Journal of Hazardous Materials 148 (2007) 122–135

Cement-based stabilization/solidification of oil refinery sludge:

Leaching behavior of alkanes and PAHs
Athanasios K. Karamalidis 1 , Evangelos A. Voudrias ∗
Department of Environmental Engineering, Democritus University of Thrace, GR 671 00 Xanthi, Greece
Received 7 July 2006; received in revised form 2 February 2007; accepted 7 February 2007
Available online 15 February 2007

Abstract
Stabilization/solidification is a process widely applied for the immobilization of inorganic constituents of hazardous wastes, especially for
metals. Cement is usually one of the most common binders for that purpose. However, limited results have been presented on immobilization
of hydrocarbons in cement-based stabilized/solidified petroleum solid waste. In this study, real oil refinery sludge samples were stabilized and
solidified with various additions of I42.5 and II42.5 cement (Portland and blended cement, respectively) and subject to leaching. The target
analytes were total petroleum hydrocarbons, alkanes and 16 polycyclic aromatic hydrocarbons of the EPA priority pollutant list. The experiments
showed that the waste was confined in the cement matrix by macroencapsulation. The rapture of the cement structure led to the increase of
leachability for most of the hydrocarbons. Leaching of n-alkanes from II42.5 cement-solidified samples was lower than that from I42.5 solidified
samples. Leaching of alkanes in the range of n-C10 to n-C27 was lower than that of long chain alkanes (>n-C27 ), regardless the amount of cement
addition. Generally, increasing the cement content in the solidified waste samples, increased individual alkane leachability. This indicated that
cement addition resulted in destabilization of the waste. Addition of I42.5 cement favored immobilization of anthracene, benzo[a]anthracene,
benzo[b]fluoroanthene, benzo[k]fluoroanthene, benzo[a]pyrene and dibenzo[a,h]anthracene. However, addition of II42.5 favored 5 out of 16, i.e.,
naphthalene, anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene and dibenzo[a,h]anthracene.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Stabilization; Solidification; Cement; Alkanes; PAHs; Leaching; Refinery oily sludge; Alkane quantification

1. Introduction Because the oil acts as an adhesive, 1 kg of crude oil can generate
10–20 g of residue. Oily residues are collected at several points
Cement-based stabilization/solidification (S/S) is a widely within the refinery, such as oil/water separators, dissolved air
applied and well-established technique for the immobilization flotation units, heat exchanger cleanings, and tank bottom clean-
of inorganic hazardous constituents. Many industrial wastes ings [3]. The use of cement-based stabilization/solidification as
are well treated with this cost-effective technology. However, a treatment process can restrain the inorganic species mobil-
solidification technology has run into difficulties when trying ity. However, the leaching behavior of organic compounds from
to solidify organic wastes [1,2]. In a well solidified prod- treated industrial wastes is still under investigation.
uct, hazardous contaminants are chemically immobilized in the It has been reported that the solidification of organic loaded
cement hydration products or physically entrapped by encapsu- wastes often produces materials with poor strength character-
lation. The resulting solidified specimen has improved structural istics [1]. If organics are admixed with cement (e.g. phenols
integrity and physical characteristics. [4]), they would affect the cement hydration kinetics by retard-
Oily materials are the primary source of waste for most ing the reactions via formation of a protective film around the
refineries and are generated when oil coalesces on solids. cement grain, hindering the formation of calcium hydroxide,
and accelerating the reaction of modification of the colloidal
∗
C–S–H (C: CaO, S: SiO2 , H: H2 O) gel precipitated at very
Corresponding author. Tel.: +30 25410 79377; fax: +30 25410 79376.
early stages around the cement grains [5,6]. Some examples
E-mail addresses: akaramal@env.duth.gr (A.K. Karamalidis),
voudrias@env.duth.gr (E.A. Voudrias). have been reported, 3-chlorophenol retards the hydration of
1 Tel.: +30 25410 79395; fax: +30 25410 79376. cement paste and stabilizes the ettringite phase, slowing its

0304-3894/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2007.02.032
 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135 123

