Professional Documents
Culture Documents
The Netherlands Soil Partnership (NSP) was initiated by a group of Dutch consultants,
suppliers of technology and contractors companies which have expertise in the field
of soil remediation technologies and management. In order to offer a full scale and
integrated solution for all soil and groundwater problems, specialized companies are
working closely together with Dutch institutions for soil remediation and universities.
They are also supported by the Dutch ministry of Housing, Spatial Planning and Environment (VROM), the Ministry of Agriculture, Nature and Food Quality (LNV) and the
Ministry of Economic Affairs (EZ). NSP was officially established on the 9th of July 2008
in Den Haag, the Netherlands.
SKB Cahiers
SKB Cahiers are handbooks that contain summarised and concise descriptions of important subjects relating to soil. The SKB Handbooks are aimed at a wide audience and are
written in a readable and accessible manner. It must be possible for readers to use the
subject in their profession on the basis of application-oriented practical examples.
SKB Cahier
SKB
The Netherlands Centre for Soil Quality Management and Knowledge transfer (SKB)
develops and transfers the knowledge that owners and managers of plots and land
require in order to improve or maintain the quality of the soil that is appropriate for
the envisaged purpose in an effective manner. SKB supports the development and
demonstration of new forms of cooperation, new approaches and methods for the
improvement of the harmonisation between soil use and soil quality and promotes
their broad-based social acceptance in society.
Methods table
Individual remediation methods
Suitable for
source or
plume
approach
Suitable for
floating layer
removal?
Experience level in
the Netherlands?
Duration of
remediation?
Space occupied?
Intensity/costs of
Impact on
the method per m surroundings
of soil treated?
and/or business
process?
Soil types?
Safety aspects?
Source area
Yes
All types
Limited
High
No restrictions
Source
approach
No
Unsaturated zone
Initial moderate,
feasible
Especially in highly
permeable soils
Source
approach
No
Saturated &
Lubrication zone
Initial moderate,
feasible
Especially in highly
permeable soils
Control evaporation to
ground level
Groundwater extraction
and/or infiltration
Removal of dissolved,
lower concentrations
Plume
approach
No
All types
Initial moderate,
feasible
Especially in highly
permeable soils
Source
approach
Yes
All types
Initial moderate,
feasible
Especially in highly
permeable soils
Electroreclamation
Source
approach
Source
approach
No
Yes
Initial moderate,
feasible
Initial moderate,
feasible
Especially in highly
permeable soils
Especially in highly
permeable soils
Source
approach
No
Unsaturated zone
Initial moderate,
feasible
Removal dissolved,
lower concentrations
Source &
plume area
No
Unsaturated zone
Initial moderate,
feasible
Especially highly
permeable sandy soils
Removal dissolved,
lower concentrations
Source &
plume area
No
Saturated zone
Initial moderate,
feasible
Especially highly
permeable sandy soils
Removal dissolved,
lower concentrations
Source &
plume area
No
Limited
Especially highly
permeable sandy soils
Removal dissolved,
lower concentrations
Removal dissolved,
lower concentrations
Source &
plume area
Source &
plume area
No
Initial moderate,
feasible
Initial moderate,
feasible
Especially highly
permeable sandy soils
Especially highly
permeable sandy soils
Removal dissolved,
lower concentrations
Source &
plume area
No
Low
Limited
Anaerobic
Regular (shock load) or
degradation
continuous injection of
nitrates, sulphates and/or
nutrients
Removal dissolved,
lower concentrations
Source &
plume area
No
BTEX
Medium, 5 - 25 sites
Low
Limited
Source area
No
Saturated zone
Short, 3 - 6 months
High
Initial moderate,
feasible
Continuous injection of
ozone, possibly in combination with hydrogen peroxide
Removal dissolved,
lower concentrations
Plume area
No
Moderate
Initial moderate,
feasible
Injection of sodium or
potassium
Removal dissolved,
lower concentrations
Plume area
No
Saturated zone
Medium, 5 - 25 sites
Short, 3 - 6 months
Moderate
Limited
Excavation
Extractive
remediation
Steam Stimulated
extraction
Six Phase Heating
Biological
remediation
Groundwater extraction
and infiltration of nutrients
Chemical
remediation
Cahier
Remediation
method
Dealing
with
soil
Oil in
the soil
Contents
Introduction and preamble
1.
What is oil?
1.1 Introduction
1.2 Crude oil
1.3 Refining
1.4 Composition
9
9
10
10
11
2.
15
15
15
17
18
19
20
21
3. Risks
3.1 Introduction
3.2 Exposure risks
3.2.1 Evaluation of exposure risks
3.2.2 Evaluation of risks for humans with
the fraction approach
3.2.3 Odours
3.2.4 Consequences
3.2.5 Risks for the ecosystem
3.2.6 Summary
3.3 Damage
3.4 Danger of fire and explosions
25
25
25
25
26
28
28
29
29
29
30
32
4. Research strategies
4.1 Introduction
4.2 Research goals
4.3 Conventional research methods
4.3.1 Historical research
4.3.2 Conventional research
4.4 Follow-up research on the source zone and plume
4.4.1 Conventional methods
4.4.2 New methods
4.5 Age and origins of oil contaminations
37
37
38
39
39
40
46
46
48
49
52
5. Remediation methods
5.1 Introduction
5.2 Realistic remediation goals
5.3 General remediation goals
5.3.1 Excavation
5.3.2 Physical, extractive remediations
5.3.3 Biological remediation
5.3.4 Chemical remediation
5.4 Individual remediation methods
5.4.1 Classic groundwater extraction
and/or infiltration
5.4.2 Soil air extraction
5.4.3 Multiple Phase Extraction (MPE)
5.4.4 Compressed air injection (in-situ stripping)
5.4.5 Stimulation of aerobic degradation:
regular of shock load injections
5.4.6 Auxiliary method: heat (electroreclamation)
5.4.7 Auxiliary method: surfactants
5.4.8 Steam-stimulated extraction
57
57
59
61
61
62
63
64
64
65
67
68
70
71
73
73
73
5.5
5.6
74
74
75
75
76
77
78
6.
