0.1% of the above-ground tissue of said at least one plant, on a dry weight basis, is nickel;
(c) harvesting said at least one plant; and
(d) recovering nickel from said harvested plant.
The invention further relates to a method for recovering cobalt from cobalt-containing soil comprising:
(a) lowering the pH of the soil;
(b) cultivating at least one cobalt-hyperaccumulator plant in the soil under conditions such that at least 0.1% of the above-ground tissue of said at least one plant, on a dry weight basis, is cobalt;
(c) harvesting said at least one plant; and
(d) recovering cobalt from said harvested plant.
The invention further relates to the identification of new hyperaccumulating species of Alyssum whereby collected plants are screened by comparing nickel-uptake by the plants to nickel-uptake by the bench-mark nickel-hyperaccumulator A. murale 103. These new metal-hyperaccumulating species, cultivated on nickel-containing soil, accumulate nickel in above-ground tissue at a concentration of 1.55% or greater by weight based on the gross dry weight of the tissue.
The invention further relates to seeds of the Alyssum plant species.
The invention further relates to pollen of the Alyssum plant species.
The invention further relates to plants that have all the physiological and morphological characteristics of the Alyssum plant species.
The invention further relates to propagation material of the Alyssum plant species.
The invention further relates to a method for decontaminating metal-containing soil, comprising cultivating at least one hyperaccumulator plant in metal-containing soil, whereby the concentration of metal in the above-ground plant tissue of the at least one hyperaccumulator plant exceeds the concentration of metal in the soil by a factor of at least 2.
In the present invention, it was discovered that certain metals can be selectively recovered from metal-rich soil using phytoextraction or phytomining techniques employing plants classified as hyperaccumulators of metals. By cultivating selected plants on metal-containing soil, the metals absorbed by the roots can be translocated to above-ground tissues, such as the stems, leaves, flowers and other leaf and stem tissues. This feature facilitates recovery of the metal extracted from the soil. Metal concentrations can be as high as about 5.0% in above-ground plant tissues, when leaves are included, which renders the metal recovery very economical. However, recovering metal in concentrations of less than about 5.0%, such as about 4.0%, 3.0%, 2.5%, 1.0% or 0.1% remains useful. For example, a recovery of about 1.0% or more offers economic return for decontaminating polluted soil and for phytomining. However, it should be recognized that economic return may depend on the market price for a particular metal, so that a higher market price for a metal may provide for an economic return for decontaminating polluted soil and/or phytomining at even lower metal concentration recovery, for instance recovering metal at a concentration of about 0.1%. Furthermore, a recovery of about 0.1% to about 1.0% of cobalt is sufficient to decontaminate polluted soil at a low cost, and a recovery of even less than about 0.1% of some metals can still effectively decontaminate polluted soils.
The invention further relates to a method for selectively increasing the amount of at least one metal recovered from metal-containing soil comprising:
(a) elevating or lowering the pH of the soil;
(b) cultivating at least one metal-hyperaccumulator plant in the soil under conditions sufficient to permit said at least one plant to accumulate at least one metal from the soil in above-ground tissue;
(c) elevating the pH of the soil if the pH was lowered in step (a) or lowering the pH of the soil if the pH was elevated in step (a); and
(d) cultivating the at least one metal-hyperaccumulator plant in the soil under conditions sufficient to permit said at least one plant to accumulate at least one second metal from the soil in above-ground tissue.
The invention further relates to a method for recovering nickel from nickel-containing soil comprising:
(a) elevating the pH of the soil;
(b) cultivating at least one nickel-hyperaccumulator plant in the soil under conditions such that at least 0.1% of the above-ground tissue of said at least one plant, on a dry weight basis, is nickel;
(c) harvesting said at least one plant; and
(d) recovering nickel from said harvested plant.
The invention further relates to a method for recovering cobalt from cobalt-containing soil comprising:
(a) lowering the pH of the soil;
(b) cultivating at least one cobalt-hyperaccumulator plant in the soil under conditions such that at least 0.1% of the above-ground tissue of said at least one plant, on a dry weight basis, is cobalt;
(c) harvesting said at least one plant; and
(d) recovering cobalt from said harvested plant.
The invention further relates to the identification of new hyperaccumulating species of Alyssum whereby collected plants are screened by comparing nickel-uptake by the plants to nickel-uptake by the bench-mark nickel-hyperaccumulator A. murale 103. These new metal-hyperaccumulating species, cultivated on nickel-containing soil, accumulate nickel in above-ground tissue at a concentration of 1.55% or greater by weight based on the gross dry weight of the tissue.
