Physical-chemical

remediation of soils under

in-situ and ex-situ
conditions
In-situ Physical and Chemical
treatments
 Soil flushing: basics and application (a)
Introduction (infiltration) of liquid phases consisting of agents (i.e., water,
basic or acid solutions –in situ lisciviation- , surfactants, alcohols, etc) able
to solubilize and mobilize the pollutants occurring in the vadose zone. The
obtained phase is collected and treated on site.
Soil flushing: basics and application (b)
Extraction Recycled
phase phase
Recovery &
treatment of
contaminats
Additives

Contaminants
 Soil flushing: mobilizing agents

Agents Pollutants removed

Water Organics highly soluble in water

Inorganic salts soluble in water
Water + Organics of modest solubility in water
surfactants
Surfactants Poorly water soluble organics, hydrocarbons

Co-solvents Hydrophobic contaminants

(ex. alcohols)
Acids Metals, alkaline contaminants

Alkali Phenols, metals

Oxidants/ Metals
reducing agents
 Soil flushing: role of soil properties

Properties Impacts on the process

Repartition coefficient Low efficiency if the pollutants are highly
sorbed onto the soil
Hydraulic conductivity High values provide higher interactions
between extraction phase and pollutants
Soil surface area High values increase the pollutant adsortion
pH and buffer ability They affect the extraction/mobilizing effects
of the extraction phase
Cation Exchance High values favor the pollutant adsoption
Capacity and Clay and adversely affect their recovery
Content of organic High values favor the pollutant adsoption
Carbon and adversely affect their recovery
Rock fractures They adversly affect the efficiency of the
extraction
 Soil flushing: role of pollutant features
Parameters Influence

High solubility in water Extractable with water

High affinity towards the Low recovery efficiency

soils
High vapor pressure Highly available in the soil gas phase

Technology advantages:
Low costs
Treatment compatible with other activities in progress at the site;
No or limited impact on the soil life and natural features

Technology disadvantages
Requirement of pollutant monitoring to assess the pollutant fate at
the site;
Limited applicability on pooly homogenous soils
 Soil venting: basics and application (a)
Removal of volatile pollutants from the vadose zone via vacum application.
The obtained gaseous phase is collected and treated on site (via catalytic
oxidation, activated carbon, condensation unit).
Vacuum and stream
separation

Stream
Impermeable treatment
layer

Vadose
zone

Polluted zone

Saturated
zone
 Soil venting: basics and application (b)
SOIL VENTING with horizontal wells
Treatment

Polluted
zone

SOIL VENTING with vertical wells

Treatment

Polluted
zone
 Soil venting: basics and application (c)

MAIN CHEMICAL-PHYSIAL MECHANISMS INVOLVED

• Volatilization of contaminants;

• Partitioning of the contaminant into the three soil phases (soil -

water - air) -> determination of volatility by:

– Water-soil partitioning coefficient (adsorption);

– Air-water partitioning coefficient (Liquid gas equilibrium and
Henry's law)

• In the presence of NAPL (non aqueous phase liquids) the

phases become four the contaminant is present in the form of
immiscible liquid -> evaluation of volatility by means of Raoult's
law;

• Convective gas transport and mechanical actions

Soil venting: basics and application (d)
MAIN PHYSICAL-CHEMICAL MECHANISMS INVOLVED

3 PHASES WITHOUT NAPL

4 PHASES WITH NAPL

 Soil venting: basics and application (e)

Contaminants recoverable from soils

All contaminants characterized by high volatility (VOC) and low
solubility in water;

Among these, the most frequently found in contaminated sites are:

• Trichloroethane;
• Trichlorethylene;
• Benzene;
• Toluene;
• Ethylbenzene;
• Xylene;
• BTEX.
 Soil venting: basics and application (f)

