Advanced technologies 12(1) (2023) 57-74

BIOCHAR AND HYDROCHAR AS ADSORBENTS FOR THE REMOVAL

OF CONTAMINANTS OF EMERGING CONCERN FROM WASTEWATER
Aleksandra Adamović1, Mirjana Petronijević2*, Sanja Panić2, Dragan Cvetković1,
Igor Antić2, Zoran Petrović3, Nataša Đurišić-Mladenović2 (MINI-REVIEW PAPER)
UDC 631.878:628.316.12
DOI: 10.5937/savteh2301057A
1University of Niš, Faculty of Technology, Leskovac, Serbia
2University of Novi Sad, Faculty of Technology Novi Sad, Novi Sad, Serbia
3University of East Sarajevo, Faculty of Technology, Zvornik, Republic of Srpska, Bosnia and Herzegovina

Carbon materials have been used extensively in water treatment, and among
them, biochar (BC) and hydrochar (HC) have been studied in recent decades as
eco-friendly adsorbents in water treatment. Specific physicochemical characteris­
tics of chars allow for the effective removal of a wide range of water contaminants, Keywords: biochar, hydrochar, adsorp­
including emerging contaminants (e.g. pharmaceutically active compounds, agro­ tion, contaminants of emerging concern
chemicals, and endocrine disrupting compounds). BC and HC can be synthesized (CECs), water treatment
from different biomass sources, even from biowaste, which makes them low-cost
materials. In fact, the application of waste biomass for char production can be
designated as a promising way towards achieving sustainable development goals
concerning solid waste management. The selection of feedstock material and op­
timization of the reaction conditions of the carbonization process (pyrolysis, hydro­
thermal carbonisation, etc.) influence the performances of char-based materials
leading to the products with desired characteristics suitable for the removal of a
certain group of compounds. The objective of this review is to provide an overview
of the current status of research regarding the use of BC and HC as adsorbents in
the removal of contaminants of emerging concern (CECs) from wastewater. The
physicochemical properties of the substrates, types of synthesis, characterization
techniques, as well as mechanism and influence of process parameters in the
removal of selected CECs from wastewater, will also be addressed.

Introduction

Population growth demands the invention of new and human health, as well as the impact of their decom­
technologies and/or the improvement of existing ones in position and transformation products, is still unknown.
order to provide enough energy and food for mankind. At The majority of these compounds are not covered by
the same time, constant industrialization is among the environmental quality standards (EQS) based on annual
main sources of harmful pollutants in the environment. average (AA-EQS) and maximum allowable (MAC-EQS)
An indispensable product of industrial and living activi­ concentrations defined by Directive 2013/39/EU under
ties is the production and discharge of wastewater con­ the currently active European Union (EU) water legis­
taining various contaminants. Contaminants that can be lation, the Water Framework Directive (WFD, 2000/60/
found in wastewater are pharmaceutically active com­ EC) [3]. Only for a limited number of pharmaceutically
pounds, currently used pesticides, endocrine-disrupting active compounds, does the appropriate data exist on
compounds, phenols, X-ray contrasting agents, food ad­ ecotoxicity that is adequate for risk assessment. The
ditives, surfactants, personal care products, veterinary European regulation failed to impose allowed limits for
products, steroids and engineered nanomaterials. Most CECs presence in the environment with the exception of
of the mentioned organic contaminants have been iden­ some compounds (five pharmaceuticals, one synthetic
tified as potentially dangerous to environmental health and two natural hormones, one antioxidant and one or­
and/or humans recently. The commonly accepted name ganic UV filter, and eight pesticides) listed under the EU
for such compounds is compounds of emerging con­ Watch List for Which Predicted No-Effect Concentrations
cerns, CECs. CECs enter the environment in different (PNECs) where established [4].
pathways. These contaminants can be found in surface There are several techniques that could be used
waters in a wide concentration range (from a few ng/L to for organic contaminants removal from water matrices,
μg/L), and up to a few mg/L in wastewater [1, 2]. However, such as different oxidation processes, coagulation, ad­
the impact of all these components on the environment sorption, etc. However, liquid-solid adsorption stands out

*Author address: Mirjana Petronijević, University of Novi Sad, Faculty of Technology Novi Sad,
Bulevar cara Lazara 1, Novi Sad, Serbia;
email: mirjana.petronijevic@uns.ac.rs
The manuscript received: February, 20, 2023.
Paper accepted: June, 12, 2023.