The invention further relates to seeds of the Alyssum plant species.
The invention further relates to pollen of the Alyssum plant species.
The invention further relates to plants that have all the physiological and morphological characteristics of the Alyssum plant species.
The invention further relates to propagation material of the Alyssum plant species.
The invention further relates to a method for decontaminating metal-containing soil, comprising cultivating at least one hyperaccumulator plant in metal-containing soil, whereby the concentration of metal in the above-ground plant tissue of the at least one hyperaccumulator plant exceeds the concentration of metal in the soil by a factor of at least 2, preferably by a factor of 2, 3 or 4.
In a preferred aspect of the invention, nickel is selectively accumulated by growing one or more nickel-hyperaccumulating plants in metal-rich, e.g., nickel-rich, soil and elevating the pH of the soil. The pH of the soil may be elevated before, during or after the plants are cultivated. Preferably, the pH is elevated prior to plant cultivation. Thus, the invention relates to the surprising discovery that raising the pH of the metal-rich soil favors nickel accumulation in plant tissue over other metals. The soil pH can then be lowered to selectively accumulate, in the plant tissue, other metals such as cobalt. The preferred pH will depend, inter alia, upon the particular metal and the soil. For example, the preferred pH for nickel extraction ranges between about 6.3 and about 7.0 when the soil is a serpentine soil or when the soil contains high iron oxide levels. The most preferred pH ranges from about 6.3 to about 6.7. However, when the iron oxide level is low, a more alkaline pH may be used. Moreover, those of ordinary skill in the art will recognize, and it has now been uncovered, that nickel accumulation in general may occur over a wide range of soil pH, including elevated soil pH. In fact, it is now recognized that nickel accumulation may occur at soil pH of up to about 10.0, and even higher. For example, in a preferred embodiment of the present invention, nickel accumulation occurs at a pH between about 5.6 and 10.0. In another preferred embodiment of the present invention, nickel accumulation occurs at a pH between about 5.6 and 9.5. In another preferred embodiment of the present invention, nickel accumulation occurs at a pH between about 5.6 and 9.0. In another preferred embodiment of the present invention, nickel accumulation occurs at a pH between about 5.6 and 8.5. In another preferred embodiment of the present invention, nickel accumulation occurs at a pH between about 5.6 and 8.0. In another preferred embodiment of the present invention, nickel accumulation occurs at a pH between about 5.6 and 7.5. In another preferred embodiment of the present invention, nickel accumulation occurs at a pH between about 5.6 and 7.0.
Cobalt extraction is also affected by the soil chemistry. For example, the most preferred pH for cobalt extraction is about 5.5 when aluminum and/or manganese are present in the soil. For metal extraction in general, the preferred pH ranges between about 5.5 and about 7.0. However, it should also be recognized that cobalt accumulation in general may occur over a wide range of soil pH, including elevated soil pH. In fact, it is now recognized that cobalt accumulation may occur at soil pH of up to about 10.0, and even higher. For example, in a preferred embodiment of the present invention, cobalt accumulation occurs at a pH between about 5.6 and 10.0. In another preferred embodiment of the present invention, cobalt accumulation occurs at a pH between about 5.6 and 9.5. In another preferred embodiment of the present invention, cobalt accumulation occurs at a pH between about 5.6 and 9.0. In another preferred embodiment of the present invention, cobalt accumulation occurs at a pH between about 5.6 and 8.5. In another preferred embodiment of the present invention, cobalt accumulation occurs at a pH between about 5.6 and 8.0. In another preferred embodiment of the present invention, cobalt accumulation occurs at a pH between about 5.6 and 7.5. In another preferred embodiment of the present invention, cobalt accumulation occurs at a pH between about 5.6 and 7.0.
Soil pH can be raised and lowered with bases and acids. Such bases and acids may be either naturally occurring or synthetic. To raise the pH, bases such as limestone (calcitic (CaCO3) or dolomitic (CaMgCO3), lime (CaO), hydrated lime (Ca(OH)2), industrial, municipal or agricultural alkaline by-products that contain any of the above bases or a limestone equivalent, or the like can be used. The phrase “limestone equivalent” is intended to encompass bases that have the same alkalinity as limestone. To lower the pH, acids such as organic and inorganic acids can be used. Examples of such organic and inorganic acids include acetic acid, aqueous hydrogen chloride, aqueous sulfuric acid, sulfur, ammonium, urea-containing fertilizers, nitric acid, sulfide minerals, including, but not limited to, pyrite, and the like.
