1 s2.0 S2214714420302580 Main

Journal of Water Process Engineering 38 (2020) 101380
Contents lists available at ScienceDirect
Journal of Water Process Engineering

journal homepage: www.elsevier.com/locate/jwpe
Adsorption of endocrine disrupting compounds and other emerging T

contaminants using lignocellulosic biomass-derived porous carbons: A
review
U.A. Qureshia, B.H. Hameedb,*, M.J. Ahmedc
a
Department of Chemistry, Government Boys Degree College, Qasimabad, Hyderabad, 71000, Pakistan
b
Department of Chemical Engineering, College of Engineering, Qatar University, P.O. Box: 2713, Doha, Qatar
c
Department of Chemical Engineering, Engineering College, Baghdad University, P.O. Box 47024, Aljadria, Baghdad, Iraq
ARTICLE INFO ABSTRACT
Keywords: Hydrochars from lignocellulose biomass have received an upsurge of interest in different fields, especially in the
Endocrine disrupting chemicals area of adsorption. Hydrothermally produced hydrochars are effective adsorbents for removing different pol
Kinetics lutants, and they serve as a cheap and sustainable raw material for subsequent activation to achieve porous
Isotherm activated carbons (ACs) with large surface areas. In this review, recent studies on preparation and characteristics
Hydrothermal carbonization
of adsorbents in terms of hydrochars from lignocellulose biomass and their derived ACs are presented and
Activated carbon
Emerging contaminants
discussed. The application of these adsorbents for the removal of endocrine disrupting chemicals and other
emerging pollutants is included. The sources and classification, adsorption isotherm, kinetics, and mechanism of
these pollutants and the capability of regenerating and reusing cheap and efficient adsorbents such as hydrochar
and ACs are also discussed. This review identifies knowledge gaps and proposes insights into new directions for
improving the applications of hydrochar and ACs as adsorbents.
1. Introduction concentrations in water bodies are high and thus cause many health-
threatening problems. Therefore, the presence of such toxic pollutants
Emerging contaminants (ECs) are recently discovered compounds requires the immediate development of effective treatment strategies to
and other materials that have long been existed in the environment but achieve a safe and green aqueous environment.
whose existence and influence are only now being identified. ECs in The control of environmental pollutants, namely, ECs and EDCs,
clude a wide group of contaminates, such as drugs and personal care from aqueous systems through the adsorption technique has received
products (PPCPs), herbicides, veterinary products (e.g., hormones), growing interest because it is simple and offers a wide variety of cheap
food additives, industrial compounds (e.g., metabolites and degradation and efficient adsorbent materials like hydrochars and their derived
products), and engineered nanomaterials. Studies have revealed that activated carbons (ACs). Hydrochar is a solid residue containing re
these ECs are frequently and abundantly found in wastewaters and duced hydrogen and oxygen contents from the hydrothermal carboni
surface water [1]. Another class of pollutants is referred to as endocrine zation (HTC) of biomaterials, particularly lignocellulose, in the pre
disrupting compounds (EDCs), which are known to affect the endocrine sence of subcritical liquid water [3]. Unlike those from other biomass
system, including the growth and reproduction of humans and animals. utilization techniques, such as pyrolysis, biological conversion, and
Such compounds are widely used in industrial applications, cosmetics, densification to solid fuel, hydrothermal treatment-based hydrochar
and pharmaceuticals. These compounds may include some phenolic materials have drawn significant research interest due to their nu
compounds, polyaromatic hydrocarbons, dioxins, natural steroidal es merous advantages, such as low processing temperatures
trogens, synthetic estrogens, and industrial chemicals [2]. Their (180 °C – 250 °C), low ash contents, direct applicability to wet
Abbreviations: AC, activated carbon; AFEX, ammonia fiber explosion; BET, Bruneur Emmet Teller; DDT, 2,2-bis (p-chlorophenyl)ethane; DHT, dihydrotestosterone;
E1, estrone; E2, 17β estradiol; E3, estriol; EC, emerging contaminants; EDC, endocrine disrupting compounds; FTIR, fourier transform infrared spectroscopy; HHV,
high heating values; HTC, hydrothermal carbonization; HTL, hydrothermal liquifaction; MC, magnetic carbon composites; PAH, polyaromatic hydrocarbons; PP-
HYD-ox/dorzo, oxidized activated carbon from potato peel hydrochars for dorzolamide; PP-HYD-ox/prami, oxidized activated carbon from potato peel hydrochars
for pramipexole; PZC, point of zero electric charge; WWTP, waste water treatment plant
⁎
Corresponding author.
E-mail address: b.hammadi@qu.edu.qa (B.H. Hameed).
https://doi.org/10.1016/j.jwpe.2020.101380
Received 2 March 2020; Received in revised form 16 May 2020; Accepted 18 May 2020
Available online 07 September 2020
2214-7144/ © 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
U.A. Qureshi, et al. Journal of Water Process Engineering 38 (2020) 101380
feedstock, high product yield (30 wt%–60 wt%), and zero generation of
hazardous chemical waste [4]. Other properties, such as porosity and
variety of aliphatic and aromatic functional groups, place these mate Pesticides
rials at the forefront of certain applications, such as mitigating atmo
spheric CO2, producing biofuel by curtailing the dependency on fossil Veterinary Pharmaceu
fuels, energy storage, environmental pollution control, and soil ameli medicines ticals
oration [5–8].
Owing to the versatile properties of hydrochars and their economic
viability, they have gained increasing importance and have replaced
AC-based applications, such as capacitors [9], energy storage [10], soil Personal
Industrial
Care
amelioration, and adsorbents for water purification [11]. ACs are Compounds
Emerging Products
generally prepared by physical and chemical activation processes. Both
Contaminants
processes require pyrolysis and additional activation steps by gases or
chemical agents that result in energy and economic compromise. Being
a cheap and efficient alternative, hydrochars, particularly their appli
cation to pollutant removal, have been the center of many scientific Flame Food
research interests. However, studies performed with ACs have shown retardants Additives
that carbon adsorbents with a lower content of oxygen functional
groups, would present a higher sorption capacity for removal of or
X-ray
ganics when compared with carbon adsorbents with high contents of Steroids &
contrasting
oxygen functional groups. Due to low ash contents, hydrochars serve surfactants
agents
the best precursors in preparation of AC. Hydrochars based activated
carbons from orange peels have been tested for the treatment of certain
emerging pharmaceutical pollutants. Activation process, surface tex Fig. 1. ECs pollutants.
ture, and pH reportedly exert a significant influence on adsorption
features [5]. Some anionic dyes have also been investigated in terms of water exchange [23]. Generally, ECs can be introduced to environment
the removal efficiency of food waste-based hydrochars with an ad from two main sources, namely, point and diffuse sources. First sources
vanced approach in which an artificial neural network design is de are identified or specific sites of pollutants, and the input can be
veloped for an automated wastewater treatment plant [12]. Surface identified in a spatially separated way. Examples of such sources in
modified hydrochars have also been investigated for metal removal [4]. clude different industrial effluents, cosmetics, hospitals, sewage treat
Meanwhile, hydrochars outperform ACs in certain applications, but no ment plants, mining activities, buried septic tanks, and waste lagoons.
review article has focused on the applications of lignocellulose based The discharge of contaminants from these sources is usually con
hydrochars and activated carbons derived from them to the adsorption centrated. Meanwhile, diffuse sources refer to unidentified or indistinct
of ECs and EDCs. Dai et al. [13,14] reviewed the application of agri sources. Examples include run-offs from biosolids or manure and floods
culture wastes and biochars to the removal of different contaminants in industrial or urban regions. The discharge from these sources is often
and organic contaminants, respectively. Bhatnagar and Anastopoulus low and cannot be controlled. Fig. 2 schematically explains the different
[15] summarized the different types of adsorbents for bisphenol A re sources from which ECs are discharged and enter the surface and
moval, and Kim et al. [16] reviewed the use of graphene-based ad ground waters. Surface water is more frequently loaded with ECs than
sorbents for various organic and inorganic contaminants. Therefore, the groundwater is [24]. The animal, domestic, hospital and industrial
present review focuses on and discusses the recent advances in hydro wastes along with landfill represent the major source relative to a minor
char and activated carbon formation, their applications in removing aerial source of ECs in surface and ground waters. Moreover, among
ECs and EDCs, and the gaps associated with the adsorption performance these sources both landfill and aerial are the minor ECs pathways. The
of hydrochars and activated carbons derived from them. Re disposal from the households are considered important point sources as
commendations for the future improvement of these materials are also most of the unused or expired drugs are disposed through household
detailed from economic and applied industrial perspectives. solid waste or flushed down in the toilet. Artificial recharge/infiltra
tion, with treated waste water from industrial and domestic or urban
2. Classification and sources of ECs and stormwater runoff may become important basis of re-introducing
these contaminants that might be still present in these waters. Animal
ECs are new and known toxic pollutants that belong to different feeding operations also present a major source of ECs as the significant
classes, such as pharmaceuticals containing nonsteroidal anti-in portion of given antibiotics, pesticides or hormones passes through the
flammatory drugs, antibiotics and antifungal/antimicrobial agents, livestock and is excreted and stored in waste lagoons.
fragrances, pesticides, food additives, artificial sweeteners, lipid reg
ulators, hormones, UV filters, flame retardants, and other industrial
products [17,18]. Despite these classifications, confusion remains in 3. Classification and sources of EDCs
categorizing different pollutants. For example, some plasticizers that
are considered endocrine disrupting compounds are also called ECs. EDCs are exogenous agents that alter the natural functions of the
This ambiguity indicates that ECs are a broad spectrum of pollutants hormones in our body that are responsible for homeostasis, develop
that pose hazardous impacts on humans and aquatic organisms in all ment, and reproduction [25]. According to the review by Tijani et al.
aspects [17]. Fig. 1 shows the classification of ECs, which are chiefly [26], nearly 38,000 different chemicals and elements have been iden
found in many commercial and household products, according to the tified as EDCs. These are classified to synthetic and natural hormones
literature [19]. such as estrone, 17 β estradiol (E2), estriol testosterone, dihy
The common sources and pathways of ECs that lead to contamina drotestosterone [27]; ethynylestradiol and phytoestrogens [28]; in
tion in the environment include wastewaters from local wastewater dustrial compounds such as bisphenol A, phthalates, parabens, non
treatment units [20], hospitals [21], livestock activities [22], food ylphenol, and perfluorooctanesulfonate [29,30]; dioxins; flame
processing plants, agriculture waste, subsurface storage of industrial retardants, including polybrominated diphenyl ethers; various medi
and household wastes, and indirect means of ground water surface cines such as diethylstilbestrol; pesticides such as endosulfan and
2
Fig. 2. Schematic presentation of sources and pathways of ECs discharged into the environment [24].
organophosphorus pesticides; and synthetic birth control pills [28]. added products [38,43].
EDCs are also considered ECs due to their uncertain prolonged The adsorption performance of lignocellulose biomass may be im
health impacts. The sources of EDCs are widespread and diverse in proved via substantial treatments, such as chemical, physical, physico-
nature. Similar to ECs, EDCs are commonly found in low concentrations chemical, and thermochemical treatments. These treatments may in
(ng-μg/L level) in sewage wastewater treatment plants, surface water, troduce novel functionalities that are compatible with target pollutants.
ground water, hospital wastewater, soil, sediments, air, and even Among the numerous treatment protocols, HTC is considered as an eco-
drinking water [31–35]. Mostly industrial effluents after being treated friendly and cost-effective technique and is further discussed in the next
are directly introduced to the ground water where traces of EDCs still section.
remain and thereby enter to the aqueous environment. Some pesticides
in agriculture applications directly absorb into soil and may leach to the 5. Hydrothermal carbonization
ground water and then make their way to the food chain by building up
in fish, animals and humans. According to the recent research of Saeed Hydrothermal carbonization or wet torrefaction is a thermo
et al. [36], significant concentrations of phthalates, alkyl phenols, and chemical method of converting biomass of low heating value and large
estrogens have been detected in coastal areas receiving sewage dis moisture content into carbonaceous solid residues with chemical
charge. Different alarming concentrations of phthalates have also been characteristics identical to those of lignite coal, surrounding liquids
found in the sediments of the northern part of the Arabian Gulf, and (e.g., furfurals and small organic acids, including acetic, lactic, and
they may have entered via industrial and agricultural activities [37]. levulinic acids), and gaseous by-products [44,45]. The aqueous sus
This finding suggests that EDCs prevail heavily in water and airborne pension of biomass is treated at the subcritical temperature of ap
dust particles. Therefore, strict guidelines and protocols must be im proximately 180 °C – 250 °C in a closed reactor under autogenous
plemented to restrain the discharge of these toxic and hazardous pol pressure. The solid residue from the hydrothermal treatment is called
lutants from their sources. hydrochar by the European Biomass Industry Association [46]. HTC is
considered a simple and easily scalable technology that is suitable for
4. Lignocellulosic biomass any organic raw biomass.
In addition to its valorization, HTC is made advantageous by its use
In terms of renewability, recyclability, and sustainability, biomass- of water as a reaction medium and catalyst that is nontoxic, cheap, and
based resources are a main concern from the economic and energy ecofriendly; under a subcritical temperature, the characteristic features
perspectives. Lignocellulosic biomass is a non-edible and renewable of water dramatically change, the hydrogen bonds weaken, the di
resource in different industrial applications, such as production of electric constants decrease, and the ionization of water begins as the
biofuels (i.e., bioethanol, biobutanol, and biomethanol), value-added number of hydronium ions (H3O+) increase to facilitate the hydrolysis
chemicals, and new polymers [38–40]. Lignocellulose biomass forms a of glycosidic linkages in the hemicelluloses in biomass into hexoses and
significant fraction of forestry and agricultural crop wastes. Decreasing pentoses for subsequent transformation into value-added chemicals
sources of fossils, increasing economic demands, and environmental [47]. Moreover, this technique is applicable to biomasses with high
pollution from greenhouse gases have urged today’s scientific commu moisture contents (60 % humidity) and is different from pyrolysis,
nity to utilize lignocellulose biomass as an alternate renewable source. which is unsuitable for biomasses with high moisture contents and
In the context of agricultural and environmental restraints, biomass those that require sufficient pre-drying before being properly utilized.
resources are expected to supply power of 130–270 EJ/year in 2050. Such treatment may enhance the consumption of energy. Moreover,
This value can satisfy 15 %–25 % of the future total energy requirement toxic heavy metals are concentrated in chars after pyrolysis due to their
[41]. Lignocellulose biomass mainly consists of three main structural thermal stability. By contrast, in HTC treatment, these heavy metal
components, namely, hemicellulose (20–40 %), cellulose (40 %–60 %), contents are sufficiently removed from hydrochars through transfor
and lignin (10–25 %) [42]. Depending on a wide variety of sources, mation into the liquid phase, which leaves stable carbonized fractions
these materials may be processed to achieve different industrially im [48,49].
portant chemicals and biofuels for internal combustion engines. Given
the recalcitrance of the lignocellulose network, these materials undergo 5.1. Hydrothermal carbonization of lignocellulosic biomass to hydrochar
different modes of pretreatment, such as hydrothermal methods (in
cluding steam and CO2 explosions), hot water treatment, chemical The hydrothermal carbonization process is generally affected by
methods (involving acid and base treatments), organosolv methods operation temperature and residence time. The properties of resulting
using organic solvents, ammonia recycle percolation, ammonia fiber hydrochars depend not only on these factors but also on the nature and
explosion, and ozonolysis [40], to destroy their structures and achieve composition of feedstock. Table 1 summarizes the yields and char
different fermentable sugars for obtaining alcohols and other value- acteristics of hydrochars and their lignocellulose feedstocks [50–55].
3
Table 1
Mass yields and the characteristics of hydrochars and their lignocellulose biomass feedstocks.
Lignocellulose biomass or its hydrochar (HC) Mass Yield (%) C (%) H (%) O (%) Other elements (%) Ash (%) HHV (MJ/kg) References
Wood-HC 60.3 % 52.4 5.8 48.8 – – – [50]