SOIL LIMITING FACTORS

Parameter Impacts on the process

homogeneity It improves efficiency
Permeability/ They help interaction pollutant/vapor thus reducing
porosity the head of the blower
Umidity It increases the soil ability to assorb VOC thus
reducing the venting efficiency.
Organic matter It increases the soil ability to assorb VOC thus
content reducing the venting efficiency.
Rock fractures Secondary fractures create preferential routes for
the air.
 Soil venting: basics and application (g)

POLLUTANT LIMITING FACTORS

Parameter Impacts on the process

Molecular pollutant removals decrease with it (organic
weight pollutants are poorly removed when with a MW >
200 [g/mole] )
Vapor pressure It should be > 0.5 [mmHg] at the working
temperature;

Henry constant It should be below > 0.01 [mg/cm3aria/mg/cm3acqua] ay

the working temperature;

Solubility in It should be < 20000 [mg/L].

water
 Soil venting: basics and application (h)

Advantages
• It does not require the excavation of the soil
• It allows to reclaim underneath pre-existing buildings.
• Low costs even for large volumes of polluted land
• There is no impact on the original characteristics of the soil.

Disadvantages

 Long time to carry out the remediation;

 It may require surface waterproofing of the area to avoid short-
circuiting the extraction wells with atmospheric air;
 Special safety measures may be required in the presence of
substances with concentrations close to the lower explosive
level (LEL)
Thermal desorption: basics and application (a)

Technique used for the extraction of volatile organic compounds

(VOC) and semivolatile organic compounds (SVOC) from the
soil

OPERATIONAL PHASES
 Soil heating with different energy sources:
• Electric resistors;
• Radio frequency / electromagnetic heating;
• Injection of hot air or steam

 Volatilization / vaporization of contaminants;

 Extraction of contaminants with suction systems similar to those

used in soil venting;

 On-site treatment of vapors

 Thermal desorption: basics and application (b)

CHEMICAL PHYSICAL MECHANISMS

• Dependence of vapor pressure on temperature (Antoine's Law)
> increase in the partial pressure of contaminants in the soil
atmosphere > volatilization of semi-volatile compounds at
ambient T too;
• Increase in soil permeability by evaporation of interstitial water >
facilitation of advective and diffusive phenomena;
• Decrease in the solubilization of contaminants in water
• Catalysis of oxidative and degradative phenomena;

HEATING WITH ELECTRIC RESISTANCES

• An electric current is used to heat the less permeable parts of
the soil;
• The metal electrodes are placed directly in the ground which
acts as a resistor which transforms the current into heat due to
the joule effect;
 Thermal desorption: basics and application (c)

HEATING WITH ELECTRIC RESISTANCES

 Thermal desorption: basics and application (d)

RADIO WAVE HEATING

• Use of vertical electrodes inserted into the ground in special
holes or antennas that emit electromagnetic waves in the radio
frequency range;

• Induction of eddy currents that dissipate energy by the Joule

effect;

• The frequency of the waves varies between 6 [MHz] and 2.45

[GHz];

• Temperatures reached by the soil ~ 300 [° C];

• Extraction and purification of vapors with the same systems

seen for air sparging.
Thermal desorption: basics and application (e)

RADIO WAVE HEATING

 Thermal desorption: basics and application (f)

STEAM HEATING
• The technique is borrowed from the practices of the oil industry
for the recovery of hydrocarbons.

• The technique is completely analogous to soil venting with the

difference due to the presence of a pressurized steam injection
pipe and an extraction pipe.

• In addition to the advantages deriving from the increased

temperature, there are a number of disadvantages such as:

• Formation of a condensation front in the vicinity of the suction

area with possible semi-saturation of the soil in the vicinity of the
collection area;

• Need for pressure regulation in order to avoid ground fracturing

and formation of short circuits or escape routes.
Thermal desorption: basics and application (g)

STEAM HEATING
CONSENSATION
WATER UNIT

VAPOR + CONTAMINANTS
POLLUTANTS
TRAP
STEAM
GENERATION
STEAM INJECTION

SEPARATION
UNIT

ANTS
POLLUT
LIQUID
POLLUTANTS
TRAP

CONTAMINANTS
INJECTION AIR,STEAM  EXTRACTION
WEEL WATER  WEEL
 Thermal desorption: basics and application (h)
CONTAMINANTS TREATED
• VOC;
• SVOC;
• pesticides and fuels, on the basis of the achieved temperatures.