The amount of base or acid to add depends upon the existing pH of the soil and the soil chemistry. Methods used to determine the amount include, but are not limited to, adding acid or a base, such as CaCO3, to the soil sample and measuring the resulting pH, then drawing a pH response curve to extrapolate the amount needed to obtain the desired pH.
After cultivation, the hyperaccumulator plant is harvested in a conventional fashion, i.e., by cutting the plant at soil level. The harvested materials are then left to dry in the field in the manner in which hay is dried. Alternatively, the harvested materials are dried in much the same fashion that alfalfa is dried, so as to remove most of the water present in the plant tissue by forced heated air drying. After drying, the plant tissue is collected by normal agricultural practices of hay-making, incinerated and reduced to an ash with or without energy recovery. Alternatively, the dried plant material may be hydrolyzed with concentrated acid to produce sugars and the metals recovered according to U.S. Pat. Nos. 5,407,817, 5,571,703 and 5,779,164. The sugars may then be fermented to produce ethanol.
The resulting dried plant material may alternatively be further treated by known roasting, sintering or smelting methods which allow the metals in the ash or ore to be recovered according to conventional metal refining methods such as acid dissolution and electrowinning.
Conventional smelting, roasting and sintering temperatures from about 260° C. to about 1000° C. are sufficient to combust the dried plant material to oxidize and vaporize the organic material present and to prevent dioxin accumulation during incineration. The preferred temperature is sufficient to remove the organic carbon to free the ash. The most preferred temperature is about 1000° C. The process leaves a residue of the accumulated metal with few contaminants known to interfere with metal refining. Further, it is expected that the concentration of other components in the ash will be much lower than with conventional mined ore concentrates. For example, serpentine laterite ores generally contain over 10,000 ppm (1%) Fe whereas a biomass obtained using phytomining techniques only contains about 100-500 ppm (0.01-0.05%) Fe.
By definition, nickel-hyperaccumulating plants accumulate at least about 1000 mg of nickel per 1 kg dry weight of plant tissue (obtained from a plant grown in soil where the plant naturally occurs). Similarly, cobalt-hyperaccumulating plants are defined as plants that accumulate at least about 1000 mg of cobalt per 1 kg dry weight of plant tissue (obtained from a plant grown in soil where the plant naturally occurs). However, zinc- and manganese-hyperaccumulators are defined as plants that accumulate at least about 10,000 mg of zinc and manganese, respectively, per 1 kg dry weight of plant tissue (obtained from a plant grown in soil where the plant naturally occurs). Finally, cadmium-hyperaccumulators are defined as plants that accumulate at least about 100 mg cadmium per 1 kg dry weight of plant tissue (obtained from a plant grown in soil where the plant naturally occurs).
By screening a wide variety of plants, those of the Alyssum genus (Brassicaceae family) have been identified as hyperaccumulators of nickel. These plants also naturally accumulate cobalt and may accumulate metals such as Zn, Mn and Cd, and metals from the platinum and palladium families including Pd, Rh, Ru, Pt, Ir, Os and Re.
More specifically, plants which naturally concentrate nickel in above-ground tissues and generally exhibit an enhanced uptake of cobalt and other metals include members of the section Odontarrhena of the genus Alyssum. The metals accumulate in nickel-hyperaccumulating Alyssum plant species when the plants are grown in contaminated soils. Some 48 taxa within the section Odontarrhena of the genus Alyssum are known to be hyperaccumulators of nickel. These include the following species: A. akamasicum, A. alpestre, A. anatolicum, A. callichroum, A. cassium, A. chondrogynum, A. cilicicum, A. condensatum, A. constellatum, A. crenulatum, A. cypricum, A. davisianum, A. discolor, A. dubertretii, A. eriophyllum, A. euboeum, A. floribundum, A. giosnanum, A. hubermorathii, A. janchenii, A. markgrafii, A. masmenaeum, A. obovatum, A. oxycarpum, A. penjwinensis, A. pinifolium, A. pterocarpum, A. robertianum, A. samariferum, A. singarense, A. smolikanum, A. syriacum, A. trapeziforme, A. troodii, A. virgatum, A. murale, A. pintodasilvae (also known as A. serpyllifolium var. lusitanicum), A. serpyllifolium, A. malacitanum (also known as A. serpyllifolium var. malacitanum), A. lesbiacum, A. fallacinum, A. argenteum, A. bertolonii, A. tenium, A. heldreichii, A. corsicum, A. pterocarpum and A. caricum as well as newly discovered species such as A. corsicum G116, A. murale G69 and A. murale G82. These species were deposited on Nov. 6, 1998, under the provisions of the Budapest Treaty at the American Type Culture Collection, 10801 University Blvd., Manassas, Va. 20110-2209, and assigned ATCC nos. 203436, 203437 and 203438, respectively.
