Environmental Pollution 175 (2013) 110e116

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Environmental Pollution
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Isosteric heats of sorption and desorption of phenanthrene in soils and

carbonaceous materials
Guohui Wang 1, Peter Grathwohl*
Center for Applied Geoscience, University Tübingen, Hölderlinstr. 12, D-72074 Tübingen, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Isosteric heats (DH) of sorption/desorption of phenanthrene were determined for carbonaceous materials
Received 26 June 2012 (Pahokee peat, lignite, and high-volatile bituminous coal) and two soils based on reported equilibrium
Received in revised form sorption/desorption isotherms at four different temperatures (4, 20, 46 and 77
C). In addition, DH for
20 December 2012
desorption of native phenanthrene was determined to elucidate the “aging” effect by equilibrating
Accepted 21 December 2012
samples with water at six temperatures (20, 40, 53, 61, 73, and 86
C). Isosteric heats decreased with
increasing solute concentration and were in a range of 19e35 kJ mol1. Values higher than the heat of
Keywords:
octanolewater phase transfer for phenanthrene (19 kJ mol1) imply that both partitioning and
Isosteric heat
Sorption/desorption
adsorption processes are involved for these materials, where the sorptive contributions from both
Phenanthrene processes were estimated based on the phenanthrene thermodynamic data. Moreover, on the basis of DH
Carbonaceous material values of desorption, release of native and spiked phenanthrene from our samples was similar.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction isosteric heats (DH) transferred in the sorption/desorption pro-

Sorption and desorption are major processes influencing the
fate, transport and bioavailability of hydrophobic organic com-
pounds (HOC) in the environment. In the literature, organic con-
taminants partitioning into “soft” organic matter and adsorption on
“hard” organic sorbent surface are well accepted as the two main
sorption mechanisms in the natural environment (Weber et al.,
1992; Xing and Pignatello, 1997; Xia and Ball, 1999). However,
a quantitative separation of sorption contributions resulting from
these two sorption mechanisms is lacking in the literature. Tradi-
tionally, sorption has been classified into three categories according
to the attractive forces governing the molecular interactions be-
tween solute and sorbent, namely, physical, chemical and electro-
static. Thermodynamically, at equilibrium the contaminant
distribution between the solid and aqueous phases is ultimately
governed by the isosteric heats (also called enthalpy, DH) and en-
tropies of sorption or desorption. The magnitude and sign of DH
values gives valuable insight to the molecular interactions between
sorbate and sorbent. For sparingly soluble HOC molecules, the
London dispersion or Van der Waals forces between solutes and
sorbents, which can be determined from measurements of the
* Corresponding author.
E-mail address: grathwohl@uni-tuebingen.de (P. Grathwohl).
1
Present address: Pacific Northwest National Laboratory, P.O. Box 999, MS P7-54,
Richland, WA 99352, USA.
cesses, contribute predominantly to the sorption. It will be valuable
if the sorption contributions resulting from partitioning and
adsorption could be distinguished through isosteric heat mea-
surements. Theoretically partitioning and adsorption processes
involve different sorbate and sorbent interactions, thus different
DH values could be expected.
The isosteric heats of sorption for various organic chemical
compounds on different types of natural sorbents, including in-
teractions on mineral surfaces and polymers in vapour phase and
aqueous systems, have been reported previously (Adams et al.,
2007; Arp et al., 2008; Chiou et al., 1979, 1985; Costanza and
Pennell, 2007; Farrell et al., 1999; Haftka et al., 2010; Kleineidam
et al., 2004; Krauss and Wilcke, 2001; Lüres and Ten Hulscher,
1996; Mader et al., 1997; Madlener et al., 2003; Pitta et al., 1996;
Pre et al., 2002; Ten Hulscher and Cornelissen, 1996; Tremblay et al.,
2005; Werth and Reinhard, 1997; Woodburn et al., 1989). Table 1
compiles literature values of DH for PAHs as well as other hydro-
phobic compounds to different sorbents. Most of these studies
focused on the temperature dependence of sorption without con-
sidering separation of the heat contributions resulting from either
partitioning or adsorption processes. Sorption mechanisms can be
distinguished by varied DH values in the data compiled in Table 1, in
which the isosteric heats on pure substances or surfaces could be
used as a reference in separating different sorption mechanisms.
Relatively low values of 13 to 23 kJ mol1 are reported for
phenanthrene on hydrophilic mineral surfaces (such as Al2O3 or

0269-7491/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
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 G. Wang, P. Grathwohl / Environmental Pollution 175 (2013) 110e116 111

Table 1
List of reported DH of PAHs as well as other hydrophobic compounds in different sorbents (1 standard deviation).

