Water Air Soil Pollut (2009) 197:381393

DOI 10.1007/s11270-008-9819-4

Amphoteric Surfactants for PAH and Lead Polluted-Soil

Treatment Using Flotation
Julia Mouton & Guy Mercier & Jean-Franois Blais

Received: 7 March 2008 / Accepted: 24 July 2008 / Published online: 11 August 2008
# Springer Science + Business Media B.V. 2008

Abstract Polluted soils are a problem of major concern

impacting the health of the global environment and
human beings. Without any safe technology for polluted
soil treatment, most of the contaminated soils go to
landfill especially when metals are the pollutants. This
research compares the performance of non ionic (Brij 35
and Tween 80) and amphoteric (cocamydopropyl
hydroxysultaine (CAS) and coamydopropylbetaine
(BW)) surfactants for polycyclic aromatic hydrocarbons
(PAHs) and metals (mainly Pb) removal from three
contaminated soils. Best removal yields have been obtained using 0.5% (w/w) of CAS surfactant with 46
2% for PAHs and 215% for Pb simultaneously
removed. Sodium chloride and EDTA have been
shown to considerably enhance Pb solubilization
(respectively 555% and 3512% for [NaCl]=5.5 M
and [EDTA]=0.025 M). Flotation technology has been
tested as a separating technique of PAHs micelles and
Pb from aqueous solution and has given good results
for both contaminants (547% for both PAH and Pb,
using [CAS]=0.5%, [NaCl]=5.5 M, pH=3). Finally,
this study proposes a soil washing process using
flotation to treat soil polluted with both organic and
inorganic compounds. The suggested process concenJ. Mouton : G. Mercier : J.-F. Blais (*)
Institut National de la Recherche Scientifique (Centre Eau,
Terre et Environnement), Universit du Qubec,
490 rue de la Couronne,
Qubec, QC, Canada, G1K 9A9
e-mail: blaisjf@ete.inrs.ca

trates the organic compounds in the froth and the

inorganic pollutants in the liquid fraction.
Keywords Amphoteric surfactant .
Cocamydopropylhydroxusultaine . Soil-washing .
Contaminated soil . PAH . Pb . Flotation

1 Introduction
Surfactants are amphiphilic chemicals possessing both
hydrophilic and hydrophobic groups (hydrocarbon chain
(the tail) and a hydrophilic polar group (the head)). They
can be: anionic, non-ionic, cationic, amphoteric. A
surfactant reduce interfacial energies (Rosen 1989).
Hydrophiliclipophilic balance (HLB) is an important characteristic for surfactants. This unit value translates the relative importance of the polar groups
compared to the non-polar part. HLB varies between 0
and 20, 0 to 1012 are lipophilic, and hydrophilic for
1012 to 20 (Griffin 1949). This scale is applied to
nonionic surfactants. At low concentrations, surfactants
dissolve as solubilized macromolecules. At high concentrations, surfactants forms micellar structures (Banat
1994). The concentration at which first micelle appears
is called critical micellar concentration (CMC). Surfactants solubilize hydrophobic compounds in aqueous
solutions. At the CMC, the physical properties of
surfactant solutions change abruptly (Osipow 1962).
The CMC governs surfactant choice and defines the
optimal detergent characteristics and froth conditions.

382

Beyond the CMC, addition of surfactant has no effect

on surface tension. CMC varies for each surfactant and
is a function of temperature, ionic bonds and the
presence of organic and/or mineral additives (Haigh
1996), nature of the functional groups at the interface,
molecular structure, aqueous phase environment (pH,
temperature, additives, electrolyte) (Rosen 1989). In a
soil/solution system, the solubilization of organic
compounds occurs at effective surfactant concentrations (CMCeff) higher than CMC in pure water (Zheng
and Obbard 2002).
Contaminants are many and varied. Inorganic contaminants toxicity is dependent of metal speciation,
absorption mode, type of impacted organisms, and
metal concentrations. If some metals are known as life
essential oligo-elements (Zn, Cu), many others are toxic
and cumulative (Pb, Cd) (Lippmann 2000; Allen 2002).
Various treatment processes exist (biological,
physico-chemical, thermal) (USEPA 2004). Soil
washing is an ex situ process. This is done by
dissolving/transferring or concentrating (Mulligan et
al. 2001a). Biosurfactants for soil and groundwater
treatment can be used (Mulligan et al. 2001b). Metals,
the semi-volatile organics, PAHs, pesticides and
PCBs can be treated by soil washing (Mann 1999).
Many studies concern surfactants in groundwater
assessment (Abdul et al. 1990; Edwards et al. 1991).
Surfactants in ex situ soil washing process is less
studied (Deshpande et al. 1999; Iturbe et al. 2003).
The solubilization of PAH is a function of surfactant
nature and concentration, washing time, soil/surfactant interactions, hydrophobicity (Yeom et al. 1995).
Many methods exist to remove organic compounds:
surfactant-enhanced solubilization (Lopez et al. 2005),
solvent-enhanced solubilization (Lee and Hosomi
1999), chemical oxidation (Flotron et al. 2004; Rivas
2006), biological oxidation (Mulligan 2005). Non ionic
surfactants are well studied (Zhao et al. 2005b) (Tween
80). Anionic/nonionic surfactants mixture are also used
(Zhao et al. 2005b; Zhou and Zhu 2004, 2005; Zhu
and Feng 2003). Various operating conditions govern
process efficiency (Deshpande et al. 1999). Research
about amphoteric surfactants for soil treatment is rare.
Among all amphoteric surfactants, betaine structures is
very effective for metallic complexation and oil
dispersion (Kudaibergenov 2002). The use of N(3-Dodcyloxy-2-hydroxypropyl)-N,N-dimthylglycine (DHDG) for pyrene has been shown possible
(Guan and Tung 1998).