Species of Alyssum that naturally accumulate nickel in amounts of up to 20% greater than any known Alyssum hyperaccumulator have been isolated. Species A. murale G49, A. murale G54, A. murale G69 and A. murale G82 isolated in Greece and species A. corsicum G616 isolated in Turkey all accumulate nickel in amounts greater than the known species A. murale 103 which accumulates nickel such that nickel makes up 1.14% by dry weight of a plant shoot from a test field of serpentine soil. The new hyperaccumulators accumulate nickel in amounts such that 1.55-1.60% by dry weight of the shoot is nickel. The results of nickel accumulation of these five new accumulators relative to the benchmark accumulator A. murale 103 is shown in Example 4.
About 250 other plant taxa, including those of tropical origin, have been shown to accumulate quantities of nickel and other metals. However, many of these plants do not exceed about 10,000 mg of metal per kg of plant tissue dry weight. Other metal-accumulating plants includes species of the genus Cyanotis such as Cyanotis longifolia; species of the genus Bulbostylis such as Bulbostylis mucronata; species of the genus Combretum such as Combretum decandrum; species of the genus Crassula such as C. alba, C. vaginata and C. argyrophylla; species of the genus Clethra such as Clethra barbinervis; plants from the Cunoniaceae family such as species of the genus Geissois including G. intermedia, G. magnifica, G. montana, G. pruinosa, G. trifoliata and G. racemosa; species of the genus Argophyllum; members of Brassicaceae family such as species of the genus Thlaspi such as Thlaspi caerulescens, Thlaspi montanum var. montanum sand Thlaspi montanum var. siskiyouense; species of the genus Serpentine such as Serpentine polygaloides; species of the genus Sebertia such as Sebertia acuminata; species of the genus Hybanthus such as Hybanthus floribundas; species of the genus Psychotria such as Psychotria douarrei; species of the genus Rinorea such as Rinorea bengalensis; species of the genus Pearsonia such as Pearsonia metallifera; species of the genus Sebertia such as Sebertia acuminata; and species of the following genera: Homalium, Myristica, Trichospermum, Planchonella and Peltaria. Additional plants include, but are not limited to, Streptanthus polygaloides, Berkheya coddii, Phyllanthus palawanensis, Dichapetalum gelonioides ssp. tuberculatum and Stackhousia tryonii.
Additional metal hyperaccumulators are listed below:
Acanthaceae Blepharis acuminata, Justicia lanstyakii, Lophostachys villosa, Phidiasia lindavii, Ruellia geminiflora
Adiantaceae
Adiantum sp.
Anacardiaceae
Rhus wildii
Asteraceae
Berkheya coddii, Chromolaena sp. cf. meyeri, Dicoma niccolifera, Gochnatia crassifolia, G. recurva, Koanophyllon grandiceps, K. prinodes, Leucanthemopsis alpina, Pentacalia, Senecio Seneciopauperculus, Shaferaplatyphylla, Solidago hispida
Boraginaceae
Heliotropium sp.
