Accepted Manuscript

Title: The inuence of soil composition on the leachability of

selected hydrophobic organic compounds (HOCs) from soils
using a batch leaching test
Author: <ce:author id="aut0005"> Silviu-Laurentiu
Badea<ce:author id="aut0010"> Staffan Lundstedt<ce:author
id="aut0015"> Per Liljelind<ce:author id="aut0020"> Mats
Tysklind
PII: S0304-3894(13)00195-7
DOI: http://dx.doi.org/doi:10.1016/j.jhazmat.2013.03.019
Reference: HAZMAT 14986
To appear in: Journal of Hazardous Materials
Received date: 17-11-2012
Revised date: 6-3-2013
Accepted date: 8-3-2013
Please cite this article as: S.-L. Badea, S. Lundstedt, P. Liljelind, M. Tysklind, The
inuence of soil composition on the leachability of selected hydrophobic organic
compounds (HOCs) from soils using a batch leaching test, Journal of Hazardous
Materials (2013), http://dx.doi.org/10.1016/j.jhazmat.2013.03.019
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The influence of soil composition on the leachability of 1
selected hydrophobic organic compounds (HOCs) from 2
soils using a batch leaching test 3
4
5
Silviu-Laurentiu Badea *
1
, Staffan Lundstedt
1
, Per Liljelind
1
, Mats Tysklind
1
6
1
Department of Chemistry, Ume University, SE-901 87, Ume, Sweden 7
8
*Corresponding author: 9
Silviu-Laurentiu Badea 10
E-mail: silviu.badea@chem.umu.se 11
Phone: +46-90-786 9323 12
Fax: +46-90-7867655 13
14
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Abstract 14
The influence of soil composition (peat and clay content) on the leachability was investigated in batch 15
leaching experiments for chemically diverse hydrophobic organic compounds (HOCs: PCP, PAHs, 16
HCB, HCHs, PCBs, and TCDD/Fs). An experimental design was applied to generate 8 diverse soil 17
matrices, and the results were evaluated by orthogonal projections to latent structures (OPLS), as well as 18
compound specific response surface models. Overall, the distribution coefficients (log K
d
) of model 19
HOCs were in the range of approx. 2.0 5.7. The K
d
-values of HCHs, phenanthrene and PCP were 20
positively correlated with the peat content. K
d
-values of benzo(a)anthracene, HCB, and PCB 47 were 21
positively correlated with both peat and clay content. The K
d
-values of 1,3,6,8-TCDD and 1,3,6,8- 22
TCDF were positively correlated with peat content but negatively correlated with clay content, while for 23
PCB 153 and PCB 155 the correlations were reversed. The correlation between the K
d
-values and the 24
compounds K
ow
-values was linearly for compounds with log K
ow
<6. For HOCs with log Kow > 6, the 25
K
d
-values were leveling off, possibly due to small particles in the leachates. Our study demonstrated 26
how complex interaction between both the organic matter and clay components influences the 27
leachability of HOCs in a compound-specific manner. 28
Keywords: Contaminated soil; Hydrophobic organic compounds; Leaching tests; Distribution 29
coefficient; 30
31
32
33
34
35
36
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1. Introduction 37
Contaminated soils may function as secondary sources of hazardous compounds in the environment and 38
organic contaminants may be spread through evaporation, particle migration and leaching from soil to 39
groundwater. Consequently, in order to perform thorough risk assessments of contaminated sites all 40
these distribution pathways must be considered and estimated. Leaching tests may be useful tools to 41
estimate the mobility of contaminants via the water phase and thereby the risk for groundwater and 42
surface water contamination [1]. The leachability of the compounds is dependent on the inherent 43
physico-chemical properties of the compounds, the soil type, the presence of other contaminants, as well 44
as the age of the contamination. 45
Soil is composed of many different components, of which clays, oxides and organic matter are reported 46
to be the primary constituents responsible for the sorption of organic contaminants [2]. Organic matter 47
has a high affinity for many non-polar compounds and is considered to have a dominating influence on 48
the sorption. For soils and sediments with low organic matter content, clay minerals may have a more 49
important role [3]. When it comes to the properties of the contaminants, their solubility as well as their 50
partitioning behavior between water and organic phases, often described by the octanol-water partition 51
coefficient (K
ow
), are thought to be the most important [4]. The most hydrophobic compounds (K
ow
> 6) 52
are unlikely to leach, due to their low water solubility and high affinity for particle surfaces. In contrast, 53
less hydrophobic compounds (K
ow
< 6) are generally weakly sorbed and will leach to varying degrees 54
depending on their solubility. In response to the need for leaching tests, methods for organic compounds 55
have been recently developed [5-15]. Generally, all leaching tests aim to determine the fraction of 56
contaminants that are loosely bound and therefore may be mobilized into the water phase. Leaching tests 57
may be performed in the form of equilibrium column tests or batch tests. In the batch tests, the soil is 58
agitated in the leachate for a fixed time to obtain equilibrium between contaminants in solution and 59
contaminants in the soil. The distribution of the contaminants between the soil and leachates are usually 60
calculated as soil-water distribution coefficients (K
d
), which are widely used in modeling of 61
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environmental behavior of contaminants in soils. Hydrophobic organic compounds (HOCs), often 62
present in the contaminated soils, including a wide array of compounds, such as organochlorine 63
pesticides (OCs), polychlorinated benzenes (PCBz), polycyclic aromatic hydrocarbons (PAHs), 64
polychlorinated biphenyls (PCBs), polychlorinated dibenzofurans (PCDFs) and polychlorinated 65
dibenzo-p-dioxins (PCDDs). These compounds are often toxic, persistent in the environment and can 66
bioaccumulate [16-19]. The mobility of HOCs is generally low mainly because to their strong 67
association with the organic matter in soils [4, 6, 20, 21], but their mobility may also be limited by other 68