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Advanced technologies 12(1) (2023) 57-74

among them as an economically profitable process that residues, can all be utilized to produce high-quality chars
can be used to achieve a high degree of pollutant re­ [14, 20]. BC produced from lignocellulosic biomass at
moval [5]. At the same time, adsorption is a technologi­ temperatures ≥500 °C is characterized by a high content
cally simple process that could be easily implemented as of carbon (>60%) and low to medium ash content (10-
a new one or within the existing water treatment systems. 21%) [20]. In contrast, BC produced from animal manure
The efficiency of pollutant removal by adsorption occurs has high ash content (48-67%) and a very high pH value
on active sites located on the surface of the adsorbent due to the inorganic materials present in the biomass
material. Numerous factors, including temperature, pH, sources [9, 20]. HCs derived from different lignocellu­
and adsorbate concentration, can influence the capacity losic biomass (crop and forestry residues) are mostly
of the adsorption process. Fluctuations of these factors characterized by low ash content (up to 13%) [14]. The
can also result in the desorption of pollutants from the total carbon content in the structure of HCs obtained
surface back into the water [6]. The primary mechanisms from lignocellulosic biomass is high (38-91%) [14]. HCs
involved in the adsorption of organics are hydrophobic obtained from non-lignocellulosic biomass (e.g. sewage
and electrostatic interactions, the formation of hydrogen sludge), are characterized by a wide range of ash (23-
bonds, partitioning, pore-filling, and π-π interactions be­ 82%) and the total carbon content (11-85%) [14]. The
tween the adsorbent and organic pollutant molecules [7]. application of waste biomass for char production can
Carbon materials represent a group of very important be designated as a promising way towards achieving
cost-effective and eco-friendly sustainable adsorbents sustainable development goals in relation to solid waste
with high efficacy for organic pollutants removal [6, 8-10]. management.
Biochar (BC) and hydrochar (HC) are carbon materials This review aims to provide the latest research data in
obtained by dry/wet carbonization of biomaterial, respec­ the area of CECs removal from water matrices using BC,
tively. In general, characteristics such as specific surface HC and their composites. The methods for preparation
area (SSA) and porosity are significantly higher for BC and physicochemical characterization of BC and HC are
than HC. However, those parameters are affected by the comprehensively reviewed, along with the adsorption
type of raw material and reaction conditions. Still, there mechanisms of organic pollutants (pesticides, pharma­
are cases where HC with a high SSA is also obtained, or ceutics, etc.) on the appropriate chars.
HCs have to be activated. For example, authors Kabakcı
and Baran synthetized HC from different lignocellulosic PRODUCTION OF BIOCHAR AND HYDROCHAR
biowastes (wood sawdust, olive pomace, walnut shell, The most widely used biomass conversion technique
apricot seed, tea stalk, hazelnut husk) [11]. The HCs for the production of BC is pyrolysis. Formation of BC
yield was in the range of 55.7-71%, and the SSA of HCs also follows the process of biomass gasification, but in
after KOH activation was 308.9-666.7 m2/g [11]. Car­ much lower yields than is the case for pyrolysis. On the
bonization encompasses a variety of technologies which other hand, HCs are primarily produced through hydro­
can be classified into three main processes - pyrolysis, thermal processes such as HTC and HTL. The reaction
hydrothermal processes and gasification [12, 13]. BC conditions such as temperature, pH, heating rate, resi­
is produced by pyrolysis in the absence of oxygen and dence time, substrate concentration and feedstock type
generates bio-oil and combustible gas as by-products. play significant roles in the carbonization process, influ­
On the other hand, HC is obtained from hydrothermal encing yield and physicochemical characteristics of the
processes, such as hydrothermal carbonization (HTC) produced chars. The parallel between the two mean car­
and hydrothermal liquefaction (HTL) [10, 13]. The pro­ bonisation processes and obtained products is present
duction of HCs is significantly higher when using the in Figure 1.
HTC method (12-91% from lignocellulosic biomass and
31-94% from sewage sludge) [14], compared to HTL Pyrolysis
(16-38% from lignocellulosic biomass [14] and 29-43% Pyrolysis represents a method for producing BC from
from soils [16]). The advantage of the hydrothermal pro­ biomass due to its versatility and effectiveness. This ther­
cess in relation to pyrolysis is that wet biomass can be mal decomposition process is carried out at high tempera­
used directly, without the need for drying. The yield and tures (typically 400-800 °C) without the presence of oxy­
characteristics of chars largely depend on the conditions gen [21]. This process breaks down the natural polymers
of the applied process (pressure, temperature, reactor present in biomass such as cellulose, hemicellulose, and
design, heating rate, residence time, and the nature of lignin, resulting in the production of biochar, bio-oil, and
the raw biomaterial) [14, 17, 18]. Also, the properties of non-condensable gases [22, 23]. Natural polymers un­
chars could be tailored by using different catalysts during dergo several transformations [23], such as disintegration,
their production [19]. cross-linking, and then fragmentation [24]. Hemicellulose
Biomass from a wide range of sources can be used decomposes at temperatures between 200-260 °C, fol­
to produce both BC and HC with favourable characteris­ lowed by cellulose (240-350 °C), and lignin (280-500 °C)
tics. Lignocellulosic biomass, such as crop and forestry [25]. Pyrolysis can be classified into different categories
residues, as well as non-lignocellulosic materials, such based on product requirements, operating conditions, and
as sewage sludge, algae, sugar, hair, bone, and meat feedstock type, which are described below.

