Bioresource Technology 246 (2017) 176–192

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

Challenges and recent advances in biochar as low-cost biosorbent: From

batch assays to continuous-flow systems
Emilio Rosales, Jessica Meijide, Marta Pazos, María Angeles Sanromán ⇑
Department of Chemical Engineering, University of Vigo, Campus Universitario As Lagoas – Marcosende, E-36310 Vigo, Spain

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

It is proved that biochar can be

Alkali
considered as low-cost adsorbent. Nanoparcles Acid

Advances on biochar’ synthesis to
Steam Coang
enhance their adsorptive capacity
Biochar Organic Heavy
have been examined. Magnec
modificaon metals
compounds

Recent findings on organic and
inorganic pollutants by biochars are
summarized.

Identification of knowledge gaps
Nitrogen and
before scale-up in continuous-flow phosphorus
system.

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

Article history: Over the past few years, the increasing amount of pollutants and their diversity demand to develop ver-
Received 31 May 2017 satile low-cost adsorption systems. The use of biomass feedstock such as agricultural residues, wood
Received in revised form 14 June 2017 chips, manure or municipal solid wastes as source to produce low-cost biosorbent, and the new advances
Accepted 15 June 2017
in their synthesis have encouraged remarkable efforts towards the development of biochar ‘‘on demand”
Available online 19 June 2017
in which their characteristics can be improved. This new trend opens the potential of biochar application
in the removal of pollutants from wastewater, however, its use in environmental management requires
Keywords:
the development of full-scale biosorption in engineered systems. Thus, this paper provides a brief review
Adsorption
Biochar
of recent progress in the research and practical application of biochar with a special emphasis on its
Fixed-bed potential to reduce the pollutants present in wastewater or to render them harmless. Furthermore,
Water pollution research gaps and uncertainties detected in their scale-up in continuous-flow systems are highlighted.
Regeneration Ó 2017 Elsevier Ltd. All rights reserved.
Modelling

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
2. Inorganic ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
2.1. Nitrogenated ions: ammonium and nitrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2.2. Phosphorous ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3. Heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3.1. Mercury . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
3.2. Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
3.3. Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

⇑ Corresponding author.
E-mail address: sanroman@uvigo.es (M.A. Sanromán).

http://dx.doi.org/10.1016/j.biortech.2017.06.084
0960-8524/Ó 2017 Elsevier Ltd. All rights reserved.
 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192 177

3.4. Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182

3.5. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.6. Cadmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.7. Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
4. Organic pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
4.1. Adsorption mechanisms for organic pollutant removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
4.2. Influence of biochar aging and solution chemistry on organic pollutant adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
4.3. Biochar enhacements for organic pollutant removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
4.3.1. Coating biochar. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
4.3.2. Physical and chemical pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
5. Continuous flow system for adsorption: Fixed-bed columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
5.1. Operational management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
5.1.1. Particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
5.1.2. Porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.2. Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
5.3. Modelling fixed bed adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.3.1. Influence of bed height . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.3.2. Effect of flow rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.3.3. Effect of inlet concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.3.4. Modelling of the column data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190

1. Introduction cultures would use biochar obtained by burning agricultural

Nowadays, in the management of aqueous waste streams is
essential to comply the stringent environmental regulations of
the different countries (EPA, 2017). One option is the development
of alternative systems for the treatment and disposal of wastewa-
ter, such as evaporation to reduce the volume of effluents gener-
ated or pre-treatment prior to disposal or referral to the
management company including simple treatments such as pre-
cipitation or adsorption. Useful technical innovations are sought
to save energy and reduce the wastewater treatment cost (Cobas
et al., 2015). Among these numerous techniques for removing inor-
ganic and organic pollutants (lead, arsenic, cadmium, phosphates,
trichloroethylene, furfural, diclofenac, carbamazepine, etc.),
adsorption is considered to be one of the most promising
techniques, especially for effluents containing moderate or low
concentrations of these pollutants, and when their rapid removal
or immobilization are required (Ahmed et al., 2017).
Many materials can be used as adsorbents, and the selection of
one or the other will depend primarily on its application. In recent
years, the efforts of the scientific community have focused on the
search for new adsorbents having low price, good mechanical
and chemical resistance, abundance, easy handling, easy regenera-
tion, high adsorption capacity or high specific surface area (Crini,
2006). It is not easy that a material meets all these characteristic
simultaneously, but accomplish the largest number of these prop-
erties is required (Abdolali et al., 2014). Among them, cost is an
important parameter and depends on the degree of processing
required and local availability of the material based to manufac-
ture the adsorbent.
Normally, so-called ‘‘low cost adsorbents” are characterised for
requiring scarce processing, are abundant in nature, or are by-
products or waste materials from another industry (Rosales et al.,
2015). The economic crisis of the 2000s led researchers to turn
their interest in this kind of adsorbent materials with lower cost.
In addition, recently an environmentally friendly waste manage-
ment of agricultural and animal wastes, which can contaminate
surface water as well as aquifers, focuses its attention on the pro-
duction of biochar with several applications pointing up in adsorp-
tion process (Mohan et al., 2014). Although the origin of the term
‘‘biochar” is unknown, it is believed that ancient South American
wastes in order to increase soil productivity (Aller, 2016). This
term defines a low-density carbon-rich solid with a stable porous
structure that is produced from a variety of biomass feedstock by
different thermal decomposition methods including slow and fast
pyrolysis, gasification, carbonization, torrefaction and hydrother-
mal treatment (Jung et al., 2015a). As is described in the next sec-
tions, numerous studies have demonstrated that biochar is a low-
cost adsorbent for the removal of different kind of pollutants. The
production cost of biochar is in relation to biomass feedstock and
procedure used in its production, being estimated a cost from a
typical biochar around 0.076 $/kg which is approximately 3–6%
the price of other commercial carbon-based adsorbents (Yoder
et al., 2011).
By revision of a basedata as ScopusÒ, a search for articles,
reviews, books, data studies and reports including the keyword
‘‘biochar” reveals that the number of studies published per year
has grown from 1 in 2000 to over 1332 in 2016 (Fig. 1). The num-
ber of relevant publications increased over the 10-year period.
Only 33 papers in relation to adsorption were published between
2005 and 2010, but the number of published papers had increased
to 989 from 2011 until 2016. In addition, it has been detected a
higher increase of studies focused on the metal adsorption which
represent around 62% of the papers published in relation to pollu-
tants adsorption.
Initially, the studies have been focused on different biochars’
capacity for uptake of nutrients such as ammonium, nitrate, and
phosphate for its application as a soil amendment with the intent
of improving soil or promoting other environmental services
(Lehmann et al., 2006). However, in recent years, an emerging sub-
set of biochar research pertains to its application as an environ-
mentally sustainable and cost-effective adsorbent for greenhouse
gases, heavy metals, and organic compounds (Li et al., 2017a). In
these studies, the pollutant uptake under appropriately related
experimental conditions by different biochars were determined.
However, our efforts in this review are also focused specifically
on biochar adsorption of pollutants from aqueous solutions in
engineered systems. Until date, most of the adsorption studies
for the removal of pollutants are based on batch kinetic and batch
equilibrium studies. However, the data obtained during batch
adsorption are not enough and in the practical operation of full-
178
1400
1200
Articles published per year
1000
800
600
400
200
0
2008
Fig. 1. Graph depicting the increase in the number of publications using the search term ‘biochar’ (Source: ScopusÒ).
scale biosorption processes, continuous-flow systems
requested to understand the real application potential.
2. Inorganic ions
The widespread application of agrochemicals on agriculture has
increased the release of nitrogenated and phosphorous compounds
to aquatic ecosystems (Wang et al., 2015a). According to EPA
(2017), nitrate concentration in freshwater is generally ranging
from 0.1 to 4 mg/L NO3-N whereas unpolluted waters usually con-
tain nitrate levels below 1 mg/L NO3-N. Nevertheless, effluents
from sewage treatment plant may have concentrations above
10 mg/L NO3-N, which may cause health problems. Phosphate con-
centration in unpolluted lakes and streams is typically below to
0.03 mg/L whereas phosphate concentration above 1.0 mg/L stim-
Fig. 2. Overview of proposed mechanisms for inorganic and organic pollutant adsorption on biochars.
E. Rosales et al. / Bioresource Technology 246 (2017) 176–192
Adsorption
All publications
2009 2010 2011 2012 2013 2014 2015 2016
are ulate plant and algal growth and promote eutrophication of aqua-
tic ecosystems. Among the different available processes,
adsorption represents an appropriate technology, and several
authors have proposed the use of biochar as low-cost adsorbent
to prevent eutrophication and water quality deterioration (Wang
et al., 2015a; Vu et al., 2017). The negative surface charge of
unmodified biochar provides non-attraction/weak interactions
with anionic ions and for this reason, several modifications on bio-
char surface and structure are required to increase the maximum
adsorption capacity (Micháleková-Richveisová et al., 2017). The
presence of acidic functional groups such as phenolic and
carboxylic groups on surface probably promotes ammonium
adsorption whereas electrostatic interactions and in a minor
extent, ionic exchange mechanism are responsible for nitrate
adsorption (Fig. 2).
Table 1
Adsorption characteristics of various inorganic contaminants with biochars.