conversion to monosulphate. Experiments with ethylene gly- potential leaching of organic constituents to soil and possibly
col, p-chlorophenol and p-bromophenol with Portland cement to groundwater. Application of cement-based S/S to oily sludge
type I revealed that ethylene glycol inhibited the setting of can be significant for two reasons: the potential co-disposal of
cement and significantly decreased the compressive strength [7]. the treated waste in a sanitary landfill instead of a hazardous
Chlorophenol was found in crystals in the cement paste which waste landfill, and the abated cost of the process against other
also contained calcium. Chloronaphthalene was immiscible with waste management technologies, such as vitrification and incin-
the inorganic cement matrix and had no effect on hydration [8]. eration [19,20]. Especially, in countries where infrastructure for
Stabilization of organic contaminants can occur through a alternative management technologies has not been established,
number of processes, including sorption. Although there are S/S for refinery oily sludge could be an economically feasible
substantial amounts of surface area in wastes treated by cement- and ready to use technology.
based S/S, the surfaces are polar and are not as suitable for The present work focuses on the leaching behavior of hydro-
removal of organics as solids with more non-polar surfaces carbons from stabilized/solidified refinery oily sludge. Real
[9]. Another concern aside from the problems associated with samples taken from an oil refinery were stabilized using two
cement setting is that organic waste constituents usually do not types of cement, type I42.5 (Portland) and II42.5 (Blended).
form the strong chemical bonds within the cement that some The samples were subject to leaching and the concentrations
inorganics do. Thus, because organic constituents are not chem- of hydrocarbons in the leachate were determined by gas chro-
ically bound in the waste, their retention is strongly dependent matography. The results were used to assess the extent of
upon physical entrapment [10]. The presence of organic material leaching and understand the leaching mechanism.
causes retarding of setting or hardening of cement.
For example, this was observed when cement was mixed with 2. Materials and methods
water, methanol and 2-monochloroaniline in volume ratios of
100/76/4 [11]. The basic cement reactions remained the same, 2.1. Oily sludge
but they became slower. Vipulanandan [7] reported that the pres-
ence of 10% phenol caused the final setting time of cement to Sludge samples were obtained from a Greek refinery (R). The
increase by approximately seven-fold. Another study [12] indi- R samples originated from a centrifuge unit, which contained a
cated that the organic components of hazardous wastes interfered mixture of different kinds of oily sludge, such as API type grav-
with the confinement and strength characteristics of solidified ity separator sludge and dissolved air flotation (DAF) sludge.
products of wastes. It was concluded that oil, grease and phe- The purpose of the centrifuge unit was to recover and reuse the
nol were generally deleterious to the strength and durability of hydrocarbon fraction contained in the sludge.
Portland cement, cement-fly ash and lime-fly ash, when used
as binders for metal immobilization. Nestle et al. [13] con- 2.2. Binding materials and oily sludge characterization
cluded that organic solvents (toluene, cyclooctanol, hexanol)
delayed the hydration kinetics. While non-polar organic com- The two kinds of cement, CEM I42.5N and CEM II42.5N,
pounds only lead to a minor delay and qualitatively to the same were obtained from TITAN Cement Company SA. These names
hydration kinetics compared to the uncontaminated cement mix- are effective since 2002 [21] and correspond to previously used
ture, the polar solvents lead to much more pronounced delays in names I-45 and II-45, respectively. The I42.5 cement does not
the hydration kinetics. For example, Gussoni et al. [6] reported contain pozzolanic material, whereas the II42.5 contains natural
large liquid pockets formed during first hours and days of hydra- pozzolanic material (7%, w/w) (Table 1). For the S/S process,
tion in the presence of methanol and 2-chloroaniline using MRI. ultra-pure water was used in order to minimize contamination of
They also confirmed using XRD analysis that the solution con- the solidified specimens by constituents contained in the water.
taining these two chemicals behaves as a retarder to the hydration Ultra-pure water (18.2 M/cm, ASTM Type 1, ISO 3696) was
reactions even after 6 months of aging [6]. The use of cement as a prepared using a PURELAB UHQ II water purification unit
binder to stabilize wastes containing hydrocarbons is not a com- (USF-ELGA, Spain).
mon practice, although it has been reported [14,15] that some The chemical characterization of the sludge was deemed
polycyclic aromatic hydrocarbons (PAHs) were well stabilized necessary, before the implementation of the stabilization exper-
with cement. Although the PAH-molecules cannot be built into iments. The determined parameters were: chemical oxygen
the cement matrix, physical encapsulation in the matrix may demand (COD), total solids (TS), volatile solids (VS), fixed
occur to some extend [16]. In addition, it has been proposed solids (FS) and moisture, as is shown in Table 1. The analyt-
that cement-based S/S could be used under certain conditions ical methods used for parameters determination were according
for waste (e.g. oily sludge) containing non-polar organics, such to Standard Methods [22].
as aromatic hydrocarbons, halogenated hydrocarbons and PCBs
[17,18]. 2.3. Stabilization and solidification
Experimental data for hydrocarbon leaching from cement-
stabilized/solidified refinery oily sludge, in various percentages Measured amounts of cement were added to known amount
of cement, do not exist. Oily sludge is usually piled-up untreated of oily sludge, followed by addition of ultra-pure water at water
on-site, unless its management is forced by regulations. This on- to sample (wet weight) ratio of approximately 0.4. The slurries
site storage results in various environmental problems, such as were mixed manually, using a plastic bowl and a rubber spatula.
124 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135

