Journal of Cleaner Production 255 (2020) 120263

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Review

Applications of carbonaceous adsorbents in the remediation of

polycyclic aromatic hydrocarbon-contaminated sediments: A review
Fang Li a, b, Jianjun Chen c, Xin Hu d, Feng He e, Eban Bean b, Daniel C.W. Tsang f,
Yong Sik Ok g, Bin Gao b, *
a
College of Economics and Management, Shandong Agricultural University, Tai’an, 271018, China
b
Department of Agricultural and Biological Engineering, University of Florida, Gainesville, FL, USA
c
Mid-Florida Research & Education Center, University of Florida, Apopka, FL, 32703, USA
d
Center of Material Analysis, Nanjing University, Nanjing, 210093, PR China
e
College of Environment, Zhejiang University of Technology, Hangzhou, 310014, China
f
Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hong Kong, China
g
Korea Biochar Research Centre & Division of Environmental Science and Ecological Engineering, Korea University, Seoul, South Korea

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

Article history: Polycyclic aromatic hydrocarbons (PAHs) are widely accumulated in sediments and thus impose great
Received 1 October 2019 risks to the ecosystem and public health. There is increasing effort on the development of technologies
Received in revised form for remediation of PAH-contaminated sediments. Adsorption is one of the most promising remediation
13 January 2020
technologies is to PAH-contaminated sediments. Carbonaceous adsorbents (CAs) have been considered
Accepted 24 January 2020
Available online 25 January 2020
desirable for adsorbing PAHs due to their cost-effective and eco-friendly nature. The effectiveness of CAs
in removal of PAHs, however, can be greatly affected by adsorbent properties, sediment characteristics,
Handling editor: Prof. Jiri Jaromir Kleme
s and environmental conditions. An accumulating evidence largely from laboratory experiments has
shown that CAs can be used for immobilization and decontamination of PAHs in sediments, however,
Keywords: their full potential has not been demonstrated, particularly with respect to field applications. The present
Biochar review aims to summarize the current progress on CA physical and chemical properties, and mechanisms
Activated carbon of the stabilization of PAHs in sediments as well as key factors controlling field applications. In addition,
Carbon nanoparticles potential environmental effects associated with CA-mediated PAH stabilization is also discussed. Among
Sediment remediation
various CAs, activated carbon and biochar are the most commonly used adsorbents for sediment
Organic pollutants
remediation and thus are the focuses of this review.
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Adsorption mechanisms of PAHs on CAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Effects of carbon properties on sediment remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Morphological characteristics of CAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Chemical characteristics of CAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. Carbonaceous adsorbent dosage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Effects of PAH properties on sediment remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5. Effects of environmental conditions on sediment remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.1. Initial PAH concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.2. pH and ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.3. Natural organic matters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.4. Contact time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.5. Mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

* Corresponding author.
E-mail address: bg55@ufl.edu (B. Gao).

https://doi.org/10.1016/j.jclepro.2020.120263
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263

6. Potential environmental impacts and the recovery of CA amended . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

6.1. Potential environmental impacts of CAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6.2. CA recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
7. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1. Introduction focuses on the applications of CAs as an adsorbent to immobilize

PAHs and to reduce their impacts on sediments. In geology, soil can
Polycyclic aromatic hydrocarbons (PAHs) are a group of ubiq- be considered as a collection of various sediments, generated from
uitous, highly toxic and persistent pollutants that are comprised of parent rock through the interactions of physical, chemical, and
at least two linear, angular or cluster fused aromatic rings. PAHs are biological weathering processes and transported by the natural
formed from either natural or manmade combustion sources and forces.
ultimately sink in the soils and sediments, which pose a serious Since 1900, there have been many studies on the applications of
threat to both human health and the environment because of their CAs to water and sediments/soils for PAH sorption/remediation.
well-recognized carcinogenic, teratogenetic, and genotoxic char- Fig. 2 shows an increasing trend in the investigation of PAH
acteristics (Boffetta et al., 1997; Li et al., 2017). PAH contamination remediation by CAs (data from the Web of Science database). Until
in sediments can be abatable by physical, chemical, thermal and now, a number of papers have examined PAH remediation in sed-
biological technologies, traditionally including in situ cappings, iments by the sorption method, particularly at the laboratory scale
incineration, thermal conduction, solvent extraction/soil washing, (Maletic et al., 2019; Reis et al., 2007; Samuelsson et al., 2015). Most
chemical oxidation, bioaugmentation, biostimulation, phytor- of them are concentrating on the adsorptive removal of PAHs from
emediation, composting/biopiles, and bioreactors (Kuppusamy sediments, conducted in laboratory under ideal conditions with the
et al., 2017). These methods are largely focused on the removal of participation of aqueous solutions (Dabrowski et al., 2005;
PAHs, which either are rather costly and difficult to realize in situ Lamichhane et al., 2016; Smol and Włodarczyk-Makuła, 2016).
remediation or require a long remediation cycle. Another approach Choi et al. built a decision-support framework to assess the effec-
is to reduce the bioavailability of PAHs, minimizing their effects on tiveness of AC in sediment remediation with considerations of the
human health and the environment. The sorption method is following factors: site-specific kinetic coefficients, AC dosage and
considered to be an economical and environmental-friendly tech- particle size, sediment and AC sorption parameters, and pore-water
nique to reduce the bioavailability of PAHs (Funada et al., 2018; Yin velocity (Choi et al., 2016a). The importance of the sorption process
et al., 2019). has been highlighted in several studies of the application of AC in
PAHs are released to the atmosphere and enter into the water, the remediation of PAH-contaminated sediments (Choi et al.,
soil, or sediment through wet and dry deposition processes 2016b; Ghosh et al., 2011; Lin et al., 2015; Thompson et al., 2016).
controlled by precipitation, turbulence, gravity and other factors Several reviews have paid attention to the remediation of PAHs
(Bandowe et al., 2018; Dat and Chang, 2017; Zhang et al., 2019). in sediments (Gan et al., 2009; Kuppusamy et al., 2017; Lau et al.,
PAHs in soils or sediments tend to be sorbed on the particles. In 2014; Maletic et al., 2019). However, only a few have attempted
1992, Weissenfels demonstrated that PAHs are tightly adsorbed to comprehensively evaluate the mechanisms and the controlling
onto soil organic matter to form persistent micropollutants, due to factors of the remediation of PAH-contaminated sediments by CAs,
their highly hydrophobic feature (Weissenfels et al., 1992). Such and determine the connections between laboratory test results and
adsorbed PAHs are generally non-bioavailable and non- filed engineering applications. Many laboratory studies have been
biodegradable (Weissenfels et al., 1992). In 1995, Wild and Jones published in this field, while the urgent need for sediment reme-
presented that soil is the ultimate sink of PAHs, with more than 90% diation prompts demands in summarizing efficient methods for
of the UK environmental PAH burden present in soils, while about filed applications. The overarching goal of this review, therefore, is
5.3% is associated with freshwater sediment (Wild and Jones, 1995). to emphasize the current state of the knowledge on how the
The sources, fluxes, and sinks of PAHs and their effects on flora, influencing factors act on the effectiveness of the treatment, to
fauna, and environment are summarized in Fig. 1. point out the directions for possible future investigations by opti-
Due to their large specific surface area (SSA), rich porous mization the key factors controlling or hindering the applications of
structure, and high adsorption capacity, carbonaceous adsorbents CAs in the remediation of PAHs in sediments.
(CAs) have been widely used in organic pollutant sorption (Zhang
et al., 2017). A variety of CAs such as activated carbon (AC), bio-
char, carbon nanotube, and their derivatives have shown good ef- 2. Adsorption mechanisms of PAHs on CAs
fects in laboratory experiments. Among them, AC and biochar are
the most commonly used CAs in sediment remediation due to the For a long time, carbon-based adsorbents (e.g., black carbon, AC,
dual consideration of environmental and economic value (Beesley biochar, carbon nano-tube, graphene, and their derivatives) have
et al., 2011; Gomez-Eyles et al., 2013; Oleszczuk et al., 2012). The been widely used for abating organic pollutants, due to their
in-situ capping technique using CAs is a frequently used engineer- abundant porous structure and large surface area (Tasco n, 2012).
ing measure to treat aqueous sediment contamination, but this Organic pollutants adsorbed onto carbon absorbents can even be
method has a strict requirement for the environmental and func- visualized by scanning electron microscope imagery (Fig. 3). Hence,
tional condition of the plot (Murphy et al., 2006; Zimmerman et al., CAs, such as AC and biochar have been extensively used for
2005). To emphasize the adsorptive function of the CAs and the removing PAHs from aqueous solutions or for immobilizing PAHs in
interactions between PAHs and the adsorbent, this review mainly contaminated sediments (Lamichhane et al., 2016). Thus a firm
understanding of the adsorption mechanisms of PAHs onto carbon
 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263 3