Biochar Pyrolysis Pre-treatment (PR) Post-treatment (PO) Pollutant qm Sorption mechanism Reference
(mg/g)
Oak sawdust 300 °C (PR) Dried at 105 °C for 6 h (<0.2 mm sieved) NH+4 5.31* Electrostatic interactions (acidic Wang et al. (2015a)
functional groups)
(PO) Immersed in deionized water
La-oak sawdust (PR) Dried at 105 °C for 6 h (<0.2 mm sieved) 10.10*
(PO) Immersed LaCl3 solution 0.1 M for 6 h
Giant reed 500 °C (PR) Dried at 100 °C for 48 h NH+4 1.805** Ion exchange Hou et al. (2016)
(PO) < 0.2 mm sieved and dried at 80 °C for 24 h
Corn biochar 400 °C (PR) Dried at 100 °C for 2 h (0.5–2 mm sieved) NH+4 3.93* Ion exchange Vu et al. (2017)
Acid/alkali modified corn (PR) Dried at 100 °C for 2 h (0.5–2 mm sieved) 22.63* Ion exchange/electrostatic interactions
(PO) Immersed HNO3 6 M for 8 h, NaOH 0.3 M for 24 h (1:5 ratio)
Oak sawdust 600 °C (PR) Dried at 105 °C for 6 h (<0.2 mm sieved) NO
3 8.94* Electrostatic interactions Wang et al. (2015a)
(PO) Immersed in deionized water
*
La-oak sawdust (PR) Dried at 105 °C for 6 h (<0.2 mm sieved) 100.0
(PO) Immersed LaCl3 solution 0.1 M for 6 h
MgFe-LHD modified wheat-straw 600 °C under (PR) Dried (<2 mm sieved) NO
3 24.8* Ion exchange Xue et al. (2016)

E. Rosales et al. / Bioresource Technology 246 (2017) 176–192

N2 flow
(PO)Immersed MgCl2 0.3 M and FeCl3 0.1 M (1:100 ratio)
Peanut shell 700 °C n.a. PO3
4 7.56* Electrostatic interactions Jung et al. (2015b)
Corncob 500 °C (PR) 0.5–1.0 mm sieved PO3
4 0.036* Ion exchange Micháleková-Richveisová
et al. (2017)
Garden wood 0.132*
Wood chip 0.269*
Fe-corncob (PR) 0.5–1.0 mm sieved 1.988*
(PO) Immersed Fe(NO3)3, dried at 105 °C overnight
Fe-garden wood 2.754*
Fe-wood chip 3.201*
Oak sawdust 500 °C (PR) Dried at 105 °C for 6 h (<0.2 mm sieved) PO3
4 32.0* Electrostatic interactions (basic Wang et al. (2015a)
functional groups)
(PO) Immersed in deionized water
La-oak sawdust (PR) Dried at 105 °C for 6 h (<0.2 mm sieved) 142.7*
(PO)Immersed LaCl3 solution 0.1 M for 6 h
Malt spent rootlets 850 °C (PR) Dried at 50 °C overnight (0.15–0.18 mm sieved) Hg2+ 103* Physical adsorption Boutsika et al. (2014)
Bi impregnation- wheat straw 500 °C (PR) 0.6–0.8 mm sieved Immersed bismuth sol., HCl (1:100 ratio) As3+ 0.273* Ligand exchange Zhu et al. (2016)
(PO) Washed NaHCO3 0.01 M and distilled water
Algae Slow pyrolysis (PR) Dried at 75 °C for 24 h (<0.5 mm sieved) PO3
4 98.20* Electrostatic interactions Wang et al. (2016a)
500 °C
Magnetic gelatin-modified 500 °C (PO) 0.07–0.2 mm sieved, immersed mixture gelatin, FeCl3 0.02 M and As5+ 49.15* Electrostatic interactions and Zhou et al. (2017)
chestnut shell FeCl2 0.01 M innersphere complexation
Nut shield 600 °C (PO) Dried at 60 °C for 24 h Pb2+ 4.61* Ion exchange and surface complexation Trakal et al. (2016)
FeSO4- nut shield (PO) 60 °C (24 h), immersed iron oxide sol. 50.6*
2+
Sugarcane bagasse <500 °C (PR) Dried at 80 °C for 2 days Pb 86.96* Electrostatic interactions, precipitation Abdelhafez and Li (2016)
and ion exchange
Orange peel 27.86*
Algae-dairy-manure 400 °C 500 °C (PR) Anaerobic co-digestion for 92 days and dried at 65 °C (<2 mm Cu2+ 21.12* Surface complexation Jin et al. (2016)
sieved)
KOH modified-algae-dairy-manure (PR) Anaerobic co-digestion for 92 days and dried at 65 °C (<2 mm 50.71*
sieved)
(PO) Immersed KOH 2 M (1:4 ratio) Dried at 105 °C overnight
HNO3-modified cactus fibres 600 °C (PR) Hand-peeled, washed and dried at 70 °C Cu2+ 3.5* Innersphere complexation Hadjittofi et al. (2014)
(PO) Immersed HNO3 12 M at room temperature for 24 h and at 80 °C
for 3 h. Dried at 100 °C
Steam-activated Porphyra tenera 500 °C (PR) 1.0–5.7 mm sieved Cu2+ 75.1* Ion exchange and physical adsorption Park et al. (2016)
(PO) Steam activation (40% water vapour at 700 °C for 1 h)
2+ *
Composted swine manures 400 °C (PR) Immersed HCl 0.1 M (<2 mm sieved) Cu 21.88 Surface precipitation Meng et al. (2014)
700 °C 9.15*

179
(continued on next page)
180 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192

2.1. Nitrogenated ions: ammonium and nitrate

Goswami et al. (2016)

Several researches have demonstrated the influence of pyroly-

Zhang et al. (2015a)

Trakal et al. (2016)
tic temperature on surface chemical composition. Low-
Kim et al. (2016)
Gao et al. (2015)

Li et al. (2017b)
temperature biochars exhibit high content of oxygen-containing
groups, which contribute to increase the cation exchange capac-
Reference

ity (Gao et al., 2015). Wang et al. (2015a) have analyzed the
influence of pyrolytic temperature ranging from 300 to 600 °C
on ammonium and nitrate removal by biochar prepared from
Innersphere complexes and ion exchange oak sawdust with/without LaCl3. The results exhibited ammo-
Ion exchange and surface complexation
Ion exchange and surface precipitation

nium and nitrate adsorption capacity around 10.1 and

100.0 mg/g after modification, which significantly enhances the
Electrostatic interactions and ion

adsorption ability compared to raw material. As can be seen in

Table 1, other studies have evaluated ammonium sorption on
Electrostatic interactions giant reed-biochar (Hou et al., 2016) as well as a mixture of
Electrostatic interaction
Surface complexation

brewer spent grains and sewage sludge enriched with

Sorption mechanism

magnesium and phosphorous (Zhang and Wang, 2016). However,

the obtained results showed sorption capacity below 5 mg
NH4-N/g. The combined treatment by strong acid and alkali on
exchange

corncob-biochar was analyzed by Vu et al. (2017), the highest

uptake (22.6 mg NH4-N/g) was achieved after immersion into
HNO3 6M and NaOH 0.3 M for 8 h and 24 h, respectively. This
67.363*
72.369*

167.31*
81.096*

can be explained by the formation of sodium organic salts which

71.43**
72.43**
(mg/g)
96.18*

30.0*
137*

273*
311*

increase the segregation of modified biochar. Moreover, previous

20*
qm

studies demonstrated relatively high selectivity for nitrate ions

Pollutant

on Mg/Fe layered double hydroxide (LDH) modified wheat-

straw biochar achieving 5.62 mg NO3-N/g. The modification of
Cu2+

Cd2+

Cd2+

Cd2+
Cr6+

Cr6+

metals on LDH has influence on pollutant selectivity with

Ni/Fe-LDH or Mg/Fe-LDH reported as appropriated for nitrate
(PR) Immersed Zn (NO3)2 (20%) under 130 rpm, 30 °C and 24 h. Dried

(PO) Immersed FeCl3 1 M 80 °C for 3 h, dried at 105 °C and 600 °C for

ions adsorption (Xue et al., 2016).

(PO)Immersed KOH 1 M (1:1 ratio) and dried at 100 °C for 24 h

(PO) Immersed KOH solution for 2 h (1:3 ratio), dried at 105 °C

(PO) Immersed NaOH 2 M 100 °C 12 h, rinsed NaHCO3 0.01 M

(PO) Immersed chitosan/acetic acid (2%) (1:6 ratio), 150 mL

2.2. Phosphorous ions

(PO)Steam activation (40% water vapour at 700 °C for 1 h)

Several studies exhibited poor adsorption capacity for

(PO) Dried at 60 °C for 24 h, immersed iron oxide

phosphate ions from aqueous solution with different biomass

(PR) Dried at 105 °C for 12 h (2–5 mm sieved).
(PR) Dried at 105 °C for 12 h (2–5 mm sieved)

(PR) Dried at 105 °C for 12 h (2–5 mm sieved)

(PR) Dried at 105 °C for 12 h (2–5 mm sieved)

feedstock including peanut shell, bamboo and maize waste

(Table 1) (Jung et al., 2015b). For this reason, biochar production
Pre-treatment (PR) Post-treatment (PO)

from biomass with high content of calcium, iron, magnesium or

aluminium is considered and a focus of attention on scientific com-
munity. Several authors have reported biochar modifications
through functional additives such as metals, metals oxides or
(PO) Dried at 60 °C for 24 h

1 h, rinsed NaHCO3 0.01 M

metal chlorides to enhance the maximum adsorption capacity (M

(PR) 1.0–5.7 mm sieved

(PR) 1.0–5.7 mm sieved

icháleková-Richveisová et al., 2017). Based on the literature,

(PR) < 0.2 mm sieved

glutaraldehyde (1%)

Wang et al. (2015a) produced lanthanum-modified biochar from

oak-sawdust; phosphate sorption capacity was improved
(142.7 mg/g) compared to raw material (32.0 mg/g). However, this
at 60 °C

method involves high economic costs and operational problems.

Therefore, the development of simple and cost-effective methods
to modify biochar with natural minerals such as vermiculite
represents an appropriate alternative to enhance the phosphate
adsorption onto biochar (Wang et al., 2016a). They have
Pyrolysis

successfully evaluated novel SiO2–biochar nanocomposites

450 °C

500 °C

600 °C

400 °C

600 °C

600 °C

prepared by thermal pyrolysis of vermiculite treated algal biomass.

