Phytoremediation of Metal Contaminated Mining Sites

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ISSN 0974-5904, Volume 05, No. 03

June 2012, P.P. 428-436

Phytoremediation of Metal Contaminated Mining Sites V. SHEORAN1, A. S. SHEORAN2 and P. POONIA1 1

2

Department of Zoology, Faculty of Science, Jai Narain Vyas University, Jodhpur- 342011, India Department of Mining Engineering, Faculty of Engineering, Jai Narain Vyas University, Jodhpur-342011, India Email: [email protected]

Abstract: Mining activities generate a large amount of waste rocks and tailings which deposited at the surface and become source of metal pollution. Most of conventional metal remedial technologies are expensive and inhibit the soil fertility; this subsequently causes negative impacts on the ecosystem. Phytoremediation, an emerging costeffective, and environmental-friendly alternative technology, uses plants to reduce, remove, degrade, or immobilize environmental toxins, with aim of restoring area sites to a condition useable for private or public applications. Phytoremediation of heavy metals at mining sites mainly includes the two technologies, phytoextraction and phyostabilisation. Phytoextraction involves the removal of heavy metals by the roots of the plants with subsequent transport to aerial plant organs while phytostabilization focuses on establishing a vegetative cap that does not shoot accumulate metals but rather immobilizes metals within the contaminated soils. Therefore plant community established on mine spoils, wastes and tailings is useful to minimize the impacts of mining by making soil productive either by reducing the metal concentration or immobilizing the contaminants in soil. In this paper characteristic of metal contaminated mining sites, basic concept of phytoremediation is included; phytostabilization and phytoextraction are discussed along with recent research and review. Keywords: Phytoremediation, Phytostabilization, Phytoextraction, Metal Contaminated Mining Site Introduction: There are large number of sites worldwide polluted with heavy metals as a result of human activities such as mining and smelting industries, electroplating, gas exhaust, energy and fuel production, fertilizer and pesticide application and waste disposal [1]. Mining activities such as crushing, grinding, washing, smelting, and all other processes used to extract, concentrate metals generates a large amount of waste rocks, tailings, are often very unstable and make toxic elements environmentally labile through normal biogeochemical pathways, to sink such as sediments, soils or biomass. The direct effects will be loss of cultivated land, forest or grazing land, and the overall loss of production. The indirect effects will include air and water pollution and siltation of water bodies. This will eventually lead to the loss of biodiversity, amenity and economic wealth [2, 3]. Mine wastes often contains substantial amount of various metals. There is also chance of release of left metal contaminants during rain, results to metal leaching and traced into watersheds downstream. Metals may be transferred and accumulated in the bodies of animals or human beings through food chain, which will probably cause DNA damage and carcinogenic effects by their mutagenic ability [4]. So, it is very important to remove heavy metals from these sites. Metal-

contaminated soil can be remediated by chemical, physical or biological techniques. Chemical and physical treatments irreversibly affect soil properties, destroy biodiversity and may render the soil useless as a medium for plant growth. These remediation methods are time consuming and expensive. Among the biological techniques, phytoremediation is emerging plant based environment friendly and cost-effective technology and have important role in ecology restoration at mined land [5, 6]. Phytoremedition involves the use of plants to remove, transfer, stabilize and/or degrade contaminants in soil, sediment and water. It includes various processes namely phytostabilization, phytoextraction, phytodegradation, rhizodegradation, rhizofilteration, phytovolatalisation. Phytoremediation of trace elements at mining sites mainly includes the two strategies: (1) Phytoextraction, in which metal-accumulating plants are used to extract metals from soils and concentrate them into the above-ground shoots, (2) Phytostabilization, in which metal-tolerant plants are used to reduce the mobility of metals thereby reducing risks of further environmental degradation, by leaching into the ground water or by airborne spread [7]. The goal of phytoremediation at metal contaminated mining sites is to reduce or eliminate human and wildlife exposure to metal contaminants, by developing appropriate vegetation cover that can overcome the adverse physical