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Figure 1. Main characteristics of chars produced by pyrolysis and hydrothermal carbonization.

Slow pyrolysis is a conventional method performed nomic viability [33].

at temperatures < 700 °C and is characterized by a long
retention time (>1 h) and a slow heating rate (5–7 °C/ Gasification
min). The main product at the end of the process is BC Unlike pyrolysis, gasification is a thermochemical
(35–45% yield), along with bio-oil (25–35% yield) and process that includes the degradation of carbonaceous
gas products (20–30% yield) [26-28]. feedstock at high temperatures, typically ranging be­
Fast pyrolysis is popular in the biofuels industry and is tween 700-1500 °C. The process takes place in the
characterized by high reaction temperatures (300–1000 °C), presence of an oxygen-based gasification agent (air,
high heating rates (typically >300 °C/min) and short re­ pure oxygen, steam, etc.) [18, 28, 34, 35]. While bio­
tention time (<2 s) [29]. Primarily, it is used in the biofuel mass conversion to BC via gasification is possible, it is
industry to produce bio-oil (65-70% yield), while BC and not commonly reported, as the primary product of gasi­
gas yields are lower (10% and 20%, respectively) [28]. fication is syngas (i.e. H2, CO, CO2, CH4), with a yield of
Flash or ultra-fast pyrolysis represents an improved type approximately 85% [28]. Biochar and bio-oil are consid­
of fast pyrolysis utilizing a higher heating rate (>1000 °C/s) ered by-products with a much lower yield (10% and 5%,
and a very short reaction time (0.1-1 s). The reaction respectively) [18, 28, 34].
temperature can vary between 700-1000 °C (even up
to 1200 °C) [30]. The main product of flash pyrolysis of Hydrothermal carbonization
biomass is bio-oil (70-80% yield), while BC and gas are In contrast to the aforementioned thermochemical
obtained in a markedly lower percentage (10-15 and methods of char production, hydrothermal processes
5-20%, respectively) [28, 31]. Bio-oil is viscous and con­ for biomass conversion involve suspending biomass in
tains high levels of oxygen-containing compounds [33] water under moderate temperature conditions, typically be­
and it can be used as a bioliquid for heating or as biofuel tween 180-350 °C and at pressures ranging from 2-22 MPa
in transport, but after appropriate treatment [32]. [36, 37]. These processes are characterized by relatively
The main product obtained through slow pyrolysis is short retention times (5-240 min) and involve a series
biochar, while bio-oil is the main product of flash pyroly­ of reactions such as decarboxylation, dehydration, con­
sis. Generally, the yield of bio-oil increases as the forma­ densation, and hydrolysis, which are initiated by the
tion of biochar decreases, irrespective of the pyrolysis presence of water in a subcritical state [38]. The primary
method employed, whether it is slow, intermediate, fast, product of HTC is a solid residue (HC), which accounts
or flash pyrolysis. On the other hand, the gas fraction for 35-80% of the product yield [37]. Other by-products
does not exhibit significant variations among different include liquid bio-oil and gases, mainly consisting of CO2
conventional pyrolysis techniques. Notably, the introduc­ and CO [39].
tion of catalysts alters the distribution and composition of When biomass is subjected to hydrothermal process­
the pyrolysis products, typically promoting deoxygena­ es, hemicellulose is broken down into oligosaccharides,
tion reactions. The techno-economic analysis demon­ pentoses and hexoses, while cellulose breaks down into
strates the potential for scaling up the pyrolysis process. hexose. The process of converting monosaccharides
However, current research on this topic remains frag­ into furfural and hydroxymethylfurfural involves several
mented, with limited comprehensive studies that com­ reactions, including ring opening, intramolecular cycliza­
pare conventional, advanced, and emerging approaches tion, dehydration, etc. [40]. Polymerization of furfural and
to biomass pyrolysis from an economic perspective. This hydroxymethylfurfural results in the formation of hydro­
highlights the need for extensive research in the future carbon microstructures. The hydrochar network is cre­
to address this gap and provide a more comprehensive ated through solid-solid conversions of the unhydrolyzed
understanding of biomass pyrolysis in terms of its eco­ fraction of cellulose and hemicellulose, as well as lignin