Table 1 percentage of the binder added with respect to the sludge wet
Chemical composition of I42.5 Portland cement (PC), II42.5 blended cement weight. The amount of cement used in all S/S experiments varied
(BC) and oil refinery sludge
from 10 to 70% with respect to the wet weight of sludge, as it is
Component I42.5 PC (wt.%) II42.5 BC (wt.%) shown in Table 2.
SiO2 19.79 28.31
Al2 O3 4.50 8.73 2.4. Materials
Fe2 O3 3.85 3.61
CaO 64.52 50.79
Trace analysis dichloromethane (CH2 Cl2 ) (SupraSolv), n-
MgO 1.90 2.15
K2 O 0.71 1.97 hexane (C6 H14 ) (SupraSolv) and acetone (C3 H6 O) (SupraSolv)
SO3 2.91 3.15 and silica powder (230 × 400 mesh) were obtained from Merck
(Darmstadt, Germany).
Total 98.18 98.71 Aliphatic hydrocarbon standards (n-C10 to n-C40 all even
and uneven, including pristane and phytane) and polycyclic
Oil refinery sludge characterization aromatic hydrocarbons (PAHs) standards, containing naph-
CODa (mg O2 /g) 1150 (18) thalene, acenaphtylene, acenaphthene, fluorene, phenanthrene,
TSb (%) 88.8 (0.11) anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene,
VS (%)a 23.5 (0.36) benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene,
FS (%)a 76.5 (0.36) dibenzo[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3-
Moistureb (%) 11.2 (0.11)
cd]pyrene, were obtained from Chiron Laboratory, Nor-
Numbers in parentheses are standard deviations. way. 5␣-Androstane was used as internal standard for
a On dry weight basis.
b On wet weight basis.
aliphatics, and 1-phenylhexane, 2,3-dimethylnaphthalene, 3,6-
dimethylphenanthrene and 2,2-binaphthyl as internal standards
for PAHs analysis. All internal standards were also pur-
After mixing, the slurries were poured into plastic cylindrical chased from Chiron Laboratory. For method control and
molds. Air bubbles in the paste were removed by tapping the recoveries, surrogate compounds were used. For n-alkanes,
mold with approximately 40 hits (for about 1 min). The molds 1-chlorooctadecane and for PAHs analysis a mix of 2-
then were exposed to ambient air (62–66% relative humidity). fluorobiphenyl and 1-fluoronaphthalene were used as surrogates.
The samples were cured at approximately 24 ◦ C in the laboratory All re-usable glassware used for the experiment was first son-
for 28 days. The cured samples were demolded and ground to icated for 15 min with hexane (in order to flush off non-polar
pass through a 500 ␮m sieve before used in the leaching test. The compounds), washed with detergent and tap water, rinsed sev-
total weight of a solidified sample is given by T = W + B + Wa , eral times with ultra-pure water, dried at 100 ◦ C for 1 h and then
where T is the total weight (g) of the S/S specimen, W is the waste wrapped with aluminum foil and heated at 500 ◦ C for 6 h. Vials
wet weight (g) which has been used for every S/S specimen, B were sonicated for 15 min with acetone, washed with ultra-pure
is the weight (g) of the binder and Wa is the added water (g). water, sonicated with ultra-pure water for additional 15 min,
The value of B is given by B = [(B%)W]/100 and (B%) is the dried at 100 ◦ C in an oven for 1 h and finally wrapped with

Table 2
Detailed description of sample mixtures
Mixture Oily sludge I42.5 PC II42.5 BC Water Actual % of cement in
name sample (g) addition (g) addition (g) addition (g) the specimens

R 100 – – – –
I42.5 CSa – 100 40 100
II42.5 CS – – 100 40 100
R I42.5 10%b 100 10 – 33 9.09
R I42.5 20% 100 20 – 37 16.66
R I42.5 30% 100 30 – 41 23.07
R I42.5 40% 100 40 – 45 28.57
R I42.5 50% 100 50 – 49 33.33
R I42.5 60% 100 60 – 53 37.50
R I42.5 70% 100 70 – 57 41.17
R II42.5 10% 100 – 10 33 9.09
R II42.5 20% 100 – 20 37 16.66
R II42.5 30% 100 – 30 41 23.07
R II42.5 40% 100 – 40 45 28.57
R II42.5 50% 100 – 50 49 33.33
R II42.5 60% 100 – 60 53 37.50
R II42.5 70% 100 – 70 57 41.17
a CS: cement sample.
b 10% = (10 g cement/100 g waste) × 100.
 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135 125

aluminum foil and baked at 500 ◦ C for 6 h. Tweezers, spat- flow rate of 0.8 mL/min for both fractions in a 25 mL peer shaped
ulas, chromatographic column stopcocks and screw cap vials flask. Concentration of the two fractions to final volume of 1 mL
were sonicated for 15 min with methanol (to remove polar com- each was done using a rotary evaporator. The 1 mL aliquot was
pounds), and then for additional 15 min with dichloromethane put into a 4 mL vial and was blown-down to dryness using a N2
(to remove medium to non-polar compounds) and let to dry in a stream. The samples were diluted with internal standard solu-
clean container. tion (5 ␮g/mL in hexane) to a final volume of 200 ␮L prior to
analysis. Additional dilutions were conducted with hexane as
2.5. Sample preparation needed.

