Chemosphere 144 (2016) 65e74

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

A synthesis of parameters related to the binding of neutral organic

compounds to charcoal
Sarah E. Hale a, *, Hans Peter H. Arp a, Darya Kupryianchyk a, Gerard Cornelissen a, b, c
a
Department of Environmental Engineering, Norwegian Geotechnical Institute (NGI), P.O. Box 3930, Ullevl Stadion, N-0806 Oslo, Norway
b
Department of Plant and Environmental Sciences (NMBU), Norwegian University of Life Sciences, 5003 s, Norway
c
Department of Applied Environmental Sciences (ITM), Stockholm University, 10691 Stockholm, Sweden

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Charcoal-water partitioning co-

efcients (KD values) were compiled
from the literature.

KD values were correlated with
charcoal and organic compound
properties.

Production temperature and surface
area were most strongly correlated
with KD.

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

Article history: The sorption strength of neutral organic compounds to charcoal, also called biochar was reviewed and
Received 4 May 2015 related to charcoal and compound properties. From 29 studies, 507 individual Freundlich sorption co-
Received in revised form efcients were compiled that covered the sorption strength of 107 organic contaminants. These sorption
28 July 2015
coefcients were converted into charcoal-water distribution coefcients (KD) at aqueous concentrations
Accepted 18 August 2015
Available online xxx
of 1 ng/L, 1 mg/L and 1 mg/L. Reported log KD values at 1 mg/L varied from 0.38 to 8.25 across all data.
Variation was also observed within the compound classes; pesticides, herbicides and insecticides, PAHs,
phthalates, halogenated organics, small organics, alcohols and PCBs. Five commonly reported variables;
Keywords:
Charcoal
charcoal production temperature T, surface area SA, H/C and O/C ratios and organic compound octanol
Biochar ewater partitioning coefcient, were correlated with KD values using single and multiple-parameter
Sorption linear regressions. The sorption strength of organic compounds to charcoals increased with increasing
Surface area charcoal production temperature T, charcoal SA and organic pollutant octanolewater partitioning co-
Temperature efcient and decreased with increasing charcoal O/C ratio and charcoal H/C ratio. T was found to be
Hydrophobicity correlated with SA (r2 0.66) and O/C (r2 0.50), particularly for charcoals produced from wood
Elemental composition feedstocks (r2 0.73 and 0.80, respectively). The resulting regression: log KD (0.18 0.06)
log Kow (5.74 1.40) log T (0.85 0.15) log SA (1.60 0.29) log OC (0.89 0.20)
log HC (13.20 3.69), r2 0.60, root mean squared error 0.95, n 151 was obtained for all
variables. This information can be used as an initial screening to identify charcoals for contaminated soil
and sediment remediation.
2015 Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: sarah.hale@ngi.no (S.E. Hale).

http://dx.doi.org/10.1016/j.chemosphere.2015.08.047
0045-6535/ 2015 Elsevier Ltd. All rights reserved.
66 S.E. Hale et al. / Chemosphere 144 (2016) 65e74

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2. Materials and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.1. Scope of the review article . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.2. Charcoal-water distribution coefficients (KD values) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.3. Single-parameter and multiple-parameter linear regression analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.1. Summary of previously reported charcoal properties and their inter-correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.2. Summary of previously reported charcoal-water distribution coefficients (KD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3. Single-parameter regression analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3.1. Relationship between KD and charcoal physicochemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3.2. Relationship between KD and organic pollutant KOW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.4. Multiple-parameter linear regression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.5. Biases in the single and multiple-parameter linear regressions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4. Future work and implications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