This material showed high effectiveness on phosphate removal
(159.42 mg/g) compared to unmodified biochar because the SiO2
Zinc-modified sugarcane bagasse

Chitosan- Eichhornia crassipes/c-

particles on the surface corresponds to activated sites through

KOH-modified Ipomoea fistulosa
Steam activation E. compressa

electrostatic interactions.
KOH activation E. compressa

c-Fe2O3 Eichhornia crassipes

NaOH-modified rape straw
MnOx-modified rape straw

FeOx-modified rape straw

3. Heavy metals
Fe2O3 composite
FeSO4-wheat straw
Ipomoea fistulosa
Table 1 (continued)

n.a. not available.

The presence of heavy metals in drinking water represents an

Wheat straw

Langmuir.

important threat to the environment and human health. These

Biochar

metallic elements have been recognised as mutagenic and carcino-

genic agents, and may be toxic for aquatic life (EPA, 2017). They are
*

considered systemic toxicants, which are well known to cause

 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192
multiple organ damage, even at low exposure level. The applica-
tion of adsorption methods using biochar-based materials is con-
sidered a suitable via for heavy metals remediation. Based on
literature, several mechanisms have been proposed to describe
accurately the metal adsorption on biochar including electrostatic
interactions between adsorbent surface and heavy metals, cation
exchange between metals and protons or alkaline metals on sur-
face, metal complexation with functional groups, metal precipita-
tion to form no soluble compounds, and metal reduction with
further reduced metal species adsorption (Fig. 2). The main mech-
anism depends on biochar properties (surface area, porosity, pH,
surface charge, functional groups, and mineral components) and
target metals (Li et al., 2017a). The modifications on the biochar
surface allow enhancing sorption capacity of heavy metals onto
biochar (Table 1). The impregnation of biomass feedstock with
metal ions such as AlCl3, MgCl2, KMnO4 and ZnCl2 enhances the
pore properties and oxygen-containing functional groups and,
therefore, major interactions occur between biochar and heavy
metals through the formation of surface complexes, cation-p bond-
ing, electrostatic attraction and ion exchange (Fig. 2). On the other
hand, the base activation promotes high surface areas and addi-
tional hydroxyl radicals, which increase the sorption capacity of
heavy metals. Regarding to magnetic treatments, obtained modi-
fied biochars have an expanded average pore diameter, which
enhance adsorption properties for anionic pollutants and ensure
an optimal separation of biochar particles on further treatments
(Li et al., 2017b).
3.1. Mercury
Mercury, natural element found in the Earth’s crust, has been
widely released into the aquatic environments owing to anthro-
pogenic activities such as agriculture, mining, incineration and
municipal and industrial wastewater discharges (Tan et al.,
2016). The US Environmental Protection Agency has established
maximum mercury concentration around 10 lg/L for wastewater
discharge and 2 lg/L for drinking water (EPA, 2017). Few studies
were found related to mercury adsorption using biochar over last
years. Boutsika et al. (2014) have evaluated the potential use of
biochar produced from malt-spent rootlets to remove mercury
ion from aqueous solution. The results exhibited excellent adsorp-
tion ability, 103 mg/g under optimal conditions, onto brewing
industry by-product. The speciation diagram shows mercury ion
corresponds to its main form in the solution at pH below 6 while
mercury precipitates as hydroxide at pH above 6 (Boutsika et al.,
2014). Further studies were carried out by Manariotis et al.
(2015) who reported the influence of pyrolytic temperature on
mercury adsorption using malt spend rootlets as biomass feed-
stock. The adsorption capacity increased by factor around 4 and
6 for low- and high-temperature biochars compared to the raw
material. These results corroborated that high surface area and less
functional groups promote the mercury species adsorption owing
to non-polar adsorbent with the concomitant high adsorption for
organic hydrophobic compounds and heavy metals. On the other
hand, modifications of biochar with chemical reagents provide dif-
ferent physicochemical characteristics (surface area, pore size,
molecular weight, hydrophobicity, polarity and functional groups)
leading to adsorption capacity changes (Tan et al., 2016). The
chemical modification by 2 M Na2S and 2 M KOH on corn-straw
biochar which was obtained via slow pyrolysis at 500 °C was eval-
uated by Tan et al. (2016). After alkali treatment, O-containing
groups raised suggesting higher sorption ability through electro-
static interactions. The results showed potassium and sulphur
impregnation were efficient treatments to enhance aqueous mer-
cury removal increasing by 31.12% and 76.95%, respectively, com-
pared to pristine material.
181
3.2. Arsenic
Arsenic, well-known environmental hazard, has been classified
as human carcinogenic at lower exposure levels by International
Agency for Research on Cancer (IARC). Although inorganic arsenic
is an element in the Earth’s crust, human activities such as agricul-
ture, mining or medicine contribute to the arsenic environmental
burden. Arsenic concentration in surface water is usually below
10 ppb, which has been established as maximum arsenic concen-
tration in drinking water. The removal of this metallic element
from aqueous solution is considered an important challenge on sci-
entific community owing to crucial influence of the pH on arsenic
speciation (Zhou et al., 2017). Despite iron oxy-hydroxide powders
are considered the most efficient adsorbent for arsenic removal
from aqueous solution; additional costs corresponding to further
adsorbent separation may hinder their application at industrial
scale. Several researches have reported the use of modified-
biochar as alternative low-cost adsorbent with excellent results.
Zhou et al. (2017) synthetized a novel chestnut shell-biochar mod-
ified with magnetic gelatin and ferric ion, the results showed the
biochar modification enhanced significantly the physiochemical
properties and increased the oxygen-containing functional groups.
Therefore, maximum adsorption capacity has increased after
chemical treatment achieving 45.8 mg/g under optimal conditions.
On the other hand, Zhu et al. (2016) reported bismuth oxide as an
appropriate treatment to impregnate wheat straw biochar
(16.21 mg/g for As3+); the mechanism may be attributed to the
Lewis acid-base (ligand exchange) reaction between bismuth atom
and arsenite. Moreover, two manganese oxide-modified biochar
composites were proposed by Wang et al. (2015b) to remove
arsenic from wastewater; pine wood feedstock was pyrolyzed in
the presence of MnCl24H2O and other, was impregnated with bir-
nessite via precipitation. The birnessite presents high oxidation
potential able to transform arsenite to arsenate. Although the
results showed higher adsorption capacities compared to unmodi-
fied biochar, low arsenic removal percentages were achieved.
Recent studies have evaluated the generation of LDH with different
metal combinations for As5+ removal (Wang et al., 2016b). For this
purpose, two LDH-biochar were produced by pyrolysis of Ni/Fe-
LDH-modified pine feedstock or precipitation of LDH onto pristine
biochar. The maximum arsenate adsorption capacities under neu-
tral conditions were 1.56 and 4.38 mg/g, respectively higher than
unmodified material (0.20 mg/g). The obtained results suggested
multiple mechanisms (anion exchange and surface complexation)
takes place on adsorption process.
3.3. Lead
Lead compounds have been widely used as industrial raw mate-
rial in lead-acid batteries, rolled extrusions such as lead sheet, wire
and pipe, pigments, cable sheathing, munitions and lead alloys. The
maximum allowable concentration for lead in drinking water is
15 lg/L (EPA, 2017). Several remediation technologies including
chemical precipitation, ions exchange, filtration, biosorption,
biodegradation and phytoremediation have been developed to
remove lead compounds from aqueous ecosystems. However,
energy requirements and sludge generation promote the develop-
ment of other technologies such as adsorption on biochar derived
biomass feedstock over last years (Abdelhafez and Li, 2016). The
adsorption characteristics of celery-biochar, rich in alkaline miner-
als, for lead removal from aqueous solution have been investigated
by Zhang et al. (2017a). The alkali earth metals (Na, K, Ca and Mg)
were converted into carbonates throughout high-temperature
pyrolysis leading to alkaline medium and heavy metal cation pre-
cipitation. The high biochars’ effectiveness on lead removal from
aqueous solution was reflected (around 300 mg/g). The contribu-
182 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192
tion to lead removal by insoluble organic carbon was below 4%
whereas inorganic minerals played a dominant role on lead
adsorption, these results are in accordance to previous studies
reported on literature (Wang et al., 2015c). To increase lead ion
adsorption ability on biochar derived from different biomass feed-
stock, Trakal et al. (2016) evaluated the use of microwave-
synthesised magnetic iron oxide particles. The magnetic modifica-
tion often decreases specific surface area owing to the formation of
secondary iron (hydro) oxides on the surface. This might improve
the sorption efficiency of metals and metalloids, which are fixed
on the surface of these precipitated (hydro) oxides. Although mag-
netization enhances more adsorption effectiveness with well-
developed structures and mobile metals, lead adsorption was
increased significantly after modification achieving around
300 mg/g for nut shield-biochar. As can be seen in Table 1, lead
ion showed higher affinity to biochar adsorption than other tested
metals. This fact could be explained as a result of its low hydrated
radius, high electronegativity and hydrolysis constant compared to
other metal cations.
3.4. Zinc
Zinc has been released into the environment from natural and
anthropogenic sources; however, human activities such as refining,
electroplating, steel production, carbon combustion and solid
waste incineration are mostly responsible for zinc pollution. EPA
has set the threshold limit of zinc in wastewater and drinking
water as 5 and 3 mg/L, respectively. Alkali modification has been
commonly used to increase the sorption ability of biochars by high
specific surface area and functional groups modification. For this
reason, Ding et al. (2016) used NaOH to modify biochar derived
from hickory wood chips and evaluate zinc adsorption ability.
The modified biochar showed around 2.5 times zinc adsorption
capacities than pristine biochar (0.71 mg/g). Furthermore, Frišták
et al. (2015) evaluated the pH effect on adsorption process by
two different woody-derived biochars. Zinc is present as Zn2+ ions
at pH from 3.0 to 8.5 whereas an enhancement of soluble hydrox-
ide forms concentrations such as Zn(OH)2 and ZnOH+ are generated
at pH above 7.5. The authors suggested the precipitation and ion
exchange as main processes involved into adsorption of metals
cation.
3.5. Copper
Copper and its alloys (brass and bronze) have been employed in
common household wiring, photovoltaic cells and phytosanitary
products as fungicides, fertilizers, algicides and insecticides. The
EPA has set the acceptable limit of copper in drinking water as
1.3 mg/L. The removal of Cu2+ from aqueous solution via adsorp-
tion has been widely used on wastewater treatment plant (Jin
et al., 2016). In recent times, the use of biochar as low-cost adsor-
bent has been increased because of its high efficiency for copper
removal. Among them, Meng et al. (2014) removed copper by using
biochar derived from swine manure, and the results suggested sil-
icate and phosphate particles contained on biochar were the main
sorption sites. Nitric acid modified-biochar produced from cactus
fibres was also applied for Cu2+ removal identifying carboxyl moi-