2.5.1. Leaching procedure 2.5.3. Ultrasonic extraction

A static leaching test was used for the interpretation The methylenechloride (CH2 Cl2 )-extractable hydrocarbons
of aliphatic and aromatic leaching behavior from stabi- from sludge samples were extracted using ultrasonic sequential
lized/solidified oil refinery sludge. Ultra-pure water was used extractions with CH2 Cl2 as the extractant. One gram of sludge
as leachant. About 80 g of solidified sample were weighed and was homogenized with 3 g anhydrous Na2 SO4 (heated at 150 ◦ C
placed into borosilicate glass bottles. About 800 mL of ultra- for 3 h) and placed into a cotton wool thimble (pre-extracted in
pure water, at a solid to leachant ratio 1:10, was added. The Soxhlet with CH2 Cl2 for 24 h). The thimble was placed into a
samples were mixed at 30 ± 2 rpm in a rotary agitator at room 100 mL beaker and an aliquot (30 mL) of CH2 Cl2 was added.
temperature for 18 h. At the end of the extraction, the solid The beaker was covered with aluminum foil and placed into
sample was let to settle overnight. an ultrasonic bath. The sample was sonicated for 15 min and
Our leaching test was inspired by TCLP, which is applicable then the volume of the extract was collected and measured. The
for semi-volatiles and non-volatiles, but was modified in terms extraction took place three additional times. All CH2 Cl2 extracts
of leaching fluid composition and L/S ratio. We used ultra-pure were combined and homogenized and the volume was recorded.
water instead of acetic acid solution, because disposal of oily Afterwards, silica gel fractionation was conducted, as described
sludge frequently takes place on-site, in landfills for hazardous previously.
waste or in landfills for non-hazardous waste, which accept
treated hazardous waste, but segregated, from municipal waste. 2.6. Capillary GC
The L/S ratio of 10 was used to simulate the earlier leaching
period and this is in agreement with the European leaching pro- Hydrocarbon analyses were performed on an Agilent 6890N
tocol for hazardous waste [23] and other investigators [24–26]. gas chromatograph equipped with a flame-ionization detector
Nevertheless, regulatory leaching tests specific for S/S wastes and split/splitless injector. For the analyses, a HP-5 (5% phenyl-
for hydrocarbons do not exist and usually standard leaching tests 95%methylpolysiloxane) (30 m × 0.32 mm i.d. × 0.25 ␮m film
targeting leaching of inorganic constituents are used for both thickness) (J&W Scientific) capillary column was used. Sam-
inorganic and organic compounds. ples were injected in splitless mode (splitless time: 0.80 min,
flow: 20 mL/min). The oven temperature program was at initial
2.5.2. Liquid–liquid extraction and silica fractionation temperature of 70 ◦ C (1 min) then, at 15 ◦ C min−1 to 150 ◦ C and
The supernatant leachate was used for liquid-to-liquid then at 6 ◦ C min−1 to a final temperature of 300 ◦ C, which was
extraction. Five-hundred millilitres of leachate was extracted held for 22 min. Inlet and detector temperature was held at 300
three times with aliquots of 30 mL CH2 Cl2 . The volume and 290 ◦ C, respectively. Helium was used as the carrier gas
of dichloromethane fraction was measured (dichloromethane at a flow rate of 1.2 mL/min (linear velocity 23 cm/s). System
recovery varied from 80 to 89%) and poured into a 100 mL control and data acquisition were calculated with the Agilent
peer-shaped flask. Concentration to volume of 1 mL was accom- ChemStation (G2070AA ver. A.10.02). A 5-point calibration
plished with at a rotary evaporator. An aliquot of 1 ␮L was curve was created for n-alkanes, using standards containing
analyzed by gas chromatography for total dichloromethane n-alkanes from n-C10 to n-C40 , pristane and phytane. Quantifica-
extractables. Afterwards, silica clean up and fractionation took tion of n-alkanes was based on the internal standard compound
place. For the fractionation a 1 cm in diameter column was used. 5␣-androstane (Chiron Laboratory, Norway). For PAHs analy-
A glass cotton wool plug was placed in the column, followed by sis a 16-priority pollutant standard, recommended by US EPA,
3 g silica powder (230 × 400 mesh ASTM) and Na2 SO4 to form was used to construct a 5-point calibration curve. The quantifi-
a 0.5 cm thick layer at the top of the silica column. Silica gel was cation was based on four internal standards 1-phenylhexane,
purified in Soxhlet with a mixture of hexane:CH2 Cl2 :acetone, 2,3-dimethylnaphthalene, 3,6-dimethylphenanthrene and 2,2-
1:1:1 (v/v/v) for 24 h and activated for 3 h to 150 ◦ C. The glass binaphthyl. All the results, including those from the solidified
cotton wool was also purified in Soxhlet with CH2 Cl2 for 24 h. samples, were expressed as mg/kg dry weight of oily sludge
Na2 SO4 was purified by baking at 150 ◦ C for 3 h. The packed contained in the sample.
column was rinsed with 15 mL of CH2 Cl2 and then with 15 mL Qualitative analysis of standards and unknown samples
of hexane. The first fraction (F1) of aliphatics was collected was conducted using GC–MS. For this reason a Hewlett-
with 13 mL of hexane in a 25 mL peer shaped flask. The sec- Packard (HP) 5890 gas chromatograph equipped with a
ond fraction of aromatics (F2), was collected with 15 mL, using mass-spectrometer detector VG-trio 1000 and split/splitless
a mixture of solvents hexane:ethyl acetate (9:1, v/v) at average injection port was employed. The gas chromatograph was oper-
126 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135

ated in the splitless mode and the injection port temperature

was set at 290 ◦ C. The column used was a 60 m DB-5MS
(phenyl arylene polymer virtually equivalent to the 5%-phenyl-
methylpolysiloxane) (0.25 mm i.d. and 0.25 ␮m film thickness).
Helium was used as a carrier gas, and the column head pressure
was set at 15 psi. The ionization was carried out in the electron
impact (EI) mode (70 eV). The electron multiplier voltage and
automatic gain control target were set automatically. The trans-
fer line and source were set at 300 ◦ C. The mass range scanned
was from 15 to 650 amu under full scan mode. The MS system
was tuned to m/z 69, 219, 502 and 614 for EI corresponding
to perfluorobutylamine (PFTBA). The initial oven temperature
program was 60 ◦ C (1 min), then raised at 10 ◦ C min−1 to 80 ◦ C
and then at 7 ◦ C min−1 to a final temperature of 290 ◦ C, which
was held for 37 min.