Main limiting factors

Parameter Impacts on the process
Soil Low soil homogeneity will adversely affect the
homogeneity treatment ; the presence of metallic materials can
affect the electrods
Organic Carbon Organic Carbon adsorbes VOCs; thus high Organic
contents Carbon contents adversely affect pollutant extraction

Temperature Higher temperatures can help but it depends on the

pollutants to be removed
Heating with air Air has a low thermic capacity and this does not help
or vapor
 Thermal desorption: basics and application (i)

Advantages

• It does not require excavation of the ground;

• It allows to treat poorly permeable soils;

Disadvanteges

 Additional energy costs;

 High temperatures can alter the structure of the soil;
 The high temperatures can inhibit bacterial activity in the soil.
Chemical stabilization: basics and application (a)
Reduction of the contaminated soil surface available for percolation by
binding the contaminant to the solid matrix (stabilization) obtained by
adding cement or other binders. This can be done by:
Chemical fixation:
• Precipitation;
• Complexation;
• Adsorption.

Physical fixation:
• Trapping of contaminants within the cement matrix

Operational phases
• Mixing of the additives with the soil by means of drills or other
drilling machines with a diameter of ~ 2m.
• Perforations with the method of overlapping the holes to avoid
having areas not subjected to treatment.
• Possibility to push the treatment up to 20 - 30 m depth.
• Treatment capacity of 10 - 15 m3 / hour.
Chemical stabilization: basics and application (b)

Stabilized mass
Unpermeable layer
for confinement Contaminated soils
 Chemical stabilization: basics and application (c)

Chemical/physical mechanisms

• Precipitation
– increased conc. Ca2+  formation of precipitates (insoluble salts)
promoting solidification. High pH  production of insoluble heavy
metals hydroxides;

• Complexation
– high pH  production of insoluble complexes (mainly aluminates)
able to react with several anions (NO3-, MnO42-). The tri Ca sylicate
can react with metal oxydes or hydroxides by providing insoluble
products.

• Adsorbing
– The hydration of the cement -> increase in its specific surface
which is in conditions of activation due to the presence of silica ->
adsorption reactions that determine the binding of some
contaminants to the matrix and their immobilization.

– Physical trapping of contaminants

 Chemical stabilization: basics and application (d)

Treatable contaminants
• Mainly inorganic contaminants;
• The addition of some additives allows microencapsulation and
adsorption of some organic contaminants.

Inerting with binders (in situ): Limiting factors

Parameter Impacts on the process
Mass Porosity If too high or not homogenous, it increases the
pollutant release
Umidity The optima ratio water/cement is ~ 0.5
Heavy metals Their occurrence results in a delay in the inerting
process and affect negatively the mechanical
properties of the soil
Mass resulting The initial volume of the soil increases by 10% -
from the 50%.
process
 Chemical stabilization: basics and application (e)

Advantage
• It does not require the handling of waste or contaminated land;
• Increase of the mechanical resistance characteristics of the soil;

Disantages

 Difficulty in obtaining uniform mixing;

 The presence of sulphates, chlorides, bromides can adversely affect
the process;
 Increase in volume of the inert material;
 Need to monitor the system especially as regards leaching.
 Vetrification: basics and application (a)
Operations phases
• Soil heating up to 1600 - 2000 ° C;
• Initial soil melting followed by rapid cooling;
• Formation of an amorphous and non-crystalline monolith;
• Thermal destruction of organic contaminants and Immobilization of
inorganics.