constituents of the soil, e.g. small particles of clay and active oxide surfaces [2]. On the other hand, 69
dissolved organic carbon (DOC) and fine particles may be transported through the soil profile as 70
colloids [22] and thereby function as carriers for HOCs, which then may increase the mobility [23-25]. 71
The objective of this study was to investigate the influence of the soil composition (proportion of peat, 72
clay and sand) on the leachability of a wide range of HOCs, focusing on similarities and differences 73
between the compounds. 74
2. Experimental 75
The leachability of HOCs was studied in a series of batch leaching experiments according to an 76
experimental design, which was evaluated by orthogonal projections to latent structures (OPLS). Spiked 77
artificial soils were used to control the parameters of interest, such as the soil and contaminant 78
compositions [26]. 79
2.1. Soil samples 80
OECD standard soil, containing 70% sand, 20% kaolin clay and 10% sphagnum peat [27], was used as a 81
reference soil during the batch leaching experiments. Kaolinite (Al
2
Si
2
O
5
(OH)
4
) was identified as the 82
main mineral in the clay, as determined by X-ray Diffraction (Rietveld's method) [28], while the quartz 83
(SiO
2
) was identified as the main mineral in the sand. In order to identify the moieties in the organic 84
matter responsible for interaction with the HOCs, the peat used in the preparation of the soils was 85
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investigated by X-ray photoelectron spectroscopy (XPS) [20] (see S.M.). Five chemical states of carbon 86
were identified and quantified in the C
1s
spectra: 285.0 eV (representing aliphatic C-C and C-H bonds), 87
285.7 (C-COOH, C-CON), 286.7 eV (C-O-C, C-OH, C-N), 288.2 eV (O-C-O, C=O) and 289.3 eV 88
(COOH bonds). The uncertainty of atomic concentrations determinations was approximately 8 atomic 89
%. In addition to the OECD soil, seven other artificial soils, with different proportions of the same 90
constituents were prepared in duplicates (see Table 1 for their composition), in accordance with a D- 91
optimal experimental design. 92
2.2. Model compounds and soil spiking 93
Technical hexachlorocyclohexane (HCH) containing 69.3% -HCH, 15.0% -HCH, 9.0 % -HCH, 6.5 94
% o-HCH, pentachlorophenol (PCP), hexachlorobeneze (HCB), phenanthrene (Phe), benzo(a)anthracene 95
(BaA), were all purchased from Sigma-Aldrich (Munich, Germany), while the polychlorinated 96
biphenyls: PCB 47, PCB 153, and PCB 155, 1,3,6,8-tetrachloro dibenzo-p-dioxin (1,3,6,8-TCDD) and 97
1,3,6,8-tetrachloro dibenzofuran (1,3,6,8-TCDF), were purchased from LGC Standards (Bors, 98
Sweden). The 13 HOCs, selected as representative soil contaminants of general concern, were spiked in 99
the soils using a high solvent volume method similar to the methods previously described [29, 30]. The 100
high solvent volume spiking method was chosen since it is likely to provide a homogenously 101
distribution of the target compounds in the soils [30] compared with low solvent volume spiking 102
methods. The homogeneity of the spiked soils was tested by analysis of triplicate samples prior to the 103
start leaching tests. Briefly, about 320 g of OECD soil and 200 g of each of the other soils were 104
transferred to brown glass bottles and homogenized. The soils were spiked with an acetone solution (50 105
mL per 100 g of soil) of the above mentioned compounds to reach a final concentration in the soils of: 106
402 ng/g for PCP, 1060 ng/g for Phe, 1010 ng/g for BaA, 2000 ng/g for HCB, 6930 ng/g for -HCH, 107
1500 ng/g for -HCH, 900 ng/g for -HCH, 650 ng/g for o-HCH, 5.0 ng/g for PCB 47, 4.0 ng/g for PCB 108
153, 5.3 ng/g for PCB 155, 1.0 ng/g for 1,3,6,8-TCDD, and 1.0 ng/g for 1,3,6,8-TCDF. The above 109
mentioned spiked concentrations were designed to be environmentally relevant and to mimic the 110
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contamination at industrial sites. The spiked soils were homogenized with glass rods and the solvent 111
was allowed to evaporate for one week leaving the bottles opened. The soils were mixed regularly with 112
the glass rods to accelerate the solvents evaporation. The soils were stored at +4C for four weeks in 113
order to let the contaminants migrate somewhat into the soil particles (age) before the leaching tests. 114
2.3. Batch leaching test 115
The batch leaching tests were performed using 100 g aliquots of the soils, triplicates of the OECD soil 116
and duplicates of the other seven soils. A blank consisting of 100 g clean OECD soil (with no spiked 117
contaminants) was run in parallel. The tests were performed in 0.5 L Schott Duran bottles (screw capped 118
glass, 45 mm screw thread, 78 mm side wide and 181 mm height)_at a liquid to solid ratio (L/S) of 5 119
L/kg, which was reached by adding 0.5 L of an aqueous solution containing 0.001 M CaCl
2
and 0.2 g/L 120
NaN
3
to each bottle (ionic strength of 0.012 mol/L). The bottles (18 in total) were placed in a horizontal 121
shaker, and rotated at 120 rpm for 24 hours to obtain equilibrium between the contaminants in solution 122
and contaminants in the soil. The leachates were then separated from the soil by filtration, using a 123
cellulose filter followed by vacuum filtration through a glass fiber filter with pore diameters of about 0.7 124
m (Sartorius Stedim Biotech GmbH, Gottingen, Germany). 125
2.4. Extraction of soil leachates 126
After separation, the leachates were spiked with an internal standard (IS) solution containing
13
C-labeled 127
PCP, -HCH (IS for all HCHs), PCB 52 (IS for PCB 47), and PCB 153 (IS for PCBs 153 and 155),
2
H- 128
labeled Phe and BaA and
37
Cl-2,3,7,8-TCDD (IS for 1,3,6,8-TCDD and 1,3,6,8-TCDF), all from LGC 129
Standards (Bors, Sweden). The leachates were extracted by liquid-liquid extraction using three portions 130
of 50 mL dichloromethane (DCM) each. The first round was performed in 1L Schott Duran bottles on 131
the horizontal shaker for 24 hours, and the following two rounds in separatory funnels. The organic 132
extracts were collected and evaporated using a rotavapor, and were then dried on columns of anhydrous 133
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sodium sulfate (Na
2
SO
4