1. Introduction chemical and microbial degradation (Spokas, 2010), where half-

lives of between 8 and 4000 years have been reported for char-
Charcoal is the solid product formed during the incomplete coals (Gurwick et al., 2013), but are also responsible for the high
combustion (pyrolysis) of biomass and is also referred to as biochar. sorption strength of organic compounds to charcoal.
Interest in biochar has increased dramatically in recent years owing Sorption to soils and sediments is one of the most important
in principle to the many touted environmental benets of its use as environmental processes related to organic pollutants as it controls
a soil amendment (Lehmann, 2007). Charcoal can contribute to the their environmental mobility and bioavailability and thus their risk.
mitigation of climate change (by sequestering carbon and sup- Sorption to charcoal is expected to be similar to other condensed
pressing nitrous oxide emissions) (Rondon et al., 2007; Yanai et al., organic matters such as soot (Jonker and Koelmans, 2002), coal
2007) and specically when added to acidic soils with low pH and (Cornelissen and Gustafsson, 2005; Yang et al., 2008), kerogen
often low cation exchange capacity (CEC), it can improve the agri- (Cornelissen and Gustafsson, 2005) and lampblack (Hong and
cultural properties of these soil, as charcoal is able to increase pH Luthy, 2007) based on their similar properties. The sorption of
and cation exchange capacity (CEC) (Liang et al., 2006). In addition, organic pollutants to carbonaceous geosorbents occurs via phys-
charcaol is able to improve plant available water (Glaser et al., isorption (i.e. reversible sorption that does not involve the forma-
2002), improve mycorrhizal interactions (Warnock et al., 2007), tion of covalent bonds) on the exterior surface and in meso-, macro-
and provide nutrients that are essential to plant growth (Yamato and micropores (Jonker and Koelmans, 2002; Koelmans et al.,
et al., 2006) to soils with variable physical and biological proper- 2006) and also via pore lling (Kleineidam et al., 2002). During
ties. Charcoal production can be an effective part of agricultural these physisorption processes, intermolecular forces occur be-
waste management as the process provides a utility for agricultural tween charcoal functional groups and organic pollutants, such as
waste that would otherwise be disposed of and can also generate ionic interactions, electron-donor-acceptor (EDA) interactions (e.g.
energy. Lewis acid-base (H-bonding) and pep electron donor-acceptor
In addition to these benets, many charcoals can strongly sorb (EDA) interactions) and van der Waal interactions (i.e. between
organic pollutants (Chen and Chen, 2009; Sun et al., 2012a,b) as dipoles, induced dipoles and instantly induced dipoles (i.e. London
well as some metals (Zheng et al., 2012; Khan et al., 2013) and thus dispersion)) (Israelachvili, 1992). Previous studies have indicated
for certain types of pollutants and soils or sediments, charcoal pore lling, H-bonding interactions and a specic type of EDA
amendments could be used for contaminant remediation (Ahmad interaction known as the pep EDA interaction are the prominent
et al., 2014). Similar to activated carbon (a manmade material and mechanisms of sorption of organic compounds (Zhu and Pignatello,
produced from biomass or anthracite coal and exposed to an acti- 2005). Although physisorption processes dominate, chemisorption
vation process), charcoal could thus be added to polluted soils and process may take place and sorb organic pollutants (in their
sediments as a way to sequester pollutants, thereby hindering them charged state) to carbonaceous geosrbents. Chemisorption involves
from leaching or being taken up by organisms (Zimmerman et al., surface reactions where organic compounds participate in bond-
2005; Ghosh et al., 2011). Charcoal is a form of black carbon (as is making and bond-breaking processes (Schwarzenbach et al., 2003).
activated carbon), composed of rigid and planar stacks of highly Pore lling occurs when organic pollutants enter micropores
disordered polyaromatic hydrocarbon sheets (graphene) with within the charcoal structure and can be a descriptive factor in the
relatively few polar functionalities (ketone, ether, hydroxyl, sorption strength of such materials (Kleineidam et al., 2002). The
quinoid, carboxyl and other functional groups) on its surface extent of pore lling is highly dependent on the overlap in size of
compared to other forms of soil organic matter (e.g. humus) the organic pollutant and the pore itself. The pep EDA interaction
(Cornelissen et al., 2005). Black carbon materials (including char- has been the subject of scrutiny (Grimme, 2008) and involves in-
coal) have high carbon contents, large microporous networks and teractions between a p electron rich donor and a p electron poor
high surface areas (Allen-King et al., 2002; Zhu and Pignatello, acceptor which lead to a pep EDA stacking interaction (Zhu and
2005). These properties not only render charcoal resistant to Pignatello, 2005). In a charcoal-organic pollutant system both the
 S.E. Hale et al. / Chemosphere 144 (2016) 65e74
charcoal and the organic pollutant can act as either electron donors
or acceptors. For example, graphene units of charcoal can act as
donors or other surface functional groups such as polycarboxylated
aromatics, charged heterocyclic amines and quinones can act as
acceptors. The strength of pep EDA interactions are a function of i)
degree of condensation, ii) polycondensate sheet size and iii) extent
to which sheet edges are substituted with electron withdrawing
oxygen containing functional groups (Zhu and Pignatello, 2005;
Sun et al., 2012b). H-bond interactions can also occur in charcoal-
organic pollutant system in cases where polar organic pollutants
like phenols, anilines, nitrocompounds and mono-
ourocompounds, which contain highly electronegative N, O, and F
atoms and are able to form bonds with H donor functional groups
on the surface of charcoal (Endo et al., 2009; Sun et al., 2012b).
Isolating and quantifying sorption mechanisms for all types of
charcoals in use today is very challenging and involves many
different mechanisms that are affected by charcoal production