Plant properties
• Heating by applying a potential difference on four graphite electrodes
driven into the ground;
• Activation of the process by means of a conductive layer formed by a
mixture of graphite and glass frit arranged on the surface which
represents the initial path for the flow of current;
• Melting rate of 4-6 [ton / hour];
• Speed ​of advancement of the melting front ~ 2-2.5 [cm / hour];
• Surface cylindrical hood for capturing the gases produced during the
process;
• Fume purification system.
 Vetrification: basics and application (b)

Contaminated Vetrified
soils matter

Electrodes Electrodes
 Vetrification: basics and application (c)

Chemical Physical mechanisms

Heating at T = 1600 - 2000 [° C] -> volatilization and subsequent
pyrolysis of organic compounds;

Rising of pyrolysis gases which:

• They partially dissolve in the melt;
• In part they reach the surface where oxidizing conditions and
high temperatures lead to their thermal destruction.

• Incorporation of inorganic contaminants in the glass matrix.

Contaminante

Matrice
vetrosa
 Vetrification: basics and application (d)

Treatment contaminants
• Excellent removal efficiencies for thermal destruction of all organic;
• Effective incorporation of all inorganic compounds except volatile
ones.

Vetrification (in- situ)

Limiting factors
Parameter Impacts on the process
Volume of the The final mass of the treated material is decreasing
mass with the subsidence phenomena
Undergraund They can cause short circuits
Metal bodies
Umidity It can cause short circuits

Contamination The vetrification cannot be applied at layers deeper

deepness than 6m
 Vetrification: basics and application (e)

Advantages

• Absence of excavation of the land;

• High treatment yields for many types of pollutants;
• Minimization of process residues.

Disadvantages

 High consumption of electricity

 Alteration of the original characteristics of the soil;
 Need for soils with a high content of silica and aluminum;
 Difficulty in verifying the degree of uniformity in vitrification.
Ex-situ Physical and Chemical
treatments
 Chemical stabilization: basics and application

Technique analogous to the in-situ one. However, the operational

phases include an initial phase of soil pretreatment

Additional plant Units

•Storage unit for contaminated soil and additives;

• Pretreatment unit (comminution, screening, addition of
water and reagents).
• Mixing unit;
• Maturation areas.
 Soil washing: basics and application (a)
It is the ex-situ transposition of soil flushing therefore: Chemical-
physical mechanisms, extracting solutions and removable
contaminants are similar to those seen with soil flushing but the
treatment takes place after excavation of the soil in dedicated plants;

Unit operations:

 Excavation and transport

 Increase of the specific surface of the solid through comminution
/ screening circuits;
 Washing in conditions of high turbulence (hydrocycloning);
 Phase separation (liquid / solid);
 Purification of the extracting agent;
 Treatment of the contaminated concentrated fraction
 Possible post-treatment of the purified soil fraction.
Soil washing: basics and application (b)
PLANT (Svedala process & Pumps, 1997 )
 Soil washing: basics and application (c)

ADVANTAGES (vs soil flushing)

• Better process control;

• Greater efficiency;
• There are no limitations of permeability or heterogeneity of the
soil due to the presence of comminution and screening phases;
• Shorter treatment times.

DISADVANTAGES (vs soil flushing)

 Need for excavation of the ground;

 Higher installation and management costs;
 Major plant complications;
 Need to landfill some separate solid fractions;
 Inceneration: basics and application (a)
• Same technique used in solid waste treatment
• Controlled combustion of the soil in oxidizing conditions;
• Organic compounds are destroyed by temperature while inorganic
compounds are oxidized;
• The technique is not effective for the treatment of soils contaminated
with heavy metals;

Main plant characteristics

Power supply system;
Combustion and post-combustion chamber (oven);
Dust filtration system;
Gaseous effluent abatement system;
Inertisation system of ashes and combustion residues
 Inceneration: basics and application (b)
Controllo Scarico gas
Terreno esalazioni depurati
contaminato Terreno
decontaminato

Pretrattamenti Sistema di Sistema di

alimentazione alimentazione

gassoso
Flusso
Sistema Post -
recupero di Combustione
calore

Ceneri
Scarico gas
Ceneri, depurati
acqua
lavaggio
fumi
Rimozione Rimozione
particolato particolato

Depolveratori centrifughi, Sistemi di assorbimento a

filtri elettrostatici, secco, semisecco e ad umido;
filtri a maniche Adsorbimento su carboni attivi.

