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2. ENVIRONMENTAL ChEMISTRy & TEChNOLOGy 2.1. Lectures

2. ENVIRONMENTAL ChEMISTRy & TEChNOLOGy 2.1. Lectures

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Chem. Listy, 102, s265–s1311 (2008) Environmental Chemistry & Technology<br />

P61 MICRObIOLOGIAL REMEDIATION OF<br />

METAL-CONTAMINATED SOIL<br />

VALéRIA SnOPKOVá<br />

Department of Biotechnology, Institute of Geotechnics the<br />

Slovak Academy of Sciences,<br />

Watsonova 45, 043 53 Košice, Slovak Republic.<br />

snopkova@saske.sk<br />

Introduction<br />

Soil contamination with anthropogenic heavy metals,<br />

which mainly comes from industrial activity, atmospheric<br />

deposition and land application of sewage sludge, has received<br />

much attention in the recent years. The anthropogenic<br />

heavy metals are to be easily accumulated in the topsoil1,<br />

resulting in potential problems such as toxicity to plants and<br />

animals 1,2 , accumulation in food chain, perturbation of the<br />

ecosystem and adverse health effects 4,5 . Metals, which are<br />

significantly toxic to human beings and ecological environment,<br />

include chromium (Cr), cooper (Cu), lead (Pb), mercury<br />

(Hg), zinc (Zn), manganese (Mn), cadmium (Cd), nickel<br />

(ni), arsenic (As) and iron (Fe), etc. 6 .<br />

Contaminated soil is notoriously difficult to treat because<br />

the contaminants are often tightly bound to the soil particles.<br />

Conventional remediation technologies are becoming less<br />

popular due to the high treatment costs and bioremediation<br />

processes to improve the contaminant removal efficiency<br />

and cost effectiveness. However, as an innovative technology,<br />

there are many factors to be investigated with the future<br />

development 7 .<br />

bioremediation<br />

Bioremediation is defined as a method using living organisms,<br />

or their particles (enzymes) to reduce, eliminate, fixate<br />

or transform contaminants presented in the soil, in sediments,<br />

in waters or in the air 8,9 . In the bioremediation processes<br />

bacteria, fungi, yeasts and plants present the most imposed<br />

organisms. Recently, the ability of algaes and planktons are<br />

being researched. Some technologies are based on the use<br />

of general or genetically modificated organisms 8 . Bioremediation<br />

works by either transforming or degrading contaminants<br />

to non-hazardous or less hazardous chemicals. These<br />

processes are called, respectively, biotransformation and<br />

biodegradation. Biotransformation is any alteration of the<br />

molecular or atomic structure of a compound by microorganisms.<br />

Biodegradation is the breaking down of organic substance<br />

by microorganisms into smaller organic or inorganic<br />

components 9 .<br />

Metal – Microbe Interactions<br />

Microorganisms, especially bacteria, exist in complex<br />

biogeochemical matrices in subsurface sediments and soils 9<br />

and are known to mediate many geochemical processes 10,11 .<br />

They can interact with metals via many mechanisms, some of<br />

which may be used as the basis of the potential bioremediation<br />

strategies 9 . Microbes can mobilize metals through autot-<br />

s454<br />

rophic and heterotrophic leaching, chelation by microbial<br />

metabolites and siderophores, and methylation, which can<br />

result in volatilization. Conversely, immobilization can result<br />

from sorption to cell components or exopolymers, transport<br />

into cells and intracellular sequestration or precipitation as<br />

insoluble organic and inorganic compounds, e.g. oxalates 12,13<br />

sulphides or phosphates 14,15 .<br />

M e t a l M o b i l i z a t i o n<br />

bioleaching. Metals can be leached from solid matrices<br />

via autotrophic and heterotrophic leaching. Chemolitotrophic<br />

and heterotrophic bacteria have the major role.<br />

Most autotrophic leaching is carried out by chemolithotrophic,<br />

acidophilic bacteria which fix carbon dioxide and<br />

obtain energy from the oxidation of ferrous iron or reduced<br />

sulfur compounds, which causes the solubilization of metals<br />

because of the resulting production of Fe(III) and H 2 SO 4 16,17 .<br />

The microorganisms involved include sulfur-oxidizing bacteria,<br />

e.g., Acidihiobacillus thiooxidans, iron- and sulfur-oxidizing<br />

bacteria, e.g., Acidithiobacillus ferrooxidans and ironoxidizing<br />

bacteria, e.g., Leptospirillum ferrooxidans 18,19 .<br />

In the case of oxide, carbonate and silicate ores, limits<br />

are set for the use of thiobacilli. For such ores, research is<br />

being done on the use of heterotrophic bacteria. In this case,<br />

metals are dissolved by organic acids, or complexing, or chelating<br />

agents produced by the bacteria. Heterotrophic bacteria<br />

require organic supplement for growth and energy supply.<br />

Among the bacteria, members of the genus Bacillus are most<br />

effective in metal solubilization 19 .<br />

Siderophores are low molecular weight Fe(III) coordination<br />

compounds that are excreted under iron-limiting conditions<br />

by microorganisms, particularly bacteria and fungi,<br />

to enable accumulation of iron from the environment 20,21 .<br />

Although primarily produced as a means of obtaining iron,<br />

siderophores are also able to bind other metals such as magnesium,<br />

manganese, chromium (III), gallium (III) and radionuclides<br />

such as plutonium (IV) 22,23 .<br />

biomethylation of Hg, As, Se, Sn, Te and Pb can be<br />

mediated by a range of bacteria under aerobic and anaerobic<br />

conditions. Methyl groups are enzymatically transferred to<br />

the metal, and the given species may transform a number of<br />

different metal(-loid)s. Methylated metal compounds formed<br />

by these processes differ in their solubility, volatility and<br />

toxicity 23 .<br />

M e t a l I m o b i l i s a t i o n<br />

bioacumulation and biosorption. Bacteria can physically<br />

remove heavy metals from solution through association<br />

of these contaminants with biomass. Bioaccumulation is the<br />

retention and concentration of substance within an organism.<br />

In bioaccumulation, metals are transported from the outside<br />

of the microbial cell trough the cellular membrane, into the<br />

cell cytoplasm, where the metals are sequestred 9,24 . Biosorption<br />

describes the association of soluble substances with the<br />

cell surface. Sorption does not require an active metabolism.<br />

The amount of metal biosorbed to the exterior of bacterial

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