83
83
83
83
83
85
Finances
6.1 Introduction
6.2 Source remediation
6.3 Plume or remnant remediation
6.4 Highly cost-determining factors
6.5 Risks of failure
86
8. Appendices
88
What is oil?
1.1. Introduction
Speak about oil and everyone knows what you are talking about. Everybody has an image of what oil is. The term is much more difficult
when it comes to an exact definition. Besides the definition problem,
it also seems that the complex behaviour of oil is underestimated.
The same applies to soil contamination with oil. They also behave
in a manner that is much more complicated than is often assumed.
In contrast to many other contaminations, oil is a mixture of more
than 1000 different substances. These substances consist primarily
of hydrocarbon compounds. Hydrocarbons are chemical substances
that consist exclusively of carbon (C) and hydrogen atoms (H). The
hydrocarbon compounds can be chain and ring compounds (see
diagram 1).
Despite this complexity, policy frequently handles and expresses oil as
a singular substance with unambiguous properties in the mineral oil
parameter (this being - C10- C 40). According to NEN 5733 (1997), oil
is: compounds that can be isolated with acetone/petroleum ether under the conditions of this standard and that can be chromatographed
with retention periods between the retention period of n-decane
(C10H22) and n-tetracontane (C 40H82).
Penthane
Benzene
SKB
Cahier
The parameter mineral oil (this being - C10 - C 40) only indicates the
quantity of oil. And it is not even complete in this. Only 10-20% of the
actual content of contaminations that consist largely of components
<C10 (such as a benzene and petroleum contamination) is covered
by the mineral oil analysis. This means 80 to 90% of benzene is not
detected in a mineral oil analysis. This can have major consequences.
When determining the risks, the most volatile substances and thereby
the substances with the greatest risk of exposure (see chapter 3) are
forgotten. For example, an activated carbon filter may fill up much
faster during a remediation than was estimated in beforehand.
Oil is not a substance such as e.g. lead, but a complex mixture. This
has major consequences for the entire soil remediation process, from
the very first preliminary study, the determination of the risks and
the remediation goal to and including the remediation method.
1.2 Crude oil
There are more than three hundred different types of mineral oil in
the world. Mineral oil or crude oil consists of hydrocarbons with
chain and ring compounds varying from 5 to more than 50 carbon
atoms. It also contains substances such as heavy metals and phosphor
compounds.
1.3 Refining
In The Netherlands, approximately 150 million litres of mineral oil
is imported every day. This oil is processed into usable oil products
in the refineries. Refining is a method of separating crude oil into
different oil products. The refining process produces a wide range of
products on the basis of the different types of mineral oil. The most
important process here is distillation. This is the separation of substances on the basis of differences in boiling point. The crude mineral
oil is separated into usable products such as LPG, benzene, kerosene
and diesel.
The ratio of the products after distillation does not correspond with
current market demands. For example, more fuel oil remains after
distillation than can be sold on the market. This is why fuel oil is
10
11
SKB
Cahier
Table 1
Composition of several oil products according to carbon fractions
(CONCAWE/TPH)
Product
Range
<C10
C10-C40
24 - 140
38 - 205
150 - 300
150 - 290
125 - 390
160 - 400
170 - 420
316 - 470
C5 - C15
C4 - C12
C9 - C17
C9 - C16
C8 - C24
C9 - C25
C10 - C30
C18 - C34
99%
80%
15%
15%
6%
5%
0%
0%
1%
20%
85%
85%
94%
95%
100%
100%
Paraffin
Benzene
Petroleum
Kerosene (Jet A)
Gas oil *
Diesel
Domestic fuel oil
Marine diesel
Motor oil
For the majority of products it applies that the composition and the
range are highly dependent on the manner in which they are produced. For example, the composition of benzene and diesel will be
highly dependent on the production method. Only refining produces
a different diesel to e.g. refining and cracking. To illustrate, table 2
shows the composition of diesel as a consequence of different production processes.
Table 2
Composition of diesel as a consequence of different
production processes (API, 1997)
Boiling point-
Share (mass percentage)
range
Process
Paraffins Naphthenes Alkenes Aromatics
Desulphurised
Middle distillate 1
Desulphurised
Middle distillate 2
Normal middle distillate
Light cracked 1
Light cracked 2
261 - 301
46
26.5
2.5
25.0
172 - 344
48.9
20.2
<0.1
30.9
185 - 391
240 - 372
185 - 351
54.1
13.7
23.2
25.6
10.3
8.2
<0.1
3.7
7.8
30.9
72.4
60.8
Floating
layer meter
12
13
Saturated zone
1
5
Groundwater level
3
4
Groundwater
2.1 Introduction
Insight into the behaviour and spreading of oil is essential for the
research method to and including the remediation. This chapter
discusses the way in which oil behaves on the basis of a conceptual
model. This conceptual model is the basis of the soil remediation
process. It involves question such as how the oil is in the soil - as pure
product, a floating layer, source or plume. The behaviour of oil in the
source is different to that in the plume, and this is of real importance
for the remediation method. The same applies to the given that oil is
a mixture. It behaves accordingly. The consequences of the behaviour
of the mixture and the properties of oil that are relevant for soil remediation are examined.
Statement of the problem
It is frequently believed that the removal of the floating layer is
sufficient to resolve the problem of oil contamination in the soil.
Subsequently flushing several times will then remove and groundwater contamination. This myth obstructs an effective approach to oil
contamination. In practice, this type of approach to oil contaminations in the soil is not successful. The contamination continues to
deliver forever.
2.2 Behaviour of oil in the soil
Oil on or in the soil will move through the unsaturated zone under
the influence of gravity. During this process, the oil will fi ll some
of the interstitial spaces in the unsaturated zone. If sufficient oil is
present it will eventually reach the groundwater level. Here, the oil
will form a floating layer on top of the groundwater (diagram 2).
Seasonal effects may cause the groundwater level to fluctuate. When
it drops, the oil in the floating layer follows partially. However, part of
the oil remains in the interstitial spaces. When the groundwater level
rises again, the floating layer rises with it. Some of the oil will then be
15
SKB
Cahier
16
A floating layer is present if the oil can move through the soil as a separate, unbroken phase.