LEGENDA

Flusso solido Flusso Gassoso

 Inceneration: basics and application (c)
Rotating cylinder oven
• Slightly inclined cylinders lined with refractory material that rotate at a speed of
5-25 [rpm];
• Rotation -> advancement of the soil and mixing with the combustion air;
• operating temperatures ~ 850-1200 [° C];
• Use of fuel oil for start-up;
• Presence of post-combustion chamber;
• Variable potentials between 0.5 and 6 [t / hour].
 Inceneration: basics and application (d)
Infrared oven
• Silicon carbide bars heated by an electrical resistance that emit infrared thermal
radiation (8000 [Å] <L <1 [mm]);
• Post-combustion chamber with propane burner:
• Temperatures in the combustion chamber ~ 500-1050 [° C];
• Temperatures in the afterburner chamber ~ 1200 [° C];
• Maximum potential ~ 600 [kg / h];
• Often used for PCBs contaminated soils
 Inceneration: basics and application (e)

Fluidized bed ovens

• Vertical cylindrical furnaces containing a bed of incandescent
sand kept in constant fluidization with air;

• Generally no post-combustion chamber;

• Low operating temperatures ~ 750 - 900 [° C];

• Two main configurations:

• boiling type -> air speed ~ 0.5 - 1.4 [m / s];

• recirculating type -> air speed ~ 4.5 - 6 [m / s];

• Maximum potential ~ 3 [ton / h];

 Inceneration: basics and application (f)

Plasma arch Oven

• Heat input obtained by means of a plasma torch;

• Plasma torch -> high temperature ionized gas generator (10,000

- 28,000 ° C) by means of an electric arc;

• Very high temperatures -> total thermal destruction of the

organic materials with very high yields and melting / vitrification
of the soil with the incorporation of inorganic contaminants;

• Possible thermal destruction in oxidizing conditions or in the

absence of oxygen (pyrolysis);

• Very high treatment yields and reduced plant dimensions;

• High energy costs;

Inceneration: basics and application (g)

Plasma arch oven

 Inceneration: basics and application (h)

Chemical physical mechanisms

• Oxydative combustion;
• Combustion imder redox condutions;
• Pyrolysis;

Treatable Contaminants
 All organic pollutants;
 Also heavy matals in the case of plasma arch;

Limiting factors

 The treated soils has to have humidity above 50-60% w/w

 Interestig yealds are achieved with soils with high
concentrations of organic pollutants
 Inceneration: basics and application (i)

Advantages

• High yelds of organic compounds removal;

• Energy recovery feasible;

Disadvantages

 Need to treat the resulting streams;

 Possible production of highly toxic secondary products during
combustion (ex. dioxines);
 Need of soil excavation and pre-treatments;
 Modification of the native features of the soils
Physical-chemical remediation
of contaminated groundwater
under in-situ conditions.
 Reactive barriers: basics and application (a)
Interception of the contaminated underground water flow by means of
barriers capable of removing contaminants from it thanks to different
mechanisms (reaction, precipitation, adsorption) and preventing its
transport to the surrounding areas.
 Reactive barriers: basics and application (b)

Main plant configurations

a) Trench continues
In the continuous trench configuration, the flow is entirely
intercepted by the reagent material

b) Funnel and gate

use of a funnel-shaped low permeability barrier to direct the flow of
water from the contaminated region to a permeable treatment zone
(“gate”). The gate is filled with the reagent material. The waterproof
"funnel" is, on the other hand, made with plastic diaphragms or
steel sheet piles.
 Reactive barriers: basics and application (c)

Configurazione Funnel and gate Configurazione a trincea continua

 Reactive barriers: basics and application (d)
Multiple exits configuration
Reactive barriers: basics and application (e)

Main materials applied

 Reactive barriers: basics and application (f)

Fe0 valent barriers

• Used for the removal of organo-chlorinated compounds from
groundwater

• In the presence of granular iron, the chlorinated organic solvents

degrade according to a first order kinetics.