Sorbents Compounds DH (kJ mol1) Temperature (
C) Reference

Mineral oxides (a-Al2O3/a-Fe2O3) Naphthalene 12.5 (3.6)/26 (10) 5e35 Mader et al., 1997
Phenanthrene 18.2 (1.0)
Anthracene 16 (2.8)/17.2 (1.9)
Fluoranthene 19.5 (0.4)/16.7 (3.0)
Pyrene 20.8 (0.4)/20 (0.9)
Silica gel (100e200 mm)/Al2O3 Phenanthrene 16.1/16.8 25e45 Su et al., 2006
(w150 mesh) Pyrene 23.2/18.8
Silica gels (150/40) Phenanthrene 12.6 to 17.9/19.6 to 22.8a 5e45
Graphite surface Phenanthrene 47.1a 5e45
Silty loam soil Phenanthrene 19 (2.2) 14e35 Woodburn et al., 1989
Anthracene 22.7 (0.6)
Fluoranthene 24.5 (0.8)
Pyrene 37.7 (10.7)
Aquifer sediment containing low Naphthalene 11/1.1 4e26 Pitta et al., 1996
organic carbon (batch/column) Phenanthrene 3.3/5.6
Pyrene 14/14
Soils (Bayreuth, Germany) PAHs and PCBs 0 to 20 20e80 Krauss and Wilcke, 2001
Demolition waste and harbour sediments PAHs 32 to 58 25e100 Madlener et al., 2003
Aquifer sediments and rock fragments Phenanthrene 23 to 36 20e40 Kleineidam et al., 2004
Suspended particles Phenanthrene 4.5 to 3.2 2e20 Tremblay et al., 2005
Dissolved organic carbon (DOC) Fluoranthene 18.3 16e45 Lüres and Ten Hulscher, 1996
Benzo[ghi]perylene 40.7
Polyethylene Phenanthrene 18 (1) 16e30 Adams et al., 2007
Pyrene 29 (2)
Polydimethylsiloxane Phenanthrene 16.2 (0.48)
Anthracene 15.3 (1.2)
Fluorene 14.7 (0.84)
Fluoranthene 18.9 (1.7)
Pyrene 22.1 (0.25) 3e36 Haftka et al., 2010
Low density polyethylene Acenaphthene 26
Phenanthrene 22
Fluorene 43
pyrene 46 2e30 Lohmann, 2012
Natural sorbents Hydrophobic pollutants 13 to þ3.8 3e37 Ten Hulscher and
Cornelissen, 1996
Granular activated carbon VOCs 40 to 80 20 Pre et al., 2002
Silica Gel TCE 9.5 to 45 15e60 Werth and Reinhard, 1997
Natural solids 0 to 34
Silica gel TCE 22.2 (1.5) to þ20.8 (1.7) 5e90 Farrell et al., 1999
Zeolite type NaX þ20.3 (12.1)
Silty clay soil PCE 12 (0.3) 25e95 Costanza and Pennell, 2007
a
DH values for phenanthrene of 12.6 to 17.9 kJ mol1 for silica gel 150, 19.6 to 22.8 kJ mol1 for silica gel 40, and 47.1 kJ mol1 for graphite surface were rein-
terpreted by Su et al. (2006) based on experimental data from Huang and Weber (1997).