) and divided into three aliquots for cleanup and analysis of 1) PCDDs/Fs and 134
PCBs, 2) PCP and 3) PAHs, HCHs and HCB, respectively. 135
2.5. Extraction of soil samples 136
Samples (5 g dry weight) of the spiked soils and clean OECD soil were transferred in duplicates to pre- 137
washed Soxhlet thimbles. The samples were spiked with similar IS-solutions as the ones used for the 138
leachates (ten times more concentrated), after which they were extracted with toluene using Soxhlet 139
Dean-Stark extractors for 24 hours. The resulting extracts were divided into four aliquots: one retained 140
as a precaution, and the others for determinations of 1) PCDDs/Fs and PCBs, 2) PCP and 3) PAHs, 141
HCHs and HCB, respectively. The extraction procedure for the soil particles trapped on the filter was 142
identical to that for the soil samples. 143
2.6. Clean-up and analysis of PAHs, HCHs and HCB 144
The aliquots of the extracts intended for analysis of PAHs, HCHs and HCBs were purified on columns, 145
consisting of 4 g of silica gel deactivated with 10% water (w/w) packed in 16 mm i.d. glass columns, 146
with a ca. 1 cm layer of anhydrous Na
2
SO
4
on top. The target compounds were eluted with 60 mL of 147
cyclopentane [31]. About 1 ml of toluene was added to the eluates and the cyclopentane was evaporated. 148
Recovery standard (RS), consisting of
2
H-labeled fluoranthene was added before GC/MS analysis. An 149
Agilent 6890 N gas chromatograph (GC) coupled to Agilent 5975 inert mass selective detector (MSD) 150
(Agilent Technology, Palo Alto, USA) was used for the analysis, in the selected ion monitoring (SIM) 151
mode. The GC was equipped with a 30 m x 0.25 mm x 0.25 m i.d., SLB-5ms column (Supelco, 152
Bellefonte, Pennsylvania, USA), and a HP PTV injector operated in splitless mode. Helium was used as 153
carrier gas at a flow of 1.3 mL/min. The temperature program for the GC oven was: 80 C for 1.8 min, 154
rising by 8 C/min to 180 C, and then by 12C/min to 310C and held for 10 min. 155
2.7. Clean-up and analysis of PCP 156
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The aliquots of the extracts intended for PCP analysis were diluted with 2 mL of n-hexane, then the PCP 157
was separated from other hydrophobic sample components by liquid-liquid extraction with 3 x 1 mL 158
0.5M NaOH solution. The aqueous phase, containing the sodium phenolate of PCP, was collected in 159
new vials. The PCP was acetylated by adding 1mL of acetic acid anhydride to the aqueous phase [31]. 160
After 10 min, 0.5 mL of 18.5 % HCl was added. Acetylated PCP was then extracted with 3 x 2mL of 161
cyclopentane. The extract was dried on a column containing 1 g of anhydrous Na
2
SO
4
, 0.1 to 1 mL of 162
toluene was added, and the cyclopentane was evaporated. An RS, consisting of
2
H-dibenzofuran was 163
added before GC/MS analysis. Here too, the same 6890 N GC-5975 MSD was used, equipped with the 164
same SLB-5ms column but using a slightly different temperature program in the GC: 90 C for 2 min, 165
increase by 15 C/min to 220 C, and then by 30C to 310C and held for 2 min. 166
2.8. Clean-up and analysis of PCBs and PCDDs/Fs 167
The aliquots of the extracts intended for PCB and PCDD/F analysis were spiked with 50 L of 168
tetradecane. After evaporation, the residual extracts were dissolved in 2-3 mL n-hexane and transferred 169
to multi layer silica columns for clean up [31]. The columns consisted of, 16 mm i.d. glass columns 170
packed with the following components from top to bottom: 1cm layer of Na
2
SO
4
, 4cm of H
2
SO
4
acidified silica 171
gel, 4 cm of neutral silica gel, 4 cm of KOH alkaline silica gel and a plug of glass wool. The PCBs and 172
PCDD/Fs were eluted with 50 mL of n-hexane, the eluate was collected in round flasks and evaporated 173
again until near dryness (the residual volume of 50L tetradecane). The PCDD/Fs were separated from 174
the PCBs on carbon columns [31]. The PCBs were eluted from the column with 50 mL of a mixture of 175
DCM/n-Hexane (50:50), after which the columns were turned upside-down and the PCDD/Fs were 176
eluted with 50 mL toluene. The PCB fractions were spiked with 40 L tetradecane, and 40 L of an RS 177
solution containing
13
C-labeled PCBs 97 and 188, while the PCDD/F fractions were spiked with 30 L 178
tetradecane and 40 L of an RS-solution containing
13
C-labeled 1,2,3,4-TCDD, 1,2,3,4,6-PeCDF, 179
1,2,3,4,6,9-HxCDF, and 1,2,3,4,6,8,9-HpCDF. Both fractions were evaporated until only the tetradecane 180
remained and then transferred to 200 L GC-vials for analysis. 181
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The PCBs and PCDD/Fs were analyzed using an Agilent 6890N gas chromatograph (Agilent 182
Technology, Palo Alto, USA) coupled to a Waters Autospec Ultima NT 2000D high resolution mass 183
spectrometer (Milford, USA), the latter with a mass resolution of 10000. The mass spectrometer was 184
operated in SIM mode. Analyses were performed on non-polar DB-5 column (60 m x 0.25 mm x 0.25 185
m J&W Scientific, CA, USA). The temperature program for PCDD/Fs started at 200C for 2 min, then 186
increased by 3 C/min to 278 C, followed by 10 C/min to 315 C, which was held for 5 min. The 187
temperature program for PCBs started at 190C for 2 min, then increased by 3 C/min to 278 C, then 6 188
C/min to 304 C, no hold time. 189
2.9. Total organic carbon analysis 190
Total and dissolved organic carbon was determined using a Shimadzu TOC-5000 high temperature 191
catalytic oxidation instrument with a non-dispersive infrared (NDIR) detection. Samples were acidified 192
and sparged prior to analysis. Calculation of carbon concentrations was made with potassium hydrogen 193
phtalate as standard substance. 194
2.10. Calculation of distribution coefficients 195
The distribution of the contaminants between the solid and liquid phases were expressed as soil-water 196
distribution coefficients (K
d
), calculated using the following equation: 197
w
s
d
C
C
K = 198
where C
s
and C
w
are the concentrations of a given compound in the soil and aqueous phase, respectively. 199
Since spiked soils were used, the K
d
was calculated using measured concentration of the aqueous phase 200
only, while the soil concentrations were based on the spiked levels. The concentrations in the soils 201