Wood 48.1 5.6 46.3 – – –
Corn stalk-HC 56.92 49.23 5.94 36.35 N 1.16, S 0.17 7.15 19.66 [51]
Corn stalk 43.11 5.73 42.4 N 0.92, S 0.31 7.12 17.19
Corn stalk digestate-HC 62.20 42.65 4.50 29.22 N 1.53, S 0.35 21.75 17.16 [51]
Corn stalk digestate 38.01 4.79 38.33 N 2.05, S 0.62 16.2 15.86
Wheat straw-HC 49.2 60.6 5.57 29.5 N 0.58, S 0.40 3.26 23.8 [52]
Wheat straw 45.03 5.70 44.56 N 0.44, S 0.37 3.90 17.60
Willow-HC 40 70.4 5.3 20.2 N 1.30, S 0.10 2.7 27.8 [53]
Willow 45.3 6.2 43.8 N 0.50, S 0.10 4.10 16.40
Miscanthus-HC 45 71 7.9 17.5 N 1.1, S 0.20 2.3 32.1 [53]
Miscanthus 46.0 5.7 42.8 N 0.5, S 0.1 4.9 16.1
Oak wood-HC 43 72.2 6.6 15.2 N 2.2, S 0.2 3.6 31.1 [53]
Oak wood 43.4 5.9 42.9 N 0.3, S 0.1 7.40 15.40
Greenhouse waste-HC 45 68.5 6.1 17.4 N 3.6, S 0.2 4.2 28.8 [53]
Greenhouse waste 45.7 6.7 36.4 N 1.1, S 0.2 9.9 18.5
Acacia-HC 70 59 5.85 34.5 N 0.18, S 0.0 0.47 21.5 [54]
Acacia 47.0 5.76 46.96 N 0.11, S 0.01 0.16 –
Pine-HC 79 62.7 6.49 30.5 N 0.06, S 0.0 0.2 23.8 [54]
Pine 48.10 6.57 45.12 N 0.10, S 0.01 0.10 –
Corn silage-HC 52.5 64.4 5.4 26.9 N 1.60 – 26.6 [55]
Corn silage 46.9 6.20 41.9 N 1.2 – 19.60
Fig. 3. HTC reaction pathways from lignocellulose biomass [8].
The degree of carbonization is determined by H/C and O/C ratios. chemicals (Fig. 3). This process leaves small pores on the solid residue.
Decreasing ratios of these elements suggest increased carbonization Hydrochar properties are also greatly influenced by feed water pH.
values, whereas O/C values suggest the presence of oxygenated func Hydrochars were produced from wheat straw by changing the acidic
tional groups (OFGs) [56]. During HTC, the hemicellulose part of the and basic pH of feed water. Hydrochars with great pore properties were
lignocellulose biomass is prone to degradation due to the low activation derived using the acidic pH of feed water. Furthermore, the production
energy and is converted to volatile products [54]. However, cellulose of sugars, furfurals, and organic acids under basic pH was found to be
and lignin are resistant to degradation below 220 °C. The thermal sta low [59]. The metal retention in the form of ash is also a crucial factor,
bility of these species follows the order: lignin < cellulose < that is, the ash contents in hydrochars mostly decrease relative to their
hemicellulose [57]. The HTC of lignocellulose biomass involves dif raw materials. The ash contents further decrease with reaction severity.
ferent steps of reactions that occur simultaneously, such as hydrolysis, High ash contents in hydrochars may impair the application of the
dehydration, decarboxylation, aromatization, condensation, and poly latter as solid fuel and may cause slagging and fouling during com
merization [58]. With an increase in temperature, the ionic product of bustion. The presence of inorganic species, such as Na, K, Ca, Mg, P, and
water is believed to increase, making water a weak acid/base catalyst. N, greatly affects the formation features of hydrochars [53]. However, a
Consequently, a hydrolysis reaction commences with the breakage of knowledge gap exists with regard to the role of these elements in the
the ether bonds in hemicellulose and cellulose; in this case, lignin is hydrochar formation mechanism and their effects on the composition,
mostly unaffected. The resulting monomers and oligomers then move production, and characteristics of hydrochars.
toward the aqueous phase and are further degraded into various small Lignocellulose biomass as feedstock has many benefits, such as
4
abundance and low cost. When mixed with other non-lignocellulose create efficient and cheap adsorbent or catalyst support/raw materials
biomasses, this raw feedstock can be applied as high-quality solid fuel that could efficiently replace commercially available ACs. Table 2
[60] and as an excellent material for soil amelioration [61], and it can shows the textural properties of some ACs produced through the acti
reduce heavy metal content relative to individual feedstocks [62]. Mi vation of hydrothermally treated lignocellulose biomasses [66–75].
crowave-integrated HTC is currently considered appealing as it accel Generally, the formation of ACs with superior porosities and surface
erates hydrochar formation, but this technique is underutilized due to areas is promoted by the use of suitable activation agents at optimum
its lower yields in comparison with those of conventional thermal proportion and suitable operation temperatures at a certain time.
methods, the difficulty in processing tons of biomasses, and its energy Activation agents, such as KOH, NaOH, ZnCl2, and H3PO4, have been
intensiveness [58,63]. Microwave-produced hydrochars have been re widely studied to produce porous ACs.
ported to serve as an alternative to raw coal that could reduce the cost Acid activators are preferred to alkali metal hydroxides as they re
to half when used as an energy source [64]. move inorganic impurities and can be easily recovered from the process
The pore properties and yield of hydrochars significantly depend on [76]. In addition, acid treatment can introduce abundant oxygen con
the composition of lignocellulose feedstocks in terms of hemicellulose, taining functional groups to the resulting hydrochar [77]. Rice husk-
cellulose, and lignin. Moreover, HTC temperature and acidic pH of feed based hydrochars were chemically treated with H3PO4, and AC with a
water play a role in enhancement of pore properties of hydrochars. BET surface area of 2700 m2/g was obtained at 500 °C for capacitor
From Table 1, the high carbon and oxygen contents along with the low application [68]. Activation with H3PO4 is considered to occur under
ash content of lignocellulose feedstocks result in the formation of hy mild conditions; the case is different for ACs obtained by alkali acti
drochars with large yield (40–79 %) and favorable heating value vation. In this context, both rattan stalks and coconut shell-derived
(17.16–32.1 MJ/kg) and carbon content (42.65–72.2 %). In addition, hydrochars were chemically activated with NaOH at 600 °C to produce
the low nitrogen and sulfur contents of these feedstocks produce hy ACs with BET surface areas of 1135 and 876.14 m2/g, respectively
drochars with less nitrogen (0.06–3.6 %) and sulfur (0.1−0.46%) ele [70,71]. NaOH activation resulted in a mesoporous structure and uni
ments. Thus, lignocellulose feedstocks derived hydrochar can be effi form surface (Fig. 4). The development of ACs porosity is attributed to
cient and eco-friendly precursor for ACs with low emission of noxious activator's dehydration effect, which breaks the CeOeC and CeC bonds
gases during activation. of hydrochar. NaOH is reduced to metallic sodium Na, hydrogen gas,
and sodium carbonate Na2CO3. Furthermore, Na2CO3 is degraded into
Na and CO as follows [78]:
5.2. Preparation of ACs from lignocellulosic biomass by conjunction HTC
6 NaOH + 2 C → 2 Na + 3 H2 + 2 Na2CO3 (1)
and subsequent activation
Na2CO3 + 2C → 2Na + 3CO (2)
Generally, the AC requirement increases annually by approximately
8.1 % and may reach up to 2.1 million metric tons in the coming years; Thus, both the alkaline and carbonate metals are intercalated into
this change may further increase the AC cost [65]. Therefore, many the hydrochar structure and played a role in generation and enlarge
researchers are now switching to cheap and renewable lignocellulose ment of pores. Few studies have reported the use of K2CO3 as an acti
biomasses as carbon sources. ACs are normally prepared by the car vator because it is known to be non-deleterious unlike KOH. Magnetic
bonization of precursors at the temperature range of 600 °C – 700 °C ACs have been prepared from Salix psammophila and rice straw hy
(dry method) for a certain time. In the traditional process, which is still drochars using K2CO3 as the activator with a 2:1 impregnation ratio.
used today, the smoke from the process is freely emitted to the atmo The resulting product performs well in the adsorption application due
sphere, thus contributing to environmental pollution, and most of the to its excellent surface area with microporous and mesoporous struc
ash is deposited on the resulting carbon. These results call for an en tures, respectively [69,73].
ergy-efficient separation process for obtaining pure AC. As part of the Hydrochars may serve as ideal precursors for preparing ACs for
effort to save energy and cut down the cost of AC production, HTC (wet multiple applications because they evidently reduce energy consump
process) is used to produce hydrochars before their activation to AC. tion and environmental concerns. According to Table 2, hydrochars
Normally, HTC is conducted at 180 °C – 250 °C, which is much lower derived ACs exhibit high surface areas within the range of 876 to
than that in the carbonization process. Moreover, HTC does not emit 2960 m2/g. Different basic, acidic, and metallic salt activators are ap
smoke to the atmosphere and produces minimal ash in the resulting plied for the production of ACs with well-developed pores and micro
hydrochars. Moreover, the use of water in HTC could produce hydro porous or mesoporous structures depending on the type of activator and
chars with many new functional groups (OH, −COOH, −CHO) on the activation conditions. Despite increasing research work, gaps remain in
surface that can enhance adsorption capacity. Using HTC-based hy current technology, and some of them are mentioned here. Suitable
drochars as a carbon source could offer many benefits: (i) provide an activating agents should not only be cost-effective but also en
economic, ecofriendly, and sustainable way of reutilizing waste bio vironmentally benign and easily recoverable. No work has explored the
mass; (ii) yield a purified carbon source with abundant OFGs that fa use of value-added acids, like lactic acids, levulinic acid, and acetic acid
cilitate activation to generate ACs with a large surface area; and (iii) produced from the HTL of biomass for the activation of resulting
Table 2
Textural characteristics of AC derived from lignocellulose-based hydrochars.
Lignocellulose biomass Activating agent HTC Temperature ℃ Activation Temperature ℃ Pore Volume cm3/g Surface Area m2/g References
Eucalyptus sawdust K2C2O4 and melamine (1/6/2) 250 800 1.6 2960 [66]
Eucalyptus sawdust KOH (1/4) 250 700 1.03 2252 [67]
Rice husk H3PO4 (1/2.5) 95 500 ∼1.6 2700 [68]
Rice straw K2CO3 (1:2) 300 800 1.07 1334 [69]
Rattan (Lacosperma secundiflorum) NaOH (1:3) 200 600 0.6 1135 [70]
Coconut shell NaOH 200 600 0.44 876.14 [71]
Date seeds NaOH (1:3) 200 600 0.66 1282 [72]
Salix psammophila K2CO3 (1:2) – 800 0.943 1541 [73]
Coconut shell ZnCl2 (1:3) 200 800 1.5 2050 [74]
Coconut shell ZnCl2 (1:2) 275 800 1.17 1673 [75]
5
changing the experimental parameters, especially pH. Surface texture