Water Air Soil Pollut (2009) 197:381393

Metal leaching from soil can be obtained under

many conditions: acidic pH (Neale et al. 1997),
chelators (Peters 1999), surfactants/biosurfactants
(Mulligan 2005), oxidants (Blais et al. 2001; Flotron
et al. 2004). Acids and chelators are often used
(Neilson et al. 2003). The best metal solubilization
occur with the use of anionic or amphoteric surfactant/biosurfactant (acetyltrimtehylammonium bromide/surfactin) (Doong et al. 1998; Mulligan et al.
1999). On the opposite, the best surfactants/biosurfactants for hydrocarbons removal, seem to be the non
ionic and anionic compounds (Lopez et al. 2005) or
rhamnolipids (Lafrance and Lapointe 1998). Most
surfactants are coming from petroleum and appear to
be dangerous for the environment. Tween 80 have a
pseudo-biodegraded impact on aquatic species
(Auriol et al. 2006). Alkyl-phenols can pass throughout wastewater treatment systems and join aquatic
environment (endocrine disrupting chemicals for
fishes (Desbrow et al. 1998; Routledge et al. 1998).
Flotation is a physico-chemical separation technique
widely used in mineral ore processing to separate minerals. Flotation is a complex technique related to many
parameters: collector type and dosage, conditioning
time and speed, flotation time and air flow, pulp density,
pH, temperature, additives, but is also shown as a good
method for both organic and inorganic compounds
removal from polluted soils (Vanthuyne et al. 2003;
Zhang et al. 2001). Most of studies about surfactantenhanced flotation use non ionic (Tween 80, Triton
X100) and anionic (SDS) surfactants, but a cationic
one (DTABdodecyl trimethyl ammonium bromide)
has been compared to others (Zhang et al. 2001).
Studies about cationic and amphoteric surfactants are
very few and their use is more devoted to cosmetic
industry. The objective of this research was to test and
compare non ionic and amphoteric surfactants for PAH
and Pb removal from soil. Soil quality and contamination level were estimated and compared to the regulatory
level in QuebecCanada (MDDEPQ 1999).

2 Methodology
2.1 Soil Samples
Three soils (S1, S2 and S3) coming from confidential
origins were used in this study. Physical and chemical
characteristics of these soils are given in Table 1.

Water Air Soil Pollut (2009) 197:381393

Table 1 Physical and
chemical characteristics of
the soils

383

Parameters

Units

% w w1
g cm3
%>2 mm
2<%>1 mm
1<%>0.5 mm
0.5<%>0.25 mm
0.25<%>0.125 mm
0.125<%>0.053 mm
%<0.053 mm

g kg1
g kg1
g kg1
g kg1
g kg1
g kg1
g kg1

Humidity
Density
Particle size

pH
Total carbon (C)
Total nitrogen (N)
Sulfur (S)
Phosphorus (P)
Calcium (Ca)
Sodium (Na)
Potassium (K)

Humidity was determined according to the method

2540B (APHA 1999). Total carbon (C), total nitrogen
(N) and sulfur (S) were analyzed by a CHNS Leco
analyser. Granulometry was analyzed using five sieves
sizes as follows: 210.50.250.1250.0053 mm
as described in Mercier et al. (2001). Phosphorus (P),
Table 2 Organic and inorganic pollutants concentrations in the fraction of
soils smaller than
2mm (mg kg1 of dry soil)

Regulatory level into force

in Quebec (Canada), for
commercial or industrial use
(Ministre du dveloppement durable de lenvironnement et des parcs du
Qubec 1999)

Pollutants

PAHs
NPN
ACN
FLU
PHE
ATN
FLR
PYR
BAN
CRY
BJK
BAP
INP
DBA
BPR
PAHs
Metals
Pb
Zn
Cr

Soils
S1

S2

S3

11.7
2.8
15.8
15.1
21.2
21.7
14.1
6.3
5.8
6.81
52.30.9
2.20.1
2.20.1
1.40.1
38.60.8
15.00.4
15.80.5