before and after the leaching were verified for one of the soils, i.e. the M2 soil (see Table S2 202
Supplementary Material (S.M.). Some experimental concentrations in the after-leaching M2 soil (BaA 203
and Phe) appears to be slightly lower than the concentrations calculated according to the mass balance 204
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(see S.M.) and these slightly lower concentrations might be explained by sorption of above mentioned 205
compounds on the cellulose filters during pre-filtration. 206
2.11. Multivariate data analysis 207
To evaluate the relationships between proportions of sand, clay and peat in the soil and the leachability 208
of the model compounds (log K
d
values) an orthogonal partial least square model (O-PLS) was 209
established using the SIMCA-P+12.0 multivariate statistical software package (Umetrics, Ume, 210
Sweden). A two-dimensional model with N=8 observations and K=16 variables (X=13, Y=3) was used. 211
The quality of the model is described by the R
2
X, R
2
Y and Q
2
values. R
2
X and R
2
Y are defined as the 212
proportion of variance in the data explained by the models and indicates goodness of fit, while Q
2
is 213
defined as the proportion of variance in the data predictable by the model and indicates predictability 214
[32]. 215
Furthermore, in order to evaluate the relation between the soil composition (% sand, clay and peat, 216
respectively) and the concentration of the model compounds, a screening model was developed with the 217
MODDE 9.0 software (Umetrics, Ume, Sweden). The D-optimal experimental design was generated 218
for three factors (% sand, clay and peat, respectively), with 8 experiments, to produce a model with 219
linear terms for all of the factors, and no interaction terms included. The relationships between the 220
factors and response (concentration) were analyzed using multiple-linear regression (MLR) [33]. 221
3. Results and Discussion 222
3.1. Multivariate analysis of the distribution coefficients. Variation of leachability in relation to soil 223
composition. 224
The logarithmic values of the distribution coefficients (log K
d
) for all compounds are summarized in 225
Table 1. Overall, the log K
d
varied between 2.040.04 for -HCH in the soil with 90% sand, 5% clay 226
and 5% peat (M2), and 5.690.05 for PCB 155, the compound with the highest log K
ow
value (7.2), in 227
the soil with 30% sand, 60% clay and 10% peat (M6). For the compounds with low hydrophobicity 228
(described as log K
ow
), i.e. the HCHs, PCP, Phe and PCB 47, the highest K
d
-values were recorded for 229
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the soil with the highest proportion of organic matter (M4 with 20% sand, 20% clay and 60 % peat). For 230
most of the model compounds (HCHs, PCP, HCB, PCB 47 and PCB 155), the lowest K
d
-values were 231
recorded for the soils with the lowest peat and clay contents (soils M1 and M2). While the log K
d
-values 232
of Phe from Table 1 are similarly with the one recorded by Enell et al. [5] (5.18) in a column leaching 233
test with aged soil (16 % organic matter), van Hattum et al. [34] obtained similarly values of the log K
d
234
values both for BaA (log K
d
4.56.9, average 5.6 0.7) and Phe (log K
d
3.66.3, average 4.4 0.9) for 235
their partition between water and lake and river sediments with organic carbon contents between 0.9 and 236
22%. Comparing results from van Hattum et al. [34] with the lower variation of the K
d
-values both for 237
BaA and Phe recorded in our study (although involving a large variation in soil composition), one 238
possible explanation could be higher variation of field data comparing with the data obtained from 239
controlled reference experiments performed with spiked soils [26]. 240
In order to efficiently investigate the relation between the soil composition (% sand, clay and peat, 241
respectively), the physico-chemical properties of the model compounds, and the leachability of the same 242
compounds (log K
d
values), the results were also explored with OPLS. The R
2
X and R
2
Y obtained were 243
0.811 and 0.961 respectively, while the Q
2
was 0.834 indicating that the model could explain most of 244
the variations within the data set. The resulting OPLS scatter plot (Fig. 1) shows the degree to which the 245
K
d
values for each compound were influenced by the soil constituents, and also which of the compounds 246
that behaved similarly as well as those that behaved differently. Also compound specific response 247
surfaces were calculated using screening models calculated with MODDE 9.0 software. The resulting 248
contour plots show how the leachate concentrations of the compounds varied with the soil composition 249
(see Figs. 2, 3, 4, and 5). 250
The OPLS loading scatter plot (Fig. 1) indicate four groups of compounds with different interactions 251
with the soil matrix. For the first group (group A in Fig. 1), consisting of HCHs, Phe and PCP, the K
d
252
values had a relatively strong positive correlation with the peat content, while the correlation with the 253
clay and the sand was weaker. Thus, the leachability of these compounds was mainly controlled by the 254
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peat, showing decreasing leachability with increasing peat content, while they were less affected by the 255
variations in the clay and the sand content (see also the contour plots of from Fig. 2A, 2B and 2C). The 256
contour plot from Fig. 2A show that the concentration of -HCH in the leachate is decreasing about 13 257
times, as the peat content increases from 0 to 60%. A similar behavior was also seen for the other 258
compounds of group A, for example the other HCHs, not shown in Fig.2, see S1A (S.M.). This behavior 259
of HCHs is also similarly with the one reported in other studies, as the log K
d
values for all HCHs from 260
Tab. 1 fell in the same range as those reported by Toul et al. [35] for sorption of -HCH on dusty fine- 261
grained sandstone (1.1 % organic carbon; log K
d
3.18) and fine-grained sandstone (0.28 % organic 262
carbon; log K
d
3.54) in sorption batch tests. The contour plot from Fig. 2B show that the concentration 263