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V. SHEORAN, A. S. SHEORAN and P. POONIA

and chemical and biological properties of contaminated soils. Characteristics of Metal Contaminated Soil: Mine waste/ tailings are often characterized by shales, cobbles and pebbles, which have a very low water holding capacity. In addition to low pH and elevated metal concentration at these sites, other adverse factors includes absence of topsoil, periodic sheet erosion, drought, surface mobility, compaction, and absence of soil forming fine ingredients. Metal contaminated soils inhibit soil forming processes and plant growth. There is commonly shortage of essential nutrients supportive of biological growth (P, N, and K) and contains almost no organic matter. Toxic metals can also adversely affect the number, diversity and activity of soil organisms, inhibiting soil organic matter decomposition and N mineralization processes. The original soil of mined sites is usually lost or damaged, with only skeletal material. There is change in soil texture, loss of structure; and low availability of soil moisture; uncertain structure and unstable slopes due to hilly terrain. Sometimes mine waste sites (overburden, mine tailings) contain pyrites and sulphide minerals. These minerals when exposed to air and moisture oxidize to produce acid and soluble salts. Pyrite oxidation and hydrolysis give rise to large amounts of H+ ions which, by decomposition and exchange reactions with other spoil minerals, can give rise to high concentration of Al, Mn, Fe, Zn, Cu and other metals depending upon the composition of the originating mineral [8, 9]. Phytoremediation of Metal Contaminated Mining Sites: Plants have shown several response patterns to the presence of potentially toxic concentrations of heavy metal ions. Most are sensitive even to very low concentrations; others have developed resistance and tolerance and accumulate toxic metals with in the roots and in above-ground tissues such as shoot, flower, stem, and leaves [10]. This particular capacity of the plants to tolerate and accumulate large metal concentrations has opened up the possibility to use them for remediation of metal contaminated mining sites. The term phytoremediation (‘phyto’ meaning plant, and the latin suffix "remedium") meaning to clean or restore) actually refers to a diverse collection of plant based technologies that use either naturally occurring or genetically engineered plants for cleaning metal contaminated environments [11]. Phytoremediation of metal contaminated soils at mining sites basically includes phytoextraction and Phytostabilization. Phytoextraction: Phytoextraction, is also called phytoaccumulation, refers to the uptake and translocation of metal

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contaminants in the soil by plant roots into aboveground components of the plants. Certain plants, called hyperaccumulators, absorb unusually large amounts of metals in their shoots compared to other plants and ambient metals concentration. Baker and Brooks [12] have defined hyperaccumulators as plants that can contain more than or up to 0.1% (1000mg/kg) of Ni, Cu, Co, Pb or 1% (10,000mg/kg) of Zn or Mn in the dry matter. For Cd and other rare metals it is 0.01% (100mg/kg) by dry matter weight. Hyperaccumulating plants are taxonomically widespread throughout the plant kingdom. Approximately 400 plant species from at least 45 plant families have been reported to hyperaccumulate various metals, most of which are nickel hyperaccumulators occurring in ultramafic areas all over the world [13]. There are two basic strategies of phytoextraction namely continuous phytoextraction and induced phytoextraction. Continuous phytoextraction is the removal of metals which depends on the natural ability of the plant to extract extraordinary high concentration of metals from metal contaminated soils. Natural hyperaccumulators have the ability to solubilize readily available metals from the soil matrix, efficiently absorb them in high concentration into the root and translocate them to the shoot and storage in a non-phytotoxic form in the aerial portions [14]. Metal hyperaccumulation is rare and complex phenomenon. It involves various process of bioactivation of metals in the root zone, metal absorption in root zone, shoots translocation, detoxification and finally compartmentation [15, 16] (Fig. 1). Some of the natural metal accumulating plants secrete metal chelating compounds “phytosiderophores” to the rhizosphere such as mugenic and avenic acids in response to nutrient metal ion deficiencies, and some secrete organic acids such as citric, malic, malonic and oxalic acid which acts as metal chelators and decrease the rhizosphere pH thus increase the bioavailability of metals that are tightly bound to the soil and help to carry them into plant tissues [17]. The rhizosphere also provides a complex and dynamic microenvironment where microorganisms such as free living as well as symbiotic rhizobacteria and mycorrhizal fungi, in association with roots, form unique communities that have considerable potential for detoxification of hazardous waste compounds [18]. Most of the known hyperaccumulators (Thlaspi caerulescens, Alyssum lesbiacum), although accumulates considerable amount of metal but have a low annual biomass. Hence, much research is being done to increase phytoextraction of other potential nonaccumulator, high biomass crops such as maize (Zea mays), Indian mustard (Brasica juncea), oat (Avena sativa), barley (Hordeum vulgare), poplar (Populus sp.), vetiver grass (V. zizanoides) and sunflower (Helianthus