Floating layers originate when so much oil is present in the soil that
the retention capacity of the soil is exceeded. The retention capacity
is defined as the volume of oil per volume of soil that the ground can
hold. The retention capacity depends on the soil type and the oil type.
An indication of the retention capacity for several soil types is given
in table 3. What it boils down to is the coarser the soil type, the lower
the retention capacity.
Table 3
Retention capacity of various soil types for benzene,
diesel and fuel oil (API, 1993)
Soil type
Retention capacity
(litre/m3)
Benzene
Stones,
2.5
coarse gravel
Gravel,
4.0
coarse sand
Coarse /medium
7.5
coarse sand
Medium fine/
12.5
fine sand
Fine sand
20.0
Retention capacity
(mg/kg d.s.)
Diesel
5.0
Fuel oil
10.0
Benzene
1,300
Diesel
2,900
Fuel oil
6,400
8.0
16.0
2,000
4,600
10,300
15.0
30.0
3,800
8,600
19,300
25.0
50.0
6,300
14,300
32,100
40.0
80.0
10,000
22,900
51,400
17
SKB
Cahier
away as a free phase. It should be clear that after this type of remediation there will still be considerable concentrations of mineral oil
contamination in the soil.
Oil level
Number of sites
M * Sw = Cw
M = Mass fraction of a component in the oil mixture
Sw = Water solubility of the relevant component in pure form
Cw = Concentration of the component in water with equilibrium
in the oil mixture
Oil level
Oil-on-water
reaction negative
Oil-on-water test
negative
Number of sites
Oil level
Number of sites
Oil-on-water
reaction positive
Table 4
Raoults Law calculation example for two mixtures
Oil-on-water test
positive
Substance
Mixture 1
Mixture 2
Toluene
526,000
Xylene
161,000
Hexane
9,500
Total
0.20
0.50
0.30
1.00
105,200
80,500
2,850
188,550
0.10
0.45
0.45
1.00
52,600
72,450
4,275
129,325
18
Oil level
19
SKB
Cahier
20
Intermezzo:
Care for health
In the nineteen seventies the poison scandal in the town of
Lekkerkerk lead to social uproar. Many residents were concerned about the effects of contaminated soil on health. The
possible health risks prompted one-thousand-and-one questions. For example, was it prudent to eat vegetables grown
on an allotment or to allow the children to play outside in the
sandbox unsupervised. One of the scientific disciplines that
can provide answers is medical environmental science, which
has been at the core of health policy in major urban areas
since that time. This also applies to the GGD (regional health
service) Rotterdam - Rijnmond. Carola Hegger is a physician
and a senior medical environmental advisor affiliated to
this GGD. In this capacity, she is ideally placed to discuss the
health risks associated with soil contamination.
As a medical environmental expert give independent advice regarding questions posed by governmental bodies or private citizens on
health and the environment. For example, consider health risks of soil
contamination, possible health risks associated with the electromagnetic fields of transmitter masts, or the risks when removing asbestos.
We receive 5 to 10 questions on soil contamination from residents
each year. The majority of questions are from colleagues at the various
services of Rotterdam municipal council. these may be on soil remediation projects, t also on renovation activities or the arrangement of
new construction sites. Our consultation work also covers the estimation of the risks associated with, for example, water with a floating oil
layer in crawl spaces, or the evaporation of substances. But there are
also the more complex issues, such as the evaluation of sampling results, or the standards and models used in fist-thick soil reports. This
sometimes leads to recommendations of e..g. supplemental studies,
indoor air measurements or monitoring methods.
21
SKB
Cahier
Health risks
It is not so that soil contaminations involve health risks by definition. This is even frequently not the case. The possible health risks
depend especially on the nature and degree of the contamination
- one substance is more dangerous than the other - and the contact
possibilities. Contact possibilities refers to exposure to the substance.
For example inhalation of a substance after evaporation in a house
or drinking contaminated water. Here to, the general rule is - there
must first be contact with a substance before it can have any effect on
health.
Not just oil
Possible contaminations with mineral oil occur relatively frequently.
The most well known example is that of the remediation of a filling
station in a residential area. This does not take away from the fact
that this form of contamination is very difficult to evaluate. This has
everything to do with the composition of the oil. Mineral oil can
consist of a great many different fractions. Issues such as the gravity and volatility of the fractions, the quantity and the depth of the
contamination and the degree of evaporation are very important for
22
23
Risks
3.1 Introduction
The chapter will discuss the risks associated with oil contaminations.
When determining the risks of oil contaminations a distinction is
made between the risks of exposure, risks of damage, fire and explosion. Exposure risks relate especially to humans and the ecosystem.
Risks of damage relate to materials.
3.2 Exposure risks
3.2.1 Evaluation of exposure risks
Mineral oil is one of the most common substances that cause local
contamination of soil and groundwater. Nevertheless, in the past the
potential risks of these contaminations for humans were frequently
not evaluated. This related to the fact that the evaluation of the risks
of mineral oil was not possible with the aid of the normal risk evaluation models.
This is because the exposure models calculate the exposure of people
for each separate substance. These calculations are executed on the
basis of substance data such as the water solubility, volatility, partition
coefficient and toxicological limit value for each substance. As mineral oil is a complex mixture of different substances, it is impossible to
provide a fixed value of physical-chemical parameters for mineral oil
in general. The consequence of this is that risks for humans were frequently not calculated in the past, or the risks were evaluated on the
basis of components that occur in mineral oil such as BTEX or PAH.
This is why various methods were developed to still be able to evaluate
the risks of mineral oil. One of these methods is the fraction approach. The following paragraph discusses the fraction approach as a
method of evaluating the risks associated with mineral oil contaminations in more detail
25
SKB
Cahier
Personal protection
against exposure due
to evaporation during
excavation.
26
Diagram 4: Relative contribution of different exposure routes to the total exposure at a site, calculated for the house with garden scenario. The figures
for the fractions give an indication of the chain length.
27
SKB
Cahier
3.2.3 Odours
Soil contamination with mineral oil can create unpleasant odours for
residents. Some components of mineral oil products, such as certain
organic sulphur compounds, can be smelled in the air at extremely
low concentrations.