of PCP in the leachate is decreasing about 6 times, as the peat content increases from 0 to 60%, 264
indicating a relatively strong retention of PCP in soils with the organic matter contents higher than 10 % 265
(see also S1B, S.M.). Nevertheless, this decrease cannot be entirely attributed to the hydrophobic 266
interactions since the pH of the leachates (measured in a separate DOC availability test using the same 267
liquid to solid ratio (L/S) of 5 L/kg) was decreasing from 7.70 in the case of M2 leachate (5 % peat) to 268
4.61 in the case of M4 leachate (60%). In the case of slightly alkaline M2 leachate, the sorption of 269
phenolate ion and the formation and sorption of the neutral metal-phenolate ion pair must be taken into 270
account [36]. This correlation was found also by Wahlstrm et al. [37], who observed a high 271
leachability of chlorophenols in sandy soils, while it was much lower in humus rich soils. The relative 272
high concentration of PCP in all the leachate samples, in the present study, might be associated with its 273
relatively high water solubility (0.857 mg/L), which is drastically increased as the phenol is dissociated 274
into its phenolate ion (PCP
-
), occurring at pH 7 and above [36, 37]. The contour plot from Fig. 2C 275
shows that the concentration of Phe in the leachate is decreasing about 454 times to 3.22 1.45 ng/mL, 276
as the peat content increases from 0 to 60% (see also S1C, S.M.). Both Fig. 2C and Fig. 1 show that the 277
leachability of Phe is only weakly correlated with the clay content, as compared to the influence of the 278
peat content. Quantitatively, the log K
d
-values of Phe from Tab. 1 are similarly with the one recorded by 279
Enell et al. [5] (5.18) in a column leaching test with aged soil (16 % organic matter). By XPS analysis, 280
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the following moieties were found: C-C, C-H, COOH, C-CON, C-O-C, C-OH, C-N, O-C-O, C=O. 281
Among them, the aliphatic moieties identified at 285.0 eV (C-C and C-H bonds) have the highest atomic 282
concentrations (AC), 41.91 %, followed by the components identified at the binding energy of 286.7 eV 283
(C-OH, C-N and C-O-C bonds) with 20.5 %. The high presence of aliphatic moieties in the peat 284
combined with the high influence of the peat content on the K
d
values of HCHs, Phe and PCP suggests 285
that alkyl-C moieties, in addition to aromatic moieties, can act as sorption domains for HOCs in soil 286
organic matter. The alkyl-C moieties can sorb too appreciable amounts of HOCs, in some cases with 287
even higher affinity than aromatic-rich sorbents [38]. 288
The second group of compounds (group B in Fig. 1) consists of 1,3,6,8-TCDD and 1,3,6,8-TCDF. Their 289
K
d
values were positively correlated with the peat content, but negatively correlated with the clay 290
content. Thus, 1,3,6,8-TCDD and 1,3,6,8-TCDF levels in the leachates decreased with increasing peat 291
content in the soil, but increased with increasing clay content. This is an interesting finding showing that 292
the leachability of 1,3,6,8-TCDD and 1,3,6,8-TCDF might be enhanced in the soils with high clay 293
content. The blocking of the sorption sites during the expansion of the clay [39] and also the colloidal 294
transport of the 1,3,6,8-TCDD and 1,3,6,8-TCDF on the clay particles [40] might explain their enhanced 295
leachability. This behavior for the 1,3,6,8-TCDD and 1,3,6,8-TCDF can also be seen in the contour plots 296
for these compounds (Figs. 3A and 3B) respectively. The contour plots are similar, indicating that these 297
two compounds have similar leaching behavior, and that they are affected similarly by the studied soil 298
components. 299
For the 3
rd
group of compounds (group C in Fig. 1), consisting of BaA, HCB and PCB 47, the K
d
values 300
were positively correlated with both the peat and the clay content, meaning that the leachate 301
concentrations of these compounds were decreasing as both the peat and the clay content increased. 302
However, compared to group A the correlation with the peat content was weaker for group C, and for 303
BaA even the correlation with clay was weak. The contour plot presented in Fig. 4 combined with Fig. 304
1 shows that the concentration of HCB in leachates is increasing with the decrease of both peat and clay 305
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content of the soil as we are moving from the bottom of plot (high content of clay and peat) to the top 306
(low content of clay and peat). Quantitatively, the variability of K
d
values for HCB is similar with the 307
one reported by Toul et al. [35], i.e. a log K
d
between 3.07 for sorption of HCB on dusty fine-grained 308
sandstone (1.1 % organic carbon) and 3.66 for sorption of HCB on lake sediment (2.85 % organic 309
matter). The contour plot presented in Fig. 5A combined also with the Fig. 1 shows that the 310
concentration of PCB 47 in leachates increased with the decrease of peat and very weakly with the 311
decrease of clay content of the soil, as we are moving from the bottom of plot (high content of clay and 312
peat) to the top (low content of clay and peat). Compared with the Phe, the K
d
values of BaA are weakly 313
correlated both with peat and the clay content, suggesting that the soil composition had a low influence 314
on this compound. Nevertheless, van Hattum et al. [34] recorded variable but similarly log K
d
values 315
both for BaA (log K
d
4.56.9, average 5.6 0.7) and Phe (log K
d
3.66.3, average 4.4 0.9) for their 316
partition between water and lake and river sediments with organic carbon contents between 0.9 and 317
22%, indicating a higher variation of field data comparing with the data obtained from controlled 318
reference experiments performed with spiked soils [26]. 319
The 4
th
group of compounds (group D in Fig. 1), consisting of PCB 153 and PCB 155, showed K
d
values 320
that, according to the OPLS-model, were positively correlated with the clay content while being 321
negatively correlated with the peat content. Although the K
d
values of PCB 153 appears to be slightly 322
positively correlated with the sand content while the K
d
values of PCB 155 appears to be slightly 323