eties as main binding site (Hadjittofi et al., 2014). On the other
hand, marine macroalgae are considered an appropriate alternative
biomass material to obtain biochar (Park et al., 2016). Jin et al.
(2016) analyzed biochars pyrolyzed from anaerobically digested
algae-dairy-manure slurry before and after activation by 2 M
KOH solution. The alkali modification enhanced sorption capacity
(50.71 mg/g) compared to unmodified material (21.12 mg/g).
These results are not in agreement with Park et al. (2016) who
reported KOH activation reduced the copper removal on pyrolytic
biochar derived from red macroalgae Porphyra tenera, even though
the increase of specific surface area and pore volume. On the
contrary, steam activation enhances sorption ability owing to the
formation of mesopores and macropores along decomposition of
volatile matter. The pH effect was evaluated by Kim et al. (2016)
who analyzed fast-pyrolysis biochar derived from green
macroalgae Enteromorpha compressa reaching 137 mg/g at
optimal conditions (pH around 5.5). According to the speciation
diagram, Cu2+ mostly exists at pH below 5.5 whereas the formation
of Cu(OH)+ complex and Cu(OH)2 precipitation may occur at pH
above 6, respectively. Novel biochar was synthesized through
slow pyrolysis of hickory wood pretreated with KMnO4 for Cu2+
removal from aqueous solution owing to other studies have
reported the conversion from KMnO4 to MnO2 ultrafine particles
(Wang et al., 2015d). The maximum adsorption capacity of
engineered biochar for Cu2+ removal was above 34 mg/g, which
was about 2.8 times greater than those corresponding to pristine
biochar.
3.6. Cadmium
Cadmium has been used for metal surface treatment as stabiliz-
ing agent in polyvinyl chloride products and alloys. However, the
most important cadmium source comes from cigarette smoke
owing to the average cigarette cadmium content exceeds
1.60 lg/g. The EPA has established maximum cadmium concentra-
tion as 10 lg/L for drinking water (EPA, 2017). Scarce ability of
unmodified biochars to remove heavy metals from wastewater
has been reported on literature. For this reason, to evaluate the
influence of three modifications (NaOH base treatment, MnOx
impregnation with KMnO4 and magnetic modification by thermal
pyrolysis of FeCl3), Li et al. (2017b) have investigated the use of
modified-biochars from rape straw. According to them, the main
mechanisms responsible for Cd2+ removal using MnOx-biochar
were cation exchange and cation-p bonding achieving the greatest
adsorption capacity (81.10 mg/g) as a result of the increase of the
specific surface area, number of oxygen-containing functional
groups and the pore size and structure. On the contrary, magnetic
biochar prepared by chemical precipitation showed reduced sur-
face area and more acidic groups such as carboxylic acid and phe-
nolic groups on the surface, which were occupied by protons
leading to competitive interactions with cadmium ions. As was
commented above in lead section, magnetite/maghemite modified
biochar are more efficient with well-developed structure and
mobile metals such as Cd2+ achieving 50.6 mg/g for nut shield
and 75.3 mg/g for wheat straw, which represents 10.97 and 3.17
times better than those reported for unmodified biochar (Trakal
et al., 2016). On the other hand, the use of aquatic plants such as
Ipomoea fistulosa to produce biochar able to remove Cd2+ ions from
aqueous solution was investigated by Goswami et al. (2016). The
effect of KOH activation and pyrolytic temperature on sorption
process was evaluated resulting in higher adsorption capacity for
biochar pyrolyzed at temperatures below 400 °C and after alkali
modification (41.67–72.43 mg/g). The authors suggested surface
complexation as main mechanism responsible for Cd2+ removal.
Biochar derived from biophysical dried sewage sludge through
pyrolysis at 900 °C was evaluated by Chen et al. (2015a). The pH
solution and adsorbent dosage represented the dominant factors
on adsorption process whereas the influence of temperature was
considered as negligible. The results showed a minimal
contribution of organic matters on cadmium removal whereas
alkaline earth metals such as calcium are responsible for adsorp-
tion process owing to cation exchange and surface precipitation
by the formation of insoluble cadmium salts under alkaline
conditions.
 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192
3.7. Chromium
Chromium, well known carcinogenic and mutagenic, has been
identified as hazardous pollutant by EPA, which set 0.05 mg/L as
maximum permissible concentration in drinking water. This
metal has been widely used in many industrial processes such
as photography, metallurgy, electroplating and tanneries (Shang
et al., 2017). Strong electrostatic repulsion forces take place
between biochar surface and inorganic anions HCrO 2
4 or CrO4 .
As a consequence, surface modifications have been evaluated
over past years to enhance adsorption ability. Among them,
the use of nanoscale FeS particles showed higher reactivity com-
pared to bulk particles and natural minerals owing to small par-
ticle size with the concomitant larger specific surface area.
Recently, Lyu et al. (2017) have developed novel FeS-biochar
composite using carboxymethyl cellulose as stabilizing being
the FeS particles soldered onto oxygen-containing functional
groups. Higher chromium adsorption capacity (130.5 mg/g) was
obtained compared to FeS (38.6 mg/g) and biochar (25.4 mg/g),
and the main mechanisms to describe metal removal were
adsorption, precipitation and reduction. Several authors have
proposed the use of biochars as support materials for nanoscale
zero-valent iron nanoparticles (nZVI) stabilization (Shang et al.,
2017). The carboxyl groups and silicon minerals were responsi-
ble for supporting nZVI and the main mechanisms for Cr6+
removal by nZVI include adsorption, co-precipitation and reduc-
tion of Cr6+ to Cr3+ via nZVI oxidation (Shang et al., 2017). Chi-
tosan, renewable transformed polysaccharide, has been used as
stabilizing to attach ZVI particles on bamboo biochar surface
(Zhou et al., 2014). The use of chitosan on biochar enhanced
chromium removal compared to unmodified material because
the presence of amine functional groups on chitosan structure
leads to strong chelations to cation metal in aqueous phase.
Based on previous studies, Zhang et al. (2015a) have developed
chitosan modification of magnetic biochar derived from Eichhor-
nia crassipes, aquatic tropical species characterized as aggressive
invasive plant. The results indicated an enhancement on adsorp-
tion capacity after chitosan modification (120 mg/g) compared to
raw material (30 mg/g). The effect of background electrolyte on
chromium removal may be explained by competitive mechanism
owing to monovalent anions slightly compete for positive charge
sorption sites on surface whereas multivalent anions restricted
adsorption process.
4. Organic pollutants
Several studies have demonstrated that laboratory-produced
biochars can adsorb organic pollutants comparably with com-
mercial activated carbon and, therefore, provide a cost-
effective alternative to this in water treatment applications
(Kearns et al., 2014). In addition, the regeneration of biochar
may be carried out easily by thermal treatment (Abdul et al.,
2017), microwave irradiation (Zhang et al., 2014), using organic
solvents (Reguyal et al., 2017), or milling (Shan et al., 2016).
Furthermore, organic chemicals can be directly degraded on
biochar surface by macromolecular free radicals. Thus, Yang
et al. (2016) observed obvious degradation of p-nitrophenol in
the presence of biochars, through the detection of NO 3 as well
as organic by-products.
The recent studies on biochar applications for the remediation
of aquatic environment containing organic compounds are sum-
marized in Table 2. The greatest concern of organic pollutants
has been focused on drugs and pharmaceuticals, plasticizers,
organic solvents, pesticides/herbicides, polycyclic aromatic
hydrocarbons and dyes.
183
4.1. Adsorption mechanisms for organic pollutant removal
The adsorption mechanisms for organic removal depend on the
pollutant properties as well as biochar surface chemistry, which
varies greatly with raw material and proposed pyrolysis condi-
tions. In general, high treatment temperatures increase the aro-
maticity, hydrophobicity, and surface area of biochars making
them more accessible to hydrophobic organic pollutants. Thus,
Chen et al. (2017) perceived that the increase in pyrolytic temper-
ature resulted in the enlarged pore volume of biochar and
enhanced affinity of carbamazepine on peanut shell-derived bio-
chars. The relationship between the H/C and O/C molar ratios rep-
resents an interesting parameter which shows the effect of the
pyrolysis conditions on the biochars. Both molar ratios decreased
by increasing heat treatment temperatures mainly due to the
demethylation and decarboxylation reactions (Devi and Saroha,
2015; Sun et al., 2016). The decrease of H/C is indicative of the for-
mation of highly carbonized and aromatic structures. Chen et al.
(2015b) determined H/C molar ratio for bamboo char was in the
range of 0.15–0.45 and the ratio decreased by increasing pyrolytic
temperature, indicating that the biochar was highly carbonized
and had a highly aromatic structure. The reduction of O/C molar
ratio is also indicative that the surfaces of the high-temperature
biochars became less hydrophilic (Reguyal et al., 2017). On the
other hand, biochars obtained at low temperature consists of
amorphous carbon that can contribute to the fast adsorption of
pollutants (Chen et al., 2017). However, some studies demon-
strated that pyrolysis at higher temperatures can reduce the
removal ability. Thus, Chen et al. (2015b) studied the adsorption
of N-nitrosodimethylamine, polar and highly water soluble com-
pound, onto bamboo biochar obtained at different temperatures
300–700 °C. The best removal efficiency was reached with the bio-
char manufactured at 500 °C. They suggested that at high temper-
atures biochar can show structural defects and the micropores on
the surface blocked.
The biochar surface is heterogeneous as a result of the co-
existed carbonized and non-carbonized fractions in which different
adsorption mechanisms take place. The various mechanisms pro-
posed (hydrophobic interaction, pore-filling adsorption/partition,
electrostatic attraction, and hydrogen bonding or p–p interaction)
for the interaction of biochar with organic pollutants are summa-
rized in Fig. 2.
The sorption of organic pollutants onto biochar can be affected
by their solubility by means of hydrophobic interactions. Thus, sol-
uble pollutants can be attached into hydrophobic biochar if they
have hydrophobic functional group, as for example methyl group,
in their structure (Reguyal et al., 2017).
Diffusion of organic compounds onto biochar can occur by dif-
fusion of sorbates into pores (adsorption-pore-filling) or into the
organic matter matrix of noncarbonized fractions (partition)
(Inyang and Dickenson, 2015). Zhang et al. (2015b) reported that
trichloroethylene (TCE) removal on soybean stover biochar was
due to partition to non-carbonized fractions and adsorption to
the carbonized fraction of the biochar. Some studies have focused
the attention in order to analyze the contribution between adsorp-
tion and partition. Thus, Devi and Saroha (2015) studied the frac-
tion of adsorption and partition of pentachlorophenol on biochar
obtained at different temperatures 200–700 °C. They found that
the fraction of adsorption increased by increasing pyrolysis tem-
perature due to the carbonized fraction increases. The sorption of
organic pollutants onto biochar by pore-filling is function of total
micropore and mesopore volumes. Han et al. (2014) found that
nanoporefilling plays a dominant role in the sorption of hydropho-
bic organic pollutants such as phenanthrene by rice straw biochar
obtained at 600 °C, which is found to be microporous solids.
Similarly, Sun et al. (2016) stablished a correlation along with
Table 2