methods and biomass feedstocks. The rst step needed in this area
is to gain an empirical overview about the variation in sorption
behaviour amongst different types of charcoals, as well as how this
variability may be accounted for by key parameters describing the
charcoal. Thus, the state of current knowledge related to the
sorption of neutral organic compounds to charcoals is the focus of
this data synthesis. The inuence of charcoal physical characteris-
tics and organic pollutant properties on the charcoal-water distri-
bution coefcient were explored empirically through single and
multiple-parameter linear regressions. As such this synthesis
builds upon that reported by Ahmad et al. (2014) in which dis-
cussion around this began, but charcoal-water distribution co-
efcients were not reported. Such knowledge is important for the
practical use of charcoal in applications such as the remediation of
contaminated soils and sediments. This review is not intended to
provide an in depth mechanistic review of sorption mechanisms,
but a synthesis and compilation of data and relationships between
parameters.
2. Materials and methods
2.1. Scope of the review article
Peer-reviewed literature about the sorption of neutral organic
compounds to charcoal was reviewed and a comprehensive list of
charcoal-water distribution coefcients (KD values) was compiled.
Commonly reported variables related to charcoal production pro-
cess, charcoal physical properties and organic compound physico-
chemical properties were also taken from these literature. Single
and multiple-parameter linear regressions were constructed to
identify whether these commonly measured parameters could
account for the variability of sorption behaviour. Note that this
review does not focus on the sorption of ionic/ionizable compounds
or metals to charcoal, (Beesley et al., 2011), charcoals formed from
hydrothermal carbonization (i.e., hydrochars (Berge et al., 2011)) or
the effects of other competing processes such as bi/multi-solute
systems and the presence of soil (and thus pore blocking and
sorption attenuation (Kwon and Pignatello, 2005)).
2.2. Charcoal-water distribution coefcients (KD values)
Twenty eight literature studies containing data for the sorption
of any neutral organic compound to any charcoal were identied
and in total 507 individual KD values (James et al., 2005;
Bornemann et al., 2007; Wang and Xing, 2007; Chen et al., 2008;
Xu et al., 2008; Chen and Chen, 2009; Loganathan et al., 2009;
Wang et al., 2009; Kasozi et al., 2010; Zheng et al., 2010; Chen
and Huang, 2011; Hale et al., 2011; Kong et al., 2011; Lian et al.,
67
2011; Sun et al., 2011; Ahmad et al., 2012; Chen et al., 2012;
Graber et al., 2012; Sun et al., 2012b; Gomez-Eyles et al., 2013; Li
et al., 2013; Qiu et al., 2013; Sun et al., 2013; Wang et al., 2013b; Xie
et al., 2013; Zhang et al., 2013; Zhao et al., 2013; Xiao et al., 2014)
were used in this review. In the majority of cases the reported data
was in the form of Freundlich sorption isotherms in which
Freundlich sorption coefcients (KFr (mg/kg) (mg/L)n) and isotherm
nonlinearity were reported:
n
Ccharcoal KFr CW
where Ccharcoal (mg/kg) is the concentration of pollutants on the
charcoal at equilibrium, n () is the Freundlich exponent and
CW (mg/L) is the concentration of pollutants in the water phase at
equilibrium. In order to allow a comparison between reported data
and to remove the dependence of sorption on the nonlinearity of
the isotherms, average Freundlich sorption coefcients were con-
verted to charcoal-water distribution coefcients (KD) by calcu-
lating them from the reported sorption isotherms at three
particular values of CW (where X 1 ng/L, 1 mg/L and 1 mg/L):
Ccharcoal at CW X
KD at CW X ;
CW X
In the majority of cases experiments were carried out at the
mg/L concentration range and therefore we chose one concen-
tration that was higher and one that was lower to investigate
whether relationships were applicable over this wide concen-
tration range. A complete list of all KD values at 1 mg/L, 1 mg/L and
1 ng/L is presented in Table S1 of the Supplementary material
(SM). Data is presented by referring to calculated KD values at
these concentrations.
Four charcoal parameters (charcoal production temperature, SA,
O/C, H/C) and one organic compound parameter (the octanole-
water partitioning coefcient, KOW) were chosen for correlation
analysis with KD values. These parameters were selected as i) there
are mechanistic links, albeit indirect, between these parameters
and KD, ii) these parameters are among those most often reported
in the literature, iii) they are also most commonly used in subse-
quent data interpretation of charcoal KD values and, iv) are those
that can be controlled in charcoal production in order to produce a
desirable product. As sorption of neutral organic compounds is
controlled by the surface functionality of the charcoal, H, C and O
content is important, and also by the pores available for sorption,
SA is also a relevant parameter. Temperature of charcoal production
is an underlying factor able to control these variables. In order to
avoid data bias and ensure full coverage and environmental rele-
vance all data was used in regressions (thus wide temperature
ranges, SA and elemental ratios were assured). For surface area
measurements, studies using N2 as the probe gas were considered
as there was only one study that reported CO2 surface area mea-
surements (Sun et al., 2013). This is noteworthy, as limited access of
N2 to pores at the experimental temperature of 77 K means that the
CO2 surface area measured at room temperature is likely more
representative of the charcoal surface area that organic pollutants
can sorb to (Pignatello and Xing, 1996).
2.3. Single-parameter and multiple-parameter linear regression
analysis
The KD values were grouped into the feedstocks; wood, grass
and crop waste (including grasses, cellulose, nutshells and other
crop refuse) and other waste (including animal waste, sewage
sludge and car tyres). Then for each feedstock, as well as for all
feedstocks, a single-parameter regression analysis was carried out
68 S.E. Hale et al. / Chemosphere 144 (2016) 65e74
in order to identify the degree to which individual property pa-