11.0
3.2
16.4
9.4
17.9
28.2
18.1
6.7
3.2
6.73
38.01.0
1.60.2
1.50.1
0.5
19.4
20.5
17.2

10.7
3.0
27.0
22.1
17.1
13.7
9.9
6.5
3.8
6.95
67.81.1
3.30.3
45.90.1
2.60.1
1185
3.70.3
8.40.8

calcium (Ca), potassium (K), and sodium (Na)

were analysed by ICP-AES as described in Djedidi
et al. (2005).
For experiments soil samples were passed through a 2
mm sieve. The fraction smaller than 2 mm was kept and
then was passed in a quarting apparatus. Table 2 shows
Criteria Ca

Soils
S1

S2

S3

2.940.79
5.201.12
6.861.59
53.113.4
15.34.2
90.914.4
74.514.0
52.19.3
54.016.2
71.415.3
44.68.0
39.711.6
11.92.3
27.610.6
558131

3.700.95
5.520.95
7.471.26
72.89.0
18.72.6
1088
84.97.1
50.25.7
48.95.9
77.612.2
46.45.7
36.17.3
11.21.9
28.47.1
63768

21.11.6
36.11.4
ND
50.25,6
76.54.6
41.86.0
16519
12314
89.313.9
10011
18724
89.818.9
28.12.6
74.813.5
1,04714

50
100
100
50
100
100
100
10
10
30 (B+J+K)
10
10
10
10

1 35034
1 20654
31955

2 990250
28215
31275

58014
2,36010
1,801231

1 000
1 500
800

384

Water Air Soil Pollut (2009) 197:381393

the PAHs and toxic metals concentrations in the soils

and the limit regulatory levels in Quebec (Canada) for a
commercial or industrial soil (criteria C).
2.2 Washing Assays in Erlenmeyer Shake Flasks
All experiments in this section were performed on soil
S1 as described in Djedidi et al. (2005) for the acid
leaching part. Assays were carried out on twenty
grams of soil for a 10% (w v1) pulp density at room
temperature (222C). After 60 min of shaking at
175 rpm (Orbital shaker, Lab-line Environ-Shaker,
model 3528), soil and washing solutions were
separated by vacuum (0.5 bar) filtration on Whatman
934-AH membrane (pore size=1.5 m). Soil was then
dried at 60C, and analyzed for both PAHs and
metals. The influence of drying on a possible
volatilization of lower molecular weight PAHs has
been controlled by extracting contaminants on dry
and wet materials. No difference was observed for
any of all analyzed PAHs.
The performance of different surfactants was
firstly tested at different concentrations (0.0, 2.5,
5.0, 10.0 and 25.0 g of surfactant/kg of dry soil). Brij

35 and Tween 80 were both obtained from Aldrich

Canada, whereas CAS and BW were bought from
ChemRon.
Tween 80 and Brij 35 are non-ionic surfactants
well referenced in literature (Zhao et al. 2005a).
Tween 80 is a polyoxyethylenesorbitan monooleate
consisting in a long esteric chain ended with a big
polar cyclic and ramified head and Brij 35 is a
polyoxyethylene (23) lauryl ether consisting in an
alcohol group at the end of a long polyoxyethylene
chain. Amphoteric surfactants CAS and BW consist
in a long hydrocarbon chain ended respectively with
amino-hydroxysultaine (Norton et al. 2005) and
amino-betaine groups (Stasiuk and Schramm 1996).
Some important characteristics of used surfactants are
given in Table 3
In a second time, washing treatment at pH 2 and 3
was studied in presence of CAS (5.0 g kg1). Additions of sodium chloride (NaCl=5.5 M) at pH 3 and
Ethylene Diamine Tetra Acetic Acid (EDTA=0.025 M)
were also tested in presence of CAS (5.0 g kg1).
EDTA and NaCl were obtained from Merck. The pH
adjustment was done using hydrochloric acid (HCl=
12 M, Fisher Scientific).

Table 3 Characteristics of the surfactants used in this study

Class

Non ionic

Abbreviations

Brij 35

Tween 80

CAS

BW

Names

Polyethylene
glycoldodecyl ether
1,200

Polyoxyethylenesorbitan
monooleate
1,310

Cocamidopropyl
Hydroxysultane
452

Cocamydopropylbetaine
387

1.05

1.00

1.11

1.04

16.9
9.2105
CH3(CH2)11
(OCH2CH2)n-OH
(n=23)
unknown

15
1.2105
C64H124O27

5105
CH3(CH2)13N(OH)(CH2)3N+(CH3)2-CH2CHOH
CH2SO3
96%

1.8105
CH3(CH2)13N(OH)
(CH2)3-N+(CH3)2-CH2
CH2COOH
99%

(Aldrich 2008)