Fig. 1. Sources, transport, and sinks of PAHs and their impacts on flora, fauna, and the environment.

materials is critical for remediation of contaminated sediments.
The mechanisms underlying the adsorption of PAHs on CAs can
be categorized into relatively weak adsorption due to the hydro-
phobic interaction, Van der Waals force and/or hydrogen bond, and
relatively strong adsorption, mainly through p-p interaction or p-
electron from the rich region on CAs, electrostatic interaction and/
or p complexation (Keiluweit and Kleber, 2009). These adsorption
mechanisms of PAHs on CAs are illustrated in Fig. 4.
Carbon adsorbents with stronger molecular polarity may have
higher PAH adsorption ability, due to the intermolecular dipole-
dipole interactions. Hydrophobic interaction can be predicted us-
ing these parameters, such as the octane-water distribution coef-
ficient (Kow) (Goss and Schwarzenbach, 2001).
Van der Waals forces (VDW) are weak intermolecular forces that

Fig. 2. (a) Increasing trend of researches on PAHs remediation applying carbon adsorbents and (b) Discipline distribution of the research.
4 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263

Fig. 3. Scanning electron microscope image (SEM) analysis of a carbon adsorbent before (a) and after (b) adsorption of PAHs (Kumar et al., 2019).

can facilitate the adsorption process. It was found that the VDW
plays an important role in stabilizing the adsorbed pyrene (Pyr)
molecule onto multiwalled carbon nanotubes (MWCNTs)
(Paszkiewicz et al., 2018). The small interaction energy consistent
with the observed low thermodynamic stability Pyr-MWCNT /
Pyr þ MWCNT process (DGr 298 ¼ 2.79 kcal/mol).
PAH derivatives contain hydroxyl groups (-OH), carboxyl groups
(-COOH), and amino groups (-NH2), which can also be adsorbed on
the CAs through a hydrogen bond. Multilayer adsorption of these
PAH derivatives also can be achieved by hydrogen bonds between
surface-adsorbed molecular and the dissolved ones (Lin and Xing,
2008).
The stable aromatic rings in PAHs contain several p electrons
and are easy to conjugate with aromatic rings or p bonds (e.g. C]C
double bonds) on CAs. p-p electron-donoracceptor (EDA) inter-
action is an important interaction between PAHs and CAs
(Keiluweit and Kleber, 2009; Zhang et al., 2014). High molecular
weight (HMW) PAHs have been shown to be more readily adsorbed
on CAs (p-acceptor/contain aromatic rings, C]C, etc.), due to a
large number of p electrons (Sun et al., 2013). Except for p-p
interaction, nitrogen and oxygen atom of adsorbent molecules can
provide lone pair electron and vacant orbitals, and form n-p
interaction with the p electrons in PAHs (Zhang et al., 2018b). The
adsorption of hydroxyl- and amino-substituted aromatic chemicals
can be enhanced by nitrogen-doped multiwall carbon nanotubes
(N-MCNT) (Zuo et al., 2016). The enhanced adsorption of the aro-
matic derivative to N-MCNT was mainly attributed to the favored n-
p interaction between the adsorbate molecule (p-donor) and the
N-heterocyclic aromatic ring (p-acceptor) on N-MCNT.
The adsorption through p complexation between adsorbent and
metal or metal cation relies on weak chemical bonds. Transferring
electrons between the metal ions presumably occurs through the
conjugated p-electron system of the bridging group (Halpern and
Orgel, 1960). Heterocyclic molecules or functional groups contain-
ing metal ions can accept the delocalized p electron provided by
aromatic rings of PAHs and thus form p complexation bond.

