Soils contamination and Remediation

PM3E
F. CHAZARENC
EMN, 2012


Part 1: Introduction/context (45 min) Part 2: Methodology (45 min) Part 3: Soils remediation (1.5 h) Part 4: Project (3 6 hours)

Part 1
Introduction / context
I. II. III.

Interest in soil pollution? What is a soil : Soil's compounds Contaminated soils and classification

I. Interest in soil pollution?

Basias sites in 2006 Basol sites in 2006

Old industrial sites recorded in 2007 400 000 sites (66 dep.)

potentially polluted sites 3 717 sites

I. Interest in soil pollution?

Soils = Natural resources
Buffer zone
Filter Interface between atmosphere/ground water
~

Atmosphere/ground water/vegetation

Wildlife habitat
Habitation of many organisms (ecosystem)

Resource
Farm and timber production Nutritive substrate, provide biomass production Raw materiel source
~

Clay reservoir, sand, gravel, minerals

Water reservoir
Underground systems, ground water

Role of foundations for infrastructures, buildings

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Effects of sols pollution

Soils pollution : impacts soil capacities
Degradation of physic, chemical or biological properties Limits soil uses (resources / construction etc.)

A given pollutant or cocktail pollutants in soil can impact :

Vegetation Primary producer Accu. in plant tissues Animals Impact animals health Accu in food chain

Humans

Example: Mercury cycle (Hg)

Source: http://www.chelationhealthproducts.com/heavy_metal_mercury.php

I. II. III.

Interest in soil pollution? What is a soil : Soils compounds Contaminated soils and classification

II. Soil constitutions

Soils are made of : - Solid organic and mineral compounds - Liquids and gaseous compounds (stored in pore volumes)

1/3 Solid compounds

Desegregation and alteration of rock (Bedrock) Physical desegregation
Fragmentation gravels, stones, sand
~ ~

Dynamic desegregation : water effect, wind, materials Static desegregation : T effect, humidity, frost

Chemical alteration
Transformation of mineral part of rock Formation of alteration complexes
~

Clay, silica, iron oxides, salts

Dissolution : water or CO2 action on soluble rocks Hydrolyze : water, acids or bases action on crystalline rocks

Biological desegregation : roots, worms

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Solid compounds: mineral fraction

Granulometry classification Granulometric Analyses * Allow to know soil structure : % of compounds - sand soil - silt soil - clay soil - clay-sand soil

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Solid compounds: organic fraction

Soil organic compounds : ~ Vegetables and living animals (bacteria, mushrooms, ) ~ Animals excrements and vegetable detritus, dead animals ~ Organic matter in decomposition intermediate organic compound ~ Stabilized organic compound: humic substances (Humus= colloidal fraction) to find as different varieties Humic acids Fulvic acids

Source: www.wikipidia.org

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2/3. Pores
Liquid fraction: - Rain - Human contribution - Decomposition of rock and organic matter Compound are: water, soluble elements, organics substances (alcohols, organic acids), minerals substances (acids, bases, salts) Gaseous fraction: - Air - Biogas from living organisms - Decomposition of organic matter

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Pores: liquid compounds

Definition and soil humidity parameters
H= (Mh - Ms) 100 Ms

H: Soil humidity rate Mh : humid soil mass Ms : dry soil mass

Water stored
Salty or fresh Moving or static
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Water availabilities
According to Soil texture, for the same amount of water :
~ ~

Available water is large with fine particles Available water is small with clay

Water movement
Water can stream and/or seep in and reach ground water
~ ~

Percolation Diffusion

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Soil Permeability
Percolation
Function of soil porosity and permeability
~ ~

Coarse elements (rocks, gravels) Favour water percolation and movement

Permeable soil

~ ~

Thin elements (thin sand, silt, clay)

Impermeable Compact soils

Soil composition
Impacts permeability
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Pores: gaseous compounds

Main sources Air
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N2, O2, CO2 CO2, CH4, H2S

Biogas
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Air in soil Enable life (vegetals, animals etc.) Increases humus production and other bio-processes

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3/3. Biological activity in soils

Soil full of life Ex. Meadow soil
4% Organic matter
~

20% living organisms

In organic soils / average

10 tons/ha mushrooms/fungi/algae 10 tons/ha bacteria 2 tons/ha earthworms

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I. II. III.

Interest in soil pollution? What is a soil : Soils compounds Contaminated soils and classification

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III. Contaminated soil and classification

What is a naturally contaminated soil ?
Due to geological activities
~ ~

H2S, TSS, MeS Radioactive compounds

(ex. Radon Rn into Granites)

Volcanic activities

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What is soil contamination?