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[40]. Due to its low solubility in water, lignin, an amor­ CHARACTERIZATION OF BIOCHAR AND HYDROCHAR
phous heteropolymer, undergoes hydrolysis to form sol­ The properties of BC and HC are influenced by sev­
uble fragments, including aromatic monomers, dimers, eral factors including the raw material, synthesis process,
and oligomers. This hydrolysis process plays a limiting and reaction conditions. To assess the quality of the ob­
factor in determining the formation of secondary char. tained chars and determine their potential application,
The remaining insoluble lignin undergoes mild dehydra­ it is necessary to carry out their detailed characteriza­
tion and decarboxylation reactions, resulting in the for­ tion (e.g. SSA, porosity, and elemental composition). To
mation of pyrolysis char [41]. Hydrochars derived from achieve this, various instrumental techniques need to
non-lignocellulosic biomass, such as sewage sludge, be applied. A thorough understanding of the relationship
typically exhibit characteristics such as low heating val­ between the production conditions and physicochemical
ue, low surface area, limited dewatering ability, and high properties of the chars is essential for their optimal uti­
concentrations of heavy metals [14]. lization.
Temperature plays a crucial role in the hydrothermal
process, as it directly affects the conversion of biomass Characterization techniques
to HC. Higher temperatures lead to higher conversion The properties of chars can be classified into four
rates of biomass to HC, but this is accompanied by a re­ main categories: chemical properties, physical proper­
duction in the HC yield and an increase in bio-oil and gas ties, surface structure and morphology, and thermal
yields [40]. Increasing the residence time of biomass in stability properties [9]. The instrumental techniques that
the process also influences the conversion rate similarly are most often used in the characterization of chars are
to temperature [42]. present in Table 1.
However, the improvement of the quality of HCs,
such as sewage sludge-derived HCs, can be done by Table 1. Instrumental techniques for char characterization
applying the HTC process that involves treating two dif­ (modified from [9, 12, 20])
ferent raw materials simultaneously (Co-HTC). During
Co-HTC, the interaction between these raw materials
leads to synergistic effects. This approach offers several
advantages over single-feedstock HTC. It overcomes
the limitations of relying solely on a single feedstock,
mitigates any undesirable characteristics of individual
raw materials, etc. [14].

Hydrothermal liquefaction
Hydrothermal liquefaction (HTL) is a process that in­
volves the use of supercritical water and high tempera­
tures (250–375 °C) and pressure (10–22 MPa) to convert
biomass into bio-oil, with relatively low yields of HC and
gas [40]. The yield of HC is dependent on various factors, Biochar and hydrochar properties
such as feedstock characteristics and reaction condi­ BC and HC show different physical and chemical
tions, and can reach up to 15% [43]. However, there are properties that significantly affect their potential applica­
examples where by using HTL a high yield of HC was tion. It is important to note that BC and HC have unique
obtained. Ahmad et al (2019) subjected the antibiotic fer­ properties that vary depending on several factors, such
mentative residue (lincomycin residue) to microwave-as­ as the type of biomass used, the reaction temperature,
sisted hydrothermal liquefaction and obtained HC yield and the residence time [46]. The synthesis process in­
in the range of 45-93% [44]. The effect of temperature volves complex chemical reactions, leading to signifi­
on biomass components can differ in HTL, with cellulose, cant differences in the physicochemical properties of BC
hemicellulose, and lignin reacting differently to temper­ and HC. Table 2 and Table 3 provide a summary of the
ature changes [37]. The reaction conditions of the HTL characteristics of BCs and HCs derived from various bio­
process also have a significant impact on the resulting mass. It is crucial to understand the correlation between
products. Panchal et al. (2017) found that increasing the char production conditions and their properties to deter­
temperature from 250 °C to 350 °C led to a decrease in mine their potential applications accurately. The relation
the yield of bio-oil, while increasing the pressure from 10 between the characteristics of BC/HC and their potential
MPa to 22 MPa led to an increase in the yield of bio-oil. application is shown in Figure 2.
Additionally, the composition and properties of the bio-oil
were found to be affected by the reaction conditions, with
higher temperatures leading to a higher concentration
of oxygen-containing compounds and lower concentra­
tions of nitrogen-containing compounds [45].

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Figure 2. Characteristics of chars important to its potential applications.