2.7. Description of petroleum hydrocarbon groups

In the present study, in addition to characterization of the indi-

vidual hydrocarbons, the determination of six additional groups
was deemed necessary for the interpretation of leaching behavior
of hydrocarbons contained in the oily sludge and in the stabi-
lized/solidified oily sludge. The definitions of these groups are
described below:
Total n-alkanes (TAlk). It was defined as the sum of all
resolved and calibrated (with internal standard calibration
method) n-alkanes (n-C10 to n-C40 ) including pristane and phy-
tane (expressed as mg/kg of dry oily sludge contained in every
sample). The calculation of concentration of total n-alkanes was
based on the internal standard 5␣-androstane. The resolved and Fig. 1. Hypothetical chromatogram of petroleum hydrocarbons. Quantification
calibrated n-alkanes peaks were integrated as shown in Fig. 1A. modes: (A) total n-alkanes (TAlk) and (B) total aliphatics (TAL). IS: internal
standard.
Total 16 PAHs (TPAH). it was defined as the sum of all
16-target polycyclic aromatic hydrocarbons (based on inter-
nal standard calibration method) (expressed as mg/kg of dry the particular section. The sum of all such concentrations, calcu-
oily sludge contained in every sample). The calculation of total lated from every section, equalled the concentration of the TAL
16 PAHs was based on the internal standards 1-phenylhexane, fraction.
2,3-dimethylnaphthalene, 3,6-dimethylphenanthrene and 2,2- Total aromatics (TAR). It consisted of all resolved aro-
binaphthyl. matic hydrocarbons determined in the aromatic fraction (F2),
Total aliphatics (TAL). It was defined as the sum of all including calibrated and uncalibrated peaks (expressed as
resolved and unresolved aliphatic hydrocarbons determined in mg/kg of dry oily sludge contained in every sample). Total
the aliphatic fraction (F1), including calibrated and uncalibrated aromatics includes total substituted and unsubstituted poly-
peaks (expressed as mg/kg of dry oily sludge contained in every cyclic aromatic hydrocarbons, and all compounds extracted
sample). This fraction includes total n-alkanes, branched alkanes after silica fractionation with hexane:ethylacetate in the frac-
cycloalkanes and compounds recovered after silica fractionation tion F2. The calculation of total aromatics was based on the
with hexane in fraction F1. The calculation of concentration of internal standards 1-phenylhexane, 2,3-dimethylnaphthalene,
total aliphatics was based on the procedure described below. 3,6-dimethylphenanthrene and 2,2-binaphthyl.
For the quantification of TAL fraction the following pro- TPHs (total petroleum hydrocarbons, GC-detectable) was
cedure was developed: the chromatogram was divided into a defined as the sum of total aliphatics (resolved and unre-
number of sections equal to the number of resolved and cali- solved, calibrated and uncalibrated peaks) and total aromatics
brated n-alkane peaks (those contained in the aliphatic standard) (expressed as mg/kg of dry oily sludge contained in every sam-
(Fig. 1). Each n-alkane was located approximately in the mid- ple): TPH = TAL + TAR.
dle of the respective section. Then, the areas of all resolved and MCE (methylenechloride extractable fraction) was defined
unresolved peaks were summed-up as one, including the area as the sum of all resolved and unresolved (calibrated and
of the known n-alkane peak of the specific section of the chro- uncalibrated peaks) peaks (expressed as mg/kg of dry oily
matogram (Fig. 1B). The total area of each such section was sludge contained in every sample). The samples originated from
quantified based on the external standard calibration curve of either liquid–liquid extraction or extraction with sonication,
the known n-alkane (known response factor), which existed in but without previous fractionation or clean-up. Therefore, it is
 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135 127

likely that the extracts contained not only hydrocarbons, but

also additional compounds extracted by methylene chloride.
Therefore MCE ≥ TPH. The resolved compounds appeared as
peaks and the unresolved as a hump area between the blank
baseline and the curve defining the base of resolved peaks
[27].

3. Results and discussion

3.1. Leaching of MCE, TPH, TAL, TAR, TAlk and TPAH

fraction

All the results were expressed as mg/kg dry weight of oily

sludge contained in the solidified sample. The MCE fraction
of the oily sludge was almost 5% on dry weight basis, as it is
shown in Table 3. Only a small part (0.18%) of MCE fraction was Fig. 2. Leaching of MCEs from oily sludge and solidified/stabilized oily sludge
transferred to the water when aqueous leaching was applied. The with I42.5 and II42.5 cement.
reason for that is that hydrocarbons are hydrophobic compounds,
which prefer to stay in the oil phase of the sludge.
Leaching of TPHs from the solidified/stabilized sludge with With regard to % leaching of hydrocarbons from S/S speci-
I42.5 cement was generally at the oily sludge leaching level mens, the aliphatic fraction showed bigger leachability than the
except for R I42.5 30% specimen, which was about half aromatic fraction (Table 3). In the case of S/S samples with type
the leached amount of the sludge alone (16.7 mg/kg versus I of cement the aliphatic fraction resulted in almost 50% release,
41.5 mg/kg) (Table 3). R I42.5 40 and 70% showed leach- whereas S/S samples with type II blended cement showed bigger
ing reduction, compared to the untreated sludge (31.7 and leachability <69% (Table 3). In contrast, aromatic compounds
29.8 mg/kg, respectively, versus 41.5 mg/kg). As shown in were better contained in the cement matrix than aliphatics by
Table 3, solidified samples with 10, 20 and 40% II42.5 cement showing maximum % leaching of 29 and 34.5 for S/S samples
exhibited remarkably high leachability, 3.5, 1.6 and 2.6 times with type I and II cement, respectively (Table 3).
higher than that of oily sludge (144, 68.5 and 109 mg/kg, respec- The presence of cement in the solidified oily sludge, in gen-
tively). Samples with 30 and 70% cement addition leached eral increased MCE fraction leaching (Fig. 2). In most cases
almost the same amount with the sludge, whereas the 50 and leaching increased by 1.4–2.8 times with addition of II42.5
60% showed a small leaching reduction. cement, and by 1.2–2.4 times with addition of I42.5 cement.