and functional groups greatly affect the adsorption mechanism.
Although suggesting the exact mechanism taking place is difficult,
many researchers favor Fourier-transform infrared spectroscopy (FTIR)
as a useful tool to investigate the interactions between solutes and
adsorbents. Relying on FTIR and surface charge results may arbitrarily
predict the mechanism; however, we feel that the assistance of further
advanced surface techniques is crucial in investigating the exact me
chanism because mechanisms are essentially complex and require
careful investigation. Table 3 shows different predominant adsorption
mechanisms that are responsible for the effective removal of ECs and
EDCs by hydrochars or the ACs derived from them [79–92].
Solution pH has a pivotal role in tuning the surface charges and
active functional groups of target analytes. It can alter the adsorption
mechanism from being hydrophobic to being electrostatic. A change in
pH induces positive/negative charges on hydrochars/AC and the mo
lecular state of solute and thereby affects electrostatic interactions. The
structure of hydrochars involves a hydrophilic shell, which results from
abundant OFGs; and a hydrophobic core, which results from fixed
carbon and aromatization [79]. Kyzas and Deliyanni [88] suggested
that ACs from potato peel hydrochars, when subjected to HNO3 oxi
dation, produce an enhanced number of OFGs for the adsorption of
pramipexole dihydrochloride and dorzolamide. FTIR spectrum results
confirmed the presence of OeH group of the phenol at 3400 cm−1 and
CeC group of the aromatic ring at 1615 cm−1. After the adsorption, the
disappearing of OeH group and shifting of CeC group was observed
which indicated the role of these groups in adsorption process. Thus,
the mechanism is mainly π-π electron coupling and Lewis acid–base
reactions between amino groups in drugs and O in AC. Furthermore, pH
exerts a strong influence on uptake behavior because acidic pH 2 pro
vides the highest removal efficiency that declines with a further rise in
pH due to electrostatic repulsions. A highly basic pH is unfavorable for
most pollutants, such as E2 that is removed by Fe–Mn binary oxide-
functionalized hydrochar (PZC∼5) as E2 remains in neutral state at
pH < 10. FTIR spectrum showed the peaks at 3415 cm−1 and
1508 cm−1 which attributed to the OeH and aromatic CeC stretching
bonds, respectively. Owing to the aromatic structure and presence of
OH groups, the principal adsorption mechanism was proposed to be π-π
interactions and hydrogen bonding [80]. A similar observation was also
found by Li et al. [87], who tested the adsorption of amoxicillin onto AC
from previously modified hydrochars from corn stalks. The presence of
amoxicillin in different chemical forms at different pH levels and zeta
potentials of the adsorbent affected the adsorption mechanism. The
Fig. 4. SEM images of (A) raw rattan and (B) rattan-based AC [70]. removal of salicylic acid and flurbiprofen on AC from orange peel hy
drochar was also found to be pH-dependent, with the acidic pH being
hydrochars. Using such biomass-derived activating agents may exert the most suitable for maximum removal. Here, dispersion was the main
some profound effects on AC production yield and textural properties interaction proposed, along with a slight electrostatic interaction be
and may reduce the cost of the method. New strategies should be de tween positively charged adsorbents and π electron of drug molecules.
veloped to overcome high temperature requirements and low AC yields. FTIR results only displayed a single peak at 1612 cm−1 that accounted
In this regard, few catalysts may be developed, or equipment design for the complete disappearance of carboxylic groups and the presence
should be engineered. Few new applications of hydrochar-based car of aromatic CeC group, indicating that only hard carbon components
bons, such as fuel cells, membrane materials for ECs, and EDC removal remained [5].
from wastewater treatment plants, should also be explored to offer In some cases, changes in pH do not affect adsorption behavior; for
sufficient removal below permissible limits. Large-scale production, example, Chen et al. [86] observed that changes in pH had no effect on
cost estimation, and the stability of hydrochars should be considered the adsorption of tetracycline using magnetic AC derived from fir saw
from an industrial point of view. dust hydrochar. In another study, the removal of E2 and 17α-ethyny
lestradiol by montmorillonite/hydrochar composites was relatively the
6. Mechanism of adsorption of ECs and EDCs on hydrochar and same within wide pH ranges due to stable hydrogen bonds, π-π inter
ACs actions, and intercalation [81]. Suo et al. [92] also found no significant
effect of pH on organophosphorus pesticides removed by AC from corn
The mechanism of adsorption involves a combination of a multitude straw cellulose and graphene composites because the main mechanism
of interactions, i.e. hydrogen bonding, pore filling, hydrophobic inter was preferentially π-π interactions.
actions, and π-π interactions. This combination depends on different In a Raman study, the degree of graphitization (ID/IG) was expected
factors, such as surface chemistry, surface area, pore size, surface to play a vital role; that is, increasing activation temperatures lead to
charge (zeta potential), pH, and the chemical structure of target com burn out that causes extensive dislocations and defects, which in turn
pounds. All these interactions occur either simultaneously or by improve the surface area and adsorption properties of the resulting
6
Table 3
Types of adsorption mechanisms of ECs and EDCs on hydrochars and ACs from hydrochars obtained from different lignocellulose biomasses.
Hydrochars
U.A. Qureshi, et al.
Lignocellulose biomass Pollutant Category Optimum pH Amount of adsorbent Temperature Mechanism responsible for adsorption Reference
(g or mg) (K or ℃) s
Argun Nut shells Bisphenol A EC as well as EDC 6.5 0.01 g 293 K • π-π interactions [79]
• Hydrogen bonding.
• Pore filling
Argun Nut shells Diuron EDC 6.7 0.01 g 293 K • π-π interactions [79]
• Hydrogen bonding.
• Pore filling
Rice husk hydrochar with Fe-Mn 17β-estradiol EDC 7 5 mg 28℃ • π-π interactions [80]
binary oxides • Hydrogen bonding
Montmorillonite/Hydrochars from 17β-estradiol and 17α-ethinylestradiol EDC 7 5 mg 25℃ • π-π interactions [81]
rice husk • Hydrogen bonding
• Intercalation between clay layers
• Electrostatic interactions
Rice husks Herbicide: octhilinone(2-octyl-4-isothiazolin-3- EC – 50 mg 20℃ • Hydrophobic interactions (based upon higher [82]
one) Antibiotics:trimethoprim, sulfamethoxasole, logK )
OW
and ciprofloxacin Pharmaceuticals (diclofenac, • Hydrogen bonding
paracetamol, diphenhydramine, and fluconazole)
Rice husks Triclosan bisphenol A EDC as well as EC – 50 mg 20℃ • Hydrophobic interactions (based upon higher [82]
logK )
OW
• Hydrogen bonding
Pistachio shells Caffeine EC – 0.01 g 25℃ • Microporous diffusion [83]
• Interaction with surface and pore OH groups
Corn digestate, miscanthus and Isoproturon EC – 195 t/ha 20℃ [84]
7
wood chips
• Hydrogen bonding
Sulfamic acid modified saw dust Benzotriazole EC 4−8 0.5 mg/L – • Electrostatic and nonelectrostatic [85]
hydrochar • Complexing bridging interactions
Activated carbon from Hydrochars
Fir saw dust with subsequent Tetracycline EC 5−9 20 mg 25℃ • π−π electron donor − acceptor interaction [86]
magnetization • Hydrogen bonding
• Large surface area
Activated carbon from fore- Amoxicillin EC 7 1 g/L 20℃ • Electrostatic [87]
modified cornstalks hydrochar
Potato Peels Hydrochar followed by Pramipexole and Dorzolamide EC 2 0.02g 25℃ • π−π electron coupling [88]
oxidation with HNO3 • Lewis acid base interactions
Magnetic carbon from sugar cane Tetracycline EC 6.8 0.05 g 30℃ • Hydrogen bonding [89]
bagasse based hydrochars • π−π electron donor acceptor
Orange peel hydrochar Diclofena, Salicylic acid, Flurbiprofen EC 7 (Diclofenac), 2 0.5 g/L 25℃ • Dispersive interactions and surface greater [5]
(Salicylic acid and surface area (Diclofenac)
Flurbiprofen) • Dispersive and electrostatic (Both Salicylic acid
and Flurbiprofen)
Magnetic hydrochars from Salix Triclosan EDC – 0.5 g/L 30℃ • Pore filling [95]
psammophila
Hydrochar from green wastes Atrazine EC – 2 mg 20℃ • Pore filling [90]
Agave Americana fibers and Tetracycline 7 0.05 g 25 ℃ • Pore diffusion [91]
mimosa tannin
Rice straw derived hydrochar Triclosan EDC – 50 mg/L 298K • Porosity and surface area [69]
carbon [86,92]. Zhu et al. [93] also observed that magnetic AC from
sawdust hydrochars with great ID/IG possessed great porosities and
great adsorption capability toward roxarsone (4-hydroxy-3-ni
trophenylarsonic acid). The predominant adsorption mechanism was
found to be pore filling, in addition to the mild surface complexation of
As and Fe on the surface of the magnetic AC [93,94]. The same ob
servation was found by Suo et al. [92] as discussed above. In another
study by Zhu et al. [73], magnetic AC from Salix psammophila hydro
chars was obtained at different temperatures. The sample was obtained
at the lowest activation temperature and fixed hydrochar; the activator
ratio had a great ID/IG ratio and the highest adsorption capacity toward
triclosan.
Pore filling may be a dominant mechanism depending on the di
mensions of the adsorbate. Fernandez et al. [5] found that the ad
sorption of salicylic acid is due to porosity development and that the
molecular size of salicylic acid is smaller (0.6 nm) than the size of the
pores on the AC from orange peel hydrochars. Zhu et al. [95] prepared
magnetic AC from hydrochar at different temperatures for the removal
of triclosan and obtained a linear increase in qe values as functions of
the surface area and pore and micropore volumes that led to the pore
filling being the suitable mechanism. The removal of diuron and bi
sphenol A, in addition to hydrogen and π-π bonding, was explained by
the presence of micropores [79]. The adsorption capacity of triclosan
on AC from rice straw hydrochars was found to be several times greater
than that of its magnetic derivative due to pore blockage by magnetic
particles [69]. This result also suggested that the adsorption of triclosan
was mainly based upon pore diffusion. FTIR spectrum displayed wide
bands at 3400 and 1080 cm−1 which attributed to OeH and CeO
groups. Being abundant in OFGs, hydrogen bonding interactions play a
major role in adsorption with AC from rice straw hydrochars.
Sun et al. [96] compared the adsorption mechanisms of three EDCs,
namely, bisphenol A, 17 ethynyl estradiol, and phenanthrene, on bio
chars and hydrochars. In addition to pore filling being the common
mechanism, the adsorption of bisphenol A and 17 ethynyl estradiol was
mainly due to hydrogen bonding, whereas phenanthrene was unable to
facilitate hydrogen bonding due to the absence of OH groups but was
able promote π-H bond and π-π interactions. In the study, the biochar
showed mainly π-π interactions due to the existence of aromatic C]O,
CeC, and CeH groups at 1700, 1600, and 885–752 cm−1, respectively.
In a special case, caffeine adsorption on AC derived from pistachio nut
shell hydrochar was studied experimentally and by molecular mod
eling. The results based upon these two methods suggested that ad
sorption was mainly due to the microporous character of ACs. Prior to
adsorption, caffeine formed aggregates that were disintegrated by sur
face OH groups on the adsorbent surface; with further disintegration,
these molecules penetrated inside the pores and bound with the OH
groups on the inner walls of the pores to make a monolayer attachment
[83]. Fig. 5 illustrates adsorption mechanisms responsible for the ad
sorption of different EDCs and ECs by hydrochars and ACs derived from
them [79,88,89].
Overall, many interaction mechanisms such as electrostatic, hy
drogen bonding, pore filing, π-π interactions, and hydrophobic are pro
posed for EDCs and ECs adsorption on hydrochars and their derived ACs
(Table 3). Solution pH, chemical structure of ECs or EDCs, and surface
texture, functional groups, and surface charge of hydrochar or its derived
AC greatly affect the adsorption mechanism. The mechanisms of ad
sorption of EDCs and ECs pollutants are mostly the same relative to other
carbon-based materials obtained without hydrothermal treatment
[97–99] but compared with hydrochars, AC derived from them offer
enhanced adsorption capacities due to wider pore volumes and enhanced
specific surface area [5,69,85]. Owing to the limited work on hydrochars Fig. 5. Adsorption mechanisms from different hydrochars/ACs, (A) [79], (B)
or ACs derived from them for a limited number of ECs and EDCs, we need [89], (C) [88].
to employ new surface techniques to explore further the mechanisms of
their adsorption and thereby understand the behavior of these pollutants. et al. [82] developed a correlation between the log KOW values of flu
Correlation models should be developed to predict the influential inter conazole, ciprofloxacin, paracetamol, sulfamethoxazole, trimethoprim,
actions predominantly involved in the adsorption process. Weidemann ochthilinone, diphenhydramine, bisphenol A, diclofenac, and triclosan
8
and those of rice husk hydrochars, horse manure hydrochars, olive hy Weber–Morris intraparticle diffusion model provided in the following
drochars, and tomato hydrochars. Among the hydrochars, those of rice equation [107]:
husk had a positive correlation with the contaminants, thereby con
firming hydrophobic interaction as the fundamental mechanism. The qt = kid t + X (9)
adsorption of additional EDCs and ECs, such as parabens, phthalates, and
other industrial products, should be studied to widen the scope of lig where kid (mg/g. min0.5) is the rate parameter and X is the initial ad
nocellulose-based hydrochars or ACs obtained by their post-treatment. sorption (mg/g). For kinetics controlled solely by this model, a plot
Further work on real sample applications and their reusability is re between qt and t should be straight line passing through the origin
quired. (i.e., X = 0). Most research findings demonstrate multilinear curves
within a studied time duration, and these curves are indicative of
7. Modeling of adsorption of ECs and EDCs on hydrochar and AC multiple mechanisms occurring simultaneously with controlling me
chanisms, such as the transfer of solute to the external adsorbent sur
7.1. Adsorption kinetic modeling face, intraparticle diffusion, and the equilibrium stage, in which the
solute adheres to the walls of the pores. These models are the most
Both adsorption kinetics and equilibrium are baselines in designing commonly studied and used to calculate rates and predict general ad
and scaling up of adsorption systems. Kinetic studies involve modeling sorption mechanisms. The suitability of each model relies on the
of experimental kinetic data collected by measuring the adsorbed characteristics of the adsorbents, adsorbates, and experimental condi
amount against time. Pseudo-first- and pseudo-second order are the tions.
most generally applied empirical equations in liquid phase adsorption Liu et al. [69] studied the removal of triclosan using AC and mag
systems. Lagergren first proposed a pseudo-first-order equation with the netic AC from rice straw-derived hydrochar. The experimental data
following expression form [100]: were applied to validate different kinetic equations, like the pseudo-
first-order, pseudo-second-order, intra-particle diffusion, and Elovich
qt = qe qe e k1 t (3) equations in linear mode. The results suggested the following order of
Linearizing the above equation gives the following: best fittings: pseudo-second-order equation > pseudo-first-order
equation > Elovich equation, according to the highest R2 magnitudes
ln (qe qt ) = ln qe k1 t (4) and the small deviation between the experimental qe and theoretical qe
where qe and qt represent the adsorption capacities (mg/g) at equili values. The adsorption equilibrium was not immediately reached when
brium and time t (min) and k1 is the rate parameter (1/min). An ad high concentrations of triclosan were used. The rate k2 of AC decreased
sorption system is likely to follow this model under initial time intervals (from 6.6 × 10−3 to 4 × 10−4 g/mg/min) with a rise in initial triclosan
or prolonged intervals when the adsorption process is near equilibrium concentration, whereas the rate for the magnetic AC increased at high
[101–103]. concentrations. The adsorption capacities of AC were higher
The pseudo-second-order equation suggests that the adsorption rate (175–588 mg/g) than those of its magnetic derivatives (161–286 mg/g)
is second order function of available active sites and is used for large due to the highly porous network. The application of the intraparticle
time intervals [104], whereas the pseudo-first-order equation is applied diffusion model indicated a multilinear curve that produced a nonzero
to describe adsorption at small time intervals. Mathematically, this intercept, which reflected the rapid diffusion of triclosan on the ex
model can be represented as ternal surfaces of the AC and magnetic AC, followed by diffusion inside
the porous body. Kyzas and Deliyanni [88] developed oxidized AC from
k2 qe2 t potato peel hydrochars and pyrolyzed potato peels for the removal of
qt =
1 + k2 qe t (5) dorzolamide and pramipexole drugs. Linear plots of pseudo-second- and
pseudo-first-order models revealed that the former can effectively ex
Linearizing the above equation gives the following form [104]: plain adsorption kinetics. According to the closeness of the experi
t 1 t mental qe values to the calculated qe values (PP-HYD-ox/prami: qe,
= +
qt k2 qe2 qe (6) cal = 31.3 mg/g and qe, exp = 31.1 mg/g), (PP-HYD-ox/dorzo:
qe,cal=30.5 mg/g and qe, exp = 30.4 mg/g) were greater than those of
where qe and qt denote the equilibrium adsorption capacities (mg/g) the AC obtained from pyrolyzed potato peels. The rate of adsorption
and adsorption capacities at a given time t (min) and k2 is the rate using AC from pyrolyzed potato peels was greater than that using a
parameter (g/mg/min). The adsorption kinetics of different pollutants hydrochar precursor; this result implied faster adsorption in the former
frequently follow this model on the basis of high regression and low than in the latter.
error analysis values and thereby signify this model’s prominence. The Given that the pseudo-second-order equation is preferentially more
fitted rate constants k1 and k2 are most probably lumped parameters valid than other kinetic models are, most research groups only applied
that join reaction and diffusion influences under particular experi this model to determine the rates and adsorption capacities of ad
mental variables; the determination of primary adsorption phenomena sorbents. Plazinski et al. [108] showed that the preferential fitting of
is scarcely discussed after model fitting [105]. Another model that the pseudo-second-order equation over the pseudo-first-order equation
predicts chemisorption is the Elovich equation [106], which is written can stem from a theoretical basis rather than a physical one. The
as: random errors in the calculated qe values did not vary to a great extent
1 during the linearization of the pseudo-second-order equation, as in the
qt = ( ln t)
(7) case of the pseudo-first-order equation. An additional benefit of using
the pseudo-second-order equation is that equilibrium qe is not required
Linearizing the above equation gives the following equation: for data fitting. Zhu et al. [93] prepared hydrochars using different
1 1 temperature ranges (i.e., 160 °C – 300 °C) for the hydrothermal treat
qt = ln( )+ ln t
(8) ment of sawdust from a furniture factory. The resultant samples were
simultaneously activated and magnetized to obtain magnetic ACs. The
The plot between qt and ln t should produce a straight line with 1
samples were studied for the removal of roxarsone. The magnetic AC
slope and ln( )