What is a contaminated soil ?
Anthropic activities
~ ~

Waste, Industrial activities Soil, above soil, ground water

Origin of Soil contamination

Caused by the presence of xenobiotic (human-made) chemicals or other alteration in the natural soil environment

Main causes
Rupture of underground storage tanks Application of pesticides Percolation of contaminated surface water to subsurface strata Oil and fuel dumping Leaching of wastes from landfills or direct discharge of industrial wastes to the soil

Most common chemicals involved

Petroleum hydrocarbons, solvents, pesticides, lead and other heavy metals
~

Correlated with the degree of industrialization and intensities of chemical usage.

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Health effects
Health risks include
From direct contact with the contaminated soil
~ ~

Vapours from the contaminants Secondary contamination of water supplies within and underlying the soil Time consuming and expensive tasks Requiring extensive amounts of geology, hydrology, chemistry and computer modeling skills

Mapping / treatment of contaminated soil sites

~ ~

North America and Western Europe

Extent of contaminated land is most well known

Developing countries
Very likely to be the next generation of new soil contamination cases

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Ecosystems effect
Significant deleterious consequences for ecosystems
Involves radical soil chemistry changes
~

Alteration of metabolism of endemic microorganisms and arthropods

Eradication of some of the primary food chain Major consequences for predator or consumer species

Accumulation of pollutant in the food chain E.g. concentration of persistent DDT materials for avian consumers

Many of these effects are now well known

~

Effects occur to agricultural lands

Certain types of soil contamination Contaminants typically alter plant metabolism
~

Most commonly to reduce crop yields Some of these chemical contaminants have long half-lives
Derivative chemicals are formed from decay of primary soil contaminants.

Secondary effect upon soil conservation

~

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Legislative aspects : Who is responsible?

Europeans and French laws (July 1992)
Responsibility of pollueur-payeur "polluter pays principle"

Several cases where the principle is not applicable

For olds activities : Identification of a responsible impossible Owner not able to pay Orphan "black point"

Collective responsibility

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Pollutant dispersion modes

Diffuse pollution
Coming from 1 single site
~ ~

Low amount of pollutants regularly discarded Chronically pollutant discards detected after a given time

Punctual or Mass Pollution

Mostly by accident Pollutant source is a classification criteria
~ ~ ~

Large source Punctual source Linear, horizontal, vertical source

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Pollutant dispersion modes

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Plan
Part 1: Introduction Part 2: Methodology Part 3: Sols remediation

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What is soil remediation/soil cleanup?

Soil remediation is the collective term for various strategies that are used to purify and revitalize soil This process of soil cleanup is part of a broader effort known as environmental remediation, which can also include efforts to purify the air and other wise repair damage done to the ecological balance of the planet

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Part 2: methodology
1. Supervision and preventive measures 2. Soils investigation 3. Pollution diagnostic

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1. Supervision and prevention

A. Supervision
Aiming at detecting contamination through a survey? Because soil contamination can be difficult to be detected Sol are often buffer zones with long answer time
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(more than 10 years)

In known industrial or landfill sites Manage a controlling system (mostly through piezzometer survey)
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Control of target pollutant or specific parameter (conductivity)

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B. Preventive measures

Preventive measures have to be taken when design a new industrial sites such as :
On new equipments: e.g. manage retention ponds in case of massive release : example ponds below Lime tower On fabrication processes: e.g. recycling and treating water after use (ex cutting fluids) On fluid/material transport: prevent leak from occurring

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Preventive measures can also be taken as good management practice or best management practice:
On new products: use less dangerous product on the market, reduce doses (pesticides, manure, phytosanitary products) Use advanced waste management procedures: advanced recylcing with industrial waste

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Part 2: Methodology
1. Supervision and prevention 2. Soils study stages 3. Pollution diagnostic

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How to perform a pollution diagnostic?

Preliminary diagnostic The site is not contaminated The site is (maybe) contaminated : Contamination is not well defined Have to be more accurately measured Diagnostic Workshop Solutions

Deeper diagnostic The site is contaminated Contamination is well known Problems identification List of possible actions to be done to solve problems Selected the most suitable treatment technology to be employed Select companies for de-pollution Selection of operators Beginning of workshops Quality control Site is clean

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Part 2: Methodology
1. Supervision and prevention 2. Soils study stages 3. Pollution diagnostic

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3. Pollution diagnostic
Actions
Prevention Depollution Characterisation of the pollution (nature and origin), Pollutants identification Soil volume need treatment

investigation
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Investigation Steps for soil clean-up

Step 1: Enquiry

History of the site, list of hosted activities Core-sampling and physico-chemical study of pollutants Lab investigations different clean-up processes

Step 2: Field investigati on

Conclusion and clean-up strategy accroding to next site function

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Step 1: Site history (documented analysis)

Gather all available data concerning the site:
Past industrial activities:
~

Chemical used, nature and amount

Raw material, intermediary products, final products, waste (advanced characterisation, e.g. solids, liquids, gas etc.)