The sensitivity of peoples sense of smell differs greatly. This is why
reference works frequently provide a maximum and minimum limit
for odour thresholds and not a single fixed value. The board of health
regards odour as an aspect that can negatively influence health. If a
contamination causes unpleasant odours for residents this is a reason
to implement remediation measures, regardless of the health risks of
the contamination.
3.2.4 Consequences
In general it is the volatile fractions that determine the exposure risks
of mineral oil contaminations (see chapter 1). This is why research
and analysis data must answer three questions in particular:
Could the contamination be present under buildings?
Can contaminations evaporate into the outside air?
Does the mineral oil product that is present contain volatile
components?
Clearly described analysis methods are now available that can provide
answers regarding the presence of volatile mineral oil components
in the soil and groundwater. Obtaining a clear picture of a contamination situation under buildings is often difficult in practice. If it
is expected that mineral oil contaminations that contain volatile
components are (partially) present under buildings, the evaporation
into the air must be verified with measurements. This can be done by
taking measurements in the crawl space and the indoor air.
If remediation measures are required, the remediation method will
have to be selected in such a way that the risks have been reduced
to a sufficient degree after remediation (and the remediation goal is
achieved). The remediation goals for volatile contaminations under
buildings will be lower (stricter) than the remediation goals for volatile contaminations that are not under buildings.
For the analysis method, this means that it is necessary to have a clear
28
3.2.6 Summary
In the past it was not possible to (effectively) evaluate the risks of
contaminations with mineral oil.
The fraction approach makes it possible to evaluate the risks of
the substance mixture more effectively.
The risks of mineral oil contamination are highly dependent on
the type of contamination (the fraction composition).
Especially volatile mineral oil components are important for the
determination of the exposure risks.
In order to be able to effectively evaluate evaporation risks, we
recommend carrying out site-specific measurements of the crawl
space air and indoor air.
3.3 Damage
Oil contaminations are able to dissolve certain materials. Plastic in
particular are sensitive to permeation (penetration) and damage. A
number of materials that are used in the sub soil and of which the
function can be negatively affected are described here:
29
SKB
Cahier
Table 5
Class
Flash points
1F
2F
30
31
SKB
Cahier
32
procedures and expenses. In rural municipalities it occasionally happens that the contractor around the corner is used to clear the job up.
A tractor with a crane behind it, hoist the tank out, and then take it
to the local scrap iron dealer. Easy as pie. Naturally, this is not how it
works.
Lieuwe Hansma:
We were not really welcomed with open arms. But this is not unusual
with our work. The garage-owner and contractor attempted to evade,
but the discussion was soon at an end. I was certain that I had absolutely not received any notification of the remediation. The case was
therefore illegal. My police colleague increased the pressure: If you
do not stop this immediately I will write out an official report and you
will be in even more trouble. These are the times when collaboration
between the police and the council pays dividends.
Luut de Jong:
A soil study must be carried out prior to the implementation of soil
remediation. Modern method such as soil analyses provide insight
into the nature and scope of the contamination. There is a duty to
report, which means that the initiator must announce the intended
remediation to the municipal council. This announcement is accompanied by the results of the soil study, the manner in which the
remediation will be conducted and specification of who will carry it
out. Naturally, that must be a specialised company that possesses the
required quality certificates. If the soil and tank remediation is carried out by a company that is not appropriately certified and without
prior announcement to the competent authority, this is an illegal
remediation. The owner will not receive a tank remediation certificate
and clean soil declaration, and this will cause a great many problems
for him if he wishes to sell the property. Every potential buyer will
ask for such a declaration. Either a remediation will still have to be
executed in accordance with the regulations or the remediation costs
will be deducted from the sale price. There are countless examples
of the buyer deciding not to go ahead with the purchase. The owner
is then left with his own mess. A contaminated site that is therefore
difficult to sell.
33
SKB
Cahier
Lieuwe Hansma:
Our first concern was to exclude and minimise the risks that were
present. You must remember that we were confronted with a tank that
had already been lifted out of the ground. It stank of petrol, and if you
know how explosive petrol fumes can be you know what the dangers
are. Immediate action was sorely needed in order to prevent danger to
the local residents. We immediately stopped the work, closed all pipes
and sealed off and screened the site. After all, the site was in a residential area. Furthermore, there are always some curious older residents
who stand and watch the work. Imagine if the tank had exploded.
Luut de Jong:
Soil remediation occurs in all shapes and sizes. Sometimes the issue
is simply the removal of the tank without causing soil contamination,
and sometimes the situations are complex and involve tank removal
and considerable soil contamination. It becomes more problematic
if cables, pipes or water pits are present or if the tanks and contaminated soil are located under buildings or high Voltage cables. There
are countless implementation variants, from cleaning the site to and
including excavation and removal.
Luut de Jong:
My urgent advice is - always act in accordance with the procedures
and regulation and, in any case, always work with certified companies. The statement pay peanuts, get monkeys might be particularly
appropriate for soil remediation. Follow all the steps in the process
carefully. An open attitude and transparent communication reinforce
the contacts between the various involved parties. A good relationship
in which you can trust each other makes the work more pleasant for
the initiator, contractor and authorities. With the final result being,
clean soil!
Note:
The Saturday afternoon remediation is a true story. The time, place and some details have
been changed without affecting the reality.
Lieuwe Hansma:
You frequently hear hit entrepreneurs complaining that the remediation costs are so high, that they have such a small company and that
it will cost them their business. It is not nearly that bad in practice.
Soil remediation carried out in accordance with the regulations has,
without doubt, added value. The clean ground declaration that is obtained is an absolute must for building activities or for the purchasing
or sale of land. You cannot do without it. The good thing is that you
usually see satisfied faces at the end of the process. I sometimes even
see pride in the sense of the job has been done completely according
to the rules and the diploma has been earned. The pain of the initial
discussion on the use, necessity and costs is definitively in the past.