184
Adsorption characteristics of various organic contaminants with biochars. Sorption mechanism: p (p-p EDA interaction), HI: (Hydrophobic interaction), Pp (Partition process), H-b (H-bonding), Ea (Electrostatic attraction), Ca (Complexes
adsorption).

Biochar Pyrolysis Pre-treatment (PR) Post- treatment (PO) Pollutant Isotherm N(%) H O (%) C(%) Surface Sorption Reference
Model (%) Area mechanism
(m2/g)
Pine needle 700 °C 2 h at 5 °C/min (PR) dip-coating with graphene oxide Dimethyl phthalate Freundlich 0.39 1.55 9.86 84.98 443.9yy p Abdul et al.
wood oxygen-limited synthesized via thermal reduction Diethyl phthalate (2017)
conditions Dibutyl phthalate
Bamboo 500 °C (PO) HCl + HF (1 M) N-nitrosodimethylamine Slips 0.75 2.44 11.7 85.11 38.47y H-b/HI/Pp Chen et al.
(2015b)
Peanut shell 500 °C 4 h oxygen- n.a. Carbamazepine Dubin- 1.60 2.71 19.1 59.45 64.73 y
HI/p/H-b Chen et al.
limited conditions Ashtakhov (2017)
Peanut shell 700 °C 4h N2 (PO) (1:3, v/v) HNO3/H2SO4 Dimethyl phthalate Freundlich 0.66 2.4 42.46 48.54 281 y
HI/p Ghaffar
atmosphere Diethyl phthalate et al. (2015)
Dibutyl phthalate
Pine wood 600 °C 1 h oxygen- (PO) 0.1 M HCl + NaClO2 + CH3COOH Phenanthrene Freundlich 0 2.2 25.8 65.1 402.1yy Nanoporefilling Han et al.
limited conditions (2014)
y
Sugarcane 600 °C 1 h at 10 °C/min (PR) dip-coating with carboxyl-functionalized Methylene blue Langmuir– 0.7 1.7 11.9 85.7 390 Ea Inyang

E. Rosales et al. / Bioresource Technology 246 (2017) 176–192

bagasse N2 atmosphere carbon nanotubes. Freundlich et al. (2014)
Phragmites 600 °C 2 h oxygen- (PO) 1 M HCl Pentachlorophenol Freundlich 0.61 2.07 8.9 87.8 88.35 y
HI/p Peng et al.
australis limited conditions (2016)
Pinus radiata 650 °C slow pyrolysis (PO) coating with Fe3O4 via oxidative Sulfamethoxazole Redlich- <0.5% 0.82 n.a. 55.77 125.8y HI Reguyal
sawdust hydrolysis in alkaline media Peterson et al. (2017)
Coconut shell 500 °C 1.5h N2 (PO) biochar mixture with Fe3O4 (3:1) was Carbamazepine tetracycline Langmuir n.a. n.a. n.a. 365y Surface Shan et al.
atmosphere milled at 550 rpm for 6 h (40:1 ratio balls complexation with (2016)
mixture) Fe3O4/p
Pelletized pine 850 °C 20 min Top-lit n.a. Sulfamethoxazole n.a. 0.12 0.54 2.54 93.7 405y p Shimabuku
forestry up-draft gassifier et al. (2016)
waste
Rice straw 450 °C 1 h at 10 °C/min (PO) 0.1 M HCl + 1 M HCl and 10% HF Propiconazole Freundlich 1.17 3.71 15.4 72.5 11.5y Pore-filling Sun et al.
oxygen-limited (2016)
Pine wood dust 600 °C 1 h oxygen- (PO) 0.1 M HCl Acetochlor dibutylphthalate Freundlich 0 n.a. 8.13 88.78 544.6yy Pore-filling Wang et al.
limited conditions 17a-ethynylestradiol (2016c)
phenanthrene
Pine wood 700 °C 4 h oxygen- n.a. p-nitrophenol n.a. 0.39 2.94 13.4 82.3 566y Adsorption- Yang et al.
limited conditions degradation by free (2016)
radicals
Rice straw 600 °C 2 h at 7 °C/min (PR) dip-coating in carboxyl functionalized Sulfamethazine Freundlich 0.51 1.83 10.45 87.21 387.2y Pp/p/H-b Zhang et al.
absence of air multi-walled carbon nanotube (2016)
y
Pristine hickory 600 °C 1 h at 10 °C/min (PR) dip-coating with carboxyl-functionalized Sulfapyridine Pb Langmuir- 0.19 2.07 20.05 77.69 359 HI/Ea Inyang
N2 atmosphere carbon nanotubes Freundlich et al. (2015)
Rice 450 °C 2 h + 200 °C 2h (PO) 0.1 M HCl Phenanthrene dibutylphthalate Freundlich 0.83 3.31 11.8 57.9 293.4 yy
Ca/p Jin et al.
N2 atmosphere (2014)
Loblolly pine 300 °C 15min N2 (PO) 4 M NaOH dried 105 + 2 h 800 °C Diclofenac naproxen ibuprofen Freundlich 0.65 0.77 21.3 72.6 1360y p/Ea Jung et al.
chip atmosphere + 0.1 M HCl (2015a)
Bamboo 550 °C (PO) 800 °C 2h N2 flow + 2 h air flow Furfural Langmuir 0.58 1.1 27.6 707.7 492.2y HI/p Li et al.
(2014)
y
Bagasse 600 °C 1h N2 (PRE) suspension with montmorillonite Methylene blue Freundlich 0.75 2.25 18.87 75.31 407 Ion exchange/Ea Yao et al.
atmosphere (2014)
Wheat straw 550 °C 5 min (PO) magnesium hydroxide-coated Direct yellow 12 Langmuir n.a. n.a. n.a. n.a. n.a. H-b Zhang et al.
(2014)
Soybean stover 700 °C 3 h 7 °C/min n.a. Trichloroethylene NR 1.3 1.27 15.45 68.81 420.3y Pp Zhang et al.
(2015b)
Peanut shell 450 °C 2h N2 (PO) impregnated Cu(NO3)2 Doxycycline hydrochloride Langmuir n.a. n.a. n.a. n.a. n.a. Ea/Strong Liu et al.
atmosphere complexation (2017)

n.a. not available.