(Aldrich 2008)

(Lucy and Tsang 2000)

(Stasiuk and Schramm 1996)

Molecular.
weight.
(g mol1)
Density
(g mL1)
HLBa
CMC (M)b
Formula

Biodegradability
(%)c
References

Amphoteric

+ Qualitative evidence for biodegradation without presentation of quantitative information

a

Hydrophiliclipophilic balance

Critical micellar concentration

Surfactants biodegradability from Swisher, R.D. (1987)

Water Air Soil Pollut (2009) 197:381393

2.3 SoilMicellar Solution Separation

The different techniques of micelles separation were
tested on soil S1 after 60 min of treatment in presence of
10 g Tween 80 kg1 of soil and in the conditions
previously described. The following separation techniques have been compared: Vacuum filtration (Whatman
934-AH membrane) and centrifugation (30 min at 500,
1,000, 1,500, 2,000 and 3,000 g) (Beckmann Coulter
Allergra 6). Soil was then collected, dried at 60C,
and analyzed for PAHs.
2.4 Flotation Cell Experiments
Experiments were carried out in triplicate using a
Denver Lab-1 flotation cell. Soils S2 and S3 were
treated with a 10% pulp density for 1 L total volume.
After a 15 min agitation period at 1,800 rpm, foams
were collected on the top of the cell during a 15
min flotation period (air flow=3 L min1). Conditioning and flotation parameters such as time, speed,
pulp density were selected from Zhang et al. (2001).
Soil and froth were separated from washing solutions
by vacuum filtration (Whatman 934-AH), then dried
at 60C, and analyzed for both PAHs and metals.
Two washing conditions have been tested: (1) CAS
(5.0 g kg1); (2) CAS (5.0 g kg1) + NaCl (5.5 M) at
pH 3.
2.5 Analytical Techniques
For every batch of analysis, a certified material
reference was used to confirm the extraction method
effectiveness: BCR no. 524 (obtained from Institute
for Reference Materials and Measurements) for PAHs
and PACS2 (obtained from National Research Council of Canada) for metals. PAHs analysis was
performed by GCMS (Perkin Elmer, model Clarus
500, with column type of VF-5MS FS 300.25 mm
0.25 m), after a Soxhlet extraction of PAHs from
10 g of soil according to a standard protocol
(Ministre du developpement durable de lenvironnement et des parcs du Quebec 2001) and a solid phase
extraction for PAHs from liquid samples (Ministre
du developpement durable de lenvironnement et des
parcs du Quebec 2006).
Twenty one compounds were identified in the
extracts: naphtalene (NPN), methyl-2-naphtalene

385

(M2NPN), acenaphtylene (ACyN), acenaphtene

(ACN), fluorene (FLU), phenanthrene (PHE), anthracene D-10, anthracene (ANT), fluoranthene (FLR),
pyrene (PYR), benzo[a]anthracne (BAN), chrysene
(CRY), benzo[b+j+k]fluoranthene (BJK), benzo[a]
pyrene (BAP), dimethylbenzanthracene (DMBAN),
3-methylcholanthrene (3MCN), benzo[ghi]perylene
(BPR), indeno[1,2,3-cd]pyrene (INP), dibenzo[a,h]
anthracene (DBA).
One of them labelled with deuterium were used as
extraction recovering standards. The average yield for
ANT-D10 reaches 89 5%. M2NPN, ACyN,
DMBAN and 3MCN were not enough abundant in
considered soils to be detected by the method. As it
was not possible to separate b, j or k benzofluoranthene and all given values are expressed as a sum of
Benzo[b+j+k]fluoranthene. The PAH extraction and
GCMS operating conditions are the same as described in Zheng et al. (2007). Initial temperature is
fixed at 80C. A first ramp of heating is maintained at
15.0C.min1 up to 220C, and a second is set at
5.0C.min1 until 320C for a total time of analysis in
36.33 min. The injection volume is 1.6 L. Analyses
were controlled using a certified solution Mix64
(obtained from Supelco). Every sample was injected
in two dilutions in order to follow every compound
present in different ranges of concentrations and to
better appreciate data. A 30% confidence interval is
given as acceptable for PAHs analysis in the certified
material (BCR no. 524) and it has always been
respected during analytic controls (Standard deviation
values are: NPN 2%, ACyN 3%, CAN 4%, FLU 3%,
PHE 2%, ANT 2%, FLR 9%, PYR 10%, BAN 15%,
CRY 11%, BJK 11%, BAP 22%, BPR 14%, INP
16%, DBA 17%).
Metals analysis was performed by ICP-AES
(Varian, model Vista-AX simultaneous ICP-AES)
after a complete mineralization of soil according the
method 3030I (APHA 1999). Analysis was controlled
using reference certified solutions obtained from SCP
science to assure a confidence interval of around 2%
for Ca, Cd, Cr, Cu, Ni, P, Pb and Zn, 1% for Fe and
5% for Na.
The pH measurement was done using a pH-meter
(Fisher Acumet model 915) equipped with a doublejunction Cole-Palmer electrode with Ag/AgCl reference cell. Oxidation reduction potential (ORP) was
measured with a platinum electrode.