rameters correlated with KD values. Correlations were carried out
on log transformed data as explained in the SM on page S2. In
addition, the data was checked to see if it was better described as
normally distributed or log-normally distributed data using Pear-
son's moment coefcient of skewness, g (see SM).
Multiple-parameter regression analysis was also carried out to
identify the degree to which all of the parameters could collectively
be used to predict KD. In addition, the inter-correlation between
parameters was investigated, the data was checked for skewness
and the multiple-parameter linear regressions were tested using a
validation set comprising 75% of the data set that was randomly
selected. Regression analysis was conducted in Microsoft Excel
2013 using the Analysis ToolPak Add-on. Further details related to
all of the statistical methods and regressions are given in the sup-
plementary material. The discussion below is primarily focused on
log KD values normalised to a water concentration of 1 mg/L as the
majority of studies were carried out in this concentration range. All
results for log KD values normalised to 1 ng/L and 1 mg/L are given
in the SM.
3. Results and discussion
3.1. Summary of previously reported charcoal properties and their
inter-correlation
An overview of compiled charcoal properties and compound
properties specic to the KD values is presented in Table 1. The
reported H/C data ranged over three orders of magnitude (from
0.001 to 1.26), O/C data over two orders of magnitude (from 0.02 to
1.0), SA over three orders of magnitude (from 0.25 to 669 m2/g),
charcoal production temperature T from 373 to 1123 K and organic
compound KOW values from 1.0 to 4.1. The distribution of these
variables was investigated in order to ascertain if the reported data
distributed normally or log-normally (see SM). H/C and O/C ratios
were distributed more log-normally than normally, though SA and
T were distributed more normally. Log values were subsequently
used for all parameters based on fundamental thermodynamic
theory (Goss and Schwarzenbach, 2001), as explained in the SM.
With the exception of H/C ratio, all parameters exhibited substan-
tial skewing (see the supplementary material). This skewing is due
to more data being available for some of the charcoals than others.
As is evident from Table S2, the data for the variables cluster around
a median value for each compound, and the inter quartile ranges
are much narrower for particular compounds than the total ranges
within a compound class.
A regression analysis was also carried out to investigate if any of
the charcoal parameters were correlated with each other, the re-
sults of which are presented in Table S3aed in the SM. The pa-
rameters exhibiting the most correlation were charcoal production
temperature and SA (coefcient of determination, r2 0.66) and
charcoal production temperature and O/C ratio (r2 0.50), partic-
ularly for charcoals from wood feedstocks (r2 0.73 and 0.80,
Table 1
Summary of previously reported charcoal and organic compound properties.
Statistic HC ratio ()
Average 0.054
Median 0.048
25th percentile 0.033
75th percentile 0.097
Maximum 1.26
Minimum 0.001
Number of data points 187
respectively). The parameters SA and O/C were correlated with a
coefcient of determination of 0.31. The coefcient of determina-
tion for other combinations (each of the ve parameters were
checked for correlation with all other parameters) of charcoal pa-
rameters were much lower (r2 0.23 or less).
3.2. Summary of previously reported charcoal-water distribution
coefcients (KD)
Tables S1 and S2 in the supplementary material provide a
summary of the average KD values (thus considering the standard
deviation across studies), normalised to a water phase concentra-
tion of 1 mg/L for each organic compound where literature existed.
Reported KD values varied over eight orders of magnitude, from
0.38 (MTBE on maize charcoal) to 8.25 (PCB 149 123 on acai pit
charcoal), depending on the compound and the charcoal. The range
of average log KD values for different compound classes was from
3.40 to 5.69 for pesticides, herbicides and insecticides, from 5.26 to
7.16 for PAHs, from 4.47 to 5.41 for phthalates, from 4.49 to 6.38 for
halogenated organics, from 3.14 to 4.18 for small organics, from 3.03
to 5.63 for alcohols and from 4.43 to 7.27 for PCBs. The compounds
for which the greatest amount of data points have been measured
were phenanthrene (range of reported values 2.02e7.71, n 42),
and naphthalene (range of reported values 2.01e7.87, n 29). The
range in this PAH data indicates that sorption to charcoal can vary
by up to 5 orders of magnitude, though tends to cluster around a
median as in the case of phenanthrene (median: 5.82, interquartile
range: 5.23e6.21).
3.3. Single-parameter regression analysis
Eqs. (1)e(5) in Table 2 show the single-parameter regressions
for log KD values normalised to 1 mg/L for the complete data set
versus; log charcoal production temperature (Eq. (1)), log charcoal
SA (Eq. (2)), log charcoal H/C (Eq. (3)), log charcoal O/C (Eq. (4)) and
log organic compound KOW (Eq. (5)). Table S4a and b show the
resulting single-parameter regressions for KD values calculated at
1 ng/L and 1 mg/L. Coefcients of determination for Eqs. (1)e(5)
ranged from 0.05 for log O/C to 0.32e0.34 for log SA and log T.
Fig. 1 shows the correlations of charcoal log KD with production
temperature T (n 349), charcoal SA (n 477), charcoal H/C ratio
(n 187), charcoal O/C ratio (n 184) and organic pollutant
octanolewater partitioning coefcient (n 507), plotted according
to feedstock materials (wood, grass and crop waste and other
waste). Fig. S1 shows the corresponding data without such a
classication.
3.3.1. Relationship between KD and charcoal physicochemical
properties
Charcoal production temperature and surface area were the two
variables that showed the strongest correlation with log KD,
although r2 values were low (log KD 7.93 0.59
log T 17.37 1.70, r2 0.34, Eq. (1), Table 2 and
OC ratio () SA (m2/g) T (K) log Kow
0.23 111 762 4.1
0.26 164 873 3.9
0.14 52 673 3.4
0.51 464 873 4.6
1.00 669 1123 8.6
0.02 0.250 373 1.0
184 472 350 507
 S.E. Hale et al. / Chemosphere 144 (2016) 65e74 69