silica gel), where London forces are the main cause for adsorption
(Su et al., 2006). Polymer sorbents, such as low density polyethyl-
ene (LDPE, often used as a passive samplers), are generally assumed
to comprise amorphous and crystalline regions where both parti-
tioning and adsorption may occur (Lohmann, 2012). A relatively
small range of DH values (16 to 22 kJ mol1) has been reported
for phenanthrene with LDPE. Graphite provides a relative homo-
geneous hydrophobic surface for strong adsorption of organic
compounds from aqueous solution, with the reported DH value of
47.1 kJ mol1 typical for solute condensation (Su et al., 2006). In
contrast to LDPE and graphite, a wide range of DH values (3.3 to
36 kJ mol1 in Table 1) has been observed for soils and sediments.
The variations observed in aqueous phase DH values among soils
and sediments could originate from two sources. Firstly, different
geosorbents vary in physico-chemical properties depending on
their origin, which again results in different values for DH. Sec-
ondly, experimental artifacts resulting from differences in exper-
imental procedures, such as variations in equilibration time periods
from a few hours to days or weeks, could result in different DH
values even in the same sorbent-sorbate system (Wang et al., 2007).
Non-equilibrium during sorption, for instance, would result in
higher DH-values of desorption because the activation energy of
diffusion would also be included (Wang and Grathwohl, 2009).
The main objective of this study was to distinguish sorption
contributions resulting from partitioning and adsorption processes
in natural geosorbents through isosteric heat measurements.
Meanwhile, sorption/desorption hysteresis is also discussed by
comparing sorption/desorption isosteric heats. Carbonaceous ma-
terials (CM) and soils containing carbonaceous materials were
selected in this study because of (1) their relative pure substances,
(2) their relevance in strong sorption of hydrophobic organic
compounds in soils and in sediments, and (3) values of DH for
sorption of PAHs on CM materials are rarely reported. High isosteric
heat values are expected if strongly sorbing carbonaceous materials
are present (Arp et al., 2008). CM is non-carbonate, carbon-con-
taining matter and the broad category of CM includes residues from
combustion and pyrolysis processes, such as soot and char, as well
as geologic processes (diagenesis and catagenesis), such as coal and
kerogen (Allen-King et al., 2002). In this study, we evaluated a data
set on sorption/desorption isotherms measured at different tem-
peratures (Wang et al., 2007) to determine DH values of phenan-
threne for CM and CM-containing natural geosorbents. Based on
the heat of solution of phenanthrene in water, the energy contri-
butions from both partitioning and adsorption processes were
estimated, which can help to elucidate the sorption/desorption
mechanisms. In addition, it should be noted that, besides the
determined sorption and desorption isosteric heats for phenan-
threne on selected materials, DH for desorption of the native
(“aged”) phenanthrene in these samples was also determined over
a similar temperature range of 20e86
C, and compared with those
112 G. Wang, P. Grathwohl / Environmental Pollution 175 (2013) 110e116
from the laboratory spiked samples. To our knowledge, no previous
studies have reported isosteric heat of desorption for native con-
taminants from such relatively pure carbonaceous materials.
2. Data evaluation
2.1. Sorption/desorption isotherms on spiked samples
In this study, we are analyzing sorption/desorption isosteric
heats by interpreting the sorption/desorption isotherms reported
in Wang et al. (2007). Sample selection, characterization, and iso-
therm experiments were described in details in Wang et al. (2007).
Briefly, three carbonaceous samples (Pahokee peat, lignite, and
high-volatile bituminous coal (HC)) and two different soil samples
(anthropogenic soil (AS5) and mineral soil (MS4)) were selected to
cover a wide range of natural geosorbents. Phenanthrene (98%,
Aldrich Chemical Corp.) was used as the probe compound in their
study as a representative PAH. By using a mass-balance-monitored
new batch sorption protocol, sorption and desorption isotherms of
phenanthrene on above selected materials at four temperatures (4,
20, 46 and 77
C) were determined. All the sorption/desorption
isotherms in their study were nonlinear (with 1/n of 0.61e0.86)
except AS5, which showed a relatively slight nonlinearity (1/
n ¼ 0.91). Sorption nonlinearity indicates that physical adsorption
played an important role in the soluteesorbent interactions
(especially pronounced in coals). In all samples, the sorption ca-