Brassicaceae
Bommuellera, Cardamine resedifolia, Cochlearia aucheri, C. sempervivum, Peltaria emarginata, Streptanthus polygaloides
Buxaceae
Buxus
Campanulaceae
Campanula scheuchzeri, Arenaria, Minuartia laricifolia, M. verna
Clusiaceae
Garcinia bakeriana, G. polyneura, G. revoluta, G. ruscifolia
Convolvulaceae
Merremia xanthophylla
Cunoniaceae
Pancheria engleriana
Dichapetalaceae
Dichapetalum gelonioides and ssp. tuberculatum and ssp. andamanicum
Dipterocarpaceae
Shorea tenuiramulosa
Escalloniaceae
Argophyllum grunowii, A. laxum
Euphorbiaceae
Baloghia sp., Bonania, Cleidion viellardii, Cnidoscolus sp. cf. bahianus, Euphorbia, Gymnanthes recurva, Leucocroton, Phyllanthus, Sapium erythrospermum, Savia
Fabaceae
Anthyllis sp., Pearsonia metallifera, Trifolium pallescens
Flacourtiaceae
Casearia silvana, Homalium, Xylosma
Juncaceae
Luzula lutea
Meliaceae
Walsura monophylla
Myristicaceae
Myristica laurifolia
Myrtaceae
Mosiera araneosa, M. ekmanii, M.×miraflorensis, M. ophiticola, Psidium araneosum, P. havanense
Ochnaceae
Brackenridgea palustris and ssp. foxworthyi and ssp. kjellbergii, Ouratea nitida, O. striata
Oleaceae
Chionanthus domingensis
Oncothecaceae
Oncotheca balansae
Poaceae
Trisetum distichophyllum
Ranunculaceae
Ranunculus glacialis
Rubiaceae
Ariadne shaferi ssp. shaferi and ssp. moaensis, Mitracarpus sp., Phyllomelia coronata, Psychotria clementis, P. costivenia, P. douarrei, P. glomerata, P. osseana, P. vanhermanii, Rondeletia
Sapotaceae
Planchonella oxyedra, Sebertia acuminata
Saxifragaceae
Saxifraga
Scrophulariaceae
Esterhazya sp. and Linaria alpina
Stackhousiaceae
Stackhousia tryonii
Tiliaceae
Tetralix brachypetalus, T. cristalensis, T. jaucoensis, T. moaensis, T. nipensis, Trichospermum kjellbergii
Tumeraceae
Turnera subnuda
Velloziaceae
Vellozia sp.
Violaceae
Agatea deplanchei, Hybanthus, Rinorea bengalensis, R. javanica, Rinorea sp.
Aceraceae
Acer pseudoplatanus
Brassicaceae
Cardaminopsis halleri, Thlaspi avalanum, T. brachypetalum, T. caerulescens, T. ochroleucum, T. rotundifolium subsp. cepaeifolium, T. praecox, T. stenopterum, T. tatrense
Caryophyllaceae
Minuartia verna, Polycarpaea synandra
Cistaceae
Cistus incanus ssp. creticus
Dichapetalaceae
Dichapetalum gelonioides
Plumbaginaceae
Armeria maritima var. halleri
Poaceae
Agrostis stolonifera, A. tenuis, Arrhenatherum elatius, Festuca ovina
Polygonaceae
Rumex acetosa
Violaceae
Viola calaminaria
Amaranthaceae
Pandiaka metallorum, Celosia trigyna
Asteraceae
Anisopappus chinensis, A. davyi, Gutenbergia pubescens, Millotia myosotidifoliab, Vernonia petersii
Caryophyllaceae
Minuartia verna ssp. hercynica and Silene cobalticola
Commelinaceae
Commelina zigzag and Cyanotis longifolia
Convolvulaceae
Ipomoea alpina
Crassulaceae
Crassula alba and C. vaginata
Cyperaceae
Ascolepis metallorum, Bulbostylis cupricola, B. pseudoperennis
Euphorbiaceae
Monadenium cupricola and Phyllanthus williamioides
Fabacaeae
Crotalaria cobalticola and Vigna dolomitica
Iridaceae
Gladiolus gregarius
Lamiaceae
Aeollanthus subacaulis var. linearis, A. homblei, A. saxatilis, A. subacaulis var. ericoides and var. linearis, Becium grandiflorum var. vanderystii, Haumaniastrum homblei, H. katangense, H. robertii, H. rosulatum
Malvaceae
Hibiscus rhodanthus
Pinaceae
Abies balsamea
Poaceae
Eragrostis racemosa, Rendlia altera, Sporoboluscongoensis
Pteridaceae
Actiniopteris sp.
Scrophulariaceae
Alectra sessiliflora var. senegalensis, Buchnera henriquesii, Crepidorhopalon tenuisa, C. perennisa, Sopubia mannii, S. metallorum, S. neptunii, Striga hermontheca
Tiliaceae
Triumfetta dekindtiana, T. digitata, T. welwitschii var. descampii
Velloziaceae
Xerophyta retinervis var. equisetoides
Apocynaceae
Alyxia rubricaulis
Celastraceae
Maytenus bureaviana, M. pancheriana, M. sebertiana
Clusiaceae
Garcinia amplexicaulis
Myrtaceae
Eugenia clusioides
Proteaceae
Beaupreopsis paniculata, Macadamia angustifolia, M. neurophylla
Asteraceae
Haplopappus fremontii, Machaeranthera glabriuscula, M. ramosa, M. venusta
Brassicaceae
Stanleya pinnata, S. bipinnata
Chenopodiaceae
Atriplex confertifolia
Lecythidaceae
Lecythis ollaria
Leguminosae
Acacia cana, Astragalus bisulcatus, A. osterhoutii, A. pattersonii, A. pectinatus, A. racemosus, Neptunia amplexicaulis
Rubiaceae
Morinda reticulata
Scrophulariaceae
Castilleja chromosa
The metals accumulated include nickel, cobalt, barium, gold, beryllium, mercury, molybdenum, copper, arsenic, selenium, antimony, manganese, silver, thallium, tin, lead, rubidium, chromium, cerium, vanadium, cesium, uranium, plutonium, strontium, yttrium, technetium, iridium, ruthenium, palladium, rhodium, platinum, osmium, rhenium, zinc and cadmium.