• Degradation of chlorinated hydrocarbons in the presence of Fe0

resulting from a redox reaction sum of a cathodic and an anodic
reaction developed on the metal surface.

Fe0  Fe2+ + 2e- anodic reaction

RCl + 2e - + H+  RH + Cl - cathodic reaction
______________________________________________
Fe0 + RCl + H+ Fe2+ + RH + Cl - Overall reaction
Reactive barriers: basics and application (g)
Fe 0 valent Barriers
Reductive dechlorination of tri-chloroethene in aquafers in the
presence of granular Fe
 Reactive barriers: basics and application (h)

Fe0 Fe2+
H2
2 e- H
2

RDX MNX, DNX, TNX, others

Abiotic
Reduction
 Reactive barriers: basics and application (i)

SEM
Immage of
Fe(0)
Sample from
a Barrier
Treating a
Chlorinated
Solvent
Plume in
Kansas City
 Reactive barriers: basics and application (l)

H2 produced by (anaerobic) iron corrosion stimulates RDX

mineralization.

Fe0 + 2H2O Fe+2 + H2 + 2OH-

Fe0 Fe2+ Cell RDX

H2
2 e- H H2
2

RDX MNX, DNX, TNX, others CO2, CH4, other?

Abiotic Microbial Reduction:

Reduction increases rate, less toxic products
 Reactive barriers: basics and application (m)

Dissimilatory Fe(III)-reducing bacteria could dissolve

oxides that passivate the iron surface, and generate reactive
solids with surface-associated Fe(II) (e.g., green rust)

Fe(III) oxide layer

Lactate
Fe3+
Fe0
e- Cell
Fe0

Acetate
Fe2+

MNX, DNX,
TNX MNX, DNX,
MEDINA TNX, HCHO,
RDX
RDX Others? Others
 Reactive barriers: basics and application (n)

Barriers based on modified Zeolites

Zeolites treated with high MW quaternary amines (es.
exadecyltrimethylammonia Br) to in situ removal of cations ,
anions and non polar organic compounds in aquafers.

exadecyltrimetylamonia Br

-
+ Br

Disposition of the amines on the surface of zeolite and sustitution

of the present cations (Na+, K+, Ca2+, Mg2+).
 Reactive barriers: basics and application (o)

Barriere di zeoliti modificate

The internal pores, whose dimensions do not allow the entry of

amines, are available for the adsorption of inorganic cations
of dimensions compatible with those of the internal cavities.

Adsorption of inorganic cations of dimensions compatible with

the internal pores of the zeolite -> removal of heavy metals
(Pb2+, Cd2+, etc.);

Absorption by organic partitioning of hydrophobic contaminants

on the surface double layer created by amines -> removal of
hydrophobic organochlorines and organics.

Electrostatic attraction on the positively charged "head" of the

amine -> removal of anionic contaminants (eg. CrO42-)
 Reactive barriers: basics and application (p)

Deposition of amines and interactions with contaminants

 Reactive barriers: basics and application (q)

Advantages
• Absence of excavation of the ground
• Possibility of dealing with situations of multiple contamination, i.e.
with the simultaneous presence of heavy metals, anions and
organic pollutants
• Good removal efficiencies;
• Simple installation and maintenance;
• Low costs;

Disadvantages

 Need to periodically regenerate the barriers;

 The permeability of the barrier decreases following precipitation
phenomena;
 Limited to shallow depths of contamination.