34
35
Research strategies
4.1 Introduction
We now know what oil is and have outlined its behaviour. The exposure risks for humans and the ecosystem and the possible damage to
materials are also now clear. This knowledge does not mean that we
can simply start the actual remediation of oil in the soil. Prior to this
we need precise insight into the nature, scope and character of the
contamination in connection with possible remediation. This chapter
discusses the necessary research questions and possible research
methods that must still be answered in this context.
Table 6 is an overview of the methods discussed in this chapter.
Table 6
Overview of research methods discussed
Method
Type
Features
Paragraph
Historical research
Desk study
Site inspection
On-Site
Conventional
Laboratory
Taking soil water samples
with boreholes and measuring pipes,
analysis at the laboratory
PID
On-Site
Measurement of volatile
compounds in the field
ROST/MIP
On-Site
Direct measurement in probe cone
Diffusion/Sorbisampler Laboratory
Alternative groundwater
Sampling method
Geophysical
On-Site
Ground radar, seismic measurements
Origin
4.3.1
4.3.2
4.3.2
4.4.1
4.4.1
4.4.2
4.4.2
4.5
37
SKB
Cahier
38
39
SKB
Cahier
Implementation of
mechanical boring for
placement of measuring
pipes (Source Tauw)
40
aromatic hydrocarbons into the atmosphere. When taking groundwater samples, a limited debit is applied in order to prevent the emission,
and thereby disappearance of the substance into the atmosphere, of
vapour bubbles produced by underpressure prior to analysis.
The placement of measuring pipes in the source area of contamination with mineral oil involves a risk of permeation of contaminants
through the plastic pipes of the measuring pipes and filters (see
paragraph 3.3). Volatile aromatic hydrocarbons in particular can
penetrate through plastic pipes and contaminate the groundwater.
Plastic may even soften in extreme cases. This may give the impres-
41
SKB
Cahier
42
hydrocarbon fraction division can be used for initial product recognition. Division into aromatic and aliphatic fractions can be used for
risk analysis. This method was developed in the first instance by
the American Total Petroleum Hydrocarbons Criteria Work Group
(TPHCWG) and is now gradually being adopted in Europe. RIVM
has also developed a method that corresponds with the TPHCWG
methodology (see paragraph 3.2.2). his method has not yet been incorporated into policy and is almost never applied in practice in The
Netherlands. Oil analysis can be used to determine remediation (im)
possibilities for unknown oil products (see box).
Oil analysis
The oil analysis is based on the measurement of the water solubility of all of the substances in the oil/tar. The boiling point of all the
substances is determined on the basis of retention period in the gas
chromatogram (a gas chromatograph separates the substances on
the basis of the difference in boiling point). The combination of water
solubility and boiling point leads to an identification of the compound
at substance group level. This categorisation is frequently used for the
identification of the oil (e.g. which type of kerosene). A categorisation
is also made into aliphatic and aromatic fractions. This categorisation
can be used for the risk evaluation of an oil.
The substances in the oil can also be categorised according to solubility in air and water. The usability of this categorisation lies in the
predictive and evaluating value for the maximum achievable yield
of remediation methods that are based on evaporation (stripping)
or flushing (pump-and-treat). In addition, a pronouncement is made
on the biological and chemical degradability of the oil. An effectively
underpinned remediation goal can be derived with the aid of the oil
analysis and the site-specific data.
43
SKB
Cahier
Diagram 5
Oil GC chromatograms of different oil products
(source: Laboratory AL-West)
44
Benzene
Hydraulic oil
45
SKB
Cahier
46
pulsating
UV laser light
glass fibre
cable
fluorescence
to photomultiplier
activated
aromatic
to
detector
heating element
sapphire window
fluorescence +
stable
aromatic
Hydrophobic
membrane permeable
for volatile compounds
friction resistance
friction resistance
cone resistance
cone resistance
Diagram 6:
Principle ROST method (source: Fugro)
Diagram 7:
Principle MIP method (source: Fugro)
47
SKB
Cahier
The probe cone is also fitted with traditional instruments for the
measurement of cone resistance and the friction resistance (= the
normal geotechnical probing) in order to determine the soil structure.
An advantage of this method is that it provides immediate insight into
oil and volatile compound concentrations in relation to depth (measured value per 2 cm soil travelled) and the soil structure. The ROST
method can reveal soil contaminations (pure product) and high levels
in the groundwater. The detection level of the MIP probe is usually in
the order of magnitude of 100 - 1,000 g/l. If desired, several verification measurements can take place in normal measuring pipes after
the MIP probing.
Recovery tests
The estimation of the contamination load in the soil can be carried out
with the aid of the floating layer thickness. However, the thickness of a
floating layer in a measuring pipe does not correspond with the actual
thickness of the floating layer in the soil. The floating layer is located in
the soil usually on and in the capillary zone. There is no capillary zone
in the measuring pipe, which means that the thickness of the floating
layer in the measuring pipe in practice will always be larger than the
actual thickness in the soil. Determination of the thickness of a floating
layer in the soil can be carried out with a recovery test. This involves
pumping the floating layer out of the measuring pipe and then observing the speed with which it reappears in the measuring pipe. The
actual thickness can be derived from the course of the reduction in the
influx speed of the floating layer. It is possible to measure a (apparent)
floating layer that does not actually exist in clay soils!
48
49
SKB
Cahier
50
51
SKB
Cahier
Intermezzo: Site
Konijnenberg 45 in Breda
You acquire a car dealership and then discover that the soil
underneath it is contaminated. Neither the former owner of
Auto van Tellingen B.V. nor the owner of the land and buildings are responsible. After legal proceedings you are eventually saddled with the costs of the soil remediation. This what
happened to Mart Rttchen of Autobedrijf Rugee B.V. For
Emiel Oomen, the owner of the land and buildings at that
time, it was just a question of common sense, look before you
leap and accept responsibility.
52
Mart Rttchen:
The polluter does not pay
I was stupid. I should not have bought Auto van Tellingen, but first
let it go bankrupt. If had bought it then I would not have had all this
trouble. This way there were skeletons in the closet, and I received a
letter from the council three months after the purchase. The contents
of that letter - the soil under my business was contaminated and I was
to take appropriate measures. I was dumbstruck. Auto van Tellingen
had told me nothing about possible contaminations before the purchase. Emiel Oomen, the owner of the land and buildings had also
said nothing about contamination. I knew nothing. I saw this as a case
of hidden defects as sometime occurs when buying a house. In these
cases, the seller can still be held liable. Justifiably, I believe. But things
went differently in my case.