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annus) [19, 20]. Regardless of the plants used, availability of heavy metals to plant roots is considered the key factor limiting the efficiency of phytoextraction [21]. Some metals such as copper, lead are largely immobile in soil as they are strongly bonded to soil particles and hence their extraction rate is limited by solubility and diffusion to root surface. To overcome these problems induced phytoextraction has been developed [22]. This approach makes use of highbiomass crops that are induced to take up large amounts of metals when their mobility in soil is enhanced by chemical treatments. Chemicals that are suggested for this purpose include various acidifying agents, fertilizer salt and chelating agents. These chemicals increase the amount of bioavailable metals in the soil solution by either liberating or displacing the metals from the solid phase of the soil or by making precipitated metal species more soluble and hence uptake by plant increases [23]. Plants for phytoextraction should be able to grow outside their area of collection, have profuse root systems and be able to transport metals to their shoots. They should have high metal tolerance, be able to accumulate several metals in large amounts, exhibit high biomass production and fast growth, resist diseases and pests, and be unattractive to animals, minimizing the risk of transferring metals to higher trophic levels of the terrestrial food chain [24]. In phytoextraction practice, metal accumulating plants are seeded or transplanted into metal polluted soil and are cultivated using established agricultural practices. The roots of established plants absorb metal elements from the soil and translocate them to the above-ground shoots where they accumulate. After sufficient plant growth and metal accumulation, the above-ground portions of the plant are harvested and removed, resulting in the permanent removal of metal from the site. Planting and harvesting may be repeated to reduce contaminant levels to allowable limits. Following harvesting of pollutantenriched plants the weight and volume of contaminated material can be further reduced by ashing or compositing. Metal enriched plants can be disposed of as hazardous material or, if economically feasible, used for metal recovery [25]. This technology can be combined with a profit making operation, which is unaffected by any elevated plant metal loadings, such as forestry and bioenergy production. Suitable crops such as poplar and willow trees could be either incinerated or used for biofuel production. As the heavy metals in the remaining ash are tightly bound; ash would not pose a threat for environment. Such ash containing heavy metals has been used for years as road base material and no leaching occurs [26, 27]. Phytoextraction can be applied to ores containing valuable metals such as Ni, Au, Ag, Tl, which cannot be economically mined by

traditional mining technology, called phytomining. Here the economic value of the recovered metal is primary motive [15, 28]. More recently, work has been carried out to improve the phytoextraction technology by genetic engineering includes changing oxidation state of metals, enhancing metal transporters and chelators, encoding metal sequestration proteins [(MTs (metallothioneins) and PCs (phytochelatins)], and encoding transport proteins such as ZIP family proteins(zinc-iron permease), ZAT (Zn transporter) etc., further identification of plant genes encoding metal-ion/metal complex transporters and their molecular components could be of immense use for phytoextraction studies [16, 29, 30]. Further, studies have been carried out to enhance the metal mobility and plant biomass by microbial-induction, advanced agronomic practices includes soil and crop management, by producing siderophore producing bacteria at root zone, by enhancing the biological factors that increases the metal solubilization such as root induced changes in pH of the rhizosphere, increased reducing capacity of the roots, quantities and composition of root exudates etc [31, 32, 33, 34].

Figure 1: Mechanism of Plant Metal Hyperaccumulation [15] Case Studies of Natural Phytoextraction: Shu et al. [35] observed potential plant species, namely Commelina communis on Cu mine spoils at Huangshi,

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V. SHEORAN, A. S. SHEORAN and P. POONIA