The composition of char is highly dependent on the achieved, resulting in chars with low heating value (HV)
feedstock used for its synthesis, with lignocellulosic [48]. As the reaction temperature increases, the HV of
waste biomass being the most common. The amounts the char increases. This happens because, at higher
of cellulose, hemicellulose, and lignin present in the temperatures, cellulose and hemicellulose are broken
feedstock greatly influence the composition of the result­ down, leaving lignin, which has a higher heating value.
ing char. Moisture (MO), ash, volatile matter (VM), and HC has a higher heating value compared to BC, due to
fixed carbon (FC) content in both BC and HC are mainly the presence of more volatile and oxygen-containing
determined by the feedstock composition (Tables 2 and functional groups. During HTC, which is performed in an
3). Industrial waste-derived BCs have higher ash con­ aqueous medium at milder temperatures, hemicellulose
tent compared to other feedstocks. The VM content can is degraded faster [49]. In contrast, BC produced via py­
range from 24.9% to 78.3%, the ash content from 2.9% rolysis has a lower heating value due to the removal of
to 65.7%, and the FC content can be up to 54.8% in vari­ oxidative functional groups during the process, resulting
ous feedstock-derived BCs (Table 2). HC is produced in in a more carbon-rich material. The atomic ratio of H/C
an aqueous medium, and therefore, inorganic substanc­ and O/C for HC is higher compared to those for BC [50].
es from the biomass are removed resulting in lower ash The temperature used in the synthesis process has a
content, while pyrolysis-derived BC retains the minerals significant impact on the physical and chemical proper­
present in the feedstock [47]. Depending on the initial ties of both BC and HC. BC produced at temperatures
biomass, the largest part of HC represents VM (16.8– around 500-600 °C is mainly aromatic and has a graph­
83.8%) and ash (0.1–82.0%), while FC ranges from 0.1 ite-like structure. In contrast, HC produced at lower tem­
to 53.9% (Table 3). In general, the highest percentage of peratures about 200-250 °C contains residues more alkyl
VM is present in HC obtained from algae, wood, and ur­ in nature [51]. BC synthesized at moderate temperatures
ban waste; while the highest yield of FC was measured may possess O and N functional groups on its surface,
in HC derived from wood waste biomass. while BC produced at temperatures over 700 °C becomes
The reaction temperature and duration of the reac­ hydrophobic and resistant to degradation due to the loss
tion have a significant influence on the physicochemical of almost all O and H in its structure [17]. Considering
properties and yield of BC and HC. There is a correlation that it is produced at low temperatures, the greater pres­
between the applied reaction temperature and HC yield ence of oxygen groups on the surface of HC contributes
and carbon conversion. When the synthesis takes place to its acidic character compared to BC, which is alkaline
at low temperatures and with a short retention time, a in nature. Additionally, BCs have an alkaline pH due to
high yield of char occurs, but a low carbon conversion is the high content of inorganic carbonates and ash. BCs

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have a large SSA and pore volume [52, 53], which in­ alized char can selectively adsorb target contaminants
creases with increasing temperature. BC with high SSA from water. Alkaline activation (with sodium hydroxide
(up to 1570 m2/g) is usually obtained from agro-waste and potassium hydroxide) can enhance the SSA of char
and lignocellulose biomass (Table 2). The BC with ex­ and attach oxygenated functional groups to its surface.
tremely low SSA (0.59 m2/g) reported in the literature This type of modification results in a positive charge cre­
was groundnut char. The hydrochars derived from agro- ated on the surface of the char which in turn helps in the
biowaste are characterized by high SSA and pore volumes adsorption of negatively charged pollutants. For exam­
amounting up to 667 m2/g and 0.39 cm3/g, respectively ple, surface-modified human hair-derived BC, resulting
(Table 3) [11]. The lowest SSA was recorded for HCs in a high porosity with an SSA of 3015 m2/g, exhibited
derived from industrial waste. enhanced adsorption performance for various organic
BC and HC were found to be effective adsorbents pollutants [89].
in water treatment. However, in order to improve their Impregnation of metals or metal oxides (such as ZnO,
adsorption capacity and selectivity, these chars are of­ Fe, CuO, and Fe3O4) into the carbon structure can also
ten subjected to activation/functionalization steps. The improve its adsorption characteristics (Table 4). Further­
characteristics of some BC/HC-based adsorbents after more, BC and HC in this form can be used as catalysts in
modification are shown in Table 4. advanced processes [58, 59, 90]. Metals or metal oxides
Activation can be achieved through physical or chem­ (especially Fe) impregnated chars are used in heteroge­
ical treatments that increase the char's porosity and neous Fenton/Fenton-like processes for water treatment
surface area, resulting in enhanced adsorption capacity. [59, 65, 90, 94]. Metal oxide/char composites have found
Physical activation (thermal or dry activation) involves their application in photocatalytic processes [58], as well
heating the char in the presence of steam or CO2, while as in persulfate oxidation processes [43, 63]. Magnetic
chemical activation implies the utilization of chemical particles can be enriched by chars in order to effectively
activation agents and mostly includes acid modification, utilize them as adsorbents [91-93]. After treatment, they
alkaline modification, metal salts, and/or oxidizing agent can be easily separated from water using an external
modification [9]. Acid activation (with sulphuric acid, hy­ magnetic field.
drochloric acid, nitric acid, oxalic acid, phosphorous acid,
and citric acid) is necessary to modify the char surface
by introducing acid functional groups and eliminating
metallic impurities. Consequently, the obtained function­