Waste management procedures Hydrogeology Visit of the site soil surface aspects, storage facilities, pipes and water network Climate, proximate environment (rivers, ponds forests etc.) Potential dangers onsite
Define risk analysis for further investigations

Knowledge of the site:

~ ~

Main outcomes
~

Orient sampling strategy to better characterise site

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Step 2: A/ Field investigation

Objectives: Confirm presence of suspected pollutants To make an estimation of soil volumes and contaminated zones To estimate potential pollutant migration zones

Methods Field measurement: geophysics, hydrology, physico-chemical physicoinvestigation.. Sampling and lab analysis (cores and water from piezzometers)

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Step 2: B/ Onsite measurements

For parameters including chemical, physical or biological

With simple technologies (portative analysing systems, water/soil kit analysis) Enable to get in a very short time qualitative data about :
Presence of a pollutant Detection of a group of product
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Possible onsite analsysis

Technology Colorimetric test kits Pollutant measured Specific element (metal, anions, cations). Group of pollutants (Phenols, hydrocarbons etc.) Persistent organic pollutants (PAH, PCB) Group or organic molecules Volatile organic compounds and other gases (ppm, ppb) Physico-chemical parameter Depth of the water table, amount of floatting pollutants Petrochemical pollutants Application Water, sometimes sludge and solids.

Immunoenzymatic test Gas chromatography (GC) PhotonIonization Detector pH meter, conductivity, temperature probes Level probes

Water Gas in soil, water Gas in soil Water In depth water

UV lamps

Water, solids

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Investigation on hydrodynamic of water table:

Evolution of pizomtric level (water depth in a well) Soil hydraulic conductivity Effect of pumping on the water table

A piezometer is a small-diameter observation well used to smallmeasure the hydraulic head of groundwater in aquifers
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Source:http://acces.inrp.fr/eduterreusages/ressources/nappe/html/Resso urces/piezo/piezo1.htm

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Soil sampling After having made a sampling protocol Different sampling strategy available
Systematic sampling
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Using a grid and samplig according to it

Target sampling
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sampling only in the worse part of the site in terms of pollutant concentration Samples are taken randomly in all the site

Random sampling
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In average 3 kind of sampling are simultaneously applied

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Soil sampling methods Using a mechanical shovel

3-5 m Pit or hole

Using mechanical core sampling gadget or a manual one

Hole 0,2 up to 1m

Using a mechanical drilling system

Hole up to several times 10 m

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Water sampling Generally directly sampled into piezometer

Using sampling pipes Syringes pumps

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Prleveur deau (A) et de seringue (B)

Source: les sites pollus. P. Lecomte

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Types de mesure sur site

Source: les sites pollus. P. Lecomte

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Sampling conditioning
Soil samples
Glass bottle (organic conpounds Plastic bags (metals and minerals)
~

Caution: soil cores have to be managed in hermetic conditioners to prevent VOC from evaporating

Water samples
Glass bottle for hydrocarbon (possible to add sulphuric acid) Minerals plastic (polypropylene) bottles

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Step 2: B/ sample analysis

Chemical analysis Soils
~ ~

Per group of products (from organics to minerals) List of most common product if generally investigated first pH Conductivity, hardness TSS, turbidity COD, BOD5 and ultimate BOD

Water
~ ~ ~ ~

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Group of products mostly investigated

Source: sols pollus, P. Lecomte

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Plan
Part 1: Introduction Part 2: Methodology Part 3: Soils remediation

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Part 3: soil remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapor Containment of the soil contaminants Phytoremediation
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After diagnostic, and risk analysis be implemented

choice of action to

should reach a good balance between Level of rehabilitation required, Population life quality, Ecosystem quality, Technico-economical constrains

State objectives
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Clean-up options for contaminated soils

Cleanup or remediation is analyzed by environmental scientists
Based on field measurement of soil chemicals and also apply computer models for analyzing transport and fate of soil chemicals.

There are several main strategies for remediation

Soil excavation and take it to a disposal/treatment site
~ ~

Away from human or sensitive ecosystem contact This technique also applies to dredging of bay muds containing toxins Increase pollutant biodegradation (with attendant risk of creating air pollution) To volatize chemical contaminants out of the soil for vapour extraction

Aeration of soils at the contaminated site

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Thermal remediation by introduction of heat

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Bioremediation, involving microbial digestion of certain organic chemicals.

~

Techniques used in bioremediation include landfarming, biostimulation and bioaugmentating soil biota with commercially available microflora

Extraction of groundwater or soil vapor with an active electromechanical system

~

With subsequent stripping of the contaminants from the extract.