Metal sequestration can be improved by optimizing soil calcium concentration, using ammonium-containing or ammonium-generating fertilizers rather than other nitrate-containing fertilizers, and by applying chelating agents to the soil in which the hyperaccumulator plants are grown.
Alyssum species which hyperaccumulate metals such as nickel and cobalt evolved in nickel-rich ultramafic and serpentine soils which have low soil calcium and a low Ca:Mg ratio. It is now known that the presence of extremely low and extremely high calcium concentrations in soil inhibits nickel hyperaccumulation by Alyssum. See PCT/US97/15109. Acceptable calcium concentrations in soil range from about 0.128 mM to about 5.0 mM. In terms of percentages, an acceptable calcium concentration in soil ranges from about 2% to about 80% of the exchangeable cations. A preferable range is from about 10% to about 80% of the exchangeable cations. The most preferred range is from about 30% to about 70% of the exchangeable cations. Such ranges can be achieved, if necessary, by adding calcium-containing agents to the soil such as limestone. In addition, gypsum could be added to the soil to raise the exchangeable calcium of the soil to benefit nickel accumulation.
The presence of intermediate concentrations of calcium, i.e., between about 0.128 mM and about 5.0 mM, increases nickel uptake whereas calcium values of about 0.128 mM and below, or about 5 mM and above, decrease nickel uptake. Combined with an exchangeable Ca:Mg ratio of between about 0.16 and about 0.40, much lower than recommended, an additional increase in nickel concentration in plant tissues is observed. By “exchangeable Ca:Mg ratio” is intended the ratio of extractable calcium and magnesium in the soil.
Although hyperaccumulators such as Alyssum have developed the ability to hyperaccumulate metals in above-ground tissues, fertilizer supportive of growth, particularly in polluted soil, can be used as an additive to increase hyperaccumulation. Ammonium fertilizers localize acidification adjacent to the root which aids hyperaccumulation of various metals such as Ni, Zn, Cd, Co, etc. The use of ammonium fertilizers per se is well-known, and acceptable fertilizers and protocols can be readily determined with no more than routine experimentation, by those of ordinary skill in the art. Other additives include, but are not limited to, nutrients such as phosphate which helps to maximize the yield of nickel, for example.
Another possible additive to the contaminated soil is a metal chelating agent. Metal chelates are commonly used in agriculture and occur naturally in living cells. The addition of chelating agents, such as nitrolotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), ethyleneglycol-bis-(p-aminoethylether-N, N-tetraacetic acid) 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 or phytoextracted improves the movement of soil metals to root surfaces for uptake and translocation into above-ground tissues. Preferred chelating agents are NTA or EDTA. Typically, chelating agents will be added at a concentration ranging from about 0.5 to about 10 millimoles per kg soil. As with the use of fertilizers, the optimum concentration of chelating agents can be readily determined with no more than routine experimentation. Chelating compounds which chelate nickel in the presence of high soil levels of Fe, Mg and Ca selectively increase nickel uptake by hyperaccumulator plants.
