Risk assessment of contaminated site

Risk assessment or hazard assessment is required to decide the extent of contaminant

remediation required for a particular site. The factors influencing risk assessment are:
Toxicity
A material is deemed toxic when it produces detrimental effects on biological tissues or
associated process when organisms are exposed to concentration above some prescribed level.
Acute toxicity is the effect that occurs immediately after exposure where as chronic toxicity deals
with long term effects. It must be noted that concentration is an important factor while deciding
toxicity. Only when a contaminant crosses a particular concentration, it becomes toxic. If the
concentration is within the prescribed limit then no remediation need to be performed. Only those
site which have toxic level of contaminant concentration needs remediation.
Reactivity
It is the tendency to interact chemically with other substances. These interactions become
hazardous when it results in explosive reaction with water and/or other substances and generate
toxic gases.
Corrosivity
Corrosive contaminants degrade materials such as cells and tissues and remove matter. It is
defined as the ability of contaminant to deteriorate the biological matter. Strong acids, bases,
oxidants, dehydrating agents are corrosive. pH < 2 or pH > 12.5 is considered as highly corrosive.
Substances that corrode steel at a rate of 6.35 mm/year is also considered hazardous.

Ignitability
It is the ease with which substance can burn. The temperature at which the mixture of
chemicals, vapour and air ignite is called the flash point of chemical substances. Contaminants are
classified as hazardous if it is easily ingnitable or its flash point is low.

Remediation methods for soil and groundwater

Based on the toxic level of contaminants and the risk it pose to the environment, a suitable
remediation method is selected. It must be noted that the remediation does not aim for entire
decontamination. The major focus is to bring the contamination level well below the regulatory toxic
limit. This is done by removing the toxic contaminants and/or immobilizing the contaminant that
prevents its movement through subsurface geoenvironment. The remediation methods are broadly
classified as physico-chemical, biological, electrical, thermal and combination of these methods.

4.4.1 Physico-chemical methods

Removal and treatment of contaminated soil
One of the simplest physical methods for remediation is by removing the contaminated soil
and replacing it with clean soil. Essentially it is a dig, dump and replace procedure. Such a method is
practically possible only if the spatial extent and depth of the contaminated region is small. The dug
out contaminated soil can be either disposed off in an engineered landfill or subjected to simple
washing
fig. 4.2 Soil washing for granular soils contaminated with inorganic pollutant

However, washing procedure is mostly suitable for granular soils with less clay content and
contaminated with inorganic pollutants. For clay dominated soils, a chemical dispersion agent need
to be added to deflocculate and then chemical washing is employed to break the retention of
contaminants with the clay surface. Incineration is suggested for soils contaminated with organic
pollutants. In case, it is necessary to remove organic pollutants then certain solvents or surfactants
are used as washing agents.
The method is directly applied in situ where solvent, surfactant solution or water mixed with
additives is used to wash the contaminants from the saturated zone by injection and recovery
system. The additives are used to enhance contaminant release and mobility resulting in increased
recovery and hence decreased soil contamination.
Vacuum extraction
This method is one of the most widely used in situ treatment technologies. The method is
cost-effective but time consuming and ineffective in water saturated soil. The technique, as depicted
in Fig. 4.3, is useful for extracting contaminated groundwater and soil vapour from a limited
subsurface depth. The contaminated water is then subjected to standard chemical and biological
treatment techniques. Vacuum technique is also useful when soil-water is contaminated with
volatile organic compound (VOC). The method is then termed as “air sparging”. Sometimes
biodegradation is clubbed with air sparging for enhanced removal of VOC. Such a technique is then
termed as biosparging.
The vacuum extraction probe is always placed in the vadoze zone. The success of the method
depends on the volatilization of VOC from water into air present in voids. An injecting medium is
used to extract soil-water and/ or soil-air. When oxygen is used instead of nitrogen as the injecting
medium, it enhances aerobic biodegradation.
Soil structure influences a lot on the passage of extracted water and vapour and hence on the
success of vacuum extraction technique. It is not only important that the injecting medium is
delivered efficiently but also the extracted product reaches the exit with less hindrance. Granular
soils provide better passage where as the presence of clay and organic matter impedes the
transmission of both fluid and vapour. Organic matter provides high retention leading to less
volatilization. High density and water content also minimize transmissivity. Apart from soil, the VOC
properties such as solubility, sorption, vapour pressure, concentration etc. also influence the
extraction process.
Solidification and stabilization
This is the process of immobilizing toxic contaminants so that it does not have any effect
temporally and spatially. Stabilization-solidification (SS) is performed in single step or in two steps. In
single step, the polluted soil is mixed with a special binder so that polluted soil is fixed and rendered
insoluble. In two step process, the polluted soil is first made insoluble and non-reactive and in the
second step it is solidified. SS process is mostly justified for highly toxic pollutants. In-situ SS process
is mostly influenced by the transmissivity characteristics of the soil, viscosity and setting time of the
binder. Well compacted soil, high clay and organic content do not favour in-situ SS.
In ex-situ methods, polluted soil is first grinded, dispersed, and then mixed with binder
material. The resultant SS material need to be disposed in a well contained landfill. It is essential that
the resultant SS product does not undergo leaching. The common binders used in practice include
cement, lime, fly ash, clays, zeolites, pozzolonic products etc. Organic binders include bitumen,
polyethylene, epoxy and resins. These organic binders are used for soil contaminated with organic
pollutants.
Chemical decontamination
This method is mostly applicable for those soils which have high sorbed concentration of
inorganic heavy metals (IHM). The first process in this method is to understand the nature of
bonding between the pollutant and the soil surface. A suitable extractant need to be selected for
selective sequential extraction (SSE) of IHM from the soil mass. The extractants include electrolytes,
weak acids, complexing agents, oxidizing and reducing agents, strong acids etc. The use of these
extractants in single or in combination will depend upon the concentration of IHM and nature of the
soil mass.
In-situ application (as depicted in Fig. 4.4) of extractants would remove IHM from the soil
surface and enter into the pore water. The pore water is pumped and treated (pump and treat
method) on the ground. While treating the pumped water, both extractants and IHM are removed.
 Fig. 4.4 A schematic diagram for in-situ chemical decontamination