Table 3
Hydrocarbon content of and hydrocarbon leaching from oily sludge and its S/S specimens
Hydrocarbon content of oily sludge (mg/kg dry weight R sludge)

MCEsa TALb TARc TAlksd TPAHse

R sludge 53,377 2743 181 925 27.6
Hydrocarbon leaching from oily sludge and its S/S specimens (mg/kg dry weight R sludge)

Rf I42.5 PC solidified samples II42.5 BC solidified samples

10%g 20% 30% 40% 50% 60% 70% 10% 20% 30% 40% 50% 60% 70%
TPHsh 41.5 43.7 43.7 16.7 31.7 36.1 48.2 29.8 144 68.5 35.2 109 30.8 25.1 46.8
% Leaching of hydrocarbons from S/S specimens with cement content
varying from 10 to 70% (calculation based on dry weight oily sludge)
S/S samples with I42.5 PC S/S samples with II42.5 BC
TAL 18–44 35.5–69
TAR 8–29 13.5–34.5
TAlk 7–50 6–38.5
TPAHs 7–27 9–26.6
a Methylenechloride extractable hydrocarbons.
b Total aliphatic fraction.
c Total aromatic fraction.
d Total alkanes.
e Total 16 PAHs.
f R: oil refinery sludge.
g 10% = (10 g cement/100 g waste) × 100.
h Total petroleum hydrocarbons.
128 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135

Fig. 3. Leaching of TAL, TAR, TAlk and TPAH from oily sludge R and solidified/stabilized sludge with I42.5 cement. The solid line is a least square fitting and
shows the leaching trend for each parameter.

Fig. 4. Leaching of TAL, TAR, TAlk and TPAH from oily sludge R and solidified/stabilized sludge with II42.5 cement. The solid line is a least square fitting and
shows the leaching trend for each parameter.
 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135 129

An exception was the sludge sample solidified with 40% I42.5 significant increase of contact area. This was observed with an
cement, in which the leached amount did not increase and the optical stereomicroscope equipped with digital camera. In addi-
sample solidified with 20% II42.5 cement, in which the leached tion, the hydrophobicity of the sample decreased with increasing
amount decreased by half (Fig. 2). The highest leachability addition of the hydrophilic cement. In performing the leaching
observed, was for the II42.5 30% and the I42.5 20% solidified test, particle size reduction and consequently cavity destruc-
samples. tion took place. When mixed with the leaching medium, the
The reason of increased leaching with increasing amount of material with lower cement content tended to form clots, thus
cement was that the polar cement resulted in a more hydrophilic reducing its interphase contact area. The higher cement content
environment and, therefore, a better contact between water and samples did not form clots, thus maintaining higher interphase
the stabilized/solidified specimen. Specifically, macroencapsu- contact area. Therefore, larger concentrations of MCEs were
lation of the sludge into the cement matrix was achieved and measured for stabilized/solidified waste with higher addition of
small spherical cavities filled with waste were formed. These cement.
cavities were smaller in size, but more abundant in solidified The leached amount of MCEs was many times higher than the
samples with higher percent of cement addition, resulting in leached amount of total aliphatics and total aromatics together

Fig. 5. Leaching of individual n-alkanes, pristane and phytane from oily sludge and its stabilized/solidified samples with I42.5 and II42.5 cement.
130 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135

(i.e., TPHs). This is justified, because during column fractiona- show the same behavior as in the case of total aromatic fraction
tion and clean up only the aliphatic and aromatic fractions were (Fig. 3D and 4D). TPAHs from solidified specimens with I42.5
recovered, whereas a significant fraction of polar compounds Portland cement seemed to be unaffected by the presence of the
(e.g., esters, ketones, ethers) remained on silica gel. The amount binder and released almost the same amount as the sludge itself,
of total aliphatics (TAL) and total alkanes (TAlk) in the leachate except for the R I42.5 50% sample, which leached two-fold
was in every case larger than the amount of total aromatics (TAR) more (Fig. 3D). TPAHs leached from solidified samples with
and TPAHs, respectively. The total aliphatics varied from 15.6 II42.5 cement showed an increasing leachability as the cement
to 47.1 mg/kg for stabilized/solidified sludge with I42.5 cement addition increased, except for the R II42.5 30% sample, which
and from 34.1 to 142 mg/kg for stabilized/solidified sludge with released 33% less than the oily sludge itself. Concentrations of
II42.5 cement (Fig. 3A and 4A). TPAHs were low, ranging from 0.063 mg/kg to 0.23 mg/kg for
Leaching of total alkanes (TAlks) (Fig. 3C and 4C) from solidified specimens with I42.5 cement (Fig. 3D). For solidified
solidified specimens with either I42.5 or II42.5 cement was much specimens with II42.5 cement the concentration values varied
higher compared to leaching from untreated sludge. In general, from 0.85 to 0.25 mg/kg on dry weight sludge basis (Fig. 4D).
leaching of TAlks increased with increase of cement addition. Some discrepancies in the leaching behavior of aromatic hydro-
For the I42.5 solidified samples the leaching trend observed was carbons could be explained on the basis of sample heterogeneity
that, for low and high percent of stabilizing agent, the leaching (existence of hot spots) and the low levels of individual aromatic
was high, whereas in samples with medium percent of cement hydrocarbon concentration (<0.25 mg/kg dry weight).
addition (e.g. 30 and 40%) the leaching was lower, but still higher
than this of the oily sludge (Fig. 3C). Also, for samples solid- 3.2. Alkanes
ified with 30 and 50% II42.5 cement, decreased leaching was
observed but still higher than this of the oily sludge (Fig. 4C). In general, leachate concentrations of individual n-alkanes
Total aromatics (TAR) varied from 0.45 to 1.54 mg/kg dry from the cement-based S/S samples were higher, in every case,
weight sludge for specimens solidified with I42.5 cement than those from untreated oily sludge (Figs. 5 and 6). The addi-
(Fig. 3B) and from 0.98 to 1.63 mg/kg for II42.5 cement addition tion of II42.5 cement resulted in lower leaching of individual
(Fig. 4B). In all cases the amount of total aromatics leached from alkanes than the addition of I42.5 cement. This was indicated
the solidified samples was lower than the amount leached from by the higher n-alkane concentration in the leachate of speci-
the oily sludge. However, leaching of TPAHs measured, did not mens stabilized/solidified with I42.5 (Fig. 5A–C and 6E and F).

