METHODS FOR HEAVY METAL REMEDIATION

The use of plants for biological remediation of heavy metal polluted soils

Phytoremediation is one of the best techniques for treatment of heavy metal-polluted sites. It is an in situ
strategy that uses vegetation and associated microbiota together with agronomic practices to aid in metal
remediation. It is based on the use of special type of plants to decontaminate soil by inactivating metals in
the rhizosphere or translocating them in the aerial parts. Thus phytoremediation is the use of certain plants
to clean up soil, sediment and water contaminated with metals and/or organic contaminants. Plant
physiology, agronomy, microbiology, hydrogeology and engineering are combined to select the proper
plant and conditions for a specific site.

Some plants developed mechanisms to remove ions selectively from the soil to regulate the uptake and
distribution of metals. Potentially useful phytoremediation technologies for heavy metal-polluted sites
include phytoextraction, phytostabilization and rhizofiltration.

Various phytoremediation processes

1. Phytoextraction/Phytomining/Phytoaccumulation
Phytoextraction uses hyper-accumulating plants to remove metals from soil by absorption into the roots
and their translocation into and accommodate in biomass e.g., shoots of the plant. The aboveground
shoots can be then harvested and incinerated to remove metals from the site and subsequently stored as
hazardous waste or employed for the recovery of metals.

Plants used for phytoextraction usually possess the following characteristics:

  rapid growth rate,
 high biomass,
 extensive root system, and
 Ability to tolerate high amounts of heavy metals. This ability to tolerate high concentration of
heavy metals by these plants may lead to metal accumulation in the harvestable part; this may be
problematic through contamination of the food chain.

Two versions of phytoextraction:

 Natural hyper-accumulation, where plants naturally take up the contaminants in soil unassisted.
 Induced or assisted hyper-accumulation, in which a conditioning fluid containing a chelator or
another agent is added to soil to increase metal solubility or mobilization so that the plants can
absorb them more easily.

Phytoextraction is time consuming, but on the other hand it is cost-effective and less labor-intensive.

Example
i) Arsenic, using the Sunflower (Helianthus annus) or the Chinese Brake Fern, a
hyperaccumulator. Chinese Brake fern stores arsenic in its leaves.
ii) Lead, using Indian Mustard (Brassica juncea), Ragweed (Ambrosia artemisiifolia), Hemp
Dogbane (Apocynum cannabinum) or Poplar trees, which sequester lead in its biomass.

2. Phytostabilization/Phytoimmobilization

Plants prevent contaminants from migrating by reducing runoff, surface erosion and ground water flow
rates. ‘Hydraulic pumping’ can occur when tree roots reach ground water, take up large amounts of water,
control the hydraulic gradient and prevent lateral migration of contaminants within a ground water zone.
Mobility is reduced by accumulation of contaminants by plant roots, absorption onto roots or precipitation
within root zone. It is mostly used when phytoextraction is not desirable or even possible. This technique
is useful for the removal of Pb, As, Cd, Cr, Cu, and Zn. This form of phytoremediation is best applied
when the soil is so heavily polluted so that using plants for metal extraction would take a long time to be
achieved and thus would not be adequate. Phytostabilization of heavy metals takes place as a result of
precipitation, sorption or complexation. The efficiency of phytostabilization depends on the plant and soil
amendment used. Soil amendments may be organic matter, phosphates, alkalizing agents which decrease
solubility of plants. Plants help in stabilizing the soil through their root systems; thus, they prevent
erosion. Metals do not degrade ultimately, so capturing them in situ is the best alternative.

Plants used for phytostabilization should have the following characteristics:

 dense rooting system,
 ability to tolerate soil conditions,
 ease of establishment and maintenance under field conditions,
 rapid growth to provide adequate ground coverage,
 And ability to self-propagate.

In general, phytostabilization is very useful when rapid immobilization of heavy metals is needed to
prevent groundwater pollution. However, because the pollutants remain in the soil, constant monitoring of
the environment is required and this may become a problem. This process is advantageous because in this
case where disposal of hazardous material/biomass is not required, and it is very effective when rapid
immobilization is needed to preserve soils or ground and surface waters. This poses a reduced human or
environmental risk while they are bound in the roots.

3. Rhizofiltration/phytofiltration
Rhizofiltration (or phytofiltration) removes metals from contaminated ground water via absorption,
concentration and precipitation by plant roots. This technique is used to remove pollutants from
groundwater and aqueous-waste streams rather than for the remediation of polluted soils. the plants to be
used for cleanup is raised in green houses with their roots in water. Contaminated water in either collected
from the waste site and brought to the plants or the plants are planted in contaminated area, where the
roots can take up the water and the contaminants dissolved in it.

Figure: Mechanisms of phytoremediation involved in purifying contaminated soils and water.