intercept. α (mg/g/min) represents the rate constant, obtained from the hydrochars at 160 °C exhibited high pore properties.
and β represents the extent of surface coverage and activation energy Applying the linear form of the pseudo-second-order equation showed
for chemisorption. Another commonly applied model is the that the adsorption rate was high, which suggested the excellent
9
adsorption of roxarsone on the as-prepared samples. The adsorption slow desorption were suggested to be the most suitable rate controlling
capacities (qe =515 mg/g) and rates of adsorption (13.2 × 10−4 g/mg/ mechanisms. Ning et al. [80] applied the nonlinear pseudo-first-order,
min) increased in the following order: MC-160 > MC-200 > MC-240 pseudo-second-order, intraparticle diffusion, and Elovich equations to
> MC-270 > MC-300. This order was mainly due to the favorable study the adsorption of E2 on Fe–Mn binary oxide-loaded hydrochars.
pore filling on the magnetic AC obtained from the hydrochars at low As anticipated, kinetics preferentially followed the pseudo-second-
temperatures. Similarly, Chen et al. [86] applied the pseudo-second- order equation (qe 47.43 mg/g and k2 4.79 g/mg/min) with the fol
order equation to the experimental data of tetracycline adsorption on lowing order: pseudo-second-order model > Elovich equation >
AC and magnetic AC from saw dust hydrochars. The maximum ad pseudo-first-order model. Error analysis results, including the root
sorption capacities achieved were 250 mg/g using ACs and magnetic mean square errors and chi-square statistics, also supported the vali
ACs, but the former achieved equilibrium earlier (10 min) than the dation of the pseudo-second-order equation. The Morris–Weber plot
latter did (30 min). On the basis of this model, the authors assumed the was multilinear, thereby implying that intraparticle diffusion was not
rate-limiting step to be chemisorption in nature. An increase in initial the only governing mechanism.
solute concentration tends to increase equilibrium time. Rattanachueskul et al. [89] used the nonlinear form of the pseudo-
Fernandez et al. [5] prepared AC from orange peel hydrochars using second-order equation to analyze the adsorption behavior of tetra
air, CO2, and phosphoric acid as activating agents for the removal of cycline on magnetic AC from sugar cane bagasse and obtained high rate
diclofenac, salicylic acid, and flurbiprofen, respectively. The kinetic constant values (k2 = 7.52 × 10−4 g/mg/min; qe =28.14 mg/g). The
data were as correlated to only the pseudo-second-order equation in authors elucidated the reason on the basis of the hierarchical structure
nonlinear mode (Fig. 6). The adsorbed amount of diclofenac was high of composites with macropores that were responsible for rapid diffu
on acid-AC, whereas those of salicylic acid and flurbiprofen were high sion; meanwhile, two-phase linear curves of intraparticle diffusion in
on air-AC. The rates of adsorption of diclofenac and flurbiprofen were dicated film and intraparticle diffusion as the rate-limiting steps. Tet
high on H3PO4-treated AC from acid-treated hydrochar, whereas those racycline adsorption with AC from hydrochars of Agave Americana
of salicylic acid were high on air-AC. The data on the adsorption of fibers and tannin was also studied by the application of the nonlinear
triclosan on γ-Fe2O3 AC prepared from Salix psammophila hydrochars modes of the pseudo-first-order and pseudo-second-order models [91].
revealed a preference for the pseudo-second-order equation. In that
study, the effects of activation conditions influenced the qe values
(170.9–787.4 mg/g), and such an increase was correlated with different
textural characteristics, like BET surface area, volume and size of pores
[95].
Mesopore size and large micropore volume are responsible for great
diffusion and fast rates of adsorption, as reported by Mestre et al. [109],
who showed three types of AC, namely, AC prepared from sucrose
hydrochars using KOH and K2CO3 as activating agents and commercial
AC for the removal of paracetamol and iopamidol. This model was
again preferentially fitted when Zhu et al. [110] studied the adsorption
of tetracycline on magnetic porous carbon obtained from Salix psam
mophila hydrochars. The order of fitting was as follows: pseudo-second-
order equation > pseudo-first-order equation > Elovich equation.
In another study, the adsorption of bisphenol A and diuron on Argan
nut shell hydrochars represented by the pseudo-second-order equation
with excellent determination coefficients better than it did the pseudo-
first-order equation. The increase in temperature reduced the qe values
(1094–664 mg/g for bisphenol A and 773–557 mg/g for diuron), and
the rate constant values dramatically increased with a rise in tem
perature (0.002–0.025 g/mg/min for bisphenol A and 0.013–0.208 g/
mg/min for diuron). This detailed analysis suggested that temperature
can only accelerate the adsorption system in some cases and that it may
not necessarily increase adsorption capacities. Furthermore, the in
traparticle diffusion model suggested two phase reactions, namely,
macropore diffusion and mesopore diffusion [79]. By contrast, Ahsan
et al. [99] suggested the first linear stage to be mesopore and macro
pore diffusion and the second stage linear curve to be micropore dif
fusion in their study of the adsorption of bisphenol A, sulfamethox
azole, and tetracycline on sulfuric acid-treated sawdust. The
preferential fitting of the pseudo-second-order equation on every ad
sorption case reveals that the mechanism of adsorption depends on the
presence of sufficient sites on adsorbents regardless of the type, pre
paration method, or aqueous environment used. Shi et al. [97] achieved
a preferential fitting of the pseudo-second-order equation in their study
of the adsorption kinetics of ciprofloxacin on Fe3O4/C from sucrose by
HTC. The controlling mechanism was chemisorption in nature with a
maximum qe of 38.6 mg/g and rate of 19.9 g/(mg.h).
Li et al. [87] fitted nonlinear kinetic equations, namely, pseudo-
first-order, pseudo-second-order, and Elovich equations, to the ad
sorption data of amoxicillin on AC from previously modified corn stalk
hydrochar. Among these three models, the Elovich equation was found Fig. 6. Pseudo-second order kinetic for adsorption of (a) diclofenac sodium, (b)
to have the best fit. Moreover, chemical adsorption, fast adsorption, and salicylic acid and (c) flurbiprofen onto the developed activated hydrochars [5].
10
U.A. Qureshi, et al.
Table 4
Kinetic models and parameters for the adsorption of different ECs and EDCs on lignocellulose-based hydrochars and their derived ACs.
Adsorbent EC/EDC Initial concentration and Pseudo First order Pseudo second order Elovich Equation References
time range
2 2 2
qe (mg/g) k1 (1/min) R qe (mg/g) k2 g/mg/min R α (mg/g/min) β (g/mg) R
Activated carbon from hydrochars of Agave Americana fibers Tetracycline 100 mg/L 45.24 0.038 0.919 49.79 0.0010 0.975 – – – [91]
in combination with tannin 0−400 min
Hydrochars from Argun nut shells Diuron 40 mg/L 5.24 0.031 0.141 775.1 0.013 0.99 – – – [79]
0−180 min
Hydrochars from Argun nut shells Bisphenol A 60 mg/L 5.24 0.010 0.115 1098.9 0.002 0.99 – – – [79]
0−180 min
Montmorillonite rice husk hydrochar composites 17β estradiol 6 mg/L 103.3 0.7 (1/h) 0.856 113.8 0.0083 0.967 – – – [81]
0−24 h
Montmorillonite rice husk hydrochar composites 17αethynyl 6 mg/L 65.77 2.25 1/h 0.842 68.8 2.21 g/mg/h 0.997 – – – [81]
estradiol 0−24 h
Magnetic activated carbon from sawdust hydrochars Tetracycline 100 mg/L – – – 250.5 0.0028 0.99 – – – [86]
0−120 min
Fe-Mn binary oxide loaded hydrochars from rice husk 17 β-estradiol 6 mg/L 42.2 0.013 0.877 47.43 4.79 0.971 4.68 0.14 0.95 [80]
5 min to 48 h
11
16
Fore modified hydrchars from cornstalks Amoxicillin 100 mg/L 88.8 3.77 0.992 89.97 0.124 0.997 1.65 × 10 2.07 0.992 [87]
0−90 min
4
Magnetic carbon composites from sugar cane bagasse Tetracycline 80 mg/L – – – 48.35 7.52 × 10 – – – – [89]
hydrochar 0−26 h
Modified activated carbon from potato peel hydrochars Pramipexole 50 mg/L 28.18 0.0153 0.976 31.3 9.6 × 10−4 0.99 – – – [88]
0−24 h
Modified activated carbon from potato peel hydrochars Dorzolamide 50 mg/L 27.44 0.0142 0.941 30.5 9.3 × 10−4 0.99 – – – [88]
0−24 h
−4
Magnetic activated carbon from sawdust Roxarsone 400 mg/L – – – 515.5 13.2 × 10 0.99 – – – [93]
0−24 h
Activated carbon from orange peel hydrochars through Diclofenac sodium 0.05 mM – – – 0.07 mmol/g 16.6 g/mmol.h 0.97 – – – [5]
phosphoric acid activation 0−36 h
Activated carbon from orange peel hydrochars through Salicylic acid 0.05 mM – – – 0.09 mmol/g 23.6 g/mmol.h 0.993 – – – [5]
Activated carbon from orange peel hydrochars through Flurbiprofen 0.05 mM – – – 0.089 mmol/g 62.7 g/mmol.h 0.995 – – – [5]
16
Activated carbon from rice straw-derived hydrochar Triclosan 10 mg/L 8.94 0.014 0.52 175 0.0066 0.99 1.8 × 10 0.24 0.87 [69]
Magnetic Activated carbon from rice straw-derived hydrochar Triclosan 10 mg/L 63.8 0.022 0.99 161 0.0010 0.99 4.6 × 102 0.05 0.95 [69]
γ-Fe2O3 carbon composite composites from hydrochars of Salix Triclosan 50 mg/L – – – 763.4 1.1 × 10−4 0.99 – – – [95]
psammophila 0−1400 min
The pseudo-second-order model, as usual, had the best fit given its high capacity from this isotherm regardless of best fit because the value of qm
determination coefficient (R2) values and low error values. The ex corresponds to the maximum monolayer adsorption capacity that other
perimental qe 51.35 mg/g was close to the calculated one, and the rate isotherm equations do not consider.
constant was 2.48 g/(mg.min). Table 5 shows two commonly applied empirical isotherm models
Furthermore, E2 and 17 α ethynyl estradiol followed the pseudo- and their parameters obtained from the adsorption data of different
second-order model with montmorillonite hydrochar composites acti EDCs/ECs on different hydrochars or ACs derived from them. These
vated by KOH [81]. The linear plots for E2 and 17 α-ethynyl estradiol isotherms greatly depend upon the nature of the adsorbent with dif
yielded qe = 113.8 mg/g and 68.8 mg/g, respectively. The rate con ferent functional groups, adsorbates, and experimental conditions.
stants for the adsorption of E2 and 17 α-ethynyl estradiol were 0.0083 Roman et al. [83] demonstrated that the adsorption of caffeine on
and 2.21 g/mg/h, respectively. The mechanism was mainly proposed to pistachio nut shell hydrochar, when processed with acidic water during
be chemical in nature with the involvement of physical interactions. hydrothermal carbonization, and that of the same sample after pyr
The above discussion clearly reveals that the pseudo-second-order olysis followed a Langmuir isotherm with preferably high adsorption
equation is the most frequently fitted model studied and that in capacities (12.95–22.6 mg/g). However, the pyrolysis of base-processed
traparticle diffusion is not the predominant rate-control step in all hydrochars followed the Freundlich isotherm with poor adsorption
studies. All the above kinetic models were studied with different EDCs/ capacity. This work explored new insights, such as the excellent ad
ECs using hydrochars and their derived ACs and are summarized in sorption capacity of acid-processed hydrochars despite their lower BET
Table 4. surface area in comparison with base-processed hydrochars and dif
ferent isotherm slopes with acid-processed hydrochars and the same
7.2. Adsorption isotherm modeling sample after pyrolysis. The reason for the former finding was attributed
to the development of steric hindrance, repulsive interactions, and
Generally, an adsorption isotherm is a curve that expresses the strong resistance of base-generated functional groups. The reason be
phenomenon that governs the retention of liquid/gas adsorbates on hind the latter finding was the removal of OFGs on thermal treatment
solid phase adsorbents by varying initial concentrations at particular that was unfavorable for adsorption when high initial concentrations
temperature and pH [111]. Its physical parameters and underlying were used. The result suggested that despite the large pores on pyr
thermodynamic assumptions provide insights into the adsorption me olyzed acid-processed hydrochars, unpyrolyzed hydrochars were more
chanism, surface properties, and degree of affinity of adsorbents. Two promising. Further insights were also obtained by simulation studies.
widely used empirical models, namely, the Langmuir and Freundlich Liu et al. [69] applied these two models to probe the interactions be
isotherms, were adopted in different studies to determine the me tween tetracycline on AC and magnetic AC from rice straw hydrochars.
chanism of adsorption and the maximum adsorption capacities. The In comparison with the Freundlich isotherm, the Langmuir isotherm in
Langmuir equation is given as [112]: linear form was a better-fitting model, resulting in qm 714 mg/g for AC
qm bCe and 303 mg/g for magnetic AC. RL value was within 0.02–0.04, which
qe = indicated a favorable adsorption.
1 + bCe (9)
Zhu et al. [93] fitted a linear Langmuir isotherm in their study of the
where qe (mg/g) is the adsorbed amount at equilibrium, qm (mg/g) is adsorption of roxorsone on magnetic AC from sawdust hydrochars ob
the highest adsorbed amount, and KL (L/mg) is the Langmuir para tained at different temperatures. The maximum adsorption capacity of
meter. qm 588 mg/g was obtained using magnetic AC derived from hydrochar
The linearization of the above equation yields the following form: obtained at 160 °C. A linear correlation between BET surface area, vo
Ce 1 C lumes of micropore and total pores, and the maximum adsorption ca
= + e pacities from the Langmuir isotherm provided the main clue to this
qe bqm qm (10)
exclusively large capacity. Chen et al. [86] prepared magnetic AC from
A dimensionless constant, also identified as the separation factor sawdust hydrochar for tetracycline adsorption. Linear plots of the
(RL) suggested by Webber and Chakkravorti [113], can be expressed as: Freundlich and Langmuir equations favored the former isotherm on the
1 basis of its high coefficient of determination. The qm value from the
RL = Langmuir equation (423.7 mg/g) was considered the greatest among all
1 + KL Co (11)
values for all adsorbents. The magnetization barely impeded the ad
where KL corresponds to the Langmuir parameter and C0 (mg/L) be sorption performance of AC. Hydrothermally obtained hydrochars and
longs to the initial adsorbate amount. The magnitude of this factor their ACs have proven to be promising adsorbents. Zhu et al. [95] also
explains the nature of adsorption as unfavorable (RL > 1), linear (RL = obtained superior adsorption capacity in their triclosan adsorption
1), favorable (0 < RL < 1), or irreversible (RL = 0). study on γ-Fe2O3 carbon. The Langmuir-fitted data presented a high
The Freundlich equation is expressed by the following [114]: regression coefficient that lacked information about the Freundlich
1 isotherm. The correlation of the different texture characteristics of ACs
qe = Kf C ne (12) prepared at different temperatures with Langmuir qm showed a linear
The linearization of the above equation gives the following form: response; in particular, micropore volume had the best correlation with
qm.
1
log qe = log Kf + log Ce Profound research interest has long been noted in the nonlinear
n (13)
optimization of adsorption modeling. Ning et al. [80] prepared Fe–Mn
1/n
Here, Kf ((mg/g) (L/mg) ) is the Freundlich parameter that represents binary oxide modified hydrochar from rice husk for the removal of E2.
adsorbed amount, and n is a parameter that indicates adsorption The nonlinear modes of the Freundlich and Langmuir equations pre
strength. The magnitude of 1/n between 0 and 1 is an index of ad dicted excellent fit to the isotherm data of E2. However, error values
sorption strength or surface heterogeneity; as this value approaches 0, were minimum with the Langmuir model (Fig. 7). The involvement of
heterogeneity rises. Values below 1 imply chemisorption, and values Fe–Mn binary oxides augmented the adsorption capacity (49.7 mg/g)
above 1 indicate cooperative adsorption. The qm values from the relative to the case of bare hydrochars (38.8 mg/g). Tian et al. [81]
Langmuir isotherm are important in the selection of a suitable ad prepared rice husk hydrochar and montmorillonite composites for the
sorbent and the design of an appropriate adsorption system. The removal of two EDCs, namely E2 and 17α ethynyl estradiol. The non
Langmuir isotherm is a preliminary and simple model that retains un linear form of the Langmuir model was the well fitted equation ac
ique importance, with almost every study determining adsorption cording to the regression coefficient values, and a close agreement was
12
Table 5
Adsorption isotherms and their parameters for the adsorption of ECs and EDCs on hydrochar/AC from lignocellulose-derived hydrochars.
Adsorbent Pollutant Langmuir Isotherm Freundlich Isotherm Experimental References
parameters
2 (1−1/n) 1/n 2
qm (mg/g) KL (L/mg) R KF mg .L /g n R
Activated carbon from hydrochars of Tetracycline 87.21 0.42 0.968 31.26 3.82 0.775 0.5−400 mg/L [91]
Agave Americana fibers in pH 7, 50 ℃,
combination with tannin Dose 0.05, g/100 m L
Hydrochars from Argun nut shells Diuron 833.3 0.200 0.992 149.45 0.949 0.912 10−40 mg/L [79]
293 K
3h
0.01 g/200 mL
Hydrochars from Argun nut shells Bisphenol A 1162.79 0.956 0.989 38.36 3.729 0.979 10−60 mg/L [79]
293 K
3h
0.01 g/200 mL
Pistachio nut shells hydrochars prepared Caffeine 22.6 0.04 0.993 0.3 0.97 0.971 0.02−1 g/L [83]
from acidic water 25℃
48 h
Dose 0.01 g/15 mL
Montmorillonite/rice husk hydrochars 17α-ethynyl 69 1.77 0.998 37 2.7 0.915 25℃ [81]
estradiol Dose 5 mg/100 m L
24 h
Montmorillonite/rice husk hydrochars 17β-estradiol 138 1.77 0.994 73 2.63 0.922 25 ℃ [81]
Dose 5 mg/100 m L
24 h
Magnetic activated carbons from sawdust Tetracycline 423.7 0.028 0.972 39.2 2.5 0.85 50−600 mg/L [86]
hydrochar 25 ℃
Dose 20 mg
Rice husk based hydrochars 17β-estradiol 38.5 0.5 0.983 15.87 0.52 0.982 0.2−8 mg/L [80]
28 ℃
Dose 5 mg
Fe-Mn loaded binary oxides on rice husk 17β-estradiol 49.7 0.53 0.985 22.31 0.53 0.981 0.2−8 mg/L [80]
based hydrochars 28℃
Dose 5 mg
Magnetic activated carbon from sugar Tetracycline 6.63 2.47 0.993 0−200 mg/L [89]
cane bagasse pH 6.8
30 ℃
24 h
0.05 g/25 mL
Oxidized activated carbon from potato Pramipexole 66 0.082 0.98 8.19 1.85 0.99 0−200 mg/L [88]
peel hydrochar 25 ℃
pH 2
dose 0.02 g/20 mL
Oxidized activated carbon from potato Dorzolamide 60 0.081 0.98 7.78 1.91 0.99 0−200 mg/L [88]
peel hydrochar 25 ℃
pH 2
dose 0.02 g/20 mL
Magnetic activated carbon from sawdust Roxarsone 588.2 0.063 0.99 – – – 50−500 mg/L [93]
hydrochar 25 ℃
Dose 0.02 g
Phosphoric acid activated carbon from Diclofenac 0.211 mmol/g 27.5 L/ 0.981 0.203 [(mmol/g)L/ 0.2 0.971 0.05−2 mmol/L [5]
orange peel hydrochars mmol mmol)nf] 25℃
0.015 g/30 mL
pH 7
Phosphoric acid activated carbon from Salicylic acid 0.66 mmol/g 10.9 L/ 0.978 0.63[(mmol/g)L/ 0.28 0.941 pH 2 [5]
orange peel hydrochars mmol mmol)nf] 0.05−2 mmol/L
25 ℃
0.015 g/30 mL
Phosphoric acid activated carbon from Flurbiprofen 0.61 mmol/g 83.9 L/ 0.981 1.45[(mmol/g)L/ 0.37 0.985 pH 2 [5]
orange peel hydrochars mmol mmol)nf] 0.05−2 mmol/L
25 ℃
0.015 g/30 mL
Magnetic activated carbon from Salix Triclosan 892.9 0.69 0.98 – – – 10−50 mg/L [95]
psammophila 303 K
Dose 500 mg/L
Activated carbon from Salix psammophila Tetracycline – – – 8.57 0.404 0.996 5−50 mg/L [115]
30℃
4 days
Dose 0.04 g/40 mL
Magnetic activated carbon from salix Tetracycline 25.4 1.08 0.85 11.78 4.34 0.99 5−80 mg/L [110]
psammophila 303K
Dose 0.05 g/50 m L
5 days
Magnetic activated carbon from rice straw Tetracycline 303 0.89 0.99 150 4.68 0.91 10−50 mg/L [69]
hydrochar 298K
Activated carbon from Rice straw Tetracycline 714 0.52 0.97 232 2.25 0.64 10−50 mg/L [69]
hydrochar 298 K
13
found between the calculated values and the experimental qm values;