Emiel Oomen:
Accept personal responsibility
It might have something to do with my education. It taught me to
emphasises structures and processes and therefore effective work
planning. I studied aerodynamics at TU Delft. After graduation as
an aircraft engineer I worked for a while in the automobile sector. As
so often happens, I stayed in that sector for the rest of my life. First
at a Volkswagen dealer in Breda. Later, I started as an independent
businessman and established my own car damage repair company.
That was at Konijnenberg 45. First I leased. When the opportunity
presented itself I purchased the land and the buildings. I used part of
it for my own garage, and I leased another part to a car dealership and
garage of which Mart Rttchen subsequently became the owner.
Auto van Tellingen, the actual polluter, was still owed money by me.
I was not planning to pay it until he had resolved the contamination
issue. However, he did not accept this and initiated legal proceedings.
The judge ruled in his favour, so I lost the case. Besides the soil remediation issue, I was not permitted to refuse to pay the money to which
he was entitled. The legal tug of war regarding the actual remediation
took years. The owner of the land and buildings at that time, Emiel
53
SKB
Cahier
you purchase land without a clean soil declaration. Examine the situation on site in advance, have zero measurements carried out, and also
study the water system and the groundwater streams.
My point of departure in normal life and my daily work is that everyone bears an important responsibility. For his family, colleagues or
employees and also the environment. Every citizen has a duty of care
to his or her descendants and future generations. The environment
deserves respect and we must be good stewards of this legacy. This is
how I ran my damage repair company, attaching a great deal of value
to effective policy on quality, working conditions and the environment right from the start. In this philosophy here is not room for I
did not know. You must always accept your own personal responsibility and investigate things thoroughly beforehand. I have always
been a proponent of this vision in my activities in the Brabantse
Zeeuwse Employers Association.
Rttchen eventually had the soil remediation carried out after the legal judgement. Completely in accordance with the rules. As it should
be. I sold my company, the land and the buildings a few years after the
remediation. I am now involved with a different branch of sport and
have an investment company in real estate management. Clean soil is
also a virtue in that sector.
54
55
Remediation methods
5.1 Introduction
Oil contaminations can be remediated with a wide range of (in-situ)
remediation methods. This chapter discusses the various remediation options on the basis of the SKB method fan. There are four basic
methods:
1. E
xcavation: excavation of the contamination and on/off site
cleaning.
2. Physical or extractive methods: actively removing the contamination from the soil.
3. Biological methods: (stimulation of) the natural degradation
in the soil.
4. Chemical methods: actively convert contaminations in the soil
into harmless end products with the aid of chemicals.
In order to carry out these remediation methods we have a number
of separate in-situ methods that can be used for various goals. For example, compressed air injection can be used to strip contaminations
from the soil (extractive) or to stimulate aerobic biological degradation (biological). For example, chemical oxidation frequently also
stimulates biological degradation.
There are also various supplementary methods, for example soil
heating or the injection of surfactants or hot water.
In this chapter, the methods table is used to explain what individual
in-situ methods are available for every remediation method. The table
also indicate the individual features of each method. For example,
consider the suitability for the approach to cores, floating layer
or plumes. Is the method suitable for the unsaturated zone or the
saturated zone and what are the levels of experience and cost? Every
method is then described briefly. This chapter also devotes attention
57
SKB
Cahier
Active
aftercare
Figuur 8
Globale stadia oliesanering
Passive
aftercare
58
59
SKB
Cahier
60
5.3.1 Excavation
The nature of oil contaminations frequently restricts them to the
shallow soil, the lubrication zone, which often makes them easily accessible for excavation. Depending on the situation, scope and remediation goal to be achieved, contaminations are completely excavated
or only the core source is removed.
The excavated soil is cleaned off-site or on-site, for example by means
of biopiling (biological soil cleaning). Depending on the scope, the
remediation period varies from days to several weeks. In the Dutch
context, temporary pumping is often required in order to be able to
excavate with dry feet.
61
SKB
Cahier
Any groundwater contamination or plume remaining after the soil remediation is either monitored for stability for several years or actively
treated with in-situ remediation methods, frequently pump & treat
approach or stimulation of biological degradation.
In the case of floating layers, excavation is often a quick, cost-effective
and reliable method in comparison with in-situ methods. Naturally,
the floating layer must be easily accessible for excavation.
A disadvantage of excavation is that vapours may be emitted, especially in the case of volatile oils, floating layers or aromatic hydrocarbons.
This pollutes the atmosphere and causes exposure risks and odour
emissions for both remediators and residents and the surrounding
area.
5.3.2 Biological remediations
Physical remediation methods are characterised by mobilisation and
extraction of the contamination from the soil. Contaminations that
are bonded to the soil or sometimes also pure product will first have
to be dissolved or evaporate. The contamination vapours, contaminated groundwater and/or pure product that are released are treated
above ground level.
5.3.3 Biological remediations
Biological remediation methods are characterised by the stimulation of natural, biological degradation processes of contamination.
Only dissolved contaminations can be treated by micro-organisms.
62
Aerobic degradation
When biological in-situ remediation methods are applied, the oil
contaminations are completely degrade into harmless end products
under the ground. Active stimulation of oil contaminations takes
place by creating an aerobic soil environment in combination with the
addition of extra nutrients. This produces biomass, heat, water and
carbon dioxide.
Anaerobic degradation
Naturally occurring anaerobic degradation is frequently very slow and
often incomplete. Stimulation of anaerobic degradation of BTEX is
applied. Sulphate or nitrates then act as the electron acceptor instead
of oxygen.
Oil types
Only the mobile, lighter oil fractions and aromatic components can
be effectively biologically degraded to a chain length of C10, at most
C12. To date, anaerobic degradation has only been demonstrated for
aromatic compounds.
Phased approach
In the case of extremely serious oil contaminations, for example with
pure product, stimulation of natural degradation is then often used
as a second remediation phase. First, the bulk of the contamination is
removed by means of physical and/or chemical remediation methods.