y
BET.
yy
CO2.
 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192
the positive relationship between normalized CO2-surface area and
aromaticity which indicates that pore-filling in nanopores within
aromatic C dominate nonlinear sorption of propiconazole by
plant-residue and animal waste-derived biochars. Depending on
the biochar type, polar and/or non-polar organic compounds can
be sorbed by pore-filling on carbonized fractions of biochar
(Inyang and Dickenson, 2015). In addition the isotherms highly
nonlinear (Freundlich n < 0.71) reflect the predominance of
adsorption/pore-filling mechanisms (Han et al., 2014).
Electrostatic interaction between biochar surface and organic
pollutants is another plausible adsorption mechanism. Biochar sur-
faces are normally negatively charged, which could facilitate the
electrostatic attraction of positively charged organic compounds
(Ahmad et al., 2014). Inyang et al. (2014) suggested that electro-
static attraction was the dominant mechanisms for the methylene
blue sorption onto the carbon nanotube–biochar nanocomposites,
though diffusion controlled its rate. Similarly, Yao et al. (2014)
described that the sorption of the same dye on the clay–biochar
composites was mainly controlled by the ion exchange (with clay)
and electrostatic attraction (with biochar) mechanisms.
Hydrogen bonding (H-bonding) is another mechanism for the
sorption of polar organic pollutants on biochars. The sorption of
dibutyl phthalate by rice straw and swine manure biochars was
attributed to H-bonding between H-donor groups or water mole-
cules on biochar and O-atoms on dibutyl phthalate ester group
(Jin et al., 2014). Chen et al. (2017) demonstrated that the fast
adsorption mechanism on carbamazepine on peanut shells biochar
is due to the H-bonding between pollutants and AOH on the sur-
face of minerals (CaCO3, KAlO2, and quartz) present in the biochar.
In addition, some researches also detected that the electrostatic
repulsion between negatively charged organic compounds and bio-
chars could promote H-bonding and induce adsorption (Ahmad
et al., 2014).
The p-p electron donor acceptor (p-p EDA) interaction has been
proposed as one of the important mechanisms responsible for the
adsorption of chemicals with benzene rings. Thus, benzene rings
can donate p electrons to p-electron acceptors as the functional
groups. Xie et al. (2014) reported that the adsorption of sulfon-
amides by different pine wood biochars correlate well with the
degree of graphitization, indicating that p-p EDA interaction
between the sulfonamides molecules and the graphitic surfaces
of the biochars was the predominant adsorption mechanism.
The presence of different mechanisms for pollutant removal
was also reported in different studies. Chen et al. (2015b) sug-
gested three sorption mechanisms H-bonding between AN@O
and the O-containing moieties, hydrophobic force between ACH3
and the ordered graphitic structure, and partition process of N-
nitrosodimethylamine into the non-carbonization part of biochar.
Furthermore, the benzene rings in polychlorinated biphenyls mole-
cules can act as p-acceptor due to the substitution of chlorine
atoms which would then interact with the electron rich aromatic
moieties of the biochar via p–p EDA interaction. Chen et al.
(2017) found that hydrophobic and p-p interactions are the dom-
inated adsorption mechanism of carbamazepine on peanut shell
biochar.
It was also reported that the presence of different organic com-
pounds could modified the mechanism. Accordingly, Jin et al.
(2014) found that phenanthrene (PHE) and dibutyl phthalate
(DBP) adsorption on plant and manure biochars may be attributed
to the sorption of PHE–DBP complexes by biochars because of EDA
interactions. DBP had more adsorption sites on the biochars in the
presence of PHE via the binding form of biochar–PHE–DBP. On the
other hand, Jung et al. (2015a) observed competitive adsorption of
diclofenac, naproxen, and ibuprofen on NaOH activated biochars.
They established that hydrophobic interactions such as EDA inter-
actions and polar interactions were the main adsorption mecha-
185
nisms. Similar findings were also detected by Zhang et al. (2016).
They reported that the primary mechanisms for the adsorption of
ionizable antibiotic, sulfamethazine, included partition caused by
Van der Waals forces and adsorption caused by hydrogen bonding
and p-p EDA interaction.
4.2. Influence of biochar aging and solution chemistry on organic
pollutant adsorption
The solution chemistry (pH, salt content, dissolved organic mat-
ter. . ..) and the aging of biochar can modify the adsorption process.
Therefore, the study of the process under different environments
and conditions is desirable in order to determine the viability of
the biochar for practical applications. Accordingly, several authors
have evaluated the influence of these parameters in the removal of
organic pollutants. Thus, Peng et al. (2016) determined that the pH
had significant effects on the adsorption of pentaclorophenol by
reed biochar which could well-explained by hydrophobic, hydro-
gen bonding, electrostatic repulsion and p-p interactions. Equally,
Liu et al. (2015) found strong pH-dependence of the adsorption of
atrazine on agricultural waste biochars. More atrazine was
removed at alkaline than at acidic pH values mainly by the occur-
rence of hydrolysis. Thus, adsorption behavior at lower pH values
could be explained by a strong affinity between the protonated
biochar surface and atrazine.
The adsorption mechanisms p-p EDA can be greatly affected by
pH value. A low pH causes protonation of the carboxyl groups,
which should favor the sorption of strong p -donor compounds
affecting to the p-p EDA interactions (Inyang et al., 2014). Xie
et al. (2014) reported that pH has significant effects on the adsorp-
tion of the sulfonamides, mainly by affecting the speciation of the
adsorbate molecules and thus, their p-electron donating capability
as well as hydrophobicity. In contrast, Shan et al. (2016) reported
that solution pH values slightly affected the sorption of the phar-
maceuticals carbamazepine and tetracicline on the different bio-
chars studied.
The presence of dissolved organic matter can negatively affect
pollutant sorption by biochars as reported by Shimabuku et al.
(2016). Likewise, when electrostatic forces between sorbent sur-
faces and sorbate ions are attractive, an increase in ionic strength
will decrease the sorption capacity of the sorbate due to competi-
tion of cations with positively charged organic pollutants for sorp-
tion sites (Inyang et al., 2014). Zhang et al. (2016) also studied the
influence of salt ionic and humic acid strength on the removal of
sulfamethazine by biochar carbonaceous nanocomposites. Their
results showed that an increase in NaCl concentration also
increased slightly pollutant uptake due to the electrostatic screen-
ing of the surface charge by the counterion species added. On the
contrary, Xie et al. (2014) observed that the presence of Cu2+ and
humic acids inhibited the adsorption of the sulfamethoxazole
and sulfapyridine through the competition of available O-
functionalities or pores, respectively. Other studies stated that
the coexisting cation has different influence on pollutant removal.
Thus, Liu et al. (2017) observed that doxycycline hydrochloride
adsorption to Cu-biochar was slightly facilitated by Na+, K+ and
inhibited by Ca2+, Mg2+, Mn2+. However, the influence of these
parameters is strongly dependent of the system studied. Thus,
solution chemistry such as pH and metal ions did not show obvious
effect on N-nitrosodimethylamine removal on bamboo biochar
(Chen et al., 2015b). In the same way, Ferreira et al. (2017)
obtained that the variation of operational conditions such as tem-
perature (8–30 °C) and salinity (0.8–35‰) did not affect the tri-
caine methanesulfonate adsorption on pyrolysed paper mill
sludge. In addition, they also proved that the presence of organic
and inorganic matter in aquaculture effluents did not interfere
186 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192
with the adsorption of the studied anesthetic onto the biological
sludge-based carbon.
Incorporation of oxygen during biogeochemical weathering of
biochar may alter its parent material properties. The elevated oxy-
gen content due to biochar aging may diversely impact its affinity
towards variety of organics pollutants (Ghaffar et al., 2015). Devi
and Saroha (2014) studied the effect of the magnetic biochar com-
posites aging on pentachlorophenol removal efficiency. They
observed that the dechlorination efficiency of the magnetic biochar
composites reduces significantly due to the conversion of zero
valent iron to iron oxides. But no significant decrease in pen-
tachlorophenol removal efficiency was noticed for the biochar.
4.3. Biochar enhacements for organic pollutant removal
4.3.1. Coating biochar
Recently the use of nanoparticles into biochar production has
been revealed as an interesting approach because the biochar
matrix and the stabilized carbon nano-materials have good sorp-
tive properties. Hence, Abdul et al. (2017) obtained large improve-
ments in the adsorption capacity of phthalic acid esters onto pine
needle wood biochar combined with graphene nanosheets. The
coating treatment transformed the structure and morphology of
the raw biochar increasing the porosity and surface area as a result
of the modification sp2 and sp3-hybridized carbon atoms that facil-
itate non-covalent linkage with chemicals via hydrophobic interac-
tions, p-p EDA interactions, or non-radiative dipole–dipole
coupling. Zhang et al. (2016) synthetized carbonaceous nanocom-
posites by dip-coating straw biomass in carboxyl functionalized
multi-walled carbon nanotubes solution and then pyrolyzed at
300 °C and 600 °C in the absence of air. Operating in this way
was possible to improve significantly the surface areas and pore
volume that showed an excellent sulfamethazine sorption. As it
has been mentioned before, magnetization of biochars has been
disclosed as an interesting alternative to reduce the recovery cost
of spent adsorbent. However, several researches detected lower
sorption of magnetized carbonaceous materials compared to the
non-magnetic carbonaceous material. This fact was due to lower
surface area of magnetic composite and the low affinity of the pol-
lutant for the magnetics particles of Fe3O4 (Reguyal et al., 2017).
4.3.2. Physical and chemical pretreatment
The presence of undesirable residues on the biochar, after the
pyrolysis process, can be reduced/eliminated by chemical treat-
ments. In addition, several researches have evidenced that chemi-
cal treatments can modify the adsorption capacity due to the
introduction/removal of functional groups on the carbon surface.
Sun et al. (2016) studied the variation in sorption of propiconazole
with biochars after de-ashed treatment with HCl and HF. They
reported that the removal of minerals from biochar elevated pollu-
tant sorption because minerals may exert certain influence on
sorption via affecting spatial arrangement of polar groups and/or
organic matter–mineral interactions. In the same way, Peng et al.
(2016) demonstrated that the adsorption capacities for penta-
clorophenol on acid-washed reed biochars were higher than that
of original reed biochars. On the other hand, Chen et al. (2017)
compared peanut shell-derived biochars treated by different acids
founding a decrease in sorption of carbamazepine on acid-washed
biochars due to the removal of inorganic minerals. Ghaffar et al.
(2015) studied the structural composition and morphology of the
peanut shells biochar, before and after oxidation with HNO3/
H2SO4. Despite surface area reduction and pore destruction, they
observed an increase on di-alkyl phthalates sorption on oxidized
biochar surfaces portrayed existence of strong pollutants binding
sites due to that oxidation introduces polar functional groups (car-
boxyl and phenolic groups) on biochar surfaces.
The physical pretratement of biochar by using of steam activa-
tion and gas purping may increase the surface area and pore vol-
ume of the biochar by removing the trapped products of
incomplete combustion during thermal treatment. This fact was
evidenced by Mondal et al. (2016), who determined the increase
of surface area of the carbonized char and steam activated char
increasing the adsorption of ranitidine hydrochloride drug mole-
cule inside the surface of the biochar.
5. Continuous flow system for adsorption: Fixed-bed columns
Although several types of systems as stirred tank and
fluidized-bed columns can be used to perform the continuous
flow treatment, fixed-bed columns seem to be the best option
due to several advantages as simplicity and easy scaled up from
a laboratory-scale (De Gama et al., 2017). Thus, continuous
fixed-bed columns are selected for large-scale wastewater treat-
ment (Zhang et al., 2015b). The knowledge of the breakthrough
curves is fundamental for the design of a continuous flow system
for adsorption of pollutants, and in general should be determined
experimentally or modelling based on the kinetic behaviour and
isotherm model (Cobas et al., 2015; Mahmood et al., 2015).
Table 3 shows the operational conditions for different fixed-bed
column treatments.
5.1. Operational management
In fixed-bed columns, several general considerations should be
taken in account in order to avoid operational problems, which are
common for the adsorption of different kind of pollutants. Liquid
flows at a relatively low velocity through the spaces between the
particles and, as result of the continuous deposition of these parti-
cles, channelling and/or preferential paths and dead zone appear
increasing the pressure drop across beds and the resistance to flow
progressively (Sanromán et al., 1994).
While one focus of this study is to evaluate the recent studies
addressed on the suitability of biochar as low-cost adsorbent for
removing organic and inorganic pollutants from water, the main
goal is to propose and evaluate strategies to operate at full-scale
in a continuous flow fixed-bed or fluidized-bed column. For this
reason, several operational variables such as particle size, density,
porosity and tortuosity should be considered to guarantee its good
working order (Russo et al., 2016).
5.1.1. Particle size
One of the main problems to the application of biochar in
adsorption column is its particle size. Normally, the particle sizes
of the biochar are highly dependent upon the nature of the raw
material used and sieving before or after thermal treatment.
Thus, particle sizes of resultant biochar from organic matter
feedstock are lower than initial matter due to the shrinkage
and attrition during pyrolysis process. In a recent study, physical
and chemical characterization of six different wood-biochars was
performed. The particle size distribution curves showed that the
percentage of fine particles (<0.075 mm) and grain sizes varies
considerably among commercially available biochars. However,
their average dry bulk density values were less than 1 g/cm3 that
reflect the high internal porosity of these materials (Yargicoglu
et al., 2015).
It is well known that the maximum bed capacities and break-
through time is increased when the size of adsorbent particles is
reduced. This fact could be explained due to the finer particles have
a shorter diffusion path, that facilities the deeper penetration of
adsorbate into the adsorbent particle, increasing the adsorption
rate. In addition, the total external surface area per unit volume
 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192 187