the adsorption capacity for E2 (138 mg/g) was the highest, followed by
that for 17α ethynyl estradiol (69 mg/g). However, the concentration
range selected was small (0.2–8 mg/L) possibly because of the limited
solubilities of both solutes that otherwise could provide a deviation
from Langmuir to Freundlich. The fabrication of these composites was
claimed as an easy and cheap method with superior adsorption capa
cities for the two model pollutants in comparison with previously used
materials.
Fernandez et al. [5] studied the adsorption of emerging pharma
ceuticals (diclofenac, salicylic acid, and flurbiprofen) on ACs achieved
by air and phosphoric acid treatment of orange peel hydrochars. An
isotherm study was performed at pH 7 in the case of diclofenac and at
pH 2 in the cases of salicylic acid and flurbiprofen in a nonlinear mode.
The Freundlich equation best fitted with the adsorption data of diclo
fenac on air AC, whereas the Langmuir isotherm was the most appro
priate when using phosphoric acid AC. The adsorption capacities in
both cases (0.164 and 0.211 mmol/g) were claimed to be higher than
those of other biomass-based ACs. In the case of salicylic acid and
flurbiprofen, the experimental data best fitted the Langmuir isotherm. Fig. 7. Adsorption isotherm data and fitted models for 17β-estradiol on raw
In some cases, the Freundlich model was the preferable isotherm, as hydrochar and Fe-Mn oxide modified hydrochar [80].
explained by Kyzas and Deliyanni [88], who applied nonlinear Freun
dlich and Langmuir equations for their study of the adsorption of two
methods supersede the features of commercially available ACs ; the use
pharmaceuticals, namely, dorzolamide and pramipexole, on oxidized
of such material encourages further investigations into the removal of
ACs prepared via hydrothermal and pyrolysis treatments. Both drugs
other wide varieties of pollutants. The commercialization and im
followed the Freundlich model, with pramipexole having higher ad
plementation of the method in practical settings are encouraged in the
sorption capacity than dorzolamide did. The ACs prepared from hy
current industrialization era.
drochars showed greater adsorption capacities than those prepared
from biochars of the same precursor via pyrolysis. Their study showed
that preparation methods greatly affect the adsorption performances of 8. Reusability of adsorbents
resulting ACs. The Freundlich isotherm was again the best fitted model
on the basis of the experimental data of tetracycline adsorption in The worth of any adsorbent material can be appraised if the mate
magnetic AC from Salix psammophila with a Langmuir adsorbed amount rial concerned is economic, efficient, and long-lasting. Reusability is
of 25.4 mg/g as a result of the many graphitic layers and porous texture. one of the important aspects in this technology because this property
The RL values within 0.011–0.16 also suggested a favorable adsorption may help reduce the cost of adsorbents, minimize disposal issues, and
process [110]. Rattanachueskul et al. [89] studied the adsorption per prevent the laborious work needed to resynthesize fresh adsorbent
formance of magnetic AC derived from sugar cane bagasse for removing materials for the consecutive adsorption system. Our extensive litera
tetracycline. The Freundlich isotherm model was the better fitted model ture survey on the topic has revealed the limited number of studies on
with a value of n = 2.47, which indicated a heterogeneous adsorption the reusability of lignocellulose-based hydrochars, their composites,
that further strengthened the assumption that the resulting adsorbent and the ACs derived from them. Good desorption depends upon the
possessed a large number of heterogeneous sites. type of interactions and solvents. Rattanachueskul et al. [89] demon
However, relying on isotherms for the prediction of adsorption strated that magnetic carbon from sugar cane bagasse hydrochar can be
mechanisms is not the exclusive method for demonstrating solute– reused for tetracycline adsorption when treated with 25 mL of 0.1 M
adsorbent interactions. Some advanced computational modeling stu NaOH solution. As a normal trend, the adsorption efficiency declined
dies, along with advanced characterization tools, should be deduced to after every cycle (from 81.84 % to 57.27 %), thereby confirming strong
learn the effect of variables like pH, molecular geometries, and surface interactions between tetracycline and the adsorbent.
and interaction energies on the mechanisms of adsorption [83]. An In an existing study, ACs from potato peel hydrochars obtained after
other remarkable study is that conducted by Flora et al. [98], who in hydrothermal treatment and oxidation showed good reusable perfor
vestigated the influence of hydrochars with and without washing for mance, that is, reusability of up to 20 times with desorption carried at
removal of atrazine. The calculation of the binding energies between an optimum pH level of 10, in dorzolamide and pramipexole removal
the atrazine hydrochars showed low favorable binding energies when [88]. The work reported only an 11 % decline in initial adsorption ef
atrazine was parallel to the hydrochar plane. The adsorptive capacities ficiency. This decreasing trend was attributed to the progressive sa
of the hydrochars obtained by acetone washing were superior to those turation of the active sites and the degradation of the materials due to
of the hydrochars without washing. This deviation in adsorption can be the highly basic pH and blockage of active sites.
related to the less preferable attraction energy of atrazine for hydro Meanwhile, Fe–Mn binary oxide-loaded rice husk-based hydrochars
chars without washing with weakly associated alkyl groups on the showed good reusability of up to five times for 6 mg/L E2 removal. The
surface relative to hydrochars with washing. desorption medium used was acetone/water mixture in the ratio of 1:1
According to Table 5, Langmuir model well represents the adsorp (v/v) based on a high octanol–water partitioning coefficient in acetone
tion isotherm data of most EDC/EC pollutants on hydrochars and their [80]. Tian et al. [81] performed a regeneration study of montmor
derived ACs. Freundlich model is also applicable in some cases. From illonite rice husk hydrochar composites with 20 mL ethanol, which
the parameters of both models the adsorption process is favorable. In were washed with water multiple times and then dried. The re
the literature, the adsorption capacities of different hydrochars or the generated adsorbent retained 82 % and 80.2 % of the initial sorption
ACs derived from them for EDC/EC removal were claimed to be su capacities for E2 and 17α ethynyl estradiol, respectively. Excellent
perior to those of other reported materials [5,79,81,86,95], thereby stability and reusability were found by Zbair et al. [79] using Argan nut
suggesting that hydrochars may open a new horizon in carbon chem shell hydrochars for the removal of diuron and bisphenol A. The des
istry as their interesting surface features and low-cost preparation orption of the retained pollutants was conducted using ethanol. The
14
frequency of recycling (up to 5 times) had no significant effect on ad