Fig. 4. The adsorption mechanisms of PAHs on carbon adsorbents (The p-p interaction diagram is from Yang et al. (2013)).
 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263
Electrostatic adsorption for the ionizable organic chemical can
be achieved through the variation of pH. Low adsorption would be
expected at pH (solution pH)> pKa (dissociation constant of PAH
derivatives) and pHpzc (point of zero charges of the CAs), because of
electrostatic repulsion between negatively charged PAH derivatives
and CAs (Pan and Xing, 2008). On the contrary, pHpzc > pH > pKa
would show high adsorption for the electrostatic attraction.
3. Effects of carbon properties on sediment remediation
3.1. Morphological characteristics of CAs
SSA and pore size distribution of CAs significantly affect their
adsorption of PAHs and thus determine the effectiveness of sedi-
ment remediation. In general, a proper pore size distribution offers
mass transfer paths for PAHs and large surface areas provide more
active sites for adsorption, thus enhancing the sorption capacity
and sorption rate. However, the surface functional groups of CAs
and chemical characteristics of the adsorbents play crucial roles in
the remediation of specific PAHs.
Zhang et al. (2018a,b) compared removal efficiencies of organic
contaminants from bio-treated coking wastewater by two ACs and
found that large SSA of CAs can improve their remediation perfor-
mance. Similarly, CAs show the same trend for reducing the PAH
porewater concentration in sediments (Choi et al., 2013; El-
Shahawi et al., 2017). The surface area of CAs is related to the
feedstocks, production processes, and modification processes (de
Jesus et al., 2019; Kumar et al., 2019). Common modification
methods for increasing carbon surface areas include treatments
with alkali, heat, acid, microwave, ozone, and plasma (Xiao et al.,
2015; Zhang et al., 2017). Regarding to the PAHs presence in
sediments, Choi et al. (2014) indicated that the particle size of AC is
one of the key factors for the reduction of the pore-water con-
centrations of sediment PAHs, which may be related to the surface
area. Table 1 summarizes the performance of different CAs in
aqueous solutions from the reviewed literature and compares the
performance of different CAs in removing PAHs from aqueous
solutions.
A large SSA, however, is not always correlated with a high
adsorption capacity. In comparison with AC, carbon nanotubes have
a smaller surface area but a higher adsorption capacity (Table 1).
This is mainly due to the different pore geometries (Pan and Xing,
2008). Generally, micropores (pore diameter < 2 nm) on the CAs
provide principal sorption sites, mesopores (2 nm < pore
diameter < 50 nm) provide both active sorption sites and intra-
particle diffusion pathways, while macropores (pore
diameter > 50 nm) mainly affect diffusion pathways (Nybom,
2015). AC possesses a similar pore volume as DMSCNs but the
much larger surface area and smaller pore size (<1 nm) than
DMSCNs (comparing row 2 with row 3 in Table 1), which signifi-
cantly restricts the remediation of Ant. Similarly, pore volume and
pore size distribution of CAs can be substantially influenced by
preparation conditions, preparation methods, and modifications as
well as the nature of stock materials (Muniandy et al., 2014; Yakout
and Sharaf El-Deen, 2016).
Besides the adsorption capacity, the adsorption rate which is
generally evaluated based on the adsorption kinetic constant is
another important parameter used for assessing the performance
of CAs in PAH decontamination. For example, rape straw porous
carbon (RC) with a pore diameter of 2.25 nm and total pore volume
of 0.72 cm3/g and corn cob porous carbon (CC) with a pore diameter
2.04 nm and total pore volume 0.55 cm3/g were fabricated in the
same way (Cheng et al., 2019). The RC contained micropores,
mesopores, and macropores, while the CC pore distribution was
concentrated in the range of micropores. The adsorption
5
equilibrium capacities of naphthalene (Nap) on RC and CC were
similar (370 and 340 mg/g, respectively), while the pseudo-first-
order adsorption rate constants were 13.332 and 1.412 (/h),
respectively (Cheng et al., 2019). The existence of mesopores and
macropores on RC led to a fast PAH adsorption rate, which is pri-
marily due to the excellent mass transfer routes provided by the
large pores (de Jesus et al., 2019; Yahya et al., 2015).
What’s more, the small pore size, narrow passage of CAs and
long crossing channels in sediment, hinder efficient mass transfer
and diffusion of PAH molecules to utilize all available adsorption
sites. In addition, the impact of large pore size distribution on CA
performance has been magnified under the influence of sediment.
Pignatello, Kwon, and Lu provided clear evidence of the blocking of
micropores due to the condensation of humic substances on black
carbon (BC) surfaces (Pignatello et al., 2006). Large molecule
organic materials in sediment cannot penetrate deeply into pore
networks and may be continuous or localized in clumps on the
external adsorbent particle surface. The condensed organic strands
will occupy the throats of many micropores open to the external
surface. Narrower pores are clogged more easily by natural organic
matter in sediment than wider pores (Josko et al., 2013). The ad-
sorbents with more micropores will face a larger degree of atten-
uation of target pollutants sorption capacity in sediment than in
aqueous solution. Future methods to efficiently enhance CA surface
area, total pore volume, and optimize pore-size distributions
promise new developments.
3.2. Chemical characteristics of CAs
Chemical characteristics of the carbon materials also play
important roles in controlling their applications in the remediation
of PAH-contaminated sediments. To enhance PAH adsorption onto
CAs, appropriate modifications of the adsorbents are needed to
either add or eliminate the surface functional groups (Koltowski
et al., 2017). The heteroatoms (mainly including oxygen, nitrogen,
hydrogen, sulfur, phosphorus, and halogens) in surface functional
groups are major determinants of adsorbents chemical properties,
which can be determined by elemental analyzer, scanning electron
microscope-energy dispersive spectrometer, and the HeO, C]C,
CeO chemical bond of CAs can be analyzed by Fourier-transform
infrared spectroscopy and nuclear magnetic resonance spectros-
copy (Wang and Wang, 2019). Low H/C and O/C ratios indicate high
aromatization and high hydrophobicity (Yahya et al., 2015). The
degree of graphitization, defect status of carbonaceous materials
can be identified by Raman spectra, X-ray diffraction analysis. (Leng
et al., 2019; Ouyang et al., 2019). It has been reported that high
carbon content is an important parameter to enhance the Ant
adsorption on to DMSCNs (Yang et al., 2014). The oxygen-
containing functional group (carboxylic, lactonic) mainly presents
acidic in the liquid phase, for the reason of hydroxyl and carbonyl
groups generation. Oxygen-containing functional groups on CAs
provide the possibility of hydrogen bonds with PAH derivatives.
Meanwhile, the high oxygen content decreases the hydrophobicity
of CAs and inhibits the remediation of PAHs. The nitrogen-
containing functional group is likely to form p complexation
adsorption under the bridging effect of metal or metal cation. The
existential form and the content of the functional groups in CAs
depend on the precursor and the activation treatment. For instance,
thermal treatment or alkali modification are the common methods
to eliminate the oxygen-containing groups, while ozone and acid
modification are two common oxygen introduction methods for
CAs (Wang and Wang, 2019).
6 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263

Table 1
Summary of the results of PAH removal by carbonaceous adsorbents from aqueous solutions.