The invention also pertains to hyperaccumulator plants as described above. Such hyperaccumulator plants were not known before the discovery of the invention described herein. In one exemplary embodiment, the invention pertains to a metal-hyperaccumulator plant grown in metal-containing soil having a soil pH of 5.6 to 10.0 with at least 0.1% of the above-ground tissue of the plant, on a dry weight basis, being metal. In another exemplary embodiment, the invention pertains to a metal-hyperaccumulator plant grown in nickel-containing soil having a soil pH of 5.6 to 10.0 with at least 0.1% of the above-ground tissue of the plant, on a dry weight basis, being nickel. In another exemplary embodiment, the invention pertains to a metal-hyperaccumulator plant grown in cobalt-containing soil having a soil pH of 5.6 to 10.0 with at least 0.1% of the above-ground tissue of the plant, on a dry weight basis, being cobalt. Preferably, the metal-hyperaccumulator plant is Alyssum, more preferably an Alyssum plant as described above. Preferably, the metal-hyperaccumulator plant is such that about 2.5% or more of the above-ground tissue of the plant, on a dry weight basis, is metal (e.g., nickel or cobalt), more preferably about 3.0% or more of the above-ground tissue of the plant, on a dry weight basis, is metal (e.g., nickel or cobalt), and more preferably about 4.0% of the above-ground tissue of the plant, on a dry weight basis, is metal (e.g., nickel or cobalt). In another preferred embodiment, the concentration of metal such as nickel or cobalt in the above-ground plant tissue exceeds the concentration of metal in said soil by a factor of at least 2.
The invention also pertains to use of the metals recovered from soil and/or the metal-containing parts of the hyperaccumulator plants described above. In one exemplary embodiment, the metal may be extracted from the hyperaccumulator plant and used for any industrial or commercial use typical for that particular metal. In another exemplary embodiment, the metal may be extracted from the plant and sold at market price. In another exemplary embodiment, the metal may used to promote the growth of other plants, for instance as a nutritional supplement (e.g., a fertilizer), such as has been previously described by at least Brown et al., Nickel: A Micronutrient Essential for Higher Plants, Plant Physiol., 85, 801-803 (1987), the content of which is herein incorporated by reference in its entirety. Brown et al. discloses that nickel is a micronutrient which is essential for all higher plant growth. Brown et al. also discloses that the addition of nickel at concentrations as low as about 0.0016 mg/liter to about 0.0026 mg/liter of nickel in a growth medium results in improved plant growth. In one preferred exemplary embodiment, a metal (e.g., nickel, cobalt, etc.) is extracted from the hyperaccumulator plant and the extracted metal is added to soil or at least one other plant as a nutritional supplement. In another preferred exemplary embodiment, a metal-containing (e.g., nickel-containing, cobalt-containing, etc.) part of the hyperaccumulator plant is added to soil or at least one other plant as a nutritional supplement. Those of ordinary skill in the art will recognize that the metal-containing part of the hyperaccumulator plant may be provided in a variety of forms, such as for the addition to soil or at least one other plant. In one example, the metal-containing part of the hyperaccumulator plant may be provided as a mulch. In another example, the metal-containing part of the hyperaccumulator plant may be ground (or milled, etc.) so as to be provided in the form of a powder or other similar form. In another example, the metal-containing part of the hyperaccumulator plant may be processed so as to be provided as part of a liquid, for example as part of a solution or suspension. Those of ordinary skill in the art will also recognize that the metal (e.g., extracted metal) may be provide in a variety of forms, with or without a carrier, for example in the form of a powder, solution or emulsion, and/or as a metal salt. Furthermore, in that Brown et al. teaches that nickel concentrations as low as about 0.0016 mg/liter to about 0.0026 mg/liter improves plant growth, those of ordinary skill in the art will recognize that higher concentrations of nickel, whether provided as nickel or as a nickel-containing part of a hyperaccumulator plant, may also improve plant growth.
The following examples are illustrative, but not limiting, of the methods of the present invention. Other suitable modifications and adaptations of the variety of conditions normally encountered which are obvious to those skilled in the art are within the spirit and scope of the present invention.
A. murale 103 plants were grown in sets of two for 120 days in 19 pot-sets (4 L) of contaminated or serpentine soils (Mg-nitrate was leached out) without acidification, the first pot in a set, and with acidification, the second pot in a set. Water was maintained near field capacity by daily watering with deionized water. The plants were cultivated at a temperature of about 28° C. during the day and about 20° C. at night. The soils were acidified using nitric acid and the pH was raised using powdered reagent-grade CaCO.sub.3. The soils included serpentine soils rich in nickel (containing from about 100 to about 5000 ppm nickel) obtained from southwest Oregon (soils 3-19), nickel-refinery contaminated Welland loam from Port Colborne, Ontario (soil 1) and nickel-refinery contaminated Quarry muck from Port Colborne, Ontario (soil 2). Fertilizers containing, inter alia, nickel, potassium, sulfur and phosphorous, were added to optimize plant growth.
Table 1 shows the results of the experiment in contaminated soil.