Table 2
Summary of statistical analysis for the single-parameter linear regression (Eqs. (1)e(5)) and the multiple-parameter linear regression (Eqs. (6)e(9)) for Log KD normalized to a
water concentration of 1 mg/L.

Feedstock Equation r2 rmse n

All log KD (7.93 0.59) log T (17.37 1.70) (1) 0.34 1.10 350
All log KD (0.91 0.06) log SA (3.67 0.13) (2) 0.32 0.97 472
All log KD (1.85 0.22) log HC (2.62 0.29) (3) 0.28 1.29 187
All log KD (0.78 0.26) log OC (4.47 0.20) (4) 0.05 1.46 184
All log KD (0.23 0.03) log Kow (4.34 0.14) (5) 0.13 1.11 507
All log KD (0.18 0.06) log Kow (5.74 1.40) 0.60 0.95 151
log T (0.85 0.15) log SA (1.60 0.29)
log OC (0.89 0.20) log HC (13.20 3.69)(6)
Grass and crop waste log KD (0.06 0.08) log Kow (5.91 1.76) 0.67 0.81 65
log T (0.09 0.19) log SA (0.49 0.44)
log OC (1.37 0.26) log HC (13.44 4.67)(7)
Wood log KD (0.04 0.10) log Kow (11.70 2.79) 0.81 0.78 55
log T (1.22 0.25) log SA (3.14 0.67)
log OC (0.01 0.45) log HC (28.10 7.05)(8)
Other feedstocks log KD (0.70 0.21) log Kow (5.83 4.05) 0.64 0.93 25
log T (1.07 0.77) log SA (1.00 0.61)
log OC (3.54 1.12) log HC (13.29 10.07) (9)

rmse root mean squared error.

log KD 0.91 0.06 log SA 3.67 0.13, r2 0.32, Eq. (2), Table 2).
On a statistical level, this is partly accounted for by the good degree
of correlation between log SA and log T as discussed below.
Charcoal production temperature has been previously identied
as a key variable affecting the resulting charcoal's physicochemical
properties and therefore in turn the sorption of organic compounds
(Chen et al., 2012; Rutherford et al., 2012; Xiao et al., 2014). During
pyrolysis, a series of complex reactions take place that convert
aliphatic components contained in the charcoal precursor biomass
to aromatic components in the resultant charcoal. The reactions
proceed via the: i) degradation of hemicellulose and partial
destruction of alkyl moieties (220e315  C), ii) degradation of cel-
lulose (315e400  C) and iii) chain fragmentation of lignin to release
monomeric phenol units (>400  C) (Chen et al., 2012; Uchimiya
et al., 2013; Wang et al., 2013a; Mimmo et al., 2014). As the amor-
phous aromatic components within charcoal begin to arrange into
turboclastic crystallites, the SA of the charcoal increases dramatically
(Chun et al., 2004; Chen et al., 2012; Wang et al., 2013a). Several
authors have noted a peak in SA at around a production temperature
of 600  C due to a structural ordering and micropore coalescence
around this temperature (Mimmo et al., 2014) or due to a restruc-
turing and onset of an ash melting process (Brown et al., 2006).
Corresponding to this, a pore selective sorption mechanism (based
upon the size of the charcoal pores and the organic compounds
themselves) often occurs for charcoals made at higher temperatures
(Chen et al., 2008; Chen and Chen, 2009) and a polarity selective
mechanism (based upon the polarity of charcoal surface functional
groups and organic compounds that are sorbing to the charcoal) at
lower temperatures.
The previously reported literature contained data for charcoals
produced between 100 and 850  C, thus providing a diverse data
set and including materials dominated by both aliphatic and aro-
matic carbon (Sun et al., 2012b). Whilst the inclusion of charcoals
produced at temperatures as low as 100  C (5 data points) in the
complete data set can be questioned, they were included for
completeness and to avoid bias. Fig. 2a shows the correlation of log
KD with charcoal production temperature for seven selected studies
in which the charcoals were produced at minimally four different
temperatures from 100 to 800  C (Chen et al., 2008; Chen and Chen,
2009; Chen and Yuan, 2011; Sun et al., 2011, 2012b; Chen et al.,
2012; Xiao et al., 2014). Fig. 2b shows the correlation of log KD
and SA for six of these same studies where SA data was reported
(Chen et al., 2008; Chen and Chen, 2009; Chen and Yuan, 2011;
Chen et al., 2012; Sun et al., 2012b; Xiao et al., 2014). The result-
ing single-parameter linear regression for this selected data set was
Log KD 9.46 log T- 21.68 and the r2 value was 0.53, indicating a
stronger correlation for these selected studies than within the
whole data set.
For two of these studies (Chen et al., 2008, 2012) a continuous
increase in KD with production temperature over the complete
temperature range (up to 700  C) was observed. For the remaining
four studies (Chen and Chen, 2009; Sun et al., 2011, 2012b; Xiao
et al., 2014) an increase in KD values was seen up to temperatures
of around 400e600  C, where they decreased, before increasing
again. These trends are mirrored by the correlation of KD with SA
(Chen and Chen, 2009; Sun et al., 2012b; Xiao et al., 2014). Several
reasons were given for the increase, decrease and further increase
in KD values by the authors of the studies, related both to the
charcoal SA itself and to the properties of the organic compound.
For example, the adsorption of phthalates to charcoals produced
from grass and wood (Sun et al., 2012b) was dependant on the size
of the phthalates which showed variable increases in adsorption
relative to SA. The sorption strength of naphthalene and 1-naphthol
was dependent on the amount of available sorption sites which was
not only affected by the absolute SA, but also by the overlap be-
tween the molecular geometry of the organic pollutants and the
sorption sites (Chen and Chen, 2009).
Charcoal elemental composition is also directly inuenced by
charcoal feedstock and production temperature as it is related to
the reactions that take place as the biomass is converted to
charcoal. As pyrolysis temperature and time of heating increase,
the amount of C increases, the amounts of H and O decrease and
this leads to lower H/C and O/C ratios (Lehmann and Joseph, 2009;
Xiao et al., 2014). This inter-relationship was observed in our
study, with logelog correlation r2 values between T and H/C and
O/C being 0.23 and 0.31, respectively. Within the data set
compiled here, the elemental H/C ratio was able to describe log KD
to a greater extent than the elemental O/C ratio (r2 0.28 and
r2 0.05, respectively); indicating that the loss of H from the
charcoal can be ascribed to a greater change in KD and is thus a
better (though still weak), indicator of increasing sorption ca-
pacity than the loss of O.
3.3.2. Relationship between KD and organic pollutant KOW
As well as those of the charcoal, the properties of the organic
pollutants (e.g. molecular weight and size, hydrophobicity,
70 S.E. Hale et al. / Chemosphere 144 (2016) 65e74