Adsorbent SSA (m2/ Pore volume (cm3/g) Pore size C% N% O% Adsorbate Capacity (Langmuir, Kinetic constant (PSO, g/ Reference
g) (nm) mg/g) mg$min)

DMCNs 1218 Total 2.23, Mesopore 2.10 and 91 e e Ant 948 3.50*109 Kalantari et al. (2019)
1.48 18.40 (XPS)
73 (EA)
DMSCNs 404 Total 0.72, Mesopore 14.10 51 e e Ant 348 1.70*107
0.41 (XPS)
35 (EA)
AC 1202 0.67 <1 e e e Ant 113 e
PC (rape 1281 0.72 2.25 90.0 1.6 8.4 Nap, 525, 1.85*103, Cheng et al. (2019)
straw) Ace, 448, 8.17*104,
Phe 808 1.00*104
PC (corn cob) 1069 0.55 2.04 86.8 1.4 11.8 Nap, 358, 1.17*104,
Ace, 357, 9.83*104,
Phe 656 1.83*104
AC (a) 1156 0.65 e 96.8 0.7 2.0 Nap 563 e Ania et al. (2007)
AC (b) 1048 0.56 e 86.4 0.5 12.5 Nap 378 e
AC (c) 1003 0.53 e 86.9 1.3 11.3 Nap 382 e
AC (d) 843 0.45 e 79.7 1.1 18.6 Nap 185 e
GNS 392 e e 76.2 5.2 17.6 Nap 71 2.24*103 Wang et al. (2014)
GO 236 e e 46.2 0.5 50.9 Nap 1 3.57*101
GAC 1218 0.53 3.40 e e e Nap, 33, 6.17*104, Eeshwarasinghe et al.
Acy, 77, 5.00*104, (2018)
Ace, 41, 5.33*104,
Flu, 46, 5.17*104,
Phe 48 6.00*104
AC 1770 0.99 2.82 e e e Nap, 89, 0.02, Xiao et al. (2015)
Phe, 116, 0.04,
Pyr 118 0.06
AC (e) 258 0.21 1.99 60.3 0.7 35.0 Nap 85 e Cabal et al. (2009)
AC (f) 1580 0.81 1.47 83.7 0.5 14.1 Nap 300 e

Note: Abbreviation: Specific surface area (SSA), Activated carbon (AC), Anthracene (Ant), Naphthalene (Nap), Acenaphthylene (Acy), Acenaphthene (Ace), Fluorene (Flu),
Phenanthrene (Phe), Dendritic mesoporous carbon nanoparticles (DMCNs), Dendritic mesoporous silica-carbon nanoparticles(DMSCNs), Pseudo-second-order kinetic model
(PSO), Porous carbons (PC), Graphene nanosheets (GNS), Graphene oxide nanosheets (GO).

3.3. Carbonaceous adsorbent dosage
The reduction of the chemical and biological availability of PAHs
in sediment pore water depends on the repartition between sedi-
ment and added adsorbents. Hence, the adsorbent dose or the
sediment to adsorbent ratio are controlling factors for PAH removal
within limits. This is because the obstacle factors, such as natural
organic carbon fouling and competitive adsorption of ionic sub-
stance can be counteracted by increasing the quantities of CAs. The
PAHs mass reduction measured by semipermeable membrane de-
vices increased from 44% to 87% after the sorbent dose increased
from 0.34% to 3.4% (Zimmerman et al., 2005). The pore water
concentrations reduction of Flu, Phe, and Ant are proportional to
the dose of adsorbents when dosing with less than 4% adsorbents.
When the amount of adsorbent added exceeds a certain range, the
removal efficiency of PAHs is not significantly improved (Rakowska
et al., 2013). Many laboratory study results have demonstrated that
a dosage range of 2%e4% AC is sufficiently responsible for more
than 90% reduction of PAH pore water concentration in well-mixed
sediments (Brandli et al., 2008; Cho et al., 2012; Cornelissen et al.,
2006b; Hale et al., 2012; Kupryianchyk et al., 2011, 2012a;
Rakowska et al., 2012). Although a number of laboratory studies
have demonstrated PAH bioavailability reductions in sediment, no
field study has been conducted in the sediment phase. Through
comparing with the few references to polychlorinated biphenyls
(PCBs), the minimum dosage of AC to effectively reduce contami-
nant bioavailability in the field is generally consistent with the
dosage in the laboratory (Abel and Akkanen, 2019; Kupryianchyk
et al., 2012a; Zimmerman et al., 2004).
4. Effects of PAH properties on sediment remediation
Adsorbate molecular sizes and shapes affect their removal
efficiencies by CAs and thus are critical to the remediation of
contaminated sediments. The mass transfer from sediments to
adsorbent particles can be faster for the smaller PAHs than that for
the larger ones. This is because since smaller PAHs are generally
more polar, they can quickly access the adsorption site of CAs
(Abdelrady et al., 2019). In addition, HMW PAHs are retarded by
stronger sorption to pore walls that inhibit their desorption from
the sediment matrix and diffusion into the adsorbent pores (Hale
et al., 2012). Several studies have shown that light molecular
weight (LMW) PAHs respond more readily to CA amendment due to
faster kinetics in the sediment desorption process and carbon up-
take, while HMW PAHs in sediment are more likely to condense on
natural organic matters, and need stronger desorption energy to
dissolve into pore water (Choi et al., 2013; Hale and Werner, 2010;
Zimmerman et al., 2004). Further, as the molar volume increases,
the penetration of PAHs into the micropores of adsorbents becomes
difficult. Generally, LMW PAHs can easily access the micropores and
bind to adsorption sites, while HMW PAHs may not enter into the
micropore, or block the entrance of narrow micropores and
decrease intra-particle diffusion. Biochar fabricated from enter-
omorpha prolifera with optimal PAH remediation efficiency in the
sorption of Pyr and benzo [a]pyrene (BaP) from aqueous solution is
characterized with large surface area (205 m2/g), high adsorption
rate during the first 2 h and high equilibrium adsorption capacity
(187.27 mg/g and 80.00 mg/g for Pyr and BaP, respectively) (Qiao
et al., 2018).
In addition to the molecule size, the spatial configuration of the
PAH molecules also affects the availability of carbon adsorption
sites in sediment remediation. Straight-chain or planar PAHs are
often adsorbed better than curved-chain or non-planar PAHs
(Liphard et al., 1980; Vollhardt et al., 1993). PAHs released from
contaminated sediments into solutions can be completely removed
by CAs. Granular AC (GAC, SSA 1218 m2/g, pore volume
 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263 7