pacity decreased with increasing temperature as expected for
exothermic sorption and endothermic desorption processes. Fig. 1
shows lignite as an example for decreasing Kd values with
increasing temperatures over an aqueous concentration range
spanning 0.01%e50% of the phenanthrene solubility. Detailed
isotherm parameters at each temperature are listed in Wang et al.
(2007).
2.2. Desorption of native phenanthrene at elevated temperatures
All samples used in Wang et al. (2007) contain trace concen-
trations of native phenanthrene as listed in Table 3. As described in
Wang et al. (2007), similar to the classical batch system, the equi-
librium concentrations of desorbed native phenanthrene in water
200000 0.5S
0.1S
0.01S
150000 0.001S
Kd [L/Kg]
0.0001S
100000
50000
0 
77°C 46°C 20°C 4°C
Temperature
Fig. 1. Lignite is shown as an example of decreasing sorption capacity (Kd) with
increasing temperature at 5 selected aqueous concentration levels (0.0001, 0.001, 0.01,
0.1, and 0.5 of the aqueous solubility, S). The Kd was calculated based on the measured
sorption isotherms covering the same concentration range. The solid aqueous solu-
bility of phenanthrene is 0.361, 0.788, 3.35, and 17.37 mg L1 at temperatures of 4, 20,
46, and 77
C, respectively (Wang et al., 2007).
Table 2
Physico-chemical properties of phenanthrene.
Melting point (
C) (Tm) 99.5a
Boiling point (
C) 340.2a
Heat of fusion [kJ mol1] (DHfus) 18.6b
Heat of solution in water [kJ mol1] (DHsol) (solid)c 36.7e39.1
Heat of solution in water [kJ mol1] (subcooled liquid)d 18.1e20.5
a
Melting point and boiling point are from Verschueren (1983).
b
Data from Chiou (2002, page 71).
c
Reported by May et al. (1983) based on a series of water solubilities (Ssolid)
measured between 4e29.9
C (May et al., 1983), 25e73.4
C (Wauchope and Getzen,
1972), and 8e30
C (Schwarz, 1977); heat of condensation (DHcond) is the reverse
heat of solution with DHcond ¼ DHsol.
d
Calculated as the difference between DHsol and DHfus.
were measured at increasing temperatures (20, 40, 53, 61, 73, and
86
C) using an automated accelerated solvent extraction (ASE)
device (Dionex ASE 300). The time for each water equilibration step
was 99 min, which was tested to be sufficient for equilibration of
these pulverized samples at low water to solid ratios as confirmed
by preliminary experiments. Note that equilibration at low water to
solid ratios is much faster than that at large water to solid ratios,
because the latter result in a more exhaustive desorption of the
sorbate (Grathwohl, 2011). Also, comparison of aqueous concen-
trations obtained after 30 min and 99 min equilibration showed no
significant differences at a given temperature in several pre-
liminary experiments, indicating that 99 min was a conservative
duration for equilibration. This is consistent with Lou et al. (1997)
and Wennrich et al. (2000), where 20e30 min was used for
optimal extraction of hydrophobic organic compounds with
solvent or water using ASE.
2.3. Thermodynamic parameters of phenanthrene
Thermodynamic parameters of phenanthrene relevant for this
study are listed in Table 2. Emphasis here is on the heats of solution
of phenanthrene in water (DHsol) based on measured water solu-
bilities (Ssolid) between 4
C and 73.4
C (May et al., 1983; Schwarz,
1977; Wauchope and Getzen, 1972). The heat of solution for solid
phenantherene (DHsol) includes the heat of fusion (DHfus) which
indicates the heats involved during phenanthrene transfer between
solid to liquid phases. The difference between DHsol and DHfus is the
heats of solution of the subcooled liquid states of phenanthrene,
which represents the heats involved in the dissolution of liquid
phenanthrene in water.
2.4. Data evaluation
The molar isosteric heat of sorption (DH) is a general expression,
which represents the enthalpy change involved in the transfer of
a solute from the dissolved to the sorbed state while holding the
solid-phase concentration (Cs) constant. It indicates the difference
in binding energies between the sorbent and the sorbate and be-
tween the solvent (water) and the solute (sorbate). DH can be
calculated using the ClausiuseClapeyron equation at a given Cs
(Chiou, 2002):
n
dlog Cw Cs
DHa=d ¼ 2:303R with Cw ¼ (1)
dð1=TÞ KFr
where DHa/d [kJ mol1] is the molar isosteric heat of sorption or
desorption (DHa and DHd have opposite signs). R is the gas constant
and T is the temperature in Kelvin. Cs [mg kg1] and Cw [mg L1]
denote the concentrations in the solid and the aqueous phase,
respectively. KFr [mg kg1:(mg L1)1/n] and 1/n [e] are the
Freundlich coefficients. The change in Cw at a given Cs level was
 G. Wang, P. Grathwohl / Environmental Pollution 175 (2013) 110e116 113