386

Tween 80
Brij 35
CAS
BW

Surfactant concentration (g kg1)

0.0

2.5

5.0

10.0

25.0

21

146
23
2413
00

5917
00
462
57

629
2010
1836
136

1920
810
268
263

3 Results and Discussion

3.1 PAH Removal
Controls of NaCl and EDTA alone have been
pursued. No PAH removal was observed without
CAS, and the results are not presented. Table 4 gives
the removal yields of all PAHs (PAH), evaluated on
contaminant concentrations in the soil before and after
treatment. Brij 35 and BW were found to be
ineffective for PAHs removal. Best PAHs removal
yields (62% and 46%) were obtained respectively at
surfactant concentration of 10 g kg1 for Tween 80
and 5 g kg1 for CAS.
As shown on Fig. 1, every PAH compound
fluctuated in the same way with an increase of
surfactant concentration (Tween 80 and CAS). During
the assays with the highest surfactant concentration (25
g kg1), solubilization from soil was decreased for each
PAH compound. This observation witnesses the interfacial behavior of selected surfactants, and confirms the
idea of an optimal concentration for PAHs removal
from soil. As discussed previously, PAHs solubilization
is maximal around the CMCeff (effective critical
micelle concentration in soil/aqueous solution). These
CMCeff values are estimated between 500 and 1,000
mg L1 for Tween 80 and near 500 mg L1 for CAS
and appear, as presented in Table 5, between 31 and 63
times higher than CMC for Tween 80 and 24 times for
CAS.
The decrease of the PAH solubilization using a high
surfactant concentration (25 g kg1) can be explained
by the interactions occurring during soil washing
between water, surfactant, mineral particles, soluble
particles, hydrophobic particles, PAH, and metals.
Surfactant concentration can influence the type of
formed micelles and so that the nature of solubilized
particles, as presented in Fig. 2. Depending on its
dosage, surfactant can mainly interact with contaminants or with soil particles. Thus, it seems that for

concentrations lower than CMCeff (alpha zone on

Fig. 2) surfactants are not engaged in the solubilization
of any material, and appear as soluble macromolecules
in the medium. Around the CMCeff (bta zone), the
main interactions include PAH/surfactant and PAH/
hydrophobic-particles/surfactant, while at higher concentrations (gamma zone) the equilibrium is moved to
increase surfactant interactions with hydrophobic
100
90
80
PHE
ATN
PYR
BAN
CRY
BJK
BAP
INP
FLR

70

PAH (mg kg-1)

Surfactants

60
50
40
30
20
10
0
0.0%

0.5%

1.0%

1.5%

2.0%

2.5%

3.0%

Tween 80 (% w w-1)
100
90
80
70

PAH (mg kg-1)

Table 4 PAH removal

(%) from soil S1 using the
different surfactants (reaction time=60 min, pulp
density=10%)

Water Air Soil Pollut (2009) 197:381393

PHE
ATN
FLR
PYR
BAN
CRY
BJK
BAP

60
50
40
30
20
10
0
0.0%

0.5%

1.0%

1.5%

2.0%

2.5%

3.0%

CAS (% w w-1)

Fig. 1 Residual PAHs concentrations in soil S1 (mg kg1 of dry

soil) after washing in Erlenmeyer shake flasks using different
concentrations of Tween 80 and CAS. Reaction time=60 min,
pulp density=10%

Water Air Soil Pollut (2009) 197:381393

387

Table 5 Comparison of CMC and CMCeff for Tween 80 and

CAS
Surfactants

Tween 80

CAS

CMC (mg L1)

CMCeff (mg L1)
Ratio (CMCeff/CMC)

16
5001000
3163

24
500
21

particles and mineral particles. High surfactant concentrations disadvantage PAH solubilization by concentrating them into soil. CMC characterizes the
concentration of surfactant at which the first micelle
is formed in pure water. Zheng and Obbard (2002)
introduced the CMCeff as the concentration at which
the first micelle is formed in soil/solution system. The
concentration we are interested in, in this research, is
the concentration at which the solubilization of PAHs
is maximal. This concentration is called CPAHopt, which
is the lowest concentration of surfactant which gives
maximal solubilization of PAHs.
As seen on Table 3, the biodegradability of TW80
is still not quantified, while CAS is known to be
biodegradable at 96%. Also considering the fact that
Tween 80 is a potential toxic molecule (Auriol et al.
2006), the surfactant CAS has been chosen to develop
a process for simultaneous removal of PAHs and
metals. Because of their ability to act as anion or
Fig. 2 Scheme of different
interactions occurring during CAS-enhanced soil
washing