negatively correlated with the sand content (this it is apparently true for all the other compounds 324
excepting 1,3,6,8-TCDD which is very weak positively correlated with the sand content), it is probable 325
that this mainly is an affect of the change in the clay and peat content. This means that these compounds 326
would be expected to show higher leachability as the clay content decreased, but also as the peat content 327
increased. For PCB 153, this agrees well with what the contour plot shows, but for PCB 155 it is 328
somewhat different (Fig. 5). For this compound the concentration in the leachate seem to increase both 329
as the peat and clay decreases. This apparent difference between predictions of the OPLS-model and the 330
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response surface model was probably due to the low significance of the correlation between peat and 331
PCB 155s leachability. 332
3.2. Variation of the distribution coefficients with hydrophobicity of the compounds 333
Since it is generally suggested that the leaching of organic compounds from soil is controlled mainly by 334
the compounds hydrophobicity, the log K
d
-values of all compounds calculated for OECD soil as well 335
for the soils with the highest amount of peat (M4) and clay (M6), respectively, were plotted against their 336
log K
ow
(See Fig. 6). The data from the log K
d
vs. log K
ow
plot for OECD soil (Fig. 6A) were fitted 337
linearly and also quadratic, and the slope of the linear curve was calculated to 1.02 0.18 (Eqn. 1 from 338
Fig.6A), close to the value of 1, as expected for sorption processes that are driven by hydrophobic 339
interactions [41]. However, for the more hydrophobic compounds (log K
ow
>6) the measured K
d
-values 340
deviated from the linear relationship, which also the regression coefficient (R
2
), calculated to 0.71, 341
indicate. Excluding the K
d
values for the four most hydrophobic compounds (PCB 153 and PCB 155, 342
1,3,6,8-TCDD and 1,3,6,8-TCDF) a better linear relationship was calculated (R
2
= 0.85), while the slope 343
of the linear curve was 1.34 0.19 (Eqn.2 from Fig.6A). According to Booij et al. (1993) [42], a plot log 344
K
d
vs. log K
ow
using true K
d
values (based on truly dissolved concentrations) should result in a linear 345
relationship with a slope close to 1, but due to the colloids present in the leachates the apparent K
d
346
values for the hydrophobic compounds are deviating from the linearity. The above mentioned study [42] 347
estimated that the differences between true and apparent K
d
values were negligible for compounds with 348
log K
ow
<6, and were up to 1 log unit for more hydrophobic compounds. The log K
d
vs. log K
ow
plots 349
for the more extreme soils in terms of peat and clay content M4 and M6 soils shown in Figs. 6B and 6C, 350
indicate an even more complex relationship. Excluding the K
d
values for the four most hydrophobic 351
compounds (PCB 153 and PCB 155, 1,3,6,8-TCDD and 1,3,6,8-TCDF), the linearity of the curves were 352
R
2
= 0.58 for M4 soil and R
2
= 0.90 for the M6 soil respectively. The linear fitting of the all K
d
data for 353
both M4 and M6 soils was resulting much more low R
2
values (data not shown) than the one calculated 354
with all K
d
data for OECD soil (R
2
= 0.71). The slopes of the curves for log K
d
vs. log K
ow
plots for the 355
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M4 and M6 soils were 0.65 0.18 for M4 and 1.47 0.17 for M6 respectively, clearly deviating from 356
the suggested value of 1 [41]. Thus the sorption in these two soils might be driven by other factors than 357
hydrophobic interactions (dissolution, the presence of dissolved organic matter and colloids, transport 358
via particles). The amount of DOC released from the spiked soil was estimated in a separate DOC 359
availability test using the same liquid to solid ratio (L/S) of 5 L/kg. The high values obtain for total 360
organic carbon (between 49.9 and 323 mg/L leachates) show that the colloid-facilitated transport of the 361
four most hydrophobic compounds (PCB 153 and PCB 155, 1,3,6,8-TCDD and 1,3,6,8-TCDF) might 362
explain the above mentioned deviation from the linearity. In order to describe the effect of small 363
colloidal particles that escape phase separation, Gschwend et al. [43] developed the non-settling 364
particles model (NPL-model ), demonstrating that the apparent K
d
values of highly hydrophobic 365
compounds are lower than the true Kd values (based on truly dissolved concentrations) [41]. Thus log 366
K
d
vs. log K
ow
plots from Fig. 6 indicated that the apparent K
d
values show a deviation from the true K
d
367
values for highly hydrophobic compounds (PCB 153 and PCB 155, 1,3,6,8-TCDD and 1,3,6,8-TCDF). 368
Similar trends, with logarithmic values of the organic carbon distribution coefficient (K
oc)
) diverging 369
from a linear relationship at log K
ow
> 6, was found by Burgess et al. [44] in a study on distribution of 370
PCBs in a colloidal system, and they suggested that the divergence was due to the lack of equilibrium 371
between colloidal and dissolved phases in the system. Possible mechanisms might include contaminant 372
diffusion rates, colloid transport dynamics, steric hindrance and colloid instability. 373
Conclusions 374
The results of this study indicate that the leachability of moderately hydrophobic compounds, such as 375
HCHs, PCP and Phe, is correlated mainly with the peat content of soil, and their leachability decreases 376
as the peat content increases, while the correlation with the clay content is much weaker. For slightly 377
more hydrophobic compounds, such as BaA, HCB and PCB 47, there are correlations with both peat and 378
clay contents implying that their leachability decreases as the proportions of either of these soil 379
constituents increases, although the correlations for BaA are weak. For the highly hydrophobic 380
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compounds the correlation was less consistent. For the PCDDs/Fs, i.e. 1,3,6,8-TCDD and 1,3,6,8- 381
TCDF, the leachability was negatively correlated with the peat content but positively correlated with the 382
clay content, while for the highly chlorinated PCBs, i.e. PCB 153 and PCB 155, the correlations were 383