Table 3
Isosteric heats of sorption and desorption (DHa, DHd) for five geosorbents calculated from sorption/desorption isotherms at five spiked concentration levels (Cs) over 4e77
C
and for the release of native phenanthrene over 20e86
C (1 standard deviation). Fadsorption indicates the contribution of adsorption to the total sorption/desorption isosteric
heat.

Pahokee peat Cs level [mg kg1] 1.38a 333 833 2083 4167 8333
DHa [kJ mol1] 26.0  0.5 25.0  1.1 23.9  1.7 23.1  2.2 22.3  2.6
R2 [e] 1.0 1.0 0.99 0.99 0.99
DHd [kJ mol1] 35.6  2.4 27.1  1.9 25.9  2.5 24.6  3.0 23.6  3.4 22.7  3.8
R2 [e] 0.98 0.99 0.99 0.99 0.98 0.97
Fadsorption 59% 25% 21% 18% 14% 11%
Lignite Cs level [mg kg1] 0.49a 256 769 2308 6923 20513
DHa [kJ mol1] 30.6  1.9 27.8  1.9 24.9  1.9 22.1  2.0 19.3  2.1
R2 [e] 0.99 0.99 0.99 0.98 0.98
DHd [kJ mol1] 40.5  2.1 31.2  1.6 28.2  1.6 25.1  1.6 22.0  1.7 19.0  1.7
R2 [e] 0.99 0.99 0.99 0.99 0.99 0.98
Fadsorption 77% 43% 32% 21% 11% 1%
HC Cs level [mg kg1] 16.94a 1389 3056 6944 13889 20833
DHa [kJ mol1] 33.5  3.2 29.7  2.6 25.7  2.0 22.4  1.5 20.4  1.2
R2 [e] 0.98 0.99 0.99 0.99 0.99
DHd [kJ mol1] 34.8  4.9 30.2  4.0 25.4  2.1 21.3  2.4 19.0  2.0
R2 [e] 0.96 0.97 0.97 0.98 0.98
Fadsorption 53% 39% 25% 11% 4%
AS5 Cs level [mg kg1] 9.29a 119 476 1905 7143 23810
DHa [kJ mol1] 31.2  2.1 31.9  2.0 32.7  2.1 33.4  2.3 34.1  2.5
R2 [e] 0.99 0.99 0.99 0.99 0.99
DHd [kJ mol1] 41.0  2.3 31.3  1.8 32.1  1.9 32.9  2.1 33.7  2.3 34.4  2.5
R2 [e] 0.98 0.99 0.99 0.99 0.99 0.99
Fadsorption 78% 44% 46% 49% 52% 54%
MS4 Cs level [mg kg1] 4.02a 59 235 882 2941 11765
DHa [kJ mol1] 30.3  0.6 28.8  0.9 27.3  1.3 26.0  1.8 24.4  2.3
R2 [e] 1.0 1.0 1.0 0.99 0.98
DHd [kJ mol1] 31.0  3.4 30.1  1.1 28.2  0.8 26.5  1.0 24.9  1.5 23.0  2.0
R2 [e] 0.97 1.0 1.0 1.0 0.99 0.98
Fadsorption 43% 39% 36% 28% 25% 18%
a
Native phenanthrene loadings; All the Cs loading were normalized by geosorbent organic carbon contents.