Containment of the soil contaminants (such as by capping or paving over in place). Phytoremediation, or using plants (such as willow) to extract heavy metals

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How to choose a remediation strategy

Technical criteria
Adapted technology
Already developed by professional companies

Has to be chosen according to :

Pollutant to be treated
~

Volatility, solubility, biodegradability

Amount of pollutant and concentration Surface to be treated and site specificity (country field, urban zone) Site nature (presence of water, soil composition etc.)

Has to consider if the site is still having industrial activity Has to fulfill legislative requirements

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Economical criteria
Cost estimations Has to take into account
~ ~ ~

Dcontamination Follow-up and de-pollution control Final depollution control and remediation efficiency

Very difficult to have a good cost estimation before depollution process is launched

Cost are then evaluated

Per time units (month, semester) Per volume units (amount of soil treated)
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Part 3: Soils remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapor Containment of the soil contaminants Phytoremediation
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There are 3 ways for soil treatment Out site treatment (excavation) In site treatment after excavation In situ treatment

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Out site Soil excavation Soil transported to - Specialised treatment centers - Specialized landfill

Treatment in situ In situ treatment using a mobile treatment system

Treatment ononsite Soil excavation Sol treated onsite and replaced

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Application hors site

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Application in situ

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Application sur site

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Part 3: Soils remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapor Containment of the soil contaminants Phytoremediation
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Soil excavation
Principle : mechanical extraction
Advantages :
~

Fast removal of pollutant from site What to do with excavated soils Costs

Disadvantages
~ ~

Mostly adapted to small volumes of highly contaminated soils

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Part 3: Soils remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapour Containment of the soil contaminants Phytoremediation
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 in situ treatment
Principle
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Injection of air and nutrients to enhance microbial degradation of pollutants

Advantages
Low cost, simultaneous treatment of soil and water

Disadvantages
Low control on biological processes

Mostly adapted : sites in activity, organic pollution under buldings

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 bioventing (unsaturated ) and biosparging (saturated)

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Part 3: Soils remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapour Containment of the soil contaminants Phytoremediation
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Out site thermal treatment

Incinration
Principle
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Soil is first excavated then transported into incineration plant Burn organic compounds at high temp (9001200 C).

Advantages
Efficiency for a large range of pollutant

Disadvantages
Problem with a couple of heavy metals Very costly
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On site thermal treatment

Thermic desoprtion
Principle : Excavated soils are heated into portative devices
~

Rotative furnace, fluidised beds

Advantage
Extraction of VOC Lower heating value, less impact on soils (250 650 C) Portable furnaces (on site treatment)

Disadvantages
Require a step to treat : gas, heavy metals

Mostly adapted to medium VOC contaminated soils

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Exemple de procd de dsorbeurs chauffage directe et indirect Source: ADEME

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In situ thermal treatment

Principe
Heating in situ soils with probes generating micro-waves, electrical resistances

Advantage
Enable to desorbs gas with in situ treatment

Disadvantages
Require gas treatment

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Source: http://www.frtr.gov/matrix2/section1/list-of-fig.html

Example : thermic resitance treatment

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Part 3: Soils remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapour Containment of the soil contaminants Phytoremediation
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Bioremediation "in site" treatment

Principle
After excavation soil is treated in a bioreactor possibility to add microorganisms

Advantages
Robust systems, simple

Disadvantages
Time for micro-organisms development, waste production

Adapted for high concentration of organic pollutants (PAH, phenols)

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* Option : biopile

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Part 3: Soils remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapour Containment of the soil contaminants Phytoremediation
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Groundwater pumping
Principe
Pump water in case groundwater is polluted Water is treated onsite or directed to a wastewater treatment plant

Advantage : simple to manage Disadvantages :

Can take a long time Can treat only partially the problem

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in situ air treatment

Principle
VOC and volatile compounds extraction :
~ ~

venting unsaturated stripping, sparging saturated

Advantages
High outputs, low costs

Disadvantages
Requires air treatment step

Adapted to low hydrocarbon polluted sites with a permeable soil

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Part 3: Soils remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapour Containment of the soil contaminants Phytoremediation
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Principle
build a wall unpermeable to contain water

Advantages
Simple workshops, can be low cost depending on the soil composition

Disadvantages
Required knowledge of hydrodynamics in the system Need to pump and treat water

Mostly adapted in case pollutants are going outside the site (migration)

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Part 3: Soils remediation

1. Choice of remediation procedure 2. Soils treatment methods 3. Depollution technologies
1. 2. 3. 4. 5. 6. 7. Soil excavation Aeration of soils Thermal remediation Bioremediation, involving microbial digestion Extraction of groundwater or soil vapour Containment of the soil contaminants Phytoremediation
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Phytoremediation
Principle : accumulation of pollutants in plant tissues Advantage : low cost disadvantages : long term treatment Adapted for HC, metals other chemicals compounds

Source:http://www.uga.edu/srel/Snapshots/phytoremediation.htm

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Flowchart of soil remediation example

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