for smaller particles inside the column is larger. Thus, the adsorp-

Rojas-Mayorga et al. (2015)

tion breakthrough curves for smaller particles follow a much more

Mayakaduwa et al. (2016)

efficient profile than larger particles, in that the breakthrough time

Shanthakumar (2017)
increased and the curves tended towards the classic shape profile

Mondal et al. (2016)

Zhang et al. (2015a)
Kizito et al. (2016)
Ding et al. (2016)

Jung et al. (2017)

(Malkoc and Nuhoglu, 2006). However, from operational point of

Vilvanathan and

Hu et al. (2015)
view, the use of finer particle sizes reduces the hydraulic conduc-
tivity and increases the high flow resistance of the adsorption col-
Reference

umn that should be avoided (Inglezakis and Grigoropoulou, 2004).

Experiments reported in the literature concluded the depen-
dency of operational conditions on particle size distribution. It is
clear in the results presented in Fig. 3 a in which the change in
the size distributions of sawdust feedstock and produced biochar
Saturation

Others 0.3
Pb,Cu 2.3
time (h)

at two temperatures 450 and 750 °C are showed. This fact could
66.3
10.5
135

149
120

be explained by the decreasing tensile strength of the material

n.a.

n.a.

n.a.

n.a.
4.8

resulting in less resistance to attrition during the biochar

25, 50, 75

processing.
500, 540,

100, 150,
100 each

5, 10, 15

10–100
(mg/L)

18.29
In several cases, the phenomena of the particles aggregation
Conc.

585

100

200

50 take place by changing the size distribution and reducing the

external surface area per unit volume, and as such addressing this
0.89–19.1 53.6 (Pb)

issue is critical to assess the viability of biochar in full-scale sys-

Ni 26.99 Co 23.63
capacity (mg/g)

tems. Several studies reported the advantages of using composite

biochar to avoid biochar’ limitations. Roh et al. (2015) reported
Adsorption

the good adsorption capacity of buffalo weed biochar-alginate

160.77
114.7

35.92

515.1

12.38
104.8

27.2

1.49

18.5

2.36

beads for treatment of cadmium, 2,4,6-trinitrotoluene and 1,3,5-tri

nitro-1,3,5-triazacyclohexane in continuous fixed-bed column
studies. They concluded that the use of biochar-alginate is able
0.7, 1.4, 2.1

to overcome the difficulties like aggregation, swelling, crumbling

Adsorbent

0.5, 1, 1.5
mass (g)

and lack of regeneration efficiency of powder biochar adsorbent

0.529
1.042

10.35
0.407

0.33

materials in large-scale wastewater treatment.

n.a.
1

Furthermore, several studies have been focused on modified

biochar as a consequence of the release of biochar powder into
Flow (mL/

15, 20, 25

2.5, 5, 7.5
1, 2.5, 5

treated effluent. The inclusion of magnetic medium (e.g., mag-

2, 4, 6
min)

netite, c-Fe2O3) by chemical co-precipitation improves the biosor-

3, 6
2

bent affinity and would be a useful method to enable the small

particle powders of biochar to be effectively separated from solu-
Breakthrough

BDST, THM,

BDST, THM,

BDST, THM,

BDST, THM,

BDST, THM,
(Langmuir)

tion with application of external magnetic fields (Chen et al., 2011).

THM, YAN

In several cases, hydrogels are used as dispersing and soldering

model
None

YNM

YNM

YNM

YNM

YNM
THM

agent to attach fine magnetic materials as zero valent iron (ZVI).

–

Thus, Zhou et al. (2014) synthetized ZVI-biochar composites con-

firmed that chitosan effectively soldered the iron particles onto
porosity

carbonaceous surfaces within the biochar pore networks.

45%

48%
42%

30%
Bed

n.a.

n.a.

n.a.

n.a.

n.a.

n.a.

n.a.

5.1.2. Porosity
3.5, 4.8, 5.8
Bed height

10, 15, 20

The diffusion in porous solids is usually the most important

1, 2, 3

1, 2, 3

controlling factor of mass transfer in adsorption and the tortuosity

(cm)
1.55

n.a.

7.5

1.2

expresses this hindrance. In thermal decomposition process, the

60

pores are formed due to water loss in dehydration process and

the volatiles release to the carbon matrix that permit to obtain dif-
Superheated steam
Alkali modification

ferent size pores encompasses from nanopores (internal diame-

Steam activation

Fe impregnated
Immobilization
alginate beads

ter < 2 nm) to macropores (internal diameter > 50 nm). Thus,

Modification

Dopping Al

biochar porosity varies significantly with pyrolysis temperature

activated

and, usually, larger pore size and surface area are achieved when
None

None

None

the temperature is increased. As example, when the temperature

Fixed-bed biochar column adsorption assays.

of pine needle pyrolysis was increased from 400 to 700 °C, porosity
of biochar increased from 0.044 to 0.19 cm3/g (Li et al., 2017a).
Trichloroethylene
Pb2+, Cu2+ Cd2+,

Furthermore, the biomass feedstock composition is another sig-

hydrochloride
Ammonium

Carbofuran

nificant variable on biochar porosity, obtaining predominantly

Phosphate
Pollutants

Zn2+, Ni2+

Co2+, Ni2+

Ranitide
Fluoride

microporous or macroporous structure biochar when the biomass

is rich in cellulose or lignin, respectively. The results showed in
As

Fig. 3b, clearly demonstrate the effect of these variables and high-
Mung bean husk

light the difference among the different feedstock used (Li et al.,
Soybean stover
Tectona grandis

n.a. not available.

doped bone
Hickory chips

Hickory chips

2017a). Similarly, Zhang et al. (2017b) determined that biochars

Aluminum-
japonica
Hardwood

produced from corn straw, rice straw and wheat straw at 400 °C
Laminaria

Rice husk
BC300
Corncobs

leaves
Sawdust
Biochar

BC700

presented different distribution of surface area and pore size. The

Table 3

abundance of nanopores of the three biochars significantly

increased as the cellulose content of the biomass increased.
188 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192

a) 70

Sawdust feedstock
60 450ºC
750ºC

Particle size distribution (%)

50

40

30

20

10

0
<= 0.6 0.6-1.18 1.18-2.36 2.36-4.75 >4.75

Particle size (mm)

b) 0.20

300
450
600
400
0.15 500
700
900
Porosity (cm /g)
3

0.10

0.05

0.00
Maize straw Pine needle Municipal biosolids Swine manure

Biomass feedstock

Fig. 3. Effect of pyrolysis temperature on: a) particle size distribution of sawdust feedstock (based on data from Downie et al., 2009) and b) biochar’ pore size distribution
(based on data from Li et al., 2017a).