As illustrated in Table 1, the plants grown on soils of less acidic pH generally accumulated far greater amounts of nickel than the plants grown on more acidic soils. In addition, plants taking up larger amounts of nickel on less acidic soils accumulated smaller amounts of other metals such as cobalt, manganese and zinc which are commonly found in lower concentrations in shoots after soil pH is raised.
To validate the above example and to obtain optimization, Alyssum plants were grown on nickel-refinery contaminated Welland loam (soil 1), wherein the pH was elevated by applying limestone (Table 2). The plants were also grown on nickel-refinery contaminated Quarry muck (soil 2) and serpentine soils (soils 3-11) (Table 3). The same cultivation conditions recited in Example 1 were used in Example 2.
murale and Alyssum corsicum grown on
The “pH series” experiments demonstrate that the application of limestone increases the uptake of nickel in Alyssum so that plant tissues accumulate an increased concentration of nickel.
The results show an increase in the geometric mean of nickel uptake in plant tissue by liming Alyssum plants cultivated on nickel-refinery contaminated Quarry muck (soil 2) (Table 4) and on nickel-refinery contaminated Welloam loam (soil 1), nickel-refinery contaminated Quarry muck (soil 2) and selected serpentine soils (soils 3-11) (Table 5) from Example 1. The cultivation conditions were the same as those for Examples 1 and 2.
Alyssum murale and Alyssum corsicum grown
The concentration of elements in the shoots of Alyssum species grown on a field of serpentine colluvial soil in Josephine County, Oreg., are shown in Table 6 below.
A. corsicum
A. corsicum
A. murale
A. murale
A. murale
A. murale
A. murale
The elements are present in mg/kg amounts.
Whole shoots or side branch samples containing stems and leaves were collected from pots or the field for each genotype, dried in forced air drying ovens and ground with a non-contaminating mill to less than about 0.1 mm. The ground samples were then placed in a borosilicate beaker and ashed at 480° C. overnight. Nitric acid was added to dissolve the resultant ash which was then heated until dry on a hot plate. Hydrochloric acid (3.0 M) was added and the beaker was refluxed for two hours to determine recovered nickel concentration. Concentrations of nickel were measured by an inductively coupled argon plasma emission spectrometer. Low concentrations were measured by atomic absorption spectrometry.
Alyssum species were cultivated in various soil types while soil pH was adjusted. The resulting concentration of metal accumulated within and phytoextracted from each species was then measured. The results are reported as shown in Table 7.
Alyssum
A. murale
A. corsicum
A. murale
A. corsicum
As seen from the results of Table 7, metal accumulation within each Alyssum species occurs at pH values above 7.0. For example, in the four pH series listed in the above table, metal accumulation (Plant Ni Concentration) is shown at soil pH values of 7.60, 7.66, 7.34 and 7.30. Table 7 also shows that metal is extracted (Quantity of Ni Phytoextracted) from each species at all pH values. In addition, the results of Table 7 show that metal concentration within each Alyssum species actually increases when soil pH is increased. For example, in three of the four pH series, the concentration of metal within each species increases at each higher pH value. Similarly, the amount of metal extracted from each species increases as soil pH is increased.
This invention has been described in specific detail with regard to specific plants and methods for increasing metal, such as nickel, uptake via phytomining or phytoextraction. Except where necessary for operability, no limitation to these specific materials is intended nor should such a limitation be imposed on the claims appended hereto. From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions without undue experimentation. All patents, patent applications and publications cited herein are incorporated by reference in their entirety.
This application is a continuation-in-part of application Ser. No. 09/437,607, filed Nov. 10, 1999, which is a continuation-in-part of application Ser. No. 09/386,373, filed Aug. 31, 1999, which is a continuation-in-part of application Ser. No. 08/879,813, filed Jun. 20, 1997, now U.S. Pat. No. 5,944,872, which is a continuation of application Ser. No. 08/470,440, filed Jun. 6, 1995, now U.S. Pat. No. 5,711,784, and this application claims priority to Provisional Application No. 60/109,443, filed Nov. 23, 1998, and Provisional Application No. 60/107,797, filed on Nov. 10, 1998, all of which are herein incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| 60109443 | Nov 1998 | US | |
| 60107797 | Nov 1998 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 08470440 | Jun 1995 | US |
| Child | 08879813 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 09437607 | Nov 1999 | US |
| Child | 11896011 | US | |
| Parent | 09386373 | Aug 1999 | US |
| Child | 09437607 | US | |
| Parent | 08879813 | Jun 1997 | US |
| Child | 09386373 | US |