cation depending on pH and salts in presence,

amphoteric surfactants like CAS can support many
operating conditions without precipitating.
As shown in Fig. 3, a decrease of the soil pulp pH
to 3 causes a considerable decrease of low (less than
five aromatic rings) molecular weight PAH removal
(45% to 16%). High molecular weight PAH (more
than five aromatic rings) removal is maintained (45
46%) in these conditions.
The addition of 5.5 M NaCl at pH 3 has slightly enhanced the removal yield of high molecular weight PAHs
(from 45% to 51%). Solubilization of low molecular
weight PAH is decreased from 45% to 16% in the cases
of both addition of 5.5 M NaCl and 0.025 M EDTA.
As can be seen from Table 2, regulatory thresholds
for PAHs vary from 100 to 10 mg kg1 of dry soil
depending on the PAH. If regulatory levels (commercial or industrial use of soil) for low molecular weight
PAHs, such as NPN, ACN, FLU, PHE, FLR, PYR are
usually around 100 mg kg1, they are reduced to
10 mg/kg in the cases of more toxic high molecular
weight PAHs, such as BAN, CRY, BAP, BJK, INP,
DBA, BPR. For that reason, it seems promising,
depending on PAH contamination and objectives of
rehabilitation, to use CAS for low molecular weight
PAHs removal and/or to use CAS + NaCl to solubilize
high molecular weight PAHs.

388
70%

Water Air Soil Pollut (2009) 197:381393

30%

PbCl3, PbCl42), or EDTA-complex ([Pb(EDTA)]2,

[Pb(HEDTA)], [Pb(H2EDTA)]) depending on the
salt added (Djedidi et al. 2005). Assays with saturated
NaCl (5.5 M) solution were maintained at pH 3 (for
maximal lead chloro-complexes stability) and reveal
that even in its cationic form, CAS is involved in
mixed micelles (Pb chloro-complexesCASPAH).

20%

3.3 Separation Techniques

10%

3.3.1 Centrifugation

60%

Control
CAS
CAS + pH 3
CAS + NaCl + pH 3
CAS + EDTA

Removal (%)

50%
40%

0%
Total PAH

PAH < 5 rings

PAH > 5 rings

Pb

Fig. 3 PAHs and Pb removal yields (%) from soil S1 after

washing in Erlenmeyer shake flasks using different conditions
(CAS, CAS + pH 3, CAS + NaCl + pH 3 and CAS + EDTA).
Reaction time=60 min, pulp density=10%

3.2 Pb Removal
Pb analysis, carried out during assays with CAS,
suggests some solubilization of Pb (215%) (Fig. 3).
This result illustrates the existence of mixed micelles
PbCASPAH as presented on Fig. 2. If the tail of
CAS can interact with PAH and hydrophobic material
as a result of hydrophobic affinity, the aminosultaine
functional group on its head can also interact with
mineral material or metal ions, creating coordinate
covalent and ionic interactions with it.
Assays at pH 2 and 3 were firstly done in presence of
CAS (results for assays at pH 2 are not shown because
of the ineffectiveness of these conditions) and were
shown as ineffective for Pb removal. At low pH (pH 3),
CAS is mainly present in its cationic form (R-N+(CH3)2CH2CHOHCH2SO3H), and as a matter of fact Pb
solubilization is decreased from 215% to 44%
(Fig. 3). This observation confirms the existence of
mixed micelles with CAS, which are inhibited under
acidic conditions, due to the loss of the negative charge
of the polar functional group of the surfactant.
If pH decrease was shown as ineffective for Pb
removal, NaCl and EDTA addition appears as good
enhancers allowing an increase of Pb removal from
215% for CAS (5 g/kg) treatment to respectively
555% and 3512% for NaCl (5.5 M) and EDTA
(0.025 M) treatments. The improved Pb solubilization
observed in presence of salts, is due to the formation of
metallic complex: chloro-complexes (PbCl+, PbCl20,