the reversed, i.e. the leachability was positively correlated with the peat content but a negatively 384
correlated with the clay content. Thus, while leachability of moderately hydrophobic compounds, such 385
as HCHs, PCP and Phe is mainly influenced by organic matter content, the clay content may also 386
influence the leachability of highly hydrophobic compounds (K
ow
> 6), positively for co-planar 387
compounds (1,3,6,8-TCDD and 1,3,6,8-TCDF), and negatively for non-planar compounds (PCB 153 388
and PCB 155). 389
Overall, the leaching behavior of -HCH and PCP seem to be quite similar despite the different 390
chemical nature of these two compounds. The low log K
d
values recorded for HCHs and PCP were 391
similar with those recorded in previous studies [35, 37] in which they both were estimated to have high 392
leachability at contaminated sites. On the contrary, the BaAs retention in the soil, was not influenced 393
significantly by the increasing proportions of organic matter in the soil matrix. The relationship log K
d
394
vs. log K
ow
investigated in our study shows that the apparent log K
d
values for highly hydrophobic 395
compounds, such as PCB 153 and PCB 155, 1,3,6,8-TCDD and 1,3,6,8-TCDF, may deviate from the 396
linear relationship seen for the less hydrophobic compounds due to colloids, present in the leachate, 397
acting as carriers for the highly hydrophobic compounds. If colloid-facilitated transport is not taken into 398
account, the concentration of dissolved contaminants in the water phase will be somewhat 399
overestimated, and the apparent K
d
lower than the true value. Furthermore, for soils with very high 400
content of organic material or clay, our results show that the relation between log K
d
and log K
ow
is less 401
linear for all compounds. Also our study demonstrated that beside the organic matter content of the soil, 402
the clay content may also influence the leachability of HOCs, especially for highly hydrophobic 403
compounds (K
ow
> 6). Our study demonstrated how complex interaction between both the organic 404
matter and clay components influences the leachability of highly hydrophobic compounds in a 405
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compound-specific manner. Therefore this study can be a step forward in the understanding and 406
assessment of mobility of organic contaminants in contaminated soil sites. 407
Acknowledgements 408
The research of Silviu-Laurentiu Badea is funded by Ume University. The work was performed within 409
the frame of the Northern Sweden Soil Remediation Center (MCN). The authors are gratefully to Dr. 410
Rui Climaco Pinto from BILS (Bioinformatics Infrastructure for Life Sciences) for his support with 411
multivariate analysis and to Dr. Andrey Shchukarev for his support with XPS analysis. 412
413
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Table Captions 413
Table 1. Summary of the distribution coefficients (log Kd values) determined for the model compounds 414
in the test soils. 415
Figure Captions 416
Fig. 1. OPLS loading scatter plots of K
d
values for the model compounds. 417
Fig. 2. Contour plots showing the variation of concentrations in leachates of -HCH (A), PCP (B) and 418
Phe (C) vs. proportions of clay and peat in the artificial soils . The R
2
values obtained from the MODDE 419
screening models were 0.80 for -HCH, 0.51 for PCP and 0.30 for Phe respectively. 420
Fig. 3. Contour plots showing the variation of concentrations in leachates of 1,3,6,8-TCDD (A) and 421
1,3,6,8-TCDF (B) vs. proportions of clay and peat in the artificial soils. The R
2
values of the MODDE 422
screening models were 0.68 for 1,3,6,8-TCDD and 0.68 for 1,3,6,8-TCDF respectively. 423
Fig. 4. Contour plots showing the variation of concentrations in leachates of HCB vs. proportions of 424
clay and peat in the artificial soils. The R
2
values of the MODDE screening model was 0.69. 425
Fig. 5. Contour plots showing the variation of concentrations in leachates of PCB 47 (A) PCB 153 (B) 426
and PCB 155 (C) vs. proportions of clay and peat in the artificial soils. The R
2
values of the MODDE 427
screening models were 0.55 for PCB 47 and 0.36 for PCB 153 and 0.43 for PCB 155 respectively. 428
Fig. 6. Log K
d
values for the target compounds vs. their log K
ow
values, calculated for OECD standard 429
soil (A), M4 soil (20% sand, 20% clay and 60 % peat) (B) and M6 soil (30 % sand, 60 % clay, 10% 430
peat) (C). The OECD data were fitted linearly (black curve for all data and green curve excluding 431
compounds 10 to 13) and quadratically (red curve for all data) (A). Eqns. (1) and (2) describe the linear 432
fits of all data and data excluding compounds 10 to 13, respectively (A). The target compounds were o- 433
HCH (1), |-HCH (2), -HCH (3), o-HCH (4), PCP (5), HCB (6), BaA (7), Phe (8), PCB 47 (9), PCB 434
153 (10), PCB 155 (11), 1,3,6,8-TCDF (12) and 1,3,6,8-TCDD (13). 435
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Secondary Kaolinitic Clays, Environ. Sci. Technol. 45 (2010) 461-467. 533
[41] K. Booij, J. van der Meer, D. Kwast, J.L. de Boer, Sorption of polychlorinated biphenyls by north 534
sea sediments, J. Sea Res. 37 (1997) 49-66. 535
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[42] K. Booij, Distribution of hydrophobic contaminants between sediment, water, and colloids in batch 536
incubations, Bull. Environ. Contam. Toxicol. 50 (1993) 205-211. 537
[43] P.M. Gschwend, S. Wu, On the constancy of sediment-water partition coefficients of hydrophobic 538
organic pollutants, Environ. Sci. Technol. 19 (1985) 90-96. 539
[44] R.M. Burgess, R.A. McKinney, W.A. Brown, Enrichment of Marine Sediment Colloids with 540
Polychlorinated Biphenyls: Trends Resulting from PCB Solubility and Chlorination, Environ. Sci. 541
Technol. 30 (1996) 2556-2566. 542
[45] A. Aberg, M. MacLeod, K. Wiberg, Physical-Chemical Property Data for Dibenzo-p-dioxin (DD), 543
Dibenzofuran (DF), and Chlorinated DD/Fs: A Critical Review and Recommended Values, J. Phys. 544
Chem. Ref. Data. 37 (2008) 1997-2008. 545
546
547
548
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Table 1. Summary of the distribution coefficients (log Kd values) determined for the model compounds in the test soils.