Table 2. Characterization of BC produced from various feedstocks (modified from [54, 55]).

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Table 3. Characteristics of HC derived from different feedstocks (modified from [14, 66]).

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Table 4. Characteristics of different BC/HC-based composites.

ADSORPTION MECHANISM OF CECs REMOVAL the π aromatic char system behaves like an electron ac­
USING BC/HC-BASED MATERIALS ceptor, while if it was prepared at a temperature >500 °C,
The heterogeneous structure of BC and HC allows the char behaves like a donor [99, 100]. The presence of
them to remove organic pollutants from water through functional groups (e.g. hydroxyl, carbonyl, carboxyl, and
various adsorption mechanisms, including physical ad­ amine) on the surface of chars increases the adsorption
sorption, precipitation and complexation, and pore filling affinity of organic contaminants onto char.
[95]. The adsorption efficiency is influenced by several The adsorption mechanism by hydrophobic interac­
factors, such as the pH, ionic strength, and polarity of the tions is characteristic of the hydrophobic and neutral or­
organic pollutant. ganic compounds due to their highly hydrophobic nature.
Electrostatic interactions primarily occur between Chars that have been prepared at high temperatures
ionisable organic compounds and the positively charged show a greater affinity for pollutant binding through hy­
surface of BC. The efficiency of adsorption using elec­ drophobic interactions. At high synthesis temperatures,
trostatic interactions is influenced by the pH and ionic there is a loss of functional groups containing oxygen
strength of the water matrices [96]. and hydrogen, which makes char more aromatic and
Adsorption of organic contaminants onto char using hydrophobic, and therefore more suitable for removing
the pore filling mechanism depends on several factors, hydrophobic organic pollutants [101].
including the total volume of micropores and mesopores In general, the adsorption of pollutants from water
of the char, the type and nature of the char, as well as matrices by BC/HC depends on the characteristics of
the polarity of the organic pollutant. High efficiency of the both pollutants and adsorbents and process conditions,
process is achieved when adsorbents with a low content involving various mechanisms. Pore filling, hydrogen
of volatile matter are applied and used to treat low-pol­ bonding, and π–π interactions with the surface of the
luted samples [97]. char are the possible mechanisms for antibiotics re­
The adsorption of organic contaminants by the parti­ moval [115, 116]. The adsorption of endocrine-disrupting
tioning mechanism takes place by diffusion of adsorbate chemicals, in addition to the mechanism of π–π interac­
into the pores of the non-carbonized part of the char and tions, hydrophobic interactions and hydrogen bonding,
interaction with it. This mechanism is more efficient us­ also includes electrostatic interactions [124].
ing char with a high content of volatile substances and in
the cases treating effluents with a high concentration of Factors affecting the efficiency of organic pollutants
organic pollutants [98]. removal
Adsorption of aromatic compounds usually takes The efficiency of removing pollutants from water us­
place via the electron donor/acceptor interaction mecha­ ing BC/HC as adsorbents depends on a lot of factors. In
nism on chars that have a structure similar to graphene, addition to the properties of the chars and the nature of
which is affected by the char production temperature. In the organic pollutants, the operating reaction conditions
the case of char synthesized at temperatures <500 °C, of the process have a great influence on the efficiency,