Centrifugation has been tested at different centrifugal

forces (500, 1,000, 1,500, 2,000, and 3,000 g) to
separate soil from washing solution and was compared
to filtration (1.5 m pore size membrane). Figure 4
shows that filtration is a more efficient solid/liquid
separation technique than centrifugation (at 500 g) for
the separation of the PAH-surfactant micelles from the
soil particles. No PAH removal was observed at the
higher centrifugal force than 500 g (results not
shown).
Under centrifugal force, micelles may readsorb to
soil particles. In fact, solubilized PAH in surfactant
micelles can easily be separated from soil particles since
micelles in aqueous phase can pass through the filter.
Centrifugation, even at low speed, pelleted out micelles
from aqueous phase, and takes the micelles back into
solid phase giving a decrease of separation efficiency
(Zheng et al. 2007). Even if less than occurring during
centrifugation, the concept of contaminants readsorption to soil during filtration, is still maintained, for that
reason flotation assays were pursued.
3.3.2 Flotation
Flotation assays have been carried out with CAS and
CAS + NaCl + pH 3 on soils S2 and S3. Particle
removal (solids in froth), presented in Table 6, is
calculated as a ratio between the amount of dry froth
collected (FM) and the amount of initial dry soil
introduced (FC). This parameter varied from 4% to
9% with soils and tested conditions.
Preliminary flotation assays under saline conditions have revealed that 97% of the solids collected in
froth were composed of NaCl. Sodium was measured
in each part of the process: 311% are collected in
froth rinsing water (FMR) and 6710% in soil rinsing
water (FLR). No sodium has been detected in froth

Water Air Soil Pollut (2009) 197:381393

70%

389
Filtration
Centrifugation

60%

Removal (%)

50%
40%
30%
20%
10%
0%
NPN ACN PHE ATN FLR PYR BAN CRY BJK BAP INP BPR
Pollutants

Fig. 4 PAH removal yields (%) from soil S1 after washing in

Erlenmeyer shake flasks using Tween 80 (10 g kg1) and solid/
liquid separation by vacuum filtration (1.5 m) and centrifugation (500 g). Reaction time=60 min, pulp density=10%

after rinsing, whereas 1.2% of added salt has been

measured in soil after complete treatment (FS).
PAHs and metals removal presented in Table 6 are
given as a weight ratio between the part of contaminants
washed (FCFS) from soil and their initial amount
(FC). For the two soils treated, NaCl addition seems to
improve PAHs removal as much as Pb removal.
Removal yields were also generally superior for soil
S2 treatment in comparison to soil S3. This can be
explained by the granulometry (particle size: S2<S3) of
soil particles and the initial PAHs concentrations
([PAH]i: S2<S3). In the case of soil S2, the average
of PAH removal reached 5814% and 4412%,
Table 6 Pollutants removal
(%) from soils S2 and S3 by
flotation (reaction time=15
min, pulp density=10%)
using (CAS) and
(CAS + NaCl + pH 3)
conditions

[CAS]=5.0 g kg1

[CAS] = 5.0 g kg1 ,

[NaCl]=5.5 M, pH 3

Conditions

pH
ORP (mV)
Solids in froth (% w w1)
PAHs
PHE
FLU
PYR
BAN
CRY
BJK
Metals
Pb
Zn
Cu
Cr

respectively for treatments without and with NaCl.

For Soil S3, under the same conditions, the PAHs
removal yields were respectively 1412% and 547%.
Finally, even if treatment with CAS and NaCl
seems efficient for both PAHs and Pb removal,
pollutant concentrations in soils after treatment
remain higher than the criteria C (regulatory level),
as illustrated in Fig. 5.
3.4 Simultaneous Process for PAH and Pb Removal
from Polluted Soil
For polluted soil treatment, some technical aspects
must be considered. If washing and flotation give
good results for both PAHs and Pb removal, under
CAS and salt conditions, pollutants are concentrated
in different medium for each treatment. Soil washing
concentrates both PAHs and Pb in aqueous solution.
Their recovery would involve precipitation or degradation techniques. In both cases, the recovery of
contaminants after soil washing requires energy to
recuperate solid material. Soil washing using flotation
concentrates organic contaminants in froth and metallic pollutants in leachates. By this way, PAHs
concentrates are already obtained as a final solid
waste, what can be measured as a gain of energy
considering a full process application.
Table 7 shows the mass balance of solids and the
concentrations of PAHs and Pb in the different
fractions of the process. A partial loss of solids (8%)

CASa

CAS + NaCl + pH 3b

Soil S2

Soil S3

Soil S2

Soil S3

6.7
102
8

7.0
131
7

3.0
234
4

3.0
269
9

51%
50%
53%
70%
68%
83%

23%
27%
10%
12%
10%
11%

67%
67%
69%
80%
78%
81%

66%
61%
53%
55%
55%
56%

37%
33%
32%

6%
22%
11%
0%

50%
34%
40%

54%
49%
29%
14%

390
FC
FS

Soil S2

PAH (mg kg-1)

120
110
100
90
80
70
60
50
40
30
20
10
0

Water Air Soil Pollut (2009) 197:381393

PAH (mg kg-1)

PHE

FLR

BAN

CRY

BJK

220
Soil S2
200
180
160
140
120

FC
FS

trations in soils before and after treatment, but as a

decrease of the amount of pollutants (in mg) in soil
between initial and final steps of washing process
using flotation.
The particles removal in froth (11%) combined
with the potential solubilization of mineral particles
(8%) cause a recovery of 82% of the initial mass of
soil in the treated fraction. This mass decrease can
create a concentration of pollutants in soil during the
process, depending on the particles mainly floated.
Although all PAHs are recovered in solid phases,
only 65% of Pb are found to be present in these
fractions (18% for FM and 47% for FS). However, Pb
removal was estimated around 54%. This confirms
the idea that Pb is mainly solubilized by complexation