calculated based on the equilibrium isotherm parameters (KFr and
1/n) determined at each temperature. In addition to the batch ex-
periments using spiked samples, DHd values of native phenan-
threne from the samples using ASE was also determined by using
Eq. (1), where the measured aqueous concentrations after DOC-
correction at each temperature were used instead of isotherm
calculated Cw values. The change in native phenanthrene Cs during
the leaching experiments was found to be insignificant (less than
2% of the total mass over the temperature range) and thus was
neglected. The DH difference between native and spiked samples at
the same Cs level would indicate different sorbateesorbent
interaction forces for native and spiked phenanthrene.
3. Results and discussion
Fig. 2 shows the regression of log Cw versus 1/RT for the deter-
mination of DH for sorption and desorption of phenanthrene on the
five sorbents each with five different Cs levels. The linear re-
gressions (Eq. (1)) fit the data very well with a coefficient of
determination r2 > 0.96 in all cases. The isosteric heats of sorption/
desorption with standard deviations determined for our samples
are compiled in Table 3. They range from 19 kJ mol1 to
35 kJ mol1, which is equal to or more exothermic than the heat of
octanolewater phase transfer for phenanthrene (about
19 kJ mol1, Lei et al., 2000; representing a partitioning process).
Yet, the observed range of isosteric heats is less than the heat of
condensation (the reverse heat of solution) of solid phenanthrene,
which is about 38 kJ mol1 in the temperature range of interest
(see Table 2). It should be noted that the Pahokee peat used in this
study is known to contain a small amount (w8%) of charcoal-like
materials (Karapanagioti et al., 2001), thus a significant sorption
nonlinearity (1/n ¼ 0.65) and higher heat effect at low loadings are
anticipated for this sorbent because of the adsorptive contributions
by the charcoal-like substance, which originated from biomass
burning and got embedded into the peat.
For (nonlinear) adsorption of nonionic solutes on porous ad-
sorbents, the total molar isosteric heat of adsorption for a partially
miscible solute in a water solution is the sum of the heats of con-
densation (to form a separate condensed phase) and the net mo-
lecular attraction energy between the condensed solute and
adsorbent (Chiou, 2002). The condensation of sorbed phenan-
threne on the micropore-containing carbonaceous materials (see
Wang et al., 2007) likely occurred by a pore-filling mechanism. For
a partially water-soluble solute, the basic Polanyi pore-filing theory
expects the solute to condense into the adsorption space as a liquid
or a solid phase, depending on the state of the pure solute at the
system temperature (Chiou, 2002). For phenanthrene with a melt-
ing point of 99.5
C, a condensed solid phase (rather than a discrete
molecular state) should be formed in the temperature range of 4e
77
C. Ordinarily, nonlinear solute adsorption is reflective of either
adsorbate condensation to form separate phase or a specific surface
interaction of the solute with the solid. However, the later effect
seems unlikely for non-polar compounds (such as phenanthrene).
For non-polar solutes, a weak linear adsorption occurs usually on
hydrophilic mineral surfaces covered with a water film (that re-
duces the net attraction between solute and mineral surfaces) to
prevent solute condensation (Su et al., 2006). Due to net attractions
between carbonaceous sorbent surfaces and phenanthrene mole-
cules and the implied phenanthrene condensation (as indicated by
nonlinear isotherms), the isosteric heat of phenanthrene would be
more exothermic than the heat of condensation. Therefore, in this
study, the total molar isosteric heat of adsorption of phenanthrene
in solid state is expected to be larger than 38 kJ mol1. Thus,
the observed isosteric heats (19 to 35 kJ mol1, which are
equal to or more exothermic than the heat of octanolewater phase
transfer, but less than the heat of condensation) indicate that both
114 G. Wang, P. Grathwohl / Environmental Pollution 175 (2013) 110e116

10 10 10

1 1 1

0.1 0.1 0.1

C w [mg/L]
C w [mg/L]

C w [mg/ L]
0.01 0.01 0.01

0.001 0.001 0.001

0.0001 0.0001 0.0001

0.00001 0.00001 0.00001

HC MS4
Pahokee peat
0.000001 0.000001 0.000001
0.32 0.34 0.36 0.38 0.4 0.42 0.44 0.32 0.34 0.36 0.38 0.4 0.42 0.44 0.32 0.34 0.36 0.38 0.4 0.42 0.44
1/TR 1/TR 1/TR
10 10

1 1

0.1 0.1
C w [mg/L]
C w [mg/L]

0.01 0.01

0.001 0.001

0.0001 0.0001

0.00001 lignite 0.00001

AS5
0.000001 0.000001
0.32 0.34 0.36 0.38 0.4 0.42 0.44 0.32 0.34 0.36 0.38 0.4 0.42 0.44
1/TR 1/TR

Fig. 2. Van’t Hoff plots for the determination of isosteric heats of sorption and desorption of phenanthrene at five different concentration levels onto lignite, high-volatile bitu-
minous coal (HC), Pahokee peat, and the soils AS5 and MS4. Squares, diamonds, triangles, circles and horizontal bars represent different levels of spiked concentrations (Cs) during
sorption and crosses () denote the corresponding desorption steps. Plus signs (þ) indicate desorption of native phenanthrene for samples where aqueous concentrations were
above the detection limit.