Another method is to allow the contaminated pore water to flow through a permeable
reactive barrier (PRB). Hence the placement of the barrier is determined by the direction of flow of
ground water. The material packed in the barrier will retain IHM by exchange (sorption),
complexation or precipitation reaction. The transmission and the reaction time determine the
thickness of the reactive barrier to be provided. The material to be provided in the barrier is
influenced by the knowledge of IHM to be removed. This is mainly due to the fact that the above
mentioned reaction occurs differently when IHM is present as single or as multiple species.
The successful use of PRB or treatment wall (TW) depends upon its location such that majority
of the contaminated groundwater flows through it. It is essential to have a good knowledge on the
hydrogeological conditions where such barriers need to be placed. In some cases, sheet pile walls
are used to confine the flow towards the permeable barrier. Some of the materials used in such
PRBs are exchange resins, activated carbon, zeolites, various biota, ferric oxides, ferrous hydroxide
etc. Hydraulic conductivity of the PRB should be greater than or equal to the surrounding soil for
proper permeation to occur. Further, reaction kinetics and permeability of the barrier would
determine the thickness of the wall to be provided such that enough residence time is achieved for
the removal reaction to occur.

4.4.2 Biological methods

Remediation by biological treatment is mostly applicable for soil contaminated with organic
pollutants and the process is termed as bioremediation. In this method, certain soil microorganisms
are used to metabolize organic chemical compounds. In the process these microorganisms degrade
the contaminant. If naturally occurring microorganisms such as bacteria, virus or fungi is not capable
of producing enzymes required for bioremediation, then genetically engineered microorganisms
would be required. At the same time, it should be ensured that such microorganisms do not produce
any undesirable effect on the geoenvironment (such as toxins). The process of bioremediation is
dependent on reactions such as microbial degradation, hydrolysis, aerobic and anaerobic
transformation, redox reaction, volatalization etc. An example of bioremediation is discussed in the
next section where in the process is used for the remediation of oil spill land.
4.4.3 Electro-kinetic methods
Electro-kinetic methods are popular field method for decontaminating a particular site by
using electrical principles. The procedure is more effective for granular type of soils. Two metal
electrodes are inserted into the soil mass which acts as anode and cathode. An electric field is
established across these electrodes that produces electronic conduction as well as charge transfer
between electrodes and solids in the soil-water system. This is achieved by applying a low intensity
direct current across electrode pairs which are positioned on each side of the contaminated soil. The
electric current results in electrosmosis and ion migration resulting in the movement of
contaminants from one electrode to the other. Contaminants in the soil water or those which are
desorbed from the soil surface are transported to the electrodes depending upon their charges.
Contaminants are then collected by a recovery system or deposited at the electrodes.

Sometimes, surfactants and complexing agents are used to facilitate the process of contaminant
movement. This method is commercially used for the removal of heavy metals from the soil such as
uranium, mercury etc. The readers are requested to go through the wide range of literature
available on this subject, which is otherwise not possible to explain fully in an introductory course
like this.
4.4.4 Thermal methods
Thermal methods include both high temperature (>5000C) and low temperature (<5000C)
methods and are mostly useful for contaminants with high volatilization potential (Evangelou 1998).
High temperature processes include incineration, electric pyrolysis, and in-situ vitrification. Low
temperature treatments include low temperature incineration, thermal aeration, infrared furnace
treatment, thermal stripping. High temperature treatment involves complete destruction of
contaminants through oxidation. Low temperature treatment increases the rate of phase transfer of
contaminants from liquid to gaseous phase there by causing contaminant separation from the soil.
Radio frequency (RF) heating is used for in situ thermal decontamination of soil having volatile and
semi-volatile organic contaminants. Steam stripping or thermal stripping is another process useful
for soils contaminated with volatile and semi-volatile organic contaminants. It is an in situ process in
which hot air, water or steam is injected into the ground resulting in increased volatilization of
contaminants. Sometimes vacuum is applied to extract air or steam back to the surface for further
treatment. The effectiveness of this method is increased by the use of chemical agents that are
capable of increasing the volatility of the contaminants. High cost and its ineffectiveness with some
contaminants make thermal method less attractive. Also, in some cases incineration process
produces more toxic gases.