Fig. 6. Leaching of individual n-alkanes, pristane and phytane from oily sludge and its stabilized/solidified samples with I42.5 and II42.5 cement.
 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135 131

This trend was not observed for samples solidified with 40 and for naphthalene, phenathrene and dibenzo[a,h]anthracene,
70% cement (Fig. 5D and 6G). Generally, the figures showed whereas immobilization of anthracene and benzo[k]fluoranthene
that when the alkane chain increased, from n-decane to n- seemed unaffected by the addition of either I42.5 or II42.5
tetracondane, the leaching of n-alkanes increased as well. cement. The addition of cement to the oily sludge usually
A remarkably similar leaching behavior was observed for increased the leachability of PAHs compared to the leaching
alkanes in the range n-C10 to n-C30 for either I42.5 or II42.5 amounts of the oily sludge itself. Unlike the leaching behavior
cement-solidified specimens with 10% binder addition. Only for of n-alkanes, where the II42.5 cement addition showed better
n-alkanes with higher molecular weight (more than 30 carbon immobilizing characteristics, in the case of PAHs I42.5 cement
atoms in the molecule), a different binder effect was observed. performed better for 10 PAH compounds out of 16 which were
Apparently, the amount of cement (10%) was very low to measured, whereas in 2 cases the difference between the two
cause a significant difference in the leaching behavior of sta- types of cement was negligible.
bilized/solidified oily sludge. With increasing cement addition The S/S process resulted in formation of cavities contain-
(>20%), the difference in leaching behavior, because of the two ing encapsulated waste. This macroencapsulation, which was
types of cement addition, was obvious (Figs. 5B–D and 6E–G). observed by optical stereomicroscope in the cement-solidified
Concentrations of n-alkanes in the leachate from untreated oily matrix implies that the leaching behavior of PAHs might be con-
sludge were lower by one order of magnitude, than those leached trolled by this mechanism of immobilization. The particle size
from the solidified specimens. This is due to clot formation reduction of the oily sludge and the solidified samples required
during the leaching, as previously explained. by the leaching protocol revealed that increasing the amount of
cement, led to the formation of smaller and more abundant clots
3.3. Polycyclic aromatic hydrocarbons and therefore increased the interphase area of the waste with
the extract. Therefore, increased amount of cement resulted in
As it is shown in Figs. 7–9, I42.5 cement addition was more increase in leaching.
effective than II42.5 in stabilizing acenaphthylene, acenaph- Compared to untreated waste, the presence of I42.5 cement in
thene, fluorene, fluoranthene, pyrene, benzo[a]anthracene, chry- the samples increased the leachability of naphthalene, by many
sene, benzo[b]fluoranthene, benzo[a]pyrene and indeno[1,2,3- times, in specimens R I42.5 20, 30 and 60% (Fig. 7A). Naph-
c,d]pyrene. In contrast, II42.5 cement seemed better stabilizer thalene leaching decreased slightly in specimens with 10, 40, 50

Fig. 7. Leaching behavior of individual PAHs (mg/kg dry weight of R sludge) from samples solidified with two different types of cement (I42.5 and II42.5). (A)
Naphthalene, (B) acenaphthylene, (C) acenaphthene and (D) fluorene.
132 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135

Fig. 8. Leaching behavior of individual PAHs (mg/kg dry weight of R sludge) from samples solidified with two different types of cement (I42.5 and II42.5). (A)
Phenathrene, (B) anthracene, (C) fluoranthene, (D) pyrene, (E) benzo[a]anthracene, (F) chrysene, (G) benzo[b]fluoranthene and (H) benzo[k]fluoranthene.
 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135 133

Fig. 9. Leaching behavior of individual PAHs (mg/kg dry weight of R sludge) from samples solidified with two different types of cement (I42.5 and II42.5). (A)
Benzo[a]pyrene, (B) dibenzo[a,h]anthracene, (C) benzo[ghi]perylene and (D) indeno[1,2,3-c,d]pyrene.