4. Phytodegradation
Contaminants are absorbed inside the plant and metabolized (broken down) to non-toxic molecules by
natural chemical processes within the plant. Specifically, phytodegradation, also called
“phytotransformation” with the subsequent breakdown, mineralization, or metabolization by the plant
itself through various internal enzymatic reactions and metabolic processes. Depending on factors such as
the concentration and composition, plant species, and soil conditions, contaminants may be able to pass
through the rhizosphere only partially or negligibly impeded by phyto-sequestration and/or
rhizodegradation. In this case, the contaminant may then be subject to biological processes occurring
within the plant itself, assuming it is dissolved in the transpiration stream and can be phytoextracted.

5. Phytovolatization

Several heavy metals absorbed by plants get converted into volatile forms and subsequently released into
the atmosphere by the process called phytovolatilization. However, this is limited by the fact that it does
not remove the metals completely but rather transfers them from one medium (soil or water) to another
(atmosphere) from which they can reenter soil and water. In some cases, a breakdown product derived
from the rhizodegradation and/or phytodegradation of the parent contaminant along the transpiration
pathway may be the phytovolatilized constituent. This process has been used for removal of some volatile
heavy metals like Hg and Se from polluted soils. Specifically, tobacco plants have been modified to be
able to take up the highly toxic methyl-mercury, alter the chemical speciation, and phytovolatilize
relatively safe levels of the less toxic elemental mercury into the atmosphere. Once volatilized, many
chemicals that are recalcitrant in the subsurface environment react rapidly in the atmosphere with
hydroxyl radicals, an oxidant formed during the photochemical cycle.

6. Rhizodegradation/ Phytostimulation

In the rhizodegradation process, the metal toxicity to plants can be reduced by the use of plant growth
promoting bacteria, free living soil organisms that exert beneficial effects on plant growth. In this process,
plants can stimulate microbial activity microbial activity about 100-1000 times by the secretion of
exudates which contain carbohydrates, flavonoids, amino acids etc. In return, the rhizosphere bacteria that
contain ACC (Aminocyclopropane carboxylate) deaminase may act to ensure that the ethylene level does
not impair root development and to facilitate the generation of larger roots which enhance seedling
survival. Example- Ni resistant soil bacterium, Kluyvera ascorbata promoted growth of Brassica
campestris in the presence of high concentration of Ni due to its ability to lower the level of ethylene
stress in the seedlings.

Advantages of phytoremediation
1. Works on a variety of organic and inorganic compounds.
2. Can be either in situ/ ex situ.
3. Easy to implement and maintain.
4. Low cost compared to other treatment methods.
5. Environmentally friendly and aesthetically pleasing to the public.
6. Reduces the amount wastes to be landfilled.
7. Cost effective.
8. Possibility of the recovery and reuse of valuable metals.
9. Applicable to wide range of heavy metals.

Limitations of phytoremediation
1. Limited to the surface area and depth occupied by the roots.
2. Slow growth and low biomass require a long term commitment.
3. Time consuming.
4. Air could be contaminated by the burning of leaves.
5. May depend on climatic conditions.
6. Possible effect on food chain.
7. Consumption of contaminated plant tissue is of concern.
8. Harvested biomass from phyto-extraction may be classified as a RCRA hazardous waste.
9. Plant is affected by the toxicity of the land.
10. It is not possible completely to prevent the leaching of contaminants into the ground water.
Following list gives the media, contaminants and typical plants for the types of phytoremediation:

Methods media Contaminations Typical Plants

Phreatophyte trees (poplar,
willow, cottonwood, aspen);
Soil, groundwater, Herbicides, Aromatics, Grasses (rye, Bermuda,
Phytovolatization landfill leachate, land Chlorinated aliphatics sorghum, fescue); Legumes
application of waste (clover, alfalfa, cowpeas)
water
Phytostimulation Soil, sediments, land Organic contaminants Aquatic plants for sediments;
application of waste (pesticide, aromatic and Grasses with fibrous roots
water polynuclear aromatic (rye, Bermuda)
hydrocarbon)
phytostabilization Soil, sediments Metals (Pb, Cd, Zn, As, Phreatophyte trees to transpire
Cu, Cr, Se, U); amounts of water; Grasses to
Hydrophobic organics stabilize soil erosion; dense
(PAH, PCB, DDT) root system are needed to
bind contaminants
phytoaccumulation Soil, Brownfields, Metals (Pb, Cd, Zn, As, Sunflowers: Indian Mustard;
sediments Cu, Cr, Se, U) with EDTA Seed plants: Barle, Hops;
addition for Pb, Se Serpentine plants; Nettles,
dandelions
Degradation Phreatophyte trees (poplar,
willow, cottonwood, aspen);
Grasses (rye, Bermuda,
sorghum, fescue); Legumes
(clover, alfalfa, cowpeas)