Fig. 1. The correlation of log KD vs. a) Log SA, b) Log T, c) Log H/C, d) Log O/C and e) log organic compound KOW for the data set split according to biomass feedstock (wood ( ), grass
and crop waste ( ) and other waste ( )).

polarity) can also affect the strength of sorption. The relationship
between Log Kow and Log KD is given in Eq. (5) in Table 2
(log KD 0.23 0.03 log Kow 4.34 0.14, r2 0.13). The corre-
lation with log Kow was not as good as with log SA and log T, which
is indicative that the SA and T inuence the charcoal KD more than
the hydrophobicity of the contaminant itself. While it can be
questioned how applicable a relationship with KOW is for some of
these compounds, KOW is an easily accessible parameter and pro-
vides a commonly used basis for correlation with other partitioning
coefcients. The molecular volume of a compound would also
provide useful information with regards to binding to charcoal,
however this parameter is rarely reported in sorption studies and
also suffers shortcomings. Whilst molecular volume provides
information about size it does not provide information about
spatial arrangement which is critical when pore lling takes place.
Of the literature surveyed, only three studies contained data for
the sorption of three or more compounds with varying hydro-
phobicity to the same charcoal (Chen et al., 2008; Lian et al., 2011;
Sun et al., 2012b) and these are shown in Fig. 2c. The sorption of
diethyl phthalate, dibutyl phthalate and butyl benzyl phthalate to
grass and wood charcoals was correlated with compound hydro-
phobicity, but was also inuenced by charcoal physicochemical
properties (Sun et al., 2012b). According to these authors, the
strongest sorption combination was observed for dibutyl phthalate
(log Kow 4.8) to charcoals produced at 500  C that had amorphous
carbon properties (and thus a possible additional absorptive
 S.E. Hale et al. / Chemosphere 144 (2016) 65e74 71

Fig. 2. The correlation of log KD with a) log T for selected studies which contain sorption data for a charcoal produced at at least four temperatures, b) log SA for selected studies that
contain sorption data for a charcoal produced from the same feedstock, but at different temperatures (and therefore having variable SA) and c) log organic compound KOW values for
selected studies that compare the sorption of at least three compounds to the same charcoal.

Fig. 3. The correlation between log KD measured and log KD predicted using the correlation coefcients in Eq. (6) in Table 2 for KD values normalised to water concentrations of
1 mg/L, 1 mg/L and 1 ng/L. MLR Multiple Linear relationship (Table 2 Eqs. (6)e(9)).