0.53e0.6 cm3/g, pore size 3.2e3.4 nm) shows different equilibrium
times (4e5 h for Nap, 5e6 h for Acenaphthylene (Acy), 8 h for
Acenaphthene (Ace), 16 h for Fluorene (Flu) and 24 h for Phenan-
threne (Phe)) for PAHs in solutions (Eeshwarasinghe et al., 2018).
The PAH removal efficiencies of Flu, Phe, Ant, Pyr, and benzo(a)
anthracene (B [a]A) from a contaminated urban soil are 96, 92.4,
90.9, 79.6, and 64.6%, respectively, after 6-week shaking extractions
by GAC (SSA 1050e1200 m2/g) (Brandli et al., 2008). The remedi-
ation efficiencies of linear molecules are significantly higher than
that of non-linear molecules, both in aqueous solutions and in
sediments (Gotovac et al., 2007). The molecular structures of PAHs
commonly used in the literature are summarized in Table 2.
Molecule hydrophobicity and weight of PAHs can also affect
sediment remediation efficiencies of CAs. Generally, high hydro-
phobicity PAHs are more likely to adsorb onto adsorbents without
polar functional groups, due to the dipole-dipole interactions be-
tween PAHs and adsorbents as well as VDW forces among PAH
molecules. The sorption Sips isothermal parameters ks and n of
Nap, Ace, and Phe onto two kinds of porous carbon are in the order
of Nap < Ace < Phe, and in line with the order of their molecule
hydrophobicity (Cheng et al., 2019). The molecule hydrophobicity
was directly demonstrated to influence the Nap, Phe and Pyr
adsorption on MCM-41, due to no hydrogen bonds or other strong
polar forces present (Yang et al., 2019a,b). The contribution of the
hydrophobic effect is 50%e85% for Phe, while the contribution is
lower than 30% for 9-phenanthrol and 9, 10-phenanthrene quinone
on functionalized MWCNTs, due to the higher hydrophobicity of
Phe (Peng et al., 2017). The adsorption efficiency decreases with the
increase of PAH molecular weight because of the relatively low
diffusion coefficients of higher molecular weight compounds
(Zhang et al., 2011). The octanol-water partition coefficient (Kow)
and weight of PAHs commonly used in the literature are shown in
Table 2.
5. Effects of environmental conditions on sediment
remediation
BC or hard carbon has sorption coefficients of PAHs in the sed-
iments up to one to two orders of magnitude higher than amor-
phous organic matter (Rakowska et al., 2012). Due to the
complexity of sediments, the remediation of PAHs by CAs is greatly
affected by the environmental conditions of contaminated
sediments.
5.1. Initial PAH concentration
The removal efficiency of sorbents is directly correlated with the
level of contaminants in sediments (Caniani et al., 2018). In a
moderately contaminated urban soil, the freely dissolved aqueous
concentration of native PAHs in a soil/water suspensions was
reduced from 64% to 99% by adding small amounts of powder AC
(PAC) and GAC (2%) (Brandli et al., 2008). While only median re-
ductions were achieved for a heavily contaminated creosote soil
(ranged from 4% to 63%) due to saturation of AC sorption sites by
the high levels of PAHs (Brandli et al., 2008). On the contrary, the
negative influence of initially high PAH concentrations for CA per-
formance in sediment amendments can be counteracted by the
increased dosage of adsorbents. A 5% amendment of AC to well-
mixed petroleum-impacted sediments slurry with total PAHs con-
tents at 125 mg/kg or 2550 mg/kg resulted in 99% or 98% reduction
of PAHs (Choi et al., 2013). Additionally, the initial PAH concentra-
tion also contributed to the amendment rate. For example, available
fractions for fast desorption rates of Phe from the soil are 79%, 46%,
40%, 39%, and 35% for initial Phe concentrations of 100, 400, 800,
1200, and 1600 mg/kg respectively (Gharibzadeh et al., 2019).
5.2. pH and ionic strength
Variation in sediment pH can result in a chemical speciation
change of the natural organic materials and the added-CAs.
Generally, increased pH can lead to increased ionization and po-
larity by changing the functional groups, therefore, decreasing the
remediation performance for PAHs (Qiao et al., 2018; Sun et al.,
2013). pH and ionic strength together play complicated roles in
affecting PAH desorption from sediment and adsorption onto CAs.
Electron donor-acceptor interaction and bridging interaction of
metal ions are the dominant mechanisms by which pH and ionic
strength are attribute to influencing PAH adsorption and desorp-
tion. The CAs would show high PAH adsorption from aqueous so-
lution when pHPZC (point of zero charges of CAs)>pH (aqueous
solution pH)>pKa (ionization equilibrium constant of PAHs), under
the condition of same ionic strength (Zhou et al., 2013). No
consistent results have been obtained for the ionic strength and pH
influence on HOC-DOM (hydrophobic organic contaminants-
dissolved organic matter) interactions (Pan et al., 2008). Ionic
strength is a complicated factor that has opposite effects (negative
or positive relationships) on KDOC (carbon-normalized sorption

Table 2
Characteristics of PAHs commonly used in the literature as target pollutants (Awoyemi, 2011; Eeshwarasinghe et al., 2018; El-Shahawi et al., 2017; Walters and Luthy, 1984;
Yang et al., 2019a,b).