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such as adsorbent content, pH, temperature, presence Utilizing KOH-activated BC, high adsorption capaci­
of other constituents of water (e.g. ions) [ 9, 102-104]. ties of tetracycline, oxytetracycline and chlortetracycline
The content of adsorbent, as well as the initial content have been achieved amounting to 476.19 mg/g, 407.5
of contaminants, affects the adsorption efficiency. The mg/g and 555.6 mg/g, respectively [113]. It is known
degree of pollutants removal from water increases with that the adsorption capacities of BC increase at higher
increasing adsorbent content, until the optimal value of temperatures of the carbonization process [117]. On
the adsorbent dosage is reached. By increasing the con­ the other hand, mesoporous HC derived from potatoes
tent beyond the optimal value no further improvements in through the soft-template method showed a maximum
pollutant removal can be achieved [102]. This tendency adsorption capacity of tetracycline of 238.7 mg/g [115].
could be justified by the optimal utilization of active ad­ The authors attributed this success to adsorption mecha­
sorption sites [105]. The efficiency of the adsorption pro­ nisms: pore filling, hydrogen bonding and n-π interaction.
cess decreases as the initial pollutant content increases NaOH-activated HC has been reported to effectively
[103] and as the activation centres on the surface of the remove sulfamethoxazole. The authors emphasized that
adsorbent become occupied by the pollutant molecules the pore filling, charge-assisted strong hydrogen bond­
[106]. The removal efficiency of organic contaminants ing, and π–π interactions with the surface of HC are the
from water by adsorption is significantly affected by the possible mechanisms [116]. Moreover, using NaOH-
initial pH of the solution due to certain charge character­ modified BC derived from Anthriscus sylvestris phar­
istics of the adsorbent surface determined by the pro­ maceuticals such as diclofenac and cephalexin could
tonation and deprotonating of oxygen functional groups also be effectively removed (adsorption capacities were
[107]. Furthermore, the pH of the solution also affects 392.9 mg/g and 724.5 mg/g, respectively) [118].
the ionization level of the pollutants [108]. At a pH be­ The removal of pesticides (e.g. atrazine, simazine,
low the PZC, the surface of the adsorbent carries a net etc.) from water by using char-based sorbents was also
positive charge, and therefore, it attracts and adsorbs investigated [119-121]. Pyrochar has shown a high ad­
negatively charged anions. Conversely, when the pH is sorption capacity for atrazine and simazine with values
above the PZC it is more favourable to adsorb positively of 1158 mg/kg and 243 mg/kg, respectively [119]. KOH-
charged ions [109]. This phenomenon is due to the in­ activated HC derived from sewage sludge showed up to
teraction between the charged functional groups present 64% removal of terbuthylazine from water [120]. Utiliza­
on the surface of the adsorbent and the charged groups tion of unmodified HCs derived from different feedstocks
of the pollutants in the solution. as adsorbents for removing 2,4-dichlorophenoxy acetic
The effect of temperature on the adsorption capac­ was reported, having adsorption capacities up to 88, 90
ity of char can vary depending on the specific pollutant and 89 mg/g, respectively [121].
and the characteristics of the char. Increasing the tem­ Endocrine disrupting chemicals, EDCs (such as bi­
perature can enhance the adsorption capacity of BC for sphenol A) are contaminants that can impact the endo­
certain organic pollutants, such as p-nitrophenol and crine system and subsequently impair the development
diclofenac, through an endothermic process [104, 110]. and fertility of animals and humans. These components
This is because an increase in temperature can lead to can be effectively removed from water using HC as an
an increase in the kinetic energy of the molecules, allow­ adsorbent [122, 123]. Adsorption of EDCs by HC de­
ing for a more efficient adsorption process. However, for pends on the characteristics of both pollutants and HCs,
other pollutants and types of char, increasing the tem­ and process conditions, involving various mechanisms,
perature may have an exothermic effect, which can re­ such as electrostatic interactions, π–π interactions, hy­
duce the adsorption capacity [111, 112]. drophobic interactions and hydrogen bonding [124].

Examples of CECs removal from water using BC/HC-

based materials as adsorbents
BC and HC have a high affinity for the adsorption of
organic pollutants. Tables 5 and 6 show summarized lit­
erature data on the effectiveness of BC, HC and their
composites in removing organic pollutants, such as anti­
biotics, pesticides, etc. from water matrices.
Antibiotics have an important function in medication;
however, their presence in the environment is undesira­
ble due to their negative impacts on health and the envi­
ronment. Antibiotics (such as tetracycline, sulfamethoxa­
zole, cefotaxime, sulfadiazine, etc.) can be effectively
removed from water matrices using BC and HC as ad­
sorbents [113-116]. In order to improve their efficiency
as adsorbents, it is necessary to perform their activation
using acids or alkaline [113].

65
Advanced technologies 12(1) (2023) 57-74

Table 5. BC-based adsorbents applied for the removal of organic pollutants from wastewater.

Table 6. HC-based adsorbents applied for the removal of organic pollutants from wastewater.