mechanism), rather than for charcoals produced at the highest
production temperatures.
In order to achieve maximum sorption, the molecular di-
mensions of the organic pollutant must match those of the pores in
the charcoal. The pollutants themselves may have restrictive
shapes and therefore contact with the charcoal surface may be
limited due to steric hindrance (Endo et al., 2009) and the distance
the pollutant can penetrate into a given pore be reduced (Pignatello
and Xing, 1996). Size exclusion becomes more severe as sorption
volume becomes dominated by small micropores (Lattao et al.,
2014) and thus larger compounds are not able to access sorption
sites, as many pollutants have sizes in the same order of magnitude
as charcoal nanopores (5e10 nm). As compound hydrophobicity
generally increases with increasing compound molecular diameter,
for a charcoal dominated by small micropores the sorption of larger
compounds would theoretically be impaired (Amstaetter et al.,
2012; Lattao et al., 2014). However, for the literature surveyed
here, pore size distribution of the charcoals was rarely reported.
3.4. Multiple-parameter linear regression
Multiple-parameter linear regressions based on all ve param-
eters were determined for the complete data set and for the data
set divided by feedstock (Eqs. (6)e(9), Table 2 for log KD at 1 mg/L
and in Table S5aed for KD at 1 ng/L and 1 mg/L). Note that this type
of multiple-parameter linear regression can only be carried out for
isotherms in which all parameter data are available. The resulting
overall regression equation for the complete data set was;
log KD 0.18 0.06 log Kow 5.74 1.40 log T 0.85 0.15
log SA 1.60 0.29 log OC 0.89 0.20 log HC 13.20 3.69
(Eq. (6), Table 2), with substantially improved coefcients of
determination compared to the single-parameter linear free energy
relationships (r2 0.60). It should be emphasized that this equation
is not meant to describe all of the mechanistic interactions occur-
ring during sorption, but rather the best possible way of estimating
this charcoal KD from commonly available data of relevance to
sorption, and therefore provides a tool that can be used for
screening purposes. Fig. 3 shows the correlation between measured
log KD values and modelled log KD values using the coefcients in
Eq. (6) and plotted according to feedstock. The multiple linear
regression ts most of the data within a factor 30 (1.5 orders of
magnitude). For KD at 1 mg/L, 9% of data lie outside this factor (3% for
KD at 1 mg/L and 30% for KD at 1 ng/L). The present data were within
a similar variability range as that previously reported for contam-
inated sediments (Arp et al., 2009). The data points that lie furthest
from the 1:1 line are mainly charcoals produced at temperatures
72 S.E. Hale et al. / Chemosphere 144 (2016) 65e74

below 350  C, as marked in Fig. 3, which is around the temperature
where amorphous aromatic components within charcoal begin to
arrange into turboclastic crystallites. Below 350  C charcoals may
contain complex amorphous subdomains that exhibit decreased or
increased sorption compared to carbonaceous fractions in the
charcoal, depending on their structure (e.g. humic materials sorb
less than charcoals but tars can sorb more strongly than charcoal)
(Arp et al., 2009). It is also interesting to note that within the data
there is a greater difference in KD values for the same compound
produced at different temperatures than for different compounds
produced at the same temperature. For example the log KD for
naphthalene for orange peel biochar produced at 150  C was 2.1
compared to 7.3 for the same biochar and compound but with a
production temperature of 700  C. However the log KD value for 1-
naphthol for the same biochar produced at 150  C was 2.1 and was
6.7 for the same biochar produced at 700  C.
The correlation statistics, in terms of r2 and rmse, differ from one
another depending on the concentration the KD values are
normalized to, be it 1 mg/L (r2 0.46, rmse 0.71), 1 mg/L
(r2 0.60, rmse 0.95) or 1 ng/L (r2 0.56, rmse 1.55). The best
correlation, as quantied by the r2, is for 1 mg/L normalized data,
and the best model performance for predicting KD values, as
quantied by rmse, is for 1 mg/L normalized data. A likely expla-
nation for the best r2 at 1 mg/L is that the majority of experiments
were carried out in the mg/L water concentration range, and thus
any errors in the reported Freundlich n values will lead to positive
or negative biases in log KD values. As evident from Fig. 3, the
overall scatter of KD values is the smallest at 1 mg/L, which accounts
for having the best rmse despite potential extrapolation biases.
Splitting the dataset up into different feedstocks (Eqs. (7)e(9),
Table 2) improved the correlations compared to considering all
feedstocks together (Eq. (6); r2 0.60). The correlation for wood
was the strongest (r2 0.81), followed by grasses and crop waste
(r2 0.67), and then other feedstocks (r2 0.64). It is likely that the
relative homogeneity of the wood charcoals (when compared to the
other freedstocks) lead to the improved correlations. The other
feedstock category contained a broad mixture of feedstocks sug-
gesting the need to further separate charcoal feedstock in order to
improve the prediction of sorption strength.
3.5. Biases in the single and multiple-parameter linear regressions
As mentioned above, the shortcoming of these multiple-parameter
linear regressions are that some of the assumed independent variables
are not completely independent of each other, such as SA and T. In
addition, the calibration data set showed non-normality of all pa-
rameters except H/C, likely because some charcoals and compounds
were represented within the data set more than others. Thus, despite
the large data set, these biases will have some impact on the re-
gressions themselves, regardless of the mechanistic basis. As dis-
cussed in the SM, the inter-correlation between SA, T and OC, indicates
that not all of these parameters may be needed to make screening level
estimations of charcoal log KD values. In Table 3, multiple linear re-
gressions excluding either just log SA or both log SA and log O/C are
presented. As can be seen, the quality of the ts (as indicated by the
coefcients of determination) are not as good as when considering all
input parameters in the majority of cases, however the differences are
quite small. For example for wood charcoals removing O/C ratio from
the statistical analysis does not change the quality of t, thus sug-
gesting in this case a knowledge of T and H/C allows a prediction about
sorption strength to be made.
Multiple-parameter linear regressions for the complete data set
were compared with those calculated based on 75% of the data set
(selected randomly) in order to tests the agreement between the

Table 3
Multiple-parameter linear regressions after considering multicollinearity (Eqs. (10)e(17)) as well as the multiple-parameter linear regressions using all variables (Eqs. (6)e(9)
from Table 2).