Hubei Province, China, which have a high uptake of Cu, in shoots, exceeding 1% of total dry weight. DahmaniMuller et al. [36] reported hyperaccumulator of Zn, and Cd namely, Cardaminopsis halleri, there concentration in leaves were >20000 and >100mg/kg respectively. Twenty four plant species comprising 16 genera and 13 families, grown on degraded soils of Sao Domingo mine (south east of Portugal) were analyzed for Ag, As, Cu, Ni, Pb, and Zn. Pb concentration in plant was rather high for some species, varying from 2.9-84.9 mg/kg dry weight. The maximum Pb concentration was found in the aerial parts of Juncus efusus. Pb above 20 mg/kg DW was found in the leaves of three species of Cisius, typical Mediterranean shrubs known for their tolerance to drought and low nutrient availability. Concentration of As (arsenic) in plant tissues ranged from 0.3-23.5 mg/kg DW. Maximum As was found in J. conglomerates, Thymus mastichina, J. efusus and S. holoschoenus. A few trees, Eucalyptus, Quercus and Pinus species, were found in the contaminated area showing accumulation of different metals in the aboveground tissues [37].

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hyperaccumulator of lead, Potentilla griffithii (Zn: 8748mg/kg) and Gentiana sp.(Zn:19,710mg/kg) hyperaccumulator of Zn, Lysimachia deltoides (Cd:212 mg/kg) hyperaccumulator of Cd. Phytostabilization: Phytostabilization, also known as phytorestoration, is a plant-based remediation technique that uses certain plant species to immobilize heavy metals in soil, through absorption, and accumulation by roots, adsorption on to roots, or precipitation within the root zone and physical stabilization of soils [44].This can reestablish a vegetation cover at site where natural vegetation is lacking due to high metal concentrations. It is also suitable for treating a wide range of sites where large areas are subject to surface contamination. It is applied in situations where there are potential human health impacts, and exposure to substances of concern can be reduced to acceptable levels by containment [45].

Gonzalez and Gonzalez-Chavez [41] reported potential of wild plants to accumulate metals from Ag, Au, and Zn mines tailings at Zacatecas state in Mexico. Plant metal analysis revealed that plant species Polygonum aviculare accumulated Zn (9236 mg/kg) at a concentration near to the criteria for hyperaccumulator plants. Jatropa dioica also accumulated high Zn (6249mg/kg) concentrations. Liu et al. [42] observed hyperaccumulation of Mn in three plant species namely, Gnaphalium affine, Conyza Canadensis and Phytolacca acinosa at Mn mine tailings, China.

Characteristics of plants appropriate for phytostabilization include: drought-resistant, fast growing crops or fodder with high root biomass, which can grow in metal contaminated and nutrient deficient soils. Plant should also be poor translocator of metal contaminants to above ground plant tissues that could be consumed by humans or animals, the lack of appreciable metals in shoot tissues also eliminates the necessity of treating harvested shoot residue as hazardous waste, Thus the ratio of shoot metal concentrations to either soil metal concentrations or root metal concentrations should be 5) by liming at contaminated site. All these treatments improve the soil quality and develop favorable conditions for growth of plant species, hence facilitate the revegetation strategies at the metalliferous sites. Hence, phytostabilization, with its lower attendant costs and easier implementation will likely to be more suitable general phytoremediation approach for mine spoils and mine tailings. The future of the technique is still in development and research phase. The majority of the research has been conducted in laboratories under relatively controlled conditions for short periods of time. More extensive research under field conditions for long durations is required for a better understanding of the potential role of both the strategies at mining sites. The challenge for phytoextraction is to identify or genetically construct plants that are hardy enough to tolerate high shoot metal concentrations and still produce large amounts of biomass to reduce the required number of cropping cycles to a minimum. The challenge for phytostabilization is to identify regional- and climaticspecific native plants that do not shoot accumulates metals and it is important to define the minimum inputs needed for plant establishment in terms of compost, fertilizer, and irrigation, since mine spoils and tailings are often in remote areas where transport of large quantities of amendments increases costs and hinders implementation. Phytostabilisation must be tailored to the physicochemical characteristics (ph, cation ion exchange capacity, electrical conductivity, and metal content) of individual mine tailings sites. It is important that public awareness of this technology be considered, with clear and precise information made available to the general public to enhance its acceptability as global sustainable technology. In countries like China, Portugal, Spain, Italy extensive research has been made for remediation of metal

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International Journal of Earth Sciences and Engineering ISSN 0974-5904, Vol. 05, No. 03, June 2012, pp. 428-436