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Advanced technologies 12(1) (2023) 57-74

Conclusion microorganisms. Water. 2021, 13, 520-532. https://doi.

org/10.3390/w13040520
BC and HC are carbon materials produced from bio­ [3] Directive 2013/39/EU of the European Parliament and
mass either via pyrolysis or hydrothermal processes, of the Council of 12 August 2013 amending Directives
2000/60/EC and 2008/105/EC as regards priority
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by optimizing the reaction conditions of the carboniza­ watch list of substances for Union-wide monitoring in the
tion process (pyrolysis, HTC, etc.), it is possible to influ­ field of water policy pursuant to Directive 2008/105/EC of
ence the obtaining of HC/BC with certain characteristics the European Parliament and of the Council, Off. J. Eur.
suitable for removing target pollutants from water. The Union. 2015, 78, 40–42
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production, it has an additional value in reducing the en­ Nguyen TD, Tran TCP, Nguyen TAH, Kim SY, Nguyen TP,
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Acknowledgements
[9] Zeghioud H, Fryda L, Djelal H, Assadi A, Kane A. A
comprehensive review of biochar in the removal of organic
This study is conducted under the project TwiNSol- pollutants from wastewater: Characterization, toxicity,
CECs which has received funding from the Horizon Eu­ activation/functionalization and influencing treatment
rope programme under grant agreement no.101059867. factors, Journal of Water Process Engineering. 2022, 47
Views and opinions expressed are however those of the 102801. https://doi.org/10.1016/j.jwpe.2022.102801
author(s) only and do not necessarily reflect those of the [10] Ighalo JO, Rangabhashiyam S, Dulta K, Umeh CT,
European Union or EU executive agency. Neither the Iwuozor KO, Aniagor CO, Eshiemogie SO, Iwuchukwu FU,
European Union nor the granting authority can be held Igwegbe CA. Recent advances in hydrochar application
for the adsorptive removal of wastewater pollutants,
responsible for them.
Chemical Engineering Research and Design. 2022, 184,
Additionally, the authors gratefully acknowledge the 419–456. https://doi.org/10.1016/j.cherd.2022.06.028
support of the Ministry of Science, Technological Devel­ [11] Kabakcı SB, Baran SS. Hydrothermal carbonization of
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01/200134 and 451-03-47/2023-01/200133. Waste Management. 2019, 100, 259–268. https://doi.
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Izvod

BIOČAĐ I HIDROČAĐ KAO ADSORBENTI ZA UKLANJANJE EMERGENTNIH

ZAGAĐUJUĆIH MATERIJA IZ OTPADNIH VODA

Aleksandra Adamović1, Mirjana Petronijević2, Sanja Panić2, Dragan Cvetković1,

Igor Antić2, Zoran Petrović3, Nataša Đurišić-Mladenović2 (MINI PREGLEDNI RAD)
UDK 631.878:628.316.12
1Univerzitet u Nišu, Tehnološki fakultet, Leskovac, Srbija DOI: 10.5937/savteh2301057A
2Univerzitet u Novom Sadu, Tehnološki fakultet Novi Sad, Novi Sad, Srbija
3Univerzitet u Istočnom Sarajevu, Tehnološki fakultet, Zvornik, Republika Srpska, Bosna i Hercegovina

Poslednjih decenija ugljenični materijali, kao što su biočađ (BC) i hidročađ (HC),
se intenzivno koriste kao isplativi i ekološki prihvatljivi adsorbenti u tretmanu vode.
Specifične fizičko-hemijske karakteristike uglja omogućavaju efikasno uklanjanje
širokog spektra zagađujućih materija iz vode, uključujući emergentne kontaminante Ključne reči: biočađ, hidročađ, adsorp­
(npr. farmaceutski aktivna jedinjenja, agrohemikalije i jedinjenja koja ometaju rad cija, emergentni polutanti, tretman vode
endokrinog sistema). BC i HC se mogu sintetisati iz različitih biljnih materijala, čak
i iz otpadne biomase, što ih čini jeftinim materijalima. U stvari, primena otpadne
biomase za proizvodnju ugljeva može se označiti kao obećavajući put ka postizanju
ciljeva održivog razvoja u vezi sa upravljanjem čvrstim otpadom. Izbor sirovine i op­
timizacija reakcionih uslova procesa karbonizacije (piroliza, hidrotermalna karboni­
zacija, itd.) utiču na performanse materijala na bazi ugljenika koji dovode do proizvo­
da sa željenim karakteristikama pogodnim za uklanjanje određene grupe jedinjenja.
Cilj ovog preglednog rada je da pruži pregled trenutnog statusa istraživanja u vezi
sa primenom BC i HC kao adsorbenata u uklanjanju emergentnih polutanata (CEC)
iz otpadnih voda. Biće obrađena i fizičko-hemijska svojstva supstrata, vrste sinteze,
tehnike karakterizacije, kao i mehanizam i uticaj parametara procesa u uklanjanju
CEC-ova iz otpadnih voda.

74