PAH Molecule Molecule Weight (g/ Aqueous solubility (25  C, Log KOW Molar Molar Toxicity Equivalency
formula structure mol) mg/L) (L/L) volume dimensions Factor

Naphthalene (Nap) C10H8 128 31.7 3.30 148 9.1*7.3*3.8 0.001

Acenaphthene (Ace) C12H10 154 3.9 3.92 173 9.1*8.3*4.2 0.001
Acenaphthylene (Acy) C12H8 152 16.1 3.94 168* e 0.001
Fluorene (Flu) C13H10 166 1.9 4.18 188 11.4*7.3*4.2 0.001
Phenanthrene (Phe) C14H10 178 1.15 4.46 199 11.6*7.9*3.8 0.001
Anthracene (Ant) C14H10 178 0.0434 4.45 170.3 e 0.01
Pyrene (Pyr) C16H10 202 0.135 4.88 186 e 0.001
Fluoranthene (Flua) C16H10 202 0.26 5.16 187.7 e 0.001
Benzao(a)anthracene (B [a]A) C18H12 228 0.0094 5.76 e e 0.1
Chrysene (Chr) C18H12 228 0.002 5.81 e e 0.01
Benzo(k)fluoranthene (B [k]F) C20H12 252 0.0015 5.78 e e 0.1
Benzo(b)fluoranthene (B [b]F) C20H12 252 0.0008 6.11 e e 0.1
Benzo(a)pyrene (B [a]P) C20H12 252 0.00162 6.13 e e 1
Dibenzo (a,h)anthracene (D C22H14 278 0.00249 6.75 e e 1
[a,h] A)
Indeno (1,2,3-cd)pyrene (I C22H12 276 0.00019 6.7 e e 0.1
[1,2,3-cd] P)
Benzo (g,h,i)perylene (B [g,h,i]P) C22H12 276 0.00026 6.63 e e 0.01

Note: Kow, n-octanol-water partition coefficients.

8 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263
coefficients) (Jones and Tiller, 1999; Marschner et al., 2004). In
addition, the ion categories also have effects on the mechanisms for
adsorption (Chen et al., 2007). Metal ions may enhance the
adsorption efficiency for PAHs by bridging interaction, such as PAH
salting-out effect. On the contrary, the large hydration shell of
metal cations may intrude or shield the hydrophobic sites and
indirectly compete with PAHs for surface sites, leading to the in-
hibition of remediation (Chen et al., 2008; Oleszczuk et al., 2012;
Wang et al., 2015). The Phe degradation was enhanced by 1.9
times, with the addition of nitrate in the biochar-river sediment
system, due to the electron acceptor role that nitrate played (Yang
et al., 2018). The binding coefficient for Phe is not independent of
pH and ionic strength, it also depends on the dissolved organic
matter concentration (Pan et al., 2007). However, many questions
remain unanswered and further research on how the pH and ionic
strength alter the CA removal efficiency for PAHs, especially in
sediments is warranted.
5.3. Natural organic matters
Previous studies have well demonstrated that natural organic
matter of sediment plays a key role in governing the remediation of
PAHs by CAs (Lamichhane et al., 2016). Limited mobility of organic
contaminants in the highly polluted San Jacinto superfund site
(waste pit) in the Houston Ship Channel, Texas, suggests that the
strong sorbing pyrogenic and petrogenic residues in the waste pit
keeps PAHs strongly sorbed to particles (Louchouarn et al., 2018). It
further supports that aromatic domains of total organic matter in
sediments are the main sorption sites for hydrophobic organic
contaminant (Choi et al., 2016c). A “dual-mode” sorption paradigm
was proposed initially by Huang et al. (1997), where the soft,
amorphous materials of the organic matter showed linear and
noncompetitive absorption, while the hard, condensed, and aro-
matic materials showed nonlinear, extensive, and competitive
adsorption (Cornelissen et al., 2006a). The PAH sorption coefficient
based solely on the amorphous organic carbon partitioning is 1e2
orders of magnitude above predicted result by total organic matter
(Brandli et al., 2008; Cornelissen et al., 2006a; Lasota and Blonska,
2018). To determine the divergent binding capabilities and dis-
similar binding strengths of PAHs with different organic matter
fractions, soil organic matter fractions including fulvic acids, humic
acids, and humin and BC in relation to PAH accumulation levels in
agricultural soils were evaluated (Ukalska-Jaruga et al., 2019). The
correlation coefficients between total organic matter, humin or BC
with PAHs are 0.73, 0.71, and 0.86, respectively. Furthermore, the BC
faction showed the highest correlations with (HMW) PAH
(r ¼ 0.92).
The CAs amended to sediment may be fouled by dissolved
organic matters or colloidal matters like amorphous organic car-
bon, mineral particles, oil, and weathered oil residues, due to site
competition and pore blockage (Cornelissen and Gustafsson, 2006).
Pyr sorption to biochar can be attenuated by up to 80% in the
presence of soils and composts (Kah et al., 2018). Until now, most of
the reported CAs (AC (Rasheed et al., 2015), porous carbon (Cheng
et al., 2019; Yuan et al., 2010), carbon nanotubes (Paszkiewicz
et al., 2018) and graphene (Huang et al., 2018; Wang et al., 2014)
show relatively high adsorption kinetics and removal rates for
PAHs. However, sediment PAH decontamination has significantly
lower removal efficiency and adsorption kinetics (days to months
vs. hours to days) than aqueous PAH decontamination (Nybom,
2015; Patmont et al., 2015; Rakowska et al., 2014a). Funada et al.
(2018) compared the removal efficiency of a magnetic AC to 12
PAHs in glass beads and road-side sediments. The removal rate was
up to 100% after 3h of remediation in the glass beads system, while
the removal rates were just 54% and 62% after 7 days and 14 days,
respectively, of remediation in a road-side sediment system. The
low adsorption kinetics of PAHs from sediment can be attributed to
the following: PAHs desorb out of the sediment matrix, dissolve in
pore water, mass transfer to the CA-pore water interface and dif-
fuses inside the particle until it reaches the adsorption site (Choi
et al., 2013; Hale et al., 2011). In general, it takes a longer time to
release bound PAHs from the sediment particles, due to the inho-
mogeneous desorption energy from the heterogeneity of sedi-
ments. Choi et al. (2013) revealed the kinetics of contaminant
desorption was a more significant factor than the pollutants’ con-
centration for the performance of AC treatment of PAH-
contaminated sediments.
In order to quantify the impact of natural organic matter, Brandli
et al. (2008) proposed a prediction model (Eq. (1) of attenuation of
AC sorption in the presence of sediments.
n
CS ¼ fTOC  KTOC  CW;free þ fAC  KF;AC  C W;free
f ;AC
(1)
n
f ;AC
whereCS , CW;free , and C W;free are the PAHs total soil contents, freely
dissolved concentration on the basis of pure AC sorption and the
amended sample, respectively. fTOC and fAC are the content of total
organic carbon and AC, respectively. KTOC and KF;AC are the organic
carbonewater distribution coefficient determined in the non-
amended system and Freundlich coefficients for sorption of Phe
to AC, respectively. By comparing the apparent sorption coefficients
determined in the low-density polyethylene-water system and the
low-density polyethylene-water-sediment system, it was demon-
strated that the presence of dissolved organic matters or colloidal
matters can interfere with the PAH sorption onto sorbents (Choi
et al., 2016c; Devault and Gourlay-France , 2017).
5.4. Contact time
Extraction quantities of PAHs from sediments by CAs are
strongly affected by the extraction time (El-Shahawi et al., 2017;
Wu et al., 2017). For instance, AC sequestration and immobiliza-
tion of hydrophobic organic contaminants increase over time due
to the progressive mass transfer in sediments (Patmont et al., 2015).
Oleszczuk et al. (2017) reported that the most rapid reductions of
bioavailable PAHs in soils may take 6 months after the addition of
the AC or biochar, compared with unamended groups. Hale et al.
(2012) conducted a long-term AC amendment study for 28
months. They found PAC and GAC amendment resulted in 93% and
56%, respectively, reduction of PAH concentrations in soil drainage
water after 12 months of amendment, but the reduction decreased
to 67% and 17%, respectively, after 20 months (Hale et al., 2012). The
free aqueous PAH concentration significantly declined from 93% to
84% at 17 months to 76% and 69% at 28 months (Hale et al., 2012). In
another study, Choi et al. (2013) reported that total PAHs decreased
from 98% at 1 month to 95% at 12 months, due to the replacement of
a fraction of LMW PAHs adsorbed onto AC by HMW PAHs. In
addition to this, other speculative explanations for the lack of
sustained AC effectiveness including natural organic matter fouling
and biodegradation retarded by the presence of AC over time, etc.
(Hale et al., 2012; Oen et al., 2012). It is worth noting that long-term
effectiveness of field-scale AC amendment in the reduction of PCBs
has been observed by passive samplers (73% reduction after 5 years,
3.7 wt% AC dose addition) (Cho et al., 2012).
5.5. Mixing
The mixing methods of adsorbent with contaminants in sedi-
ments can significantly affect the remediation efficiencies. Most lab
studies have been conducted with the mixing of shaken end-over-
 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263 9