Compound Log K
d
OECD
Log K
d
M1 Log K
d
M2 Log K
d
M3 Log K
d
M4 Log K
d
M5 Log K
d
M6 Log K
d
M7 Log
K
ow
[45]
1 o-HCH 2.440.02 2.050.02 2.040.04 2.730.29 3.190.09 2.230.01 2.360.09 2.980.03 3.8
2 |-HCH 3.150.01 3.040.17 2.700.003 3.410.20 3.960.01 2.970.05 2.950.03 3.560.11 3.78
3 -HCH 2.590.03 2.150.01 2.110.03 2.880.24 3.350.12 2.360.03 2.490.10 3.150.02 3.72
4 o-HCH 3.230.03 2.990.03 2.870.07 3.490.07 3.950.08 3.050.07 3.050.04 3.870.01 4.14
5 PCP 3.460.11 2.840.02 2.680.06 3.320.03 3.460.10 2.84 0.07 2.920.15 3.500.11 5.01
6 HCB 4.520.21 4.190.25 3.920.01 5.120.27 5.160.13 4.540.06 4.690.05 5.290.12 5.73
7 Benzo(a)anthracene 5.370.01 5.090.07 5.320.09 5.230.002 5.300.12 5.270.05 5.270.01 5.230.002 5.61
8 Phenanthrene 3.170.008 2.530.21 3.790.03 3.720.07 5.170.06 2.890.06 3.160.02 3.710.05 4.45
9 PCB 47 4.670.02 4.700.09 4.410.07 4.870.03 4.890.04 4.830.19 4.860.01 4.830.03 5.17
10 PCB 153 4.460.07 4.440.01 4.190.07 4.690.04 4.110.001 4.610.14 4.470.08 4.380.09 6.9
11 PCB 155 5.220.26 5.000.12 4.810.03 5.020.05 5.050.20 4.880.30 5.690.05 5.290.04 7.2
12 1,3,6,8-TCDF 4.650.15 5.240.07 4.770.09 5.660.08 5.400.19 4.29 4.410.03 4.600.10 5.92
13 1,3,6,8-TCDD 4.580.02 4.760.08 4.580.13 5.030.03 4.840.006 4.23 4.290.01 4.310.10 6.57
Sand % 70 85 90 50 20 50 30 10
Clay % 20 10 5 20 20 40 60 45
Composition
of the
artificial soils
Peat % 10 5 5 30 60 10 10 45
549
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-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
p
q
[
2
]
pq[1]
a-HCH
b-HCH
g-HCH
d-HCH
PCP
HCB
BaA
Phe
PCB-47
PCB-153
PCB-155
TCDF
TCDD
Sand %
Clay %
Peat %
D
B
A
C
549
Fig. 1. OPLS loading scatter plots of K
d
values for the model compounds. 550
551
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A
B
C
551
Fig. 2. Contour plots showing the variation of concentrations in leachates of -HCH (A), PCP (B) and 552
Phe (C) vs. proportions of clay and peat in the artificial soils . The R
2
values obtained from the MODDE 553
screening models were 0.80 for -HCH, 0.51 for PCP and 0.30 for Phe respectively. 554
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A
B
555
Fig. 3. Contour plots showing the variation of concentrations in leachates of 1,3,6,8-TCDD (A) and 556
1,3,6,8-TCDF (B) vs. proportions of clay and peat in the artificial soils. The R
2
values of the MODDE 557
screening models were 0.68 for 1,3,6,8-TCDD and 0.68 for 1,3,6,8-TCDF respectively. 558
559
560
561
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561
Fig. 4. Contour plots showing the variation of concentrations in leachates of HCB vs. proportions of 562
clay and peat in the artificial soils. The R
2
values of the MODDE screening model was 0.69. 563
564
565
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A
B
C
565
Fig. 5. Contour plots showing the variation of concentrations in leachates of PCB 47 (A) PCB 153 (B) 566
and PCB 155 (C) vs. proportions of clay and peat in the artificial soils. The R
2
values of the MODDE 567
screening models were 0.55 for PCB 47 and 0.36 for PCB 153 and 0.43 for PCB 155 respectively. 568
569
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3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
1
2
3
4
5
6
7
8
9
10
11
12
13
B
y =0.6578x +1.4665
R
2
=0.58
l
o
g

K
d
log K
ow
3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
1
2
3
4
5
6
7
8
9
10
11
12
13
C
y =1.4793x - 2.97163
R
2
=0.90
l
o
g

K
d
log K
ow
3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
1
2
3
4
5
6
7
8
9
10
11
12
13
A
y =1.0266x - 1.0291 (1)
R
2
=0.71
y =1.3478x - 2.4133 (2)
R
2
=0.85
l
o
g

K
d
log K
ow
569
Fig. 6. Log K
d
values for the target compounds vs. their log K
ow
values, calculated for OECD standard 570
soil (A), M4 soil (20% sand, 20% clay and 60 % peat) (B) and M6 soil (30 % sand, 60 % clay, 10% 571
peat) (C). The OECD data were fitted linearly (black curve for all data and green curve excluding 572
compounds 10 to 13) and quadratically (red curve for all data) (A). Eqns. (1) and (2) describe the linear 573
fits of all data and data excluding compounds 10 to 13, respectively (A). The target compounds were o- 574
HCH (1), |-HCH (2), -HCH (3), o-HCH (4), PCP (5), HCB (6), BaA (7), Phe (8), PCB 47 (9), PCB 575
153 (10), PCB 155 (11), 1,3,6,8-TCDF (12) and 1,3,6,8-TCDD (13). 576
577
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Highlights 577
K
d
-values were determined for 13 HOCs in batch tests with varying soil composition. 578
Log K
d
-values (ranged from 2 to 5.7) were lowest for -HCH and highest for PCB 155. 579
The clay content may influence significantly the leachability of HOCs with K
ow
> 6. 580
581