The remnant contamination is then biologically removed by means of
stimulated or natural degradation.
With biological stimulated remediations, no above-ground air and/or
water purification is needed. Refer to the methods table to see which
individual in-situ methods are suitable for the implementation of
biological remediation.
63
SKB
Cahier
Oil types
As with biological process, only the mobile, lighter oil fractions and
aromatic components are easily aerobically degradable to a chain
length of C10, and maximum C12.
Groundwater level
Lowering ground
water level
Dewatering pump
Waste water purification
Gravitational pumping
64
65
SKB
Cahier
Biological stimulation
In soil remediation, it is important to remediate where the contamination is located. This means additional food must be added at the
contamination site in order to stimulate micro-organisms. Groundwater is a means of transport in this process. It can be used to stimulate aerobic or anaerobic degradation processes. Extra food, such as
nutrients (N & P source), dissolved oxygen (salts) or - with anaerobically stimulated degradation - nitrates or sulphates are distributed
through the soil strata by means of groundwater extraction. Injection
of the food can take place periodically (shock load dosing) or continuously with infiltration equipment.
The extraction/infiltration can be stopped as soon as the food has
been distributed sufficiently. Blockage of the filter is an important
point of attention in the design in the case of continuous infiltration
of dissolved nutrients, etc.
Soil air extraction
66
67
SKB
Cahier
The strong vacuum forces the influx of a maximum quantity of soil air
and groundwater, as much as the soil in question can supply. This sucks
the filters empty at a faster rate than groundwater and/or product can
flow in, which produces an extremely dynamic extraction regime and
reduces the risk of preferential streams. The fact that the filter are placed
specifically in the lubrication zone means that this zone is also treated
much more effectively than with classic groundwater or soil air extraction.
The remediation principle behind MPE is also the flushing of the contaminated zone with clean air or water from the surrounding area. In
addition, a high level of underpressure is created, which maximises the
influx and evaporation. This method is particularly efficient due to the
focused extraction in the lubrication zone.
Once above ground, vapour and groundwater/product are separated.
Both streams are then purified before being discharged. A disadvantage
of MPE is the combined extraction of vapours, groundwater and pure
product.
The fact that the filters are placed in the lubrication zone means that
they have a limited zone of effect. For an effective MPE (floating layer)
remediation the filters must be placed at intervals of 3 to 5 or 6 metres,
Water separator
Exhaust fumes
Waste water/purification
Waste pump
Air stream
Lubrication zone
Water stream
68
69
SKB
Cahier
depending on the local soil structure. The MPE unit usually consists
of a measurement and collection section, a moisture separator with an
automatic drainage pump and a strong underpressure ventilator (to
almost absolute vacuum)
Bioslurping
Bioslurping is a certain type of Multiple Phase Extraction (MPE)
whereby the lubrication zone is intensively aerated. This method is
suitable precisely for the active aeration of this soil zone. The purpose
of the MPE system is to stimulate aerobic degradation.
5.4.4 Compressed air injection (in-situ stripping)
If compressed air injection is used to mobilise a contamination, the
remediation principle is the in-situ stripping of the contamination.
Air flowing through the soil evaporates the contamination from the
water to the air phase. This is why this method is always combined
with Multiple Phase Extraction or soil air extraction in order to intercept the emitted vapours
Pressure vessel
Measurement and
collection section
Compressor
Air bubbles
Only mobile, volatile oil components can be stripped from the soil by
means of compressed air injection. The compressed air filters are connected to a central, above-ground, compressed air injection unit. the
compressed air unit consists of a measurement and collection section
connected to an oil-free compressor.
The required filter distances are highly dependent on the local situation, such as soil structure, groundwater level and heterogeneity. In
the average oil contamination in The Netherlands, with a groundwater level of 2-3 metres below ground level, the filters are usually placed
at a depth of 6 to 7 metres, approximately 4 to 5 metres from each
other.
Air sparging
The injection of compressed air not only strips contaminations from
the soil, but the soil is also aerated of course, which stimulates aerobic
degradation processes. The effect of air sparging can be increased
with the application of micropore filters. Smaller air bubbles create
a larger exchange surface, thereby enabling oxygen to dissolve more
effectively.
5.4.5 Stimulation of aerobic degradation:
regular or shock load injections
Besides with the (continuous) injection of compressed air, aerobic
degradation can also be stimulated in the saturated zone with regular
or one-off injections of oxygen release compounds.
Oxygen Release Compound (ORC)
ORC is a phosphate-magnesium peroxide compound that releases
oxygen to its surroundings for a period of approximately 12 months
after a one-off injection into the groundwater. The advantage of
this method is that a one-off or regular addition is sufficient and no
installations are required above ground.
Oxygen release salts
As an alternative to ORC, it is also possible to inject oxygen release
salts: calcium peroxide or sodium percarbonate. These salts also
Air bubbles
70
71
SKB
Cahier
72
73
SKB
Cahier
The strength of the hydroxyl radicals that are produced lies in the
breaking of C=C, C-C and C-H bonds that are present throughout
organic contaminations. De ring structure of aromatic compounds
are easier to treat than the chains in aliphatic compounds.
The hydroxyl radical is an extremely powerful, non-selective oxidant.
It reacts quickly and frequently produces complete degradation, with
the end products being H20 and CO2. Product is frequently mobilised
(vapours) by the exothermic reactions. this remediation method is
therefore frequently combined with soil air extraction.
Modified Fentons Reagents
In modified Fentons Reagents the hydrogen peroxide is packaged in
a kind of gel, which retards the reaction speed, extends the period of
activity and maintains the effect at higher pH levels. This does reduce
the reaction strength somewhat.
When hydrogen peroxide is introduced, a (large) part of the oxidants
will automatically degrade into oxygen. This added oxygen will also
have a positive effect on natural degradation. It has been demonstrated that chemical oxidation does not sterilise the soil, and therefore
has a positive effect on the biological degradation processes.