sorption efficiency, and the material could sustain its removal efficiency
for bisphenol A (88 %) and diuron (94 %), as shown in Fig. 8. Only a 5%
decline was reported in the efficiency of bisphenol A removal, whereas
a 1% decline was reported for diuron for five consecutive ad
sorption–desorption cycles.
Hydrochars and their derived ACs can be efficiently reutilized for
several cycles after regeneration by NaOH and organic agents. Ideally, a
desorbing agent should be neither too punitive nor too expensive for
the regeneration of adsorbents to affect adsorbents’ efficiency or tech
nology. From the above discussions, we observed that mostly organic
solvents were used for the desorption of studied pollutants that are
expensive and volatile. This approach could affect process efficiency
from the ecological and economic perspectives. A systematic study with
green solvents for the regeneration of spent adsorbents is necessary to
achieve a successful adsorption of these pollutants. Moreover, the fate
of these desorbing agents remains undecided; they are mostly disposed
to the sink and may thus cause secondary pollution. Such gaps should
be considered, and recyclability techniques should be developed to
Fig. 8. Reusability of Argan nut shell derived hydrochar for the adsorption of
regenerate desorbing solvents and recollect desorbed pollutants that bisphenol A and diuron [79].
may be removed or returned to the manufacturing industry. Only Zbair
et al. [79] addressed some alternative solutions to the present dilemma;
that is, the incineration of exhausted adsorbents and conversion of re adequate attention to strengthen their replacement with ACs.
tained pollutants to less harmful byproducts. However, such a study Other gaps pointed out in the current review include the develop
requires proper waste management techniques and transport facilities ment of a systematic classification to distinguish ECs and EDCs and the
that should be considered by environmental protection agencies. establishment of proper guideline values. Strict measures should also be
taken to frame legislation on the release of these contaminants from
9. Conclusions and future perspectives industrial wastes. An accurate, precise, and sensitive standard analy
tical method is required for the simultaneous determination of well-
In this review, we focused on the recent studies on the applications known EDCs and ECs at their trace levels. Proper knowledge of the
of lignocellulose-based hydrochars and their post-hydrothermally mechanism of hydrochar formation from complex lignocellulose bio
treated ACs. This work invokes the slogan, “treatment of waste by mass is equally important. The use of green activating agents for the
waste,” and may serve as a beacon in green chemistry. These hydro preparation of ACs should be studied. Owing to the frequent presence of
chars can successfully replace commercially available resins and ACs these toxic unregulated pollutants at alarming levels, wastewater
for the removal of ECs and EDCs. Post-treated ACs from hydrochar treatments should be upgraded to resolve these rapid-growing problems
precursors have shown promising and improved results relative to their by either modifying the membrane materials with such novel and sus
precursors because of their large surface area and high porosity. The tainable materials as their components or replacing commercially ap
mechanism of adsorption greatly depends upon experimental condi plied ACs to treat recalcitrant ECs and EDCs. Such attempts may im
tions, and adsorption is controlled by a myriad of interactions, such as prove water quality and substantially reduce the costs for expensive
electrostatic, hydrophobic, and π-π interactions; pore filling; hydrogen membranes. Hydrochars and their derived ACs may leave some adverse
bonding; and intercalations. The use of hydrochars and ACs in the re effects; therefore, an evaluation of their ecotoxicity and an assessment
moval of ECs and EDCs has elicited keen interest in the last few years of their environmental influences are strongly recommended.
due to the great adsorption capacities that they offer. Adsorption ki
netics is a pseudo-second-order equation in all studies, and intraparticle Declaration of Competing Interest
diffusion is not the sole rate-limiting step. Adsorption isotherms are
frequently of Langmuir type, but some studies cited the Freundlich The authors declare that they have no known competing financial
isotherm as the best one. Efficient regeneration and reusability profiles interests or personal relationships that could have appeared to influ
have been exhibited for hydrochars and their derived ACs. Some issues ence the work reported in this paper.
remain unaddressed and must be considered to broaden the scope of
these new emerging materials. Acknowledgement
The studies discussed in the current review were mainly based on
the batch system for determining the adsorption performance of dif The publication of this article was funded by the Qatar National
ferent hydrochars and their ACs. Thus, carrying out column, pilot, full- Library.
scale, and multi-component adsorption studies is useful to appraise
these adsorbents in real applications that involve interfering sub References
stances. The adsorption behavior of other EDCs and ECs, such as
phthalates, parabens, DDT, herbicides, and pesticides, should also be [1] N. Chaukura, B.B. Mamba, S.B. Mishra, Porous materials for the sorption of
emerging organic pollutants from aqueous systems: the case for conjugated mi
investigated to apply these new materials to practical settings. The
croporous polymers, J. Water Process Eng. 16 (2017) 223–232.
proper and careful study of the exact adsorption mechanism is also [2] Commission of the European Communities, The Implementation of the
required in designing a suitable adsorbent that depends on the complex Community Strategy for Endocrine Disrupters: A Range of Substances Suspected of
structure of different ECs and EDCs. Furthermore, the magnetization of Interfering With the Hormone Systems of Humans and Wildlife, COM [1999], Vol.
706, (2001) pp. 45.
porous ACs may enhance their adsorption efficiency relative to bare [3] M. Sevilla, A.B. Fuertes, The production of carbon materials by hydrothermal
hydrochars. The regeneration and reusability of hydrochar and AC carbonization of cellulose, Carbon 47 (2009) 2281–2289.
adsorbents using nontoxic and cheap solvents should be investigated to [4] Y. Xue, B. Gao, Y. Yao, et al., Hydrogen peroxide modification enhances the ability
of biochar (hydrochar) produced from hydrothermal carbonization of peanut hull
make the process economically viable. Cost analysis studies and the to remove aqueous heavy metals: batch and column studies, Chem. Eng. J. 200-
practical implementation of these adsorbents should also be given
15
202 (2012) 673–680. [34] Z. Hao, Y. Xiao, L. Jiang, et al., Simultaneous determination of bisphenol a, bi
[5] M.E. Fernandez, B. Ledesma, S. Roman, P.R. Bonelli, A.L. Cukiermann, sphenol F, 4-Nonylphenol, 4-n-Nonylphenol, and octylphenol in grease-rich food
Development and characterization of activated hydrochars from orange peels as by Carb/PSA solid-phase extraction combined with high-performance liquid
potential adsorbents for emerging contaminants, Bioresour. Technol. 183 (2015) chromatography tandem mass spectrometry, Food Anal. Methods 11 (2018)
221–228. 589–597.
[6] P. Zhao, Y. Shen, S. Ge, et al., Clean solid biofuel production from high moisture [35] Z.-H. Liu, Y. Kanjo, S. Mizutani, Removal mechanisms for endocrine disrupting
content waste biomass employing hydrothermal treatment, Appl. Energy 131 compounds (EDCs) in wastewater treatment – physical means, biodegradation,
(2014) 345–367. and chemical advanced oxidation: a review, Sci. Total Environ. 407 (2009)
[7] M.M. Titirici, R.J. White, C. Falco, M. Sevilla, Black perspectives for a green future: 731–748.
hydrothermal carbons for environment protection and energy storage, Energy [36] T. Saeed, N. Al-Jandal, A. Abusam, et al., Sources and levels of endocrine dis
Environ. Sci. 5 (2012) 6796–6822. rupting compounds (EDCs) in Kuwait’s coastal areas, Mar. Pollut. Bull. 118 (2017)
[8] M.T. Reza, J. Andert, B. Wirth, et al., Hydrothermal carbonization of biomass for 407–412.
energy and crop production, Appl. Bioenergy 1 (2014) 11–29. [37] H. Arfaeinia, M. Fazlzadeh, F. Taghizadeh, et al., Phthalate acid esters (PAEs)
[9] L. Ding, B. Zou, Y. Li, et al., The production of hydrochar based hierarchical accumulation in coastal sediments from regions with different land use config
porous carbons for use as electrochemical supercapacitor electrode materials, uration along the Persian Gulf, Ecotox. Environ. Safe. 169 (2019) 496–506.
Colloids Surf. A Physicochem. Eng. Asp. 423 (2013) 104–111. [38] S.-Q. Tian, R.-Y. Zhao, Z.-C. Chen, Review of the pretreatment and bioconversion
[10] K.Y. Park, K. Lee, D. Kim, Characterized hydrochar of algal biomass for producing of lignocellulosic biomass from wheat straw materials, Renew. Sust. Energ. Rev.
solid fuel through hydrothermal carbonization, Bioresour. Technol. 258 (2018) 91 (2018) 483–489.
119–124. [39] J. Hoarau, Y. Caro, I. Grondin, T. Petit, Sugarcane vinasse processing: toward a
[11] E. Atallah, W. Kwapinski, M.N. Ahmad, J.J. Leahy, J. Zeaiter, Effect of water- status shift from waste to valuable resource. A review, J. Water Process Eng. 24
sludge ratio and reaction time on the hydrothermal carbonization of olive oil mill (2018) 11–25.
wastewater treatment: hydrochar characterization, J. Water Process Eng. 31 [40] A. Arvelo-Gallegos, Z. Ahmad, M. Asgher, et al., Lignocellulose: a sustainable
(2019) 100813. materials to produce value-added product with a zero waste approach-a review,
[12] G.K. Parshetti, S. Chowdhury, R. Balasubramanian, Hydrothermal conversion of Int. J. Biol. Macromol. 99 (2017) 308–318.
urban food waste to chars for removal of textile dyes from contaminanted waters, [41] G. Kabir, B.H. Hameed, Recent progress on catalytic pyrolysis of lignocellulosic
Bioresour. Technol. 161 (2014) 310–319. biomass to highgrade bio-oil and bio-chemicals, Renew. Sust. Energ. Rev. 70
[13] Y. Dai, Q. Sun, W. Wang, et al., Utilization of agricultural waste as adsorbent for (2017) 945–967.
the removal of contaminants: a review, Chemosphere 211 (2018) 235–253. [42] X. Han, Y. Guo, X. Liu, Catalytic conversion of lignocellulosic biomass into hy
[14] Y. Dai, N. Zhang, C. Xing, et al., The adsorption, regeneration and engineering drocarbons: a mini review, Catal. Today 319 (2019) 2–13.
applications of biochar for removal organic pollutants: a review, Chemosphere [43] S.S. Hassan, G.A. Williams, A.K. Jaiswal, Emerging technologies for the pretreat
223 (2019) 12–27. ment of lignocellulosic biomass, Bioresour. Technol. 262 (2018) 310–318.
[15] A. Bhatnagar, I. Anastopoulus, Adsorptive removal of bisphenol A (BPA) from [44] P. Burguete, A. Corma, M. Hitzl, et al., Fuel and chemicals from wet lignocellulosic
aqueous solution: a review, Chemosphere 168 (2017) 885–902. biomass waste streams by hydrothermal carbonization, Green Chem. 18 (2016)
[16] S. Kim, C.M. Park, M. Jang, et al., Aqueous removal of inorganic and organic 1051–1060.
contaminants by graphene-based nanoadsorbents: a review, Chemosphere 212 [45] A. Jain, R. Balasubramanian, M.P. Srinivasan, Hydrothermal conversion of bio
(2018) 1104–1124. mass waste to activated carbon with high porosity: a review, Chem. Eng. J. 283
[17] M.B. Ahmed, J.L. Zhou, H.H. Ngo, et al., Progress in the biological and chemical (2016) 789–805.
treatment technologies for emerging contaminant removal from wastewater: a [46] A. Salimbeni, Biobased Char Market Potentials, European Biomass Industry
critical review, J. Hazard. Mater. 323 (2017) 274–298. Association, 2015.
[18] N.H. Tran, M. Reinhard, K.Y.-H. Gin, Occurrence and fate of emerging con [47] T. Wang, Y. Zhai, Y. Zhu, C. Li, G. Zeng, A review of the hydrothermal carboni
taminants in municipal wastewater treatment plants from different geographical zation of biomass waste for hydrochar formation: process conditions, funda
regions-a review, Water Res. 133 (2018) 182–207. mentals and physicochemical properties, Renew. Sust. Energ. Rev. 90 (2018)
[19] M. Taheran, M. Naghdi, S.K. Brar, M. Verma, R.Y. Surampalli, Emerging con 223–247.
taminants: here today, there tomorrow, Environ. Nanotechnol. Mon. Manage. 10 [48] H. Huang, X. Yuan, G. Zeng, H. Zhu, H. Li, Z. Liu, H. Jiang, L. Leng, W. Bi,
(2018) 122–126. Quantitative evaluation of heavy metals’ pollution hazards in liquefaction residues
[20] D.W. Kolpin, E.T. Furlong, M.T. Meyer, E.M. Thurman, S.D. Zaugg, L.B. Barber, of sewage sludge, Bioresour. Technol. 102 (2011) 10346–10351.
H.T. Buxton, Pharmaceuticals, hormones, and other organic wastewater con [49] T. Liu, Z. Liu, Q. Zheng, Effect of hydrothermal carbonization on migration and
taminants in US streams, 1999-2000: a national reconnaissance, Environ. Sci. environmental risk of heavy metals in sewage sludge during pyrolysis, Bioresour.
Technol. 36 (2002) 1202–1211. Technol. 247 (2018) 282–290.
[21] K. Kümmerer, Drugs in the environment: emission of drugs, diagnostic aids and [50] N. Saha, A. Saba, M.T. Reza, Effect of hydrothermal carbonization temperature on
disinfectants into wastewater by hospitals in relation to other sources-a review, pH, dissociation constants, and acidic functional groups on hydrochar from cel
Chemosphere 45 (2001) 957–969. lulose and wood, J. Anal. Appl. Pyrol. 137 (2019) 138–145.
[22] L.S. Shore, M. Shemesh, Naturally produced steroid hormones and their release [51] D. Zhang, F. Wang, X. Shen, et al., Comparison study on fuel properties of hy
into the environment, Pure Appl. Chem. 75 (2003) 1859–1871. drochars produced from corn stalk and corn stalk digestate, Energy 165 (2018)
[23] I.J. Buerge, H.R. Buser, M. Kahle, M.D. Müller, T. Poiger, Ubiquitous occurrence of 527–536.
the artificial sweetener acesulfame in the aquatic environment: an ideal chemical [52] Q. Ma, L. Han, G. Huang, Effect of water-washing of wheat straw and hydro