adsorption and partitioning into organic matter are involved in
sorption/desorption of phenanthrene in the samples studied. The
determined DH values thus represent partitioning and adsorption
processes with different weights. Chiou et al. (1979, 1985) inves-
tigated partitioning and adsorption mechanisms and suggested
that they can be separated by comparing the isosteric heat of
sorption with the heat of condensation as well as by monitoring the
concentration dependency of the isosteric heat on loading levels. If
we use 47.1 kJ mol1 (adsorption heat of phenanthrene onto
a graphite surface, see Su et al., 2006) as the value for the standard
adsorption isosteric heat, and 19 kJ mol1 as the value for the
standard partitioning isosteric heat, then the adsorption con-
tribution (Fadsorption) from the total sorption/desorption isosteric
heat can be calculated. The Fadsorption data in Table 3 show that large
values of DH are commonly dominated by adsorption, especially for
the desorption of native phenanthrene. The partitioning con-
tribution increases with increased loading, i.e., with increasing
aqueous concentrations Cw. For example, the adsorption con-
tribution almost vanishes at a loading of 8000 mg kg1 in lignite,
which corresponds to Cw of 38% of the phenanthrene aqueous
solubility at 20
C. This is supported by the commonly assumed
superposition of sorption mechanisms where adsorption (or pore-
filling) dominates at low concentrations while linear partitioning
takes over at higher concentrations. Together, partitioning and
adsorption results in Freundlich type isotherms (Kleineidam et al.,
2002; Xia and Ball, 1999).
The dependency of the DH on the solid phase concentration (Cs)
is summarized in Fig. 3. For the three carbonaceous materials
(Pahokee peat, lignite, and HC), the isosteric heat becomes less
exothermic or endothermic with increasing Cs during sorption and
desorption, respectively. This effect is consistent with a nonlinear
adsorption mechanism, where DHa has the largest negative value
(i.e., the molar exothermic heat) at the lowest concentration (Chiou,
2002). From the five sorbents used in this study, the high-volatile
bituminous coal shows the strongest dependency of DHa/d on
concentration in coincidence with the strongest nonlinearity of
sorption for this sorbent. Here, a maximum DHa/d value of
55 kJ mol1 is reached if Cs decreases below 10 mg kg1 (i.e., the
natural loading of phenanthrene on this sample). These findings
apply in general to the other carbonaceous samples as well as for
the char-containing soil sample MS4. The AS5 sample, however,
shows an opposite trend of a slightly increasing isosteric heat with
increasing concentration levels.
Regressions for the release of native phenanthrene in cases with
Cw above the detection limit are shown in Fig. 2, and the calculated
isosteric heats are provided in Table 3 and plotted against Cs in
Fig. 3. The desorption isosteric heats of native phenanthrene (DHd)
for the soils, Pahokee peat, and lignite samples range between
31 kJ mol1 and 41 kJ mol1 and thus are in reasonable agreement
with the DHa/d values obtained from the spiked experiments (see
Table 3 and Fig. 3) at low concentration levels. In the case of high-
volatile bituminous coal, Cw for native phenanthrene was below the
detection limit at all temperatures.
In general, the determined DH values on the studied carbona-
ceous materials and carbonaceous material-containing soils are
higher than those reported for other natural aquifer sediments and
soil samples (Table 1) indicating strong adsorption of phenanthrene
onto carbonaceous materials. The adsorptive contribution could
become significant (up to 78% in this study) at low loading levels
(such as native phenanthrene loading levels). However, the deter-
mined heat contribution from adsorption process at all spiked
aqueous concentration levels was still less than 50% except sample
HC (53%). For Pahokee peat, which contains w8% charcoal-like
materials, even the DH at Cs ¼ 160 mg kg1 is no more than 15e
 G. Wang, P. Grathwohl / Environmental Pollution 175 (2013) 110e116 115

45 desorption from these same samples during column leaching ex-

periments with stepwise temperature increases which are reported
lignite in Wang and Grathwohl (2009). Overall DH indicates no significant
40
sorption/desorption hysteresis of phenanthrene within the samples
investigated in this study.
Isosteric heat [kJ/mol]

35 HC
Acknowledgements
30
Pahokee This research was funded by Deutsche Forschungsgemeinschaft
25 peat (DFG) under project number GR 971/16-1 and “AquaTerra”, a Eu-
ropean Union FP6 integrated project (Project no. 505428 (GOCE)).
20 The authors also thank Renate Seelig, Bernice Nisch and Renate
Riehle for their assistance in the geochemistry laboratory, Tuebin-
gen University.
15
0.1 1 10 100 1000 10000 100000
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