Table 3
Summary of the results of PAH removal by carbonaceous adsorbents from sediments.

Adsorbent SSA, (m2/ Particle size (um) Dose (% of Contact Initial concentration Reduction in Cw Mixing TOC Water Reference
g) DW) time (mg/kg) (%) content

GAC 1050 75e150 5% 1month 2500, 75%, 2 rpm 4% 95% Choi et al. (2013)
e1200 125 97%
12 months 2500, 97%, 2 rpm 4% 95%
125 97%
PAC 1300 <32 5% 1month 2500, 98%, 2 rpm 4% 95%
125 99%
12 months 2500, 95%, 2 rpm 4% 95%
125 99%
PAC 1300 50% particles <15 2% 6 weeks 5500 63% End over 7.2 89%e96% Brandli et al. (2008)
um, 38 99% end 2.5
3% particles >150
um
GAC 1050 1.7e0.43 2% 6 weeks 5500 4% End over 7.2 89%e96%
e1200 38 64% end 2.5
Coke 3 63e105 3.4% 1 month 8 e 3 rpm 1.7% 91% (Zimmerman et al., 2004,
105e250 2005)
6 months 64%
AC 940 75e300 3.4% 1 month 8 74% 3 rpm 1.7% 91%

6 months 84%
AC 1300 50% particles <15 1%, 2 days 1107 90%, e 6.2 99% Kupryianchyk et al. (2011)
um, 3%, 99%,
3% particles >150 6%, >99%,
um 15%, >99%,
30% >99%

Note: Granular activated carbon (GAC), Powdered activated carbon (PAC), Sample dry weight (Dw), Activated carbon (AC).