and 70% I42.5 cement. In contrast, II42.5 acted as a stabilizer (Fig. 8E). Increased leachability was observed for pyrene in all
and decreased naphthalene leaching. solidified samples with II42.5 cement (Fig. 8D).
Leaching of acenaphthylene, acenaphthene and fluorene Chrysene leaching increased with addition of both types of
increased with II42.5 cement addition, more than with I42.5 cement (Fig. 8F). Specimens with I42.5 Portland cement leached
(Fig. 7B–D). That is I42.5 cement-solidified samples showed lower amounts of the compound than those with II42.5.
better immobilizing behavior than II42.5 cement-solidified spec- I42.5 cement seemed to be a better stabilizing agent than
imens. Only the R I42.5 50% sample leached 4 times larger II42.5 in the case of benzo[b]fluoranthene. However, the addi-
amount of fluorene and double the amount of acenaphthylene tion of both types of cement resulted in reduction of leaching
and acenaphthene, compared to those of the oily sludge alone compared to the untreated sludge, by about 63% for solidified
(Fig. 7D, B and C, respectively). specimens with II42.5 cement and 81% for solidified specimens
Leaching of phenanthrene from the stabilized/solidified spec- with I42.5 cement (Fig. 8G). A similar behavior was observed
imens was almost unaffected by addition of both types of cement for benzo[k]fluoranthene (Fig. 8H). The overall leaching reduc-
(Fig. 8A). On the other hand, anthracene was well immobi- tion of this compound in S/S specimens with 70% cement, both
lized by both I42.5 and II42.5 cement, by decreasing the amount types, was 57%.
leached from the oily sludge more than 60%. In the case of R Benzo[a]pyrene was stabilized well with I42.5 cement but
I42.5 40% and R II42.5 20% the decrease was 90% compared not with II42.5 cement. The I42.5 addition decreased the ini-
to the untreated sludge (Fig. 8B). tial amount leached from the sludge as the addition of cement
Addition to sludge of I42.5 cement stabilized fluoranthene, increased in the samples. Addition of II42.5 cement had the
pyrene and benzo[a]anthracene at the leaching levels of the opposite effect (Fig. 9A).
untreated waste (Fig. 8C–E). Fluoranthene showed slight leach- Compared to untreated sludge, leaching of dibenzo[a,h]
ing reduction as the amount of the added I42.5 increased anthracene decreased with addition of I42.5 cement except for
(Fig. 8C). The leaching behavior of pyrene did not change with the 50 and 60% samples (Fig. 9B). The addition of II42.5 cement
addition of I42.5, compared with untreated oily sludge (Fig. 8D), to the waste showed significant reduction of leachability. Specif-
except for R I42.5 50% sample. I42.5 cement showed good sta- ically, in R II42.5 40–70% samples no dibenzo[a,h]anthracene
bilizing characteristics for the benzo[a]anthracene by reducing was detected. The R II42.5 10, 20 and 30% specimens leached
the leachability by 84% for R I42.5 10% sample (Fig. 8E) and to about 0.002 mg/kg, half the amount leached from the sludge
about 50% for the rest of the specimens. As an overall leaching alone (Fig. 9B).
trend for these three compounds, the addition of II42.5 cement Leaching of benzo[ghi]perylene was unaffected by the I42.5
to the waste increased the leachability five-fold in the case of cement addition. Most of the solidified samples leached the same
fluoranthene at the R II42.5 60% sample (Fig. 8C) and three- amount as the sludge did. In the case of II42.5 cement addition
fold in the case of benzo[a]anthracene, in R II42.5 40% sample the specimens R II42.5 10, 20 and 30% showed a slight reduction
134 A.K. Karamalidis, E.A. Voudrias / Journal of Hazardous Materials 148 (2007) 122–135

in leachability, but the rest of the samples increased it to the level Comparison of the leached PAHs between oily sludge
of 0.008 mg/kg (Fig. 9C). This means that the S/S process not and stabilized/solidified samples, revealed that I42.5
only was ineffective in reducing, but in contrast significantly cement favored immobilization of acenaphthene, fluoran-
increased benzo[ghi]perylene leaching. thene, benzo[a]anthracene and benzo[a]pyrene. Anthracene,
Indeno[1,2,3-cd]pyrene was not detected in the leachate of benzo[b]fluoroanthene and benzo[k]fluoroanthene leachability
the oily sludge (Fig. 9D), but, it showed great leachability in were reduced by solidification of oily sludge with both types of
both I42.5 and II42.5 solidified/stabilized specimens. The I42.5 cement, I42.5 and II42.5. Addition of II42.5 cement reduced
cement was better stabilizer than II42.5 cement. For higher the leachability of naphthalene and dibenzo[a,h]anthracene
percent of II42.5 cement addition, a higher leachability was compared to that of the untreated sludge. However, ace-
observed. Leaching of indeno[1,2,3-cd]pyrene was unaffected naphthylene, fluorene, pyrene, chrysene, benzo[a]pyrene,
by the amount of I42.5 cement addition, in the range of 10–70%. benzo[ghi]perylene and indeno[1,2,3-c,d]pyrene escaped
The leached amount of solidified samples with I42.5 cement immobilization with the addition of both types of cement to
leveled off at 0.002–0.004 mg/kg, regardless of the percent of the oily sludge. S/S process was ineffective in reducing the
cement addition in the samples (Fig. 9D). leachability of these compounds compared to that leached from
the oily sludge itself, and in contrast significantly increased it.
4. Conclusions Several recommendations for further research arose from this
study. Due to macroencapsulation of the oily sludge into cav-
A leaching test was developed by modifying existing standard ities, additional leaching tests must be considered, in order to
leaching tests and was applied to study the leaching behavior of understand the leaching behavior of organic constituents from
hydrocarbons from refinery oily sludge S/S with cement. On the solidified samples. For this case, a static leaching test applied
basis of this test, the following conclusions were drawn. Macro- to monolithic specimens or a flow-through leaching test would
scopic observation of the stabilized/solidified samples revealed be more realistic with respect to organic compounds mobility
macroencapsulation of the oily sludge into cavities, formed in in the environment, rather than leaching tests which destroy the
the cement matrix. For higher cement addition, smaller and cement admixture structure.
more abundant cavities were formed. The breakage of these
cavities for the leaching test resulted in increased hydrocar- Acknowledgement
bon leaching with cement addition. Specifically, cement addition
resulted in destabilization of the oily sludge and yielded leach- The authors would like to thank S. Alexiou for his assistance
ing of methylene chloride extractables from 5 to 186% in excess with the GC–MS experiments.
of those observed from oily sludge alone. Similarly, excess
leaching for total alkanes (TAlk) ranged from 70 to 1140% for References
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