100
80
60
40
20
0

Polluted soil
(FC)
100 g < 2 mm

PHE

FLR

BAN

CRY

BJK

BAP

INP

BPR

5.5 M NaCl
0.2 g CAS L-1

Fig. 5 Residual PAH concentrations in soils S2 and S3 (mg

kg1 of dry soil) and respect of criteria C after flotation using
the (CAS + NaCl + pH 3) condition. Reaction time=15 min,
pulp density=10%

takes place during process operation. This loss can

result from the possible solubilization of mineral
particles of soil at low pH, but can also be due to
the different operations (transfers) done during soil
treatment. This loss of weight imposes to evaluate the
removal performance, not as a decrease of concenTable 7 Mass balance of solids, and concentrations of PAHs
and Pb in the different fractions resulting of the treatment of the
soil S3 (after flotation using CAS + NaCl + pH 3 condition
(reaction time=15 min, pulp density=10%, [CAS]=5.0 g kg1,
[NaCl]=5.5 M, pH 3))

Foams

Soil and
washing
solution

Filtration

Filtration

FM

Drying

Parameters

Mass or
volume
(g or L)

PAH
(mg kg1)

Pb (mg kg )

Initial soil (FC)

Treated soil (FS)
Froth (FM)
First and second
rinsing of FS (FLR)
Rinsing of froth (FMR)
Recovery

89.0
72.7
9.3
1.6

1 050
757
4,580
<DL

580
333
983
12

0.5
92%

<DL
105%

2
105%

DL Detection limit

Flotation
pH = 3

Drying
FMR

FLR

Hazardous
waste
10 g

Treated soil
(FS)
90 g

Wastewater
treatment
(ED)

Fig. 6 Soil washing using flotation process scheme

Water Air Soil Pollut (2009) 197:381393

with chloride ions. Pb analysis in the leachates

validates the presence of 37% of Pb in FLR, 2% in
FMR. Pb can eventually precipitate in part with CAS,
a specific study could be done to test this hypothesis.
Previous studies (Djedidi et al. 2005; Mercier et al.
1996), have shown with chemical equilibrium software (MINEQL) that the formation of chloro-complexes increases dramatically the solubility of Pb at
acidic pH when a high concentration of chloride is
maintained. However, it is not possible without
performing a particular sophisticated experiment to
demonstrate that ion exchange is not playing a role as
the high chloride concentration implies strong ion
exchange driving force.
Soil washing using flotation under CAS and NaCl
conditions seems to be a promising method to treat
soils contaminated with both organic and inorganic
pollutants. This is presented as a process scheme on
Fig. 6. The main interest of the method results in the
fact that the process is done simultaneously in the
same reactor. Two distinct concentrated phases are
obtained after treatment: one solid phase (FM) mainly
polluted with PAHs, and the leachates (FLR + FMR)
mostly contaminated with metal ions. If solid wastes
are intended to be managed to waste disposal site, a
valorization of them as carbon source for bioremediation or combustion in cement factory should be
encouraged. Metal removal from leachates must be
studied to allow their reuse in a final process.
Precipitation or electrochemical treatments appear as
potential good techniques to treat these leachates.
Because of the high conductivity of the soil leachates,
Pb electrodeposition is proposed as an appropriate
treatment (Drogui et al. 2007).

4 Conclusions
Polluted soils and brownfields constitute a major
problem, in this fact that it impacts the health of the
global environment and human beings. Because of the
lack of economical technology to treat these soils,
they often are managed in landfills. This paper
demonstrates the use of an amphoteric surfactant
(CAS) in soil washing processes. CAS has a simple
chemical structure and is largely used in the cosmetic
industry. This study has shown that CAS has the
ability to form mixed micelles with organic (PAH)
and inorganic (Pb) contaminants.

391

Salts (NaCl and EDTA) have been shown to well

enhance Pb solubilization. Flotation has been tested as
a separating technique to concentrate PAH in froth
while the aqueous solution contains the metals. This
combination implies good results for both PAH and
Pb removal from soil. Flotation appears as a promising technique for soil treatment under selected
conditions. The suggested process for organic and/or
inorganic removal would not be considered as optimal
at this state. Some research works should be done to
optimize the operating conditions and the performance of the process. Finally, to pursue this project, it
is required to develop a method for the treatment of
soil leachates.
Acknowledgments This project was funded by FQRNT and
Montreal Center for Brownfield Rehabilitation. The authors would
like to express their gratitude to Pauline Fournier, Myriam Chartier
and Typhaine Schmitt for their technical assistance.

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