end (Brandli et al., 2008; Cornelissen et al., 2006a; Hale et al., 2012),
and free aqueous PAH reductions were excessively evaluated in a
continuously well-mixed CA treatment for several weeks (Brandli
et al., 2008; Oleszczuk and Koltowski, 2017). Mixing methods
have been shown to play an important role in the sediment PAH
sequestration kinetics for CA amendments (Berardi et al., 2019;
Werner et al., 2006). But it is difficult to achieve homogeneous
distribution in the large field-scale application, especially for in-situ
remediation. Lower PAH remediation efficiencies of AC amendment
observed in field trials than measured in continuously well-mixed
laboratory experiments is likely due to the limited contact between
adsorbents and PAHs caused by the heterogeneity of sediments
(Choi et al., 2014; Hale and Werner, 2010; Rakowska et al., 2014b).
In-situ adsorbent treatments of PAH-contaminated sediments
mainly involve capping and mixing (Cornelissen et al., 2012; Hale
et al., 2012; Samuelsson et al., 2015). There are several reports on
capping of marine sediments with AC (Cornelissen et al., 2011,
2012; Samuelsson et al., 2015, 2017). AC þ clay capping can
reduce PAH bioaccumulation in worms and clams by 40% and 67%,
respectively (Samuelsson et al., 2015). However, these are far less
effective than the results from laboratory studies, likely due to the
homogenization of sediments, cap integrity, new contaminated
particle deposition, and bioturbation (Cornelissen et al., 2012).
More importantly, the capping layer may alter surroundings, as
AC þ clay capping has been suspected as the cause of reducing the
abundance, biomass, and number of species of marine benthic
fauna by up to 90% (Samuelsson et al., 2017).
Adsorbents mechanically mixed into PAH-contaminated sedi-
ments can achieve better remediation efficiency due to the close
contact between adsorbents and contaminants (Oleszczuk et al.,
2019). However, there are still technical challenges in mixing de-
vices that incorporating CAs into contaminated sediment. Cho et al.
conducted a pilot-scale study to incorporate AC into a tidal mudflat
plot using a shallow-draft barge with a rotovator attachment (Cho
et al., 2007). The results showed a reduction of aqueous equilib-
rium PCB concentration in a field trial after 7 months and AC
treatment was slightly lower than well-mixed (6 months on a
roller), (62% vs. 77%). Barge-mounted rotovator system for direct
mixing and crawler-mounted AC-slurry injector were innovatively
used in the field trial at a tidal region, San Francisco (Cho et al.,
2009). The results indicate that additional mixing during or after
AC deployment for in-situ stabilization of PCBs will likely improve
AC sediment contact and overall effectiveness. Although the
mechanism and trend for removal of PAH and PCB from the sedi-
ment are similar (Luthy et al., 2004; Zimmerman et al., 2004), until
now, only a few systematic studies of AC amendment to sequester
PAHs in field-scale trials have been reported (Hale et al., 2012;
Jakob et al., 2012).
6. Potential environmental impacts and the recovery of CA
amended
6.1. Potential environmental impacts of CAs
CA amendments have proven to be an effective way to remove
PAHs from sediments. A summary of previous studies on the
effectiveness of CAs to reduce the PAH concentrations is presented
in Table 3. It is clear that PAHs bind with CAs, which reduces their
bioavailability (Bucheli and Gustafsson, 2001; Ghosh et al., 2003;
Herrchen et al., 1996; Liu et al., 2019; Spacie and Hamelink, 1985).
The decrease in the biota-to-sediment accumulation coefficient
after CA amendment can reach up to one to two orders of magni-
tude (Moermond et al., 2005; Rakowska et al., 2012; Zimmerman
et al., 2004). For example, the PAH bioaccumulation in plants
decreased by about 50% after the sediment was amended with 2%
AC (Jakob et al., 2012). The differences of adsorbent characteristics,
adsorbent dosage, particle size, contact time, mixing and many
other factors all can affect the PAH bio-uptake (Beckingham and
Ghosh, 2011).
In addition to the decrease of PAH bioavailable concentrations,
amended CAs may have some side effects to the sediment envi-
ronment (Burgess et al., 2009; Kupryianchyk et al., 2011). As an
exogenous additive, CA inevitably changes sediment characteris-
tics. If this remediation technology is not used properly, it may
10 F. Li et al. / Journal of Cleaner Production 255 (2020) 120263
bring negative effects to sediment biocenosis (Jonker et al., 2004). It
has been reported that dissolved organic carbon in sediments can
also be significantly decreased due to PAC and GAC amendment
(Hale et al., 2012). The addition of CAs more or less affects the
habitat quality and is detrimental to sediment organisms. CA
amendments can stimulate nitrifying bacteria in sediments to in-
crease nitrification activities (Berglund et al., 2004; Gundale and
DeLuca, 2007). Furthermore, the CA addition may affect the
bioremediation of PAHs in sediments by changing the growth and
activities of vegetation (Wu et al., 2018; Zhang and Fan, 2016), fauna
(Rodriguez-Campos et al., 2014), and microbes (Azah et al., 2017).
For example, the addition of biochar into sediments can enrich the
population of fungi and microorganisms, due to the improvement
of sediment permeability, water retention, and nutrient content
(Lee et al., 2017; Song et al., 2017).
Several reports have shown that when the dosage of AC or
biochar is less than 5%, the amendment has little or no effect on the
sediment environment (Janssen et al., 2012; Kupryianchyk et al.,
2012a, b; Kupryianchyk et al., 2011). When the adsorbent dosage
exceeds a threshold, the positive effect of the amendment can be
nullified by the inducing toxicity (Bielska et al., 2018). This toxic
effect depends on various factors related to the CA properties
including size, pore structure, surface area, dosage, and surface
chemistry. For example, AC of different particle size has different
biological toxicity (Hale et al., 2013; Jakob et al., 2012). Further
investigations are needed to determine relationships between CA
properties and their toxicity in the remediation of PAH-
contaminated sediments.
6.2. CA recovery
CA recovery is a means of eliminating the negative effects of
added adsorbents and removed PAHs to avoid secondary release
into the environment. One of the traditional ways of recovery is to
separate the adsorbents from the sediment by sieving and centri-
fugation (Rakowska et al., 2014b). However, this method is costly,
disturbs the soil, and the particle sizes of adsorbent and sediment
must be distinguished, which is practically infeasible. A novel
magnetic CA has shown to be separated more effectively (Choi
et al., 2016c; Funada et al., 2018; Han et al., 2015; Hao et al.,
2018; Shahriman et al., 2018; Zhou et al., 2019). This adsorbent
can be easily separated from the adsorption media using magne-
tism (Zhang et al., 2013). However, the low magnetic particle
collection efficiency (50e60%), is a new challenge for the promo-
tion of this new material (Choi et al., 2016c). A textile form of AC is
another innovative way of separation and recovery. However, the
textile form of activated carbon has exhibited low PAH sorption
kinetics resulting from its thickness (Choi et al., 2016c). By com-
parison, the magnetized AC has as high of a PAH sorption coefficient
as non-magnetized AC.
7. Conclusions and perspectives
This review summarizes the physical and chemical mechanisms
of CAs used for PAH remediation in sediments and the major factors
influencing remediation efficiencies, including the characteristics
of CAs and PAHs, and remediation conditions. Furthermore, the
potential negative effects of CAs amendment PAH-polluted sedi-
ments are existed and should be considered. The following con-
clusions can be drawn from the review: 1) CAs possess appropriate
physical and chemical adsorption properties for adsorption of PAHs,
such as large SSA and favorable pore size distribution, and
compatible functional groups, through intermolecular dipole-
dipole interaction, VDW forces, hydrogen bonds, EDA interaction,
p complexation, and electrostatic adsorption. 2) PAH
morphological characteristics, including molecular size, spatial
configuration, hydrophobicity, and weight, not only influence the
adsorption capacity of CAs but also affect CA adsorption kinetics to
a great extent. 3) The environmental conditions, such as initial PAH
concentration, pH value, ionic strength, natural organic matters, CA
dosage, contact time, and mixing method influence PAH remedia-
tion. High initial PAH concentration can be counteracted by abun-
dant dosage of adsorbents. pH value, ionic strength, and contact
time are nonsignificant factors in the sediment remediation, while
natural organic matters and mixing technology are the main bar-
riers hindering the application of this method in the field. 4) The
negative effects associated with CAs are a shortcoming of this
sediment adsorption amendment. The induced biotoxicity can be
controlled by strictly limiting adsorbent dosages. New adsorbent
activation and modification methods to reduce the biotoxicity or
enhance the recovery rate are needed further study.
The complexity of sediment environments can significantly in-
fluence the adsorption efficiency in multiple dimensions. To ensure
that CAs are viable means for PAH remediation, further research is
recommended: 1) New or modified carbon materials with high PAH
adsorption capacity and low cost should be developed. 2) Methods
for minimizing interference from natural organic carbon on CA
application should be improved. 3) Strategies for increasing the
adsorption kinetics in the sediment should be implemented. 4)
New and innovative technologies for capping or mixing CAs should
be applied to polluted sediments. 5) Technologies for reducing the
buoyancy and increasing the stability of CAs should be advanced. 6)
Integrated approaches for decreasing the negative effect on sedi-
ment ecological environment should be developed for remediating
PAHs while sustaining environmental quality.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
F.L. would like to acknowledge the support of the National
Natural Science Foundation of China (Grant No. 41807124) and the
China Scholarship Council (File No. 201809135012).
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