As was mentioned above, efforts have been made to prepare
biochar based composite with improved properties to enhance
adsorption capacity by combining biochar with organic and/or
inorganic materials through physicochemical methods. In this
framework, the porosity biochar matrix was enhanced by com-
bined electrochemical modification in which an electrolyte would
generate strong oxidants in solution by electrochemical reaction.
This method was applied by Jung and Ahn (2016) who reported
the immersion of dried marine macroalgae in MgCl2 solution under
20 V voltage for 10 min prior pyrolysis. The physical and chemical
characterization of the resultant biochar proved that is a potent
additional technique to prepare effectively modified-biochar. This
method enhances the porosity of the biochar surface but also pro-
vides the nano-sized MgO particles dispersion, which enabled
higher phosphate adsorption capability.
5.2. Regeneration
The suitability of the designed systems for their regeneration
and reuse in different cycles is also required. Few studies of biochar
regeneration at column scale have been performed. The regenera-
tion of the adsorbents can minimize the operational cost.
The desorption of the pollutants from the columns requires the
utilization of different eluents related to the compound desired to
 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192 189

remove. The use of a strong acid, HCl, as eluting agent has been
reported in the regeneration of biochars containing metals. This
eluent was applied to the removal of adsorbed metals Ni and Co
on biochar from Tectona grandis leaves (Vilvanathan and
Shanthakumar, 2017), and the removal of Pb from alkali-
modified hickory biochar (Ding et al., 2016). The systems demon-
strated their feasibility during at least four adsorption-desorption
cycles with a decrease in the efficiency due to the mass loss during
these cycles. The use of this eluent may suggest an ionic exchange
as main mechanism for metal release in the regeneration. How-
ever, another eluent NaHCO3 was proposed by Hu et al. (2015) to
remove As from Fe-impregnated biochar reaching a removal per-
centage around 85%.
In the column desorption of an organic compound as TCE, Zhang
et al. (2015b) proposed an elution with 25% of methanol for bio-
char regeneration. The desorption was performed at a low flow
rate observing initially a sharp increase of the desorption where
upon decreased over time. This fact may also suggest multiple
adsorption mechanism involved.
5.3. Modelling fixed bed adsorption
The design of an appropriate column treatment system requires
a good prediction of the effluent behaviour and, therefore, the
breakthrough curves. Breakthrough curves are one of the most
characteristic parameters in a continuous treatment system. The
scale up of the adsorption requires the definition of several param-
eters related to the column design. Among them, bed height, flow
rate and inlet concentration are factors with a significant effect in
the adsorption process and consequently the design of new treat-
ment columns.
5.3.1. Influence of bed height
Bed height represents an important effect on the dynamic per-
formance of the column and, therefore, breakthrough time and
adsorbent bed performance being a determining factor in the bio-
char capacity for the removal of the interest compounds.
Several researches have demonstrated a relationship between
the bed height and the breakthrough time with adsorption ability.
This fact was reported by Vilvanathan and Shanthakumar (2017)
on metal adsorption, Mondal et al. (2016) on carbofuran removal
and Zhang et al. (2015b) on TCE removal. When the column height
is enlarged, more adsorbent mass is added to the system and
results on (i) providing more linking points to the biochar and also
(ii) enhancing the adsorption capacity. Meanwhile, with the con-
comitant increased adsorption capacity, the residence time also
increment. Thus, the bed height is directly related to the residence
time and consequently, this implies higher diffusion through the
biochar.
5.3.2. Effect of flow rate
Flow rate is another significant parameter with strong influence
on continuous treatment system. An inverse relationship between
flow rate and adsorption capacity has been reported on adsorption
of different pollutants such as metals, phosphates and carbofuran
by biochar derived from several biomass feedstocks (Jung et al.,
2017; Kizito et al., 2016; Mondal et al., 2016). This fact may be
explained as a result of scarce contact time on biochar bed which
is not enough to attain the equilibrium, leading to a sharper slope
of breakthrough curve. On the contrary, low flows favour a higher
contact time becoming the diffusion into the pores more effective.
5.3.3. Effect of inlet concentration
The design of an efficient operational column requires the study
of the inlet concentration. The diffusion usually depends on the
concentration and a high concentration difference provides a high
driving force for the adsorption process. Hence, the available bind-
ing points are sharply reduced at high pollutant concentration,
leading to the decrease of the breakthrough time and biochar sat-
uration. On the contrary, the biochar adsorption capacity achieved
the highest values when the inlet flow was the maximum (Jung
et al., 2017; Kizito et al., 2016; Mondal et al., 2016). This fact
may be explained by the slow transport and lower diffusion value
or mass transport coefficient.
5.3.4. Modelling of the column data
Several models have been considered to accurately describe the
experimental data and predict adsorption behaviour on biochar-
fixed beds. The dynamic behaviour has been studied by empirical
or semi-empirical models due to their lower mathematical com-
plexity. Three experimental models (Thomas, Adam’s-Bohart and
Yoon-Nelson) described in Table 4 are commonly used for the anal-
ysis of the experimental data to predict the performance of the
column.
5.3.4.1. Thomas model (THM). This model, widely used for adsorp-
tion process without external/internal diffusion limitations,
assumes that the experimental data follow Langmuir adsorption
isotherm and no axial dispersion is considered based on the
assumption that the rate driving force obeys second-order reversi-
ble reaction kinetics.
This model has been successfully used to fit the biochar column
adsorption for metals by Tectona grandis biochar (Vilvanathan and
Shanthakumar, 2017), ammonium by corncob, hardwood and saw-
dust biochars (Kizito et al., 2016), for carbofuran by rice husk bio-
char (Mayakaduwa et al., 2016) or TCE by soybean stover biochar
(Zhang et al., 2015b). In all these reported studies, the increase of
inlet flow originated a rise in the adsorption rate constant, and a
decrease in the adsorption capacity of the bed due to the faster
exhaustion of the biochars. However, this rate constant decreased

Table 4
Empirical and semiempirical breakthrough models.

Model Expression Model parameters

Thomas model (THM)
Adam’s–Bohart model (BDST)
Yoon–Nelson model (YNM)
ln(C0/Ct  1) = KThq0W/Q  KThC0t
ln(Ct/C0) = KABC0t  KABN0(Z/U0)
ln(Ct/(C0  Ct) = KYNt-sKYN
KTh, rate constant (mL/minmg) Ct, outlet concentration at time t (mg/L)
q0, equilibrium uptake (mg/g) Q, flow rate (mL/min)
W, mass of biosorbent (g) t, time (min)
C0, inlet concentration (mg/L)
KAB, rate constant (L/mgmin) t, time (min)
C0, inlet concentration (mg/L) N0, sorption capacity of bed (mg/L)
Ct, outlet concentration (mg/L) Z, bed height of the column (cm)
U, linear velocity (cm/min)
KYN, rate constant (L/min) s, time required
for 50% adsorbate breakthrough (min) t,
breakthrough time (min)
190 E. Rosales et al. / Bioresource Technology 246 (2017) 176–192
and the adsorption capacity of the bed was improved when the ini-
tial concentration or the bed height was enlarged allowing more
contact time and amount of biochar to remove the pollutants.
The good fitting to this model also indicates that the main driving
force related to the adsorption is the concentration gradient of the
pollutant. This model failed to evaluate the breakthrough curves
when the adsorption process implies a significant axial dispersion
of the pollutant inside the column as reported by Rojas-Mayorga
et al. (2015) in the adsorption of fluoride or drugs as ranitidine
hypochloride by mung bean husk biochar (Mondal et al., 2016).
As it was previously stated, the fitting to this model of the data
suggested that external and internal diffusions are not the only
rate limiting steps in the adsorption (Vilvanathan and
Shanthakumar, 2017).
5.3.4.2. Adam’s-Bohart model (BDST). This model assumes that the
equilibrium is not reached instantaneously, and the adsorption
rate is proportional to both the residual capacity of the biochar
and the concentration of the adsorbate species. The adsorption rate
of the pollutants in the biochar enhances by increasing the flow
rate; however, reduce the bed adsorption capacity, and critical
bed height (Jung et al., 2017; Kizito et al., 2016). Kizito et al.
(2016) showed an increment on the bed height and flow increases
the residence time and the diffusion process in the column. Fur-
thermore, the use of high concentrations and flow rates influence
the system kinetics and affects to the column behaviour. It has
been reported that if the adsorption rate increases by increasing
the flow rate, the external mass transfer dominates the overall sys-
tem kinetics particularly in the first steps of the fixed-bed adsorp-
tion. This fact has been stated for different pollutants such as
metals (Vilvanathan and Shanthakumar, 2017), pharmaceuticals
(Mondal et al., 2016), phosphates (Jung et al., 2017) or ammonium
(Kizito et al., 2016).
5.3.4.3. Yoon-Nelson model (YNM). The basis of this method is that
the rate of decrease in the probability of adsorption for each adsor-
bate molecule is proportional to the probability of adsorbate
adsorption and the probability of adsorbate breakthrough on the
adsorbent. This model determines the rate constant of the column
adsorption and the time required for reaching 50% of adsorbate
breakthrough.
The behaviour of the modeled systems in the literature is no
dependent of the considered pollutant. The higher value of the
inlet flow and initial concentration causes a decrease in the resi-
dence time due to a faster saturation of the column and an increase
in the adsorption rate (Vilvanathan and Shanthakumar, 2017; Jung
et al., 2017; Kizito et al., 2016; Mondal et al., 2016). One of the
main drawbacks of this model is that no detailed data concerning
to the physical properties of the column bed or about pollutants
and biochar characteristics are considered. Moreover, the adsorp-
tion process is considered as a constant and linear pattern.
6. Conclusions
Based on the extensive literature reviewed, it is concluded that
biochar can be produced from a huge variety of feedstocks at dif-
ferent thermal conditions and its properties could be improved
by control of these variables and using strategies that provided
functionality and permit the synthesis of biochars ‘‘on demand”.
Until date, despite an extensive literature related to their physical/
chemical properties and adsorption kinetics and equilibrium stud-
ies for the pollutants removal, there is a lack of data concerning the
operation in continuous flow systems and their regeneration. To
close these knowledge gaps, more studies are needed in further
investigations.
Acknowledgements
The authors would like to thank to the Spanish Ministry of
Economy and Competitiveness for the financial support of Emilio
Rosales under Juan de la Cierva postdoctoral grant.
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