Feedstock Equation: log KD at water concentration of 1 mg/L r2 rmse n

All log KD (0.18 0.06) log Kow (5.74 1.40) 0.60 0.95 151
log T (0.85 0.15) log SA (1.60 0.29)
log OC (0.89 0.20) log HC (13.20 3.69) (6)
All log KD (0.17 0.06) log Kow (9.66 1.06) 0.53 1.01 177
log T (1.44 0.26) log OC (1.05 0.20)
log HC (23.35 2.81) (10)
All log KD (0.19 0.06) log Kow (5.87 0.83) 0.47 1.09 182
log T (1.11 0.21) log HC (13.66 2.24)(11a)
Grass and crop waste log KD (0.06 0.08) log Kow (5.91 1.76) 0.67 0.81 65
log T (0.09 0.19) log SA (0.49 0.44)
log OC (1.37 0.26) log HC (13.44 4.67) (7)
Grass and crop waste log KD (0.03 0.08) log Kow (6.26 1.57) 0.65 0.80 75
log T (0.41 0.41) log OC (1.44 0.24)
log HC (14.30 4.17) (12)
Grass and crop waste log KD (0.02 0.08) log Kow (4.99 0.94) 0.65 0.80 76
log T (1.54 0.23) log HC (11.03 2.63) (13)
Wood log KD (0.04 0.10) log Kow (11.70 2.79) 0.81 0.78 55
log T (1.22 0.25) log SA (3.14 0.67)
log OC (0.01 0.45) log HC (28.10 7.05) (8)
Wood log KD (0.09 0.11) log Kow (18.35 2.50) 0.69 0.95 66
log T (2.46 0.75) log OC (0.07 0.42)
log HC (44.95 6.47) (14)
Wood log KD (0.07 0.11) log Kow (11.50 1.44) 0.66 1.00 71
log T (0.04 0.44) log HC (27.06 3.55) (15)
Other feedstocks log KD (0.70 0.21) log Kow (5.83 4.05) 0.64 0.93 25
log T (1.07 0.77) log SA (1.00 0.61)
log OC (3.54 1.12) log HC (13.29 10.07) (9)
Other feedstocks log KD (0.61 0.18) log Kow (1.04 2.61) 0.63 0.95 30
log T (1.44 0.43) log OC (3.15 1.00)
log HC (2.48 6.37) (16)
Other feedstocks log KD (0.80 0.17) log Kow (0.17 1.89) 0.42 1.13 35
log T (1.14 0.92) log HC (0.06 4.81) (17)
 S.E. Hale et al. / Chemosphere 144 (2016) 65e74
regressions. Table S6 in the supplementary material shows the
regressions and indicates that there was no signicant difference in
any of the slope or intercept values. Further, there was no sub-
stantial change to the predictive performance of the models,
though a slight improvement of performance was observed for the
validation set (i.e. slightly smaller rmse and fewer percentages of
outliers more than a 1.5 log units).
4. Future work and implications
While the most often reported charcoal and compound vari-
ables were taken into consideration in this work, additional factors
possibly affecting the sorption of organic compounds to charcoals
include charring duration, pore size distribution, sorption attenu-
ation and the fraction of ash contained in the charcoal. While
charring duration is often reported in the literature, uncertainty
exists surrounding whether the desired charring temperature has
been maintained throughout the reactor during the complete py-
rolysis period. Charcoal pore size distribution is important in
determining the overlap in the molecular dimensions of the organic
pollutant and the charcoal pores and possibly quantifying pore size
exclusion effects, but unfortunately this parameter is rarely re-
ported and only one paper quantitatively investigated this theme
(Lattao et al., 2014). Sorption attenuation is a well-known phe-
nomenon in activated carbon research, where pores can be blocked
by soil organic matter following environmental exposure to soils or
sediments and has been shown that a similar phenomenon occurs
for charcoals, from a very strong effect (Teixido et al., 2013), to a
limited effect (Hale et al., 2011). Thus far, the ash fraction of char-
coal has not been considered with regard to its effect on adsorption
since the materials used in these literature studies were mostly
relatively pure plant residues. The inorganic ash fraction probably
provides only a small contribution to the total amount of sorption
sites for the studied organic compounds.
When selecting a charcoal with the purpose of sequestering pol-
lutants as part of a soil remediation strategy there are essentially two
parameters that can be manipulated: the type of feedstock biomass
and the charcoal pyrolysis temperature. Here we investigated the
effect of pyrolysis temperature more thoroughly than the effect of
feedstock, indicating an area for further research. It was shown that a
rst indication of the sorption afnity of the charcoal, often correct
within a factor of 30, can be obtain based on the charcoal production
temperature, resulting charcoal H/C ratio and octanolewater parti-
tioning coefcient of the organic compound. When better assess-
ment is needed and data are available, SA and O/C ratio can be added
for a slight further improvement in predictive power.
Acknowledgements
This work was primarily funded by a FriPro stipend from the
Research Council of Norway (grant number 217918). H.P.H. Arp was
supported by the NGI stipend fund (12116) and the Research
Council of Norway Leiv Eriksson fund (225077). Darya Kupryian-
chyk was mainly funded by the internal NGI postdoc scheme.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.chemosphere.2015.08.047.
73
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