marker of domestic wastewater in groundwater, Environ. Sci. Technol. 43 (2009) thermal temperature on its hydrochar evolution and combustion properties,
4381–4385. Bioresour. Technol. 269 (2018) 96–103.
[24] D.J. Lapworth, N. Baran, M.E. Stuart, R.S. Ward, Emerging organic contaminants [53] A.M. Smith, S. Singh, A.B. Ross, Fate of inorganic material during hydrothermal
in groundwater: a review of sources, fate and occurrence, Environ. Pollut. 163 carbonisation of biomass: influence of feedstock on combustion behaviour of hy
(2012) 287–303. drochar, Fuel 169 (2016) 135–145.
[25] S. Sifakis, Androutsopoulos, A.M. Tsatsakis, et al., Human exposure to endocrine [54] M. Wilk, A. Magdziarz, K. Jayaraman, et al., Hydrothermal carbonization char
disrupting chemicals: effects on the male and female reproductive systems, acteristics of sewage sludge and lignocellulosic biomass. A comparative study,
Environ. Toxicol. Pharmacol. 51 (2017) 56–70. Biomass Bioenerg. 120 (2019) 166–175.
[26] J.O. Tijani, O.O. Fatoba, L.F. Petrik, A review of pharmaceuticals and endocrine- [55] I. Oliveira, D. Blohse, H.G. Ramke, Hydrothermal carbonization of agricultural
disrupting compounds: sources, effects, removal, and detections, Water Air Soil residues, Bioresour. Technol. 142 (2013) 138–146.
Pollut. 224 (2013) 1770. [56] Y.O. Donar, E. Çag ˘lar, A. Sınag, Preparation and characterization of agricultural
[27] Y. Jia, M. Hammers-Wirtz, et al., Effect-based and chemical analyses of agonistic waste biomass based hydrochars, Fuel 183 (2016) 366–372.
and antagonistic endocrine disruptors in multiple matrices of eutrophic fresh [57] H. Yang, R. Yan, H. Chen, D.H. Lee, C. Zheng, Characteristics of hemicellulose,
waters, Sci. Total Environ. 651 (2019) 1096–1104. cellulose and lignin pyrolysis, Fuel 86 (2007) 1781–1788.
[28] N. Salgueiro-Gonzalez, M.J. Lopez de Alda, S. Muniateguie-Lorenzo, et al., [58] Y. Li, N. Tsend, T. Li, et al., Microwave assisted hydrothermal preparation of rice
Analysis and occurrence of endocrine-disrupting chemicals in airborne particles, straw hydrochars for adsorption of organics and heavy metals, Bioresour. Technol.
Trends Analyt. Chem. 66 (2015) 45–52. 273 (2019) 136–143.
[29] J.S. Helm, M. Nishioka, J.G. Brody, et al., Measurement of endocrine disrupting [59] M.T. Reza, E. Rottler, L. Herklotz, et al., Hydrothermal carbonization (HTC) of
and asthma-associated chemicals in hair products used by Black women, Environ. wheat straw: influence of feed water pH prepared by acetic acid and potassium
Res. 165 (2018) 448–458. hydroxide, Bioresour. Technol. 182 (2015) 336–344.
[30] J. Annamalai, V. Namasivayam, Endocrine disrupting chemicals in the atmo [60] Q. Lang, B. Zhang, Z. Liu, et al., Co-hydrothermal carbonization of corn stalk and
sphere: their effects on humans and wildlife, Environ. Int. 76 (2015) 78–97. swine manure: combustion behavior of hydrochar by thermogravimetric analysis,
[31] I.-H. Acir, K. Guenther, Endocrine-disrupting metabolites of alkylphenol ethox Bioresour. Technol. 271 (2019) 75–83.
ylates-A critical review of analytical methods, environmental occurences, toxicity [61] X. Zhang, L. Zhang, A. Li, Hydrothermal co-carbonization of sewage sludge and
and regulation, Sci. Total Environ. 635 (2018) 1530–1546. pinewood sawdust for nutrient-rich hydrochar production: synergistic effects and
[32] M. Zhong, P. Yin, L. Zhao, Nonylphenol and octylphenol in riverine waters and products characterization, J. Environ. Manage. 201 (2017) 52–62.
surface sediments of the Pearl River estuaries, South China: occurrence, ecological [62] Q. Lang, Y. Guo, Q. Zheng, et al., Co-hydrothermal carbonization of lignocellulosic
and human health risks, Water Sci. Technol. Water Supply 17 (2017) 1070–1079. biomass and swine manure: hydrochar properties and heavy metal transformation
[33] K. Gunther, T. Racker, R. Bohme, An isomer-specific approach to endocrine dis behavior, Bioresour. Technol. 266 (2018) 242–248.
rupting Nonylphenol in infant food, J. Agric. Food Chem. 65 (2017) 1247–1254. [63] Z.M.A. Bundhoo, Microwave-assisted conversion of biomass and waste materials
16
to biofuels, Renew. Sust. Energ. Rev. 82 (2018) 1149–1177. environmental-friendly adsorbents for the treatment of pharmaceutical effluents,
[64] Y. Shao, Y. Long, H. Wang, et al., Hydrochar derived from green waste by mi Chem. Eng. Res. Des. 97 (2015) 135–144.
crowave hydrothermal carbonization, Renew. Energy 135 (2019) 1327–1334. [89] N. Rattanachueskul, A. Saning, S. Kaowphong, N. Chumha, L. Chuenchom,
[65] T. Maneerung, J. Liew, Y. Dai, et al., Activated carbon derived from carbon residue Magnetic carbon composites with a hierarchical structure for adsorption of tet
from biomass gasification and its application for dye adsorption: kinetics, iso racycline, prepared from sugarcane bagasse via hydrothermal carbonization cou
therms and thermodynamic studies, Bioresour. Technol. 200 (2016) 350–359. pled with simple heat treatment process, Bioresour. Technol. 226 (2017) 164–172.
[66] M. Sevilla, G.A. Ferrero, A.B. Fuertes, Beyond KOH activation for the synthesis of [90] M. Puccini, E. Stefanelli, A.L. Tasca, S. Vitolo, Pollutant removal from gaseous and
superactivated carbons from hydrochars, Carbon 114 (2017) 50–58. aqueous phases using hydrochar-based activated carbon, Chem. Eng. Trans. 67
[67] M. Sevilla, A.B. Fuertes, R. Mokaya, High density hydrogen storage in super ac (2018) 637–642.
tivated carbons from hydrothermally carbonized renewable organic materials, [91] T. Selmi, A. Sanchez-Snachez, P. Gaddoneix, et al., Tetracycline removal with
Energy Environ. Sci. 4 (2011) 1400–1410. activated carbons produced from hydrothermal carbonisation of Agave americana
[68] L. Wang, Y. Guo, B. Zou, et al., High surface area porous carbons prepared from fibers and mimosa tannin, Ind. Crops Prod. 115 (2018) 146–157.
hydrochars by phosphoric acid activation, Bioresour. Technol. 102 (2011) [92] F. Suo, G. Xie, J. Zhang, et al., A carbonized sieve –like corn straw cellulose-
1947–1950. graphene oxide composite for organophosphorus pesticide removal, RSC Adv. 8
[69] Y. Liu, X. Zhu, F. Qian, et al., Magnetic activated carbon prepared from rice straw- (2018) 7735–7743.
derived hydrochar for triclosan removal, RSC Adv. 4 (2014) 63620–63626. [93] X. Zhu, F. Qian, Y. Liu, et al., Environmental performances of hydrochar-derived
[70] M.A. Islam, M.J. Ahmed, W.A. Khanday, M. Asif, B.H. Hameed, Mesoporous ac magnetic carbon composite affected by its carbonaceous precursor, RSC Adv. 5
tivated carbon prepared from NaOH activation of rattan (Lacosperma secundi (2015) 60713–60722.
florum) hydrochar for methylene blue removal, Ecotox. Environ. Safe. 138 (2017) [94] X. Zhu, F. Qian, Y. Liu, et al., Controllable synthesis of magnetic carbon compo
279–285. sites with high porosity and strong acid resistance from hydrochar for efficient
[71] M.A. Islam, M.J. Ahmed, W.A. Khanday, M. Asif, B.H. Hameed, Mesoporous ac removal of organic pollutants: an overlooked influence, Carbon 99 (2016)
tivated coconut shell derived hydrochar prepared via hydrothermal carbonization- 338–347.
NaOH activation for methylene blue adsorption, J. Environ. Manage. 203 (2017) [95] X. Zhu, Y. Liu, G. Luo, et al., Facile fabrication of magnetic carbon composites
237–244. from hydrochar via simultaneous activation and magnetization for triclosan ad
[72] M.A. Islam, I.A.W. Tan, A. Benhouria, M. Asif, B.H. Hameed, Mesoporous and sorption, Environ. Sci. Technol. 48 (2014) 5840–5848.
adsorptive properties of palm date seed activated carbon prepared via sequential [96] K. Sun, K. Ro, M. Guo, et al., Sorption of bisphenol A, 17a-ethinyl estradiol and
hydrothermal carbonization and sodium hydroxide activation, Chem. Eng. J. 270 phenanthrene on thermally and hydrothermally produced biochars, Bioresour.
(2015) 187–195. Technol. 102 (2011) 5757–5763.
[73] X. Zhu, Y. Liu, C. Zhou, et al., Novel and high-performance magnetic carbon [97] S. Shi, Y. Fan, Y. Huang, Facile low temperature hydrothermal synthesis of mag
composite prepared from waste hydrochar for dye removal, ACS sustain, Chem. netic mesoporous carbon nanocomposite for adsorption removal of ciprofloxacin
Eng. 2 (2014) 969–977. antibiotics, Ind. Eng. Chem. Res. 52 (2013) 2604–2612.
[74] A. Jain, R. Balasubramanian, M.P. Srinivasan, Production of high surface area [98] J.F.R. Flora, X. Lu, L. Li, et al., The effects of alkalinity and acidity of process water
mesoporous activated carbons from waste biomass using hydrogen peroxide- and hydrochar washing on the adsorption of atrazine on hydrothermally produced
mediated hydrothermal treatment for adsorption applications, Chem. Eng. J. 273 hydrochar, Chemosphere 93 (2013) 1989–1996.
(2015) 622–629. [99] M.A. Ahsan, M.T. Islam, C. Hernandez, et al., Biomass conversion of saw dust to a
[75] A. Jain, R. Balasubramanian, M.P. Srinivasan, Tuning hydrochar properties for functionalized carbonaceous materials for the removal of Tetracycline,
enhanced mesopore development in activated carbon by hydrothermal carboni Sulfamethoxazole and Bisphenol A from water, J. Environ. Chem. Eng. 6 (2018)
zation, Microporous Mesoporous Mater. 203 (2015) 178–185. 4329–4338.
[76] A.R. Guastalli, J. Labanda, J. Llorens, Separation of phosphoric acid from an in [100] S. Lagergren, About the theory of so-called adsorption of soluble substances,
dustrial rinsing water by means of nanofiltration, Desalination 243 (2009) Kungliga Svenska Vetenskapsakademiens 4 (1898) 1–39 Band 24.
218–228. [101] W. Rudzinski, W. Plazinski, Studies of the kinetics of solute adsorption at solid/
[77] X.-f Tan, S.-b Liu, Y.-g Liu, Biochar as potential sustainable precursors for activated solution interfaces: on the possibility of distinguishing between the diffusional and
carbon production: multiple applications in environmental protection and energy the surface reaction kinetic models by studying the pseudo-first order kinetics, J
storage, Bioresour. Technol. 227 (2017) 359–372. Phys Chem C 111 (2007) 15100–15110.
[78] K.Y. Foo, B.H. Hameed, Potential of jackfruit peel as precursor for activated [102] Y.S. Ho, G. McKay, The sorption of Pb (II) ions on peat, Water Res. 33 (1999)
carbon prepared by microwave induced NaOH activation, Bioresour. Technol. 112 578–584.
(2012) 143–150. [103] G. McKay, Y.S. Ho, J.C.Y. Ng, Biosporption of copper from waste waters: a review,
[79] M. Zbair, M. Bottlinger, K. Ainassaari, et al., Hydrothermal Carbonization of Argan Sep Purif Methods 28 (1999) 87–125.
Nut Shell: Functional Mesoporous Carbon with Excellent Performance in the [104] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process
Adsorption of Bisphenol a and Diuron, Waste Biomass Valori, (2018) https Biochem. 34 (1999) 451–465.
://doi.org/10.1007/s1264 9-018-00554-0. [105] K.L. Tan, B.H. Hameed, Insight into the adsorption kinetics models for the removal
[80] Q. Ning, Y. Liu, S. Liu, et al., Fabrication of hydrochar functionalized Fe-Mn binary of contaminants from aqueous solutions, J. Taiwan Inst, Chem. Eng. 74 (2017)
oxide nanocomposites: characterization and 17β-estradiol removal, RSC Adv. 7 25–48.
(2017) 37122–37129. [106] S. Roginsky, Y.B. Zeldovich, The catalytic oxidation of carbon monoxide on
[81] S. Tian, Y. Liu, S. Liu, et al., Hydrothermal synthesis of montmorillonite/hydro manganese dioxide, Acta Phys Chem USSR 1 (1934) 554.
char nanocomposites and application for 17β-estradiol and 17α-ethynylestradiol [107] W.J. Weber, J.C. Morris, Kinetics of adsorption on carbon from solution, J Sanit
removal, RSC Adv. 8 (2018) 4273–4283. Eng Div 89 (1963) 31–60.
[82] E. Weidemann, M. Niinipuu, J. Fick, S. Jansson, Using carbonized low-cost ma [108] W. Plazinski, W. Rudzinski, A. Plazinska, Theoretical models of sorption kinetics
terials for removal of chemicals of environmental concern from water, Environ. including a surface reaction mechanism: a review, Adv. Colloid Interface Sci. 152
Sci. Pollut. Res. 25 (2018) 15793–15801. (2009) 2–13.
[83] S. Román, B. Ledesma, A. Álvarez, C. Herdes, Towards sustainable micro-pollu [109] A.S. Mestre, E. Tyszko, M.A. Andrade, et al., Sustainable activated carbons pre
tants’removal from wastewaters: caffeine solubility, self diffusion and adsorption pared from a sucrose-derived hydrochar: remarkable adsorbents for pharmaceu
studies from aqueous solutions into hydrochars, Mol. Phys. (2018), https://doi. tical compounds, RSC Adv. 5 (2015) 19696–19707.
org/10.1080/00268976.2018.1487597. [110] X. Zhu, Y. Liu, F. Qian, et al., Preparation of magnetic porous carbon from waste
[84] N. Eibisch, R. Schroll, R. Fuβ, et al., Pyrochars and hydrochars differently alter the hydrochar by simultaneous activation and magnetization for tetracycline removal,
sorption of the herbicide isoproturon in an agricultural soil, Chemosphere 119 Bioresour. Technol. 154 (2014) 209–214.
(2015) 155–162. [111] G. Limousin, J.P. Gaudet, L. Charlet, S. Szenknect, V. Barthes, M. Krimissa,
[85] J. Deng, X. Li, X. Wei, et al., Sulfamic acid modified hydrochar derived from Sorption isotherms: are view on physical bases, modeling and measurement, Appl.
sawdust for removal of benzotriazole and Cu(II) from aqueous solution: adsorption Geochem. 22 (2007) 249–275.
behavior and mechanism, Bioresour. Technol. 290 (2019) 121765. [112] I. Langmuir, The constitution and fundamental properties of solids and liquids, J.
[86] S.Q. Chen, Y.L. Chen, H. Jiang, Slow pyrolysis magnetization of hydrochar for eff Am. Chem. Soc. 38 (1916) 2221–2295.
;ective and highly stable removal of tetracycline from aqueous solution, Ind. Eng. [113] T.W. Webber, R.K. Chakkravorti, Pore and solid diffusion models for fixed-bed
Chem. Res. 56 (2017) 3059–3066. adsorbers, AlChE J. 20 (1974) 228–238.
[87] H. Li, J. Hu, Y. Cao, et al., Development and assessment of a functional activated [114] H.M.F. Freundlich, Over the adsorption in solution, J. Phys. Chem. 57 (1906)
fore-modified bio-hydrochar for amoxicillin removal, Bioresour. Technol. 246 385–471.
(2017) 168–175. [115] X. Zhu, Y. Liu, C. Zhou, et al., A novel porous carbon derived from hydrothermal
[88] G.Z. Kyzas, E.A. Deliyanni, Modified activated carbons from potato peels as green carbon for efficient adsorption of tetracycline, Carbon 77 (2014) 627–636.
17