5.4.11 Chemical oxidation with ozone and perozone
Ozone or ozone in combination with hydrogen peroxide (Perozone) can also be used as an oxidising agent. In contrast to Fentons
Reagents, ozone is added in gaseous form, possibly in combination
with a hydrogen peroxide solution. The level of ozone production is
frequently relatively low. This makes the method particularly suitable
for low contamination load or only dissolved concentrations.
5.4.12 Chemical oxidation with permanganate
In theory, it is also possible to oxidise aromatic contaminations
with sodium or potassium permanganate. However, permanganate has a lower oxidising strength, which is probably why it is not
used frequently for oil/aromatics contaminations. The advantage of
permanganate is that it remains active for a long period. This makes
Zone of effect of in-situ chemical oxidation, visible after excavation (source Tauw)
74
75
SKB
Cahier
76
77
SKB
Cahier
Intermezzo: Risks
between Africa and Assen
More than 1800 people work at the Schepersmaat in Assen.
Many of them work in the imposing head office. In 2005, the
company executed around 55 soil remediation projects, of
which 14 have been completed and a total of 181,000 tons
of soil has been excavated. The Nederlandse Aardolie Maatschappij takes its duty of care for humans and the environment seriously. Hans Huissoon and Auke van der Veen, both
working as senior civil and structural engineer for NAM: In
the course of time we have developed partially into an important centre of expertise in the field of soil remediation and
soil management. Risk perception often differs from place
to place and from country to country. In some countries we
do not go far enough with our measures, and people in other
countries feel that we go much too far. it is a good thing that
we enforce our own internal environmental standard regulations as well as legislation.
Our soil remediation activities are carried out at sites where have
extracted oil and gas. For example, spillage of oil into the soil may
have occurred there in one way or another, and it must be removed.
Our point of departure is always to deliver the sites in an acceptable
condition as much as possible in consultation with the original owner
and the government. Our approach combines economic development,
environmental protection and social responsibility. These are core
values in our company. We also always try to find a subtle balance
between financial effort and environmental yield. This is sometimes
difficult to achieve. When carrying out our work we are frequently
confronted with obstacles to effective solutions. We feel that Dutch
legislators occasionally overestimate the risks associated with oil in
the soil. Naturally, there are a great many risks in the field of public
health, the environment, nature and the ecology. Without ignoring
the problem, we must not forget that oil is a natural product and that
78
79
SKB
Cahier
80
81
Finances
6.1 Introduction
Naturally, the remediation costs are highly dependent on the local situation. Refer to the digital guideline Management and Recovery of soil
quality (www.bodemrichtlijn.nl) for an indication for each method.
Unit prices for remediation methods are difficult to generate. Here are
a number of rules of thumb.
6.2 Source remediation
If the source is easily accessible or if the concentrations are extremely
high or a floating layer is present, excavation is frequently financially
very favourable in relation to an in-situ approach. Of the in-situ
remediation methods, steam-stimulated extraction, six-phase heating
and chemical oxidation with Fentons reagents are the most expensive
per m of soil volume treated, followed by multiple phase extraction
and the more traditional in-situ methods such as soil air extraction,
groundwater extraction (pump & treat) and compressed air injection.
Note well, it is frequently true that the more intensive the remediation method, the faster the result is achieved. This means that there is
always a turning point and that a less costly method may eventually
become more expensive than a short (cost) intensive approach due to
the longer remediation period.
6.3 Plume or remnant remediation
Of the plume methods, chemical oxidation with ozone and/or perozone is probably the most expensive, followed by stimulation of the
aerobic degradation by means of compressed air injection and/or soil
air extraction, possibly in combination with groundwater extraction and infiltration. Simple checking natural degradation processes
involves the lowest costs.
83
SKB
Cahier
Another clear link is between the costs and the removal yield. As was
described in chapter 5, the majority of the contamination is often removed at the start of the project. The concentrations then frequently
decrease to an asymptotic course. This asymptotic course means that
the costs of removing the last bit of contamination are relatively high
(see diagram 9).
Costs
Stable end situation proven
Concentrations
Active remediation
Active aftercare
Passive aftercare
84
85
Mineral oil is one of the most common substances that can cause local contaminations in the soil and groundwater. The risks associated
with oil in the soil are diverse and vary from risks of exposure (for
humans and the ecosystem) and damage to materials to the danger
of fire and explosions. Besides the differences in actual risks, there
are differences in the perception of risks. One person perceives risks
in one way, and others in other ways. Hard information is required
on the composition, behaviour and spreading of the oil is required in
order to reduce the risks and to be able to remediate the contaminated
soil.
In-depth research on the nature, scope and characterisation of the
contamination is required prior to the commencement of the actual
remediation. Countless research strategies can be used for this. The
research results are determining factors for the choice of research
strategy and the remediation method that will eventually be used.
The costs of the soil remediation are highly dependent on the local
situation. In general, source remediation is the most costly part of
oil remediation. The initial costs - here we mean the installation and
86
87
Appendices
SKB-project PT5408
Application of the Sorbisampler in groundwater monitoring in the
context of groundwater remediation.
2.
1. Literature consulted
Franken et al. (1999)
Proposal for revised intervention values for petroleum hydrocarbons on base of fractions of petroleum hydrocarbons. RIVM Report
711701015. RIVM, Bilthoven, NL.
SKB-project PT4104
Diffusion Samplers.
Web sites
Overview of SKB measuring methods (method fan with measuring
and monitoring methods November 2004) www.skbodem.nl
Oil characterisation
www.oliekarakterisatie.nl
ROST
www.fugro-nederland.nl
MIP
www.fugro-nederland.nl
GGD
www.ggd.nl/kennisnet
88
SKB-project PT5404
Knowledge transfer and implementation of oil characterisation.
89
SKB
Cahier
Colophon
Editing staff
Laurent Bakker
Tauw, Deventer
Marco van den Brand Hannover Milieu- en Veiligheidstechniek, Ede
Charles Pijls
Tauw, Deventer
Ingrid van Reijsen
SKB, Gouda
Gerben van der Sterren
The Three Engineers, TTE, Deventer
Readers group
G. Boer
L. Hansma
L. de Jong
R. Cornelisse
A. van de Vusse
P.M. van Es - Prins
J. Kuyper
D. Lud
Visual material
February 2010
90