1 s2.0 S2214714420302580 Main

Uploaded by

Copyright:

Available Formats

1 s2.0 S2214714420302580 Main

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

1 s2.0 S2214714420302580 Main

Uploaded by

Copyright:

Available Formats

Journal of Water Process Engineering 38 (2020) 101380

Contents lists available at ScienceDirect

Journal of Water Process Engineering

Adsorption of endocrine disrupting compounds and other emerging T

ARTICLE INFO ABSTRACT

Wood-HC 60.3 % 52.4 5.8 48.8 – – – [50]

Fig. 3. HTC reaction pathways from lignocellulose biomass [8].

changing the experimental parameters, especially pH. Surface texture

found between the calculated values and the experimental qm values;

frequency of recycling (up to 5 times) had no significant effect on ad

You might also like

1 s2.0 S2214714420302580 Main

Uploaded by

Copyright:

Available Formats

1 s2.0 S2214714420302580 Main

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

1 s2.0 S2214714420302580 Main

Uploaded by

Copyright:

Available Formats

Journal of Water Process Engineering 38 (2020) 101380

Contents lists available at ScienceDirect

Journal of Water Process Engineering

Adsorption of endocrine disrupting compounds and other emerging T

ARTICLE INFO ABSTRACT

Wood-HC 60.3 % 52.4 5.8 48.8 – – – [50]

Fig. 3. HTC reaction pathways from lignocellulose biomass [8].

changing the experimental parameters, especially pH. Surface texture

found between the calculated values and the experimental qm values;

frequency of recycling (up to 5 times) had no significant effect on ad­

You might also like

frequency of recycling (up to 5 times) had no significant effect on ad