Separation and Purification Technology 197 (2018) 345–359

Contents lists available at ScienceDirect

Separation and Purification Technology

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Review

Bio-regeneration of activated carbon: A comprehensive review T

a b c,⁎ c c
Maisa El Gamal , Hussein A. Mousa , Muftah H. El-Naas , Renju Zacharia , Simon Judd
a
College of Natural and Health Sciences, Zayed University, P.O. Box 144534, Abu Dhabi, United Arab Emirates
b
Chemical and Petroleum Engineering Department, UAE University, P.O. Box 15551, Al-Ain, United Arab Emirates
c
Gas Processing Center, College of Engineering, Qatar University, P.O. Box 2713, Doha, Qatar

A R T I C L E I N F O A B S T R A C T

Keywords: The use of microorganisms to regenerate activated carbon (AC), bio-generation, can avert costly and logistically
AC challenging ex-situ steam regeneration of carbon normally required to recover its adsorptive capacity. Bio-re-
Bio-regeneration generation employs microbial metabolism in which the microbes use the available organic substrates (con-
Mechanisms taminants) to generate energy. During this process, they generate equivalent protons and electrons, which are
Factors
transferred to the substrates to finally break them down to simpler molecules or ions, such as CO2, methane and
Quantification
Cl−. The optimal microbial conditions depend on the temperature, available nitrogen and phosphorus levels,
Efficiency
dissolved oxygen levels, and microbe/substrate stoichiometric ratios and the residence time of the AC particles
within the reactor. In this review, the authors highlight the most recent development in bio-regeneration in-
cluding the regeneration mechanism, the relationship between the reversibility of adsorption and the efficiency
of bio-regeneration, the general aspects affecting bio-regeneration, the principle and target compounds for bio-
regeneration, different established methods for quantifying the bio-regeneration and the efficiency of bio-re-
generation. Few case studies of bio-regeneration of activated carbon loaded with different contaminants are
presented. Research on microbiology regeneration has gained considerable attention in recent years, but it still
needs more contribution from other disciplines including process engineering, biochemistry and material sci-
ences for optimizing the process performance.

1. Introduction
Activated carbon is a carbonaceous material that is processed to
have high specific surface area, large pore-volumes, and small pore
diameter predominantly between 8 and 100 Å [1]. It is often described
as the best adsorbent to capture inorganic, organic, and toxic metal ions
that contaminate water resources [2]. Waste materials such as fruit
wastes, coconut shell, scrap tires, sawdust and other wood type mate-
rials, rice husk, petroleum wastes, fertilizer wastes, fly ash, sugar in-
dustry wastes, blast furnace slag, chitosan and seafood processing
wastes, seaweed and algae, peat moss, clays, red mud, zeolites, sedi-
ment and soil, and minerals have been used as adsorbents or adsorbent
precursors [3]. The development of inexpensive adsorbents from waste
materials were successfully applied for the removal of water pollutants,
using adsorption technology including batch processes and column
operations [4]. Nanomaterials as adsorbents have been effectively used
for the removal of metal ions, anions, and organic and biological species
from water. These particles rapidly remove pollutants even at low
concentration, under different conditions of pH and temperatures [5].
Owing to the high specific surface areas and micropore volumes of
AC, it has been extensively used as an adsorbent and support for che-
mical reactions. In physical activation, the precursor is initially pyr-
olyzed and the carbonaceous residue is subsequently activated by
thermal treatment in the presence of CO2 or steam. On the other hand,
in chemical activation, the precursor is impregnated with porogens
such as ZnO and KOH and the impregnated biomass is pyrolyzed to
produce the AC. As different precursor materials and activation
methods produce ACs with different properties, the selection of the raw
material and the activation routes depend on the end-use or design
specifications. ACs are commercially available in numerous forms:
powders, granular in various mesh size ranges, and shaped or molded
products extruded into rod-like shapes and monoliths, the dimensions
of which commonly range from 0.8 to 6 mm (diameter) by 3 to 10 mm
(length) [1].
The synthesis of low-cost adsorbents from inexpensive and com-
monly available carbonaceous waste materials has taken a substantial
amount of effort [6–8]. As an adsorbent, the AC has been effective in
many applications, particularly for the removal of organic and in-
organic pollutants from wastewater [9]. A major reason that AC is used
is the flexibility stemming from its heterogeneous porous structure,

⁎
Corresponding author.
E-mail address: muftah@qu.edu.qa (M.H. El-Naas).

https://doi.org/10.1016/j.seppur.2018.01.015
Received 31 August 2017; Received in revised form 18 December 2017; Accepted 7 January 2018
Available online 09 January 2018
1383-5866/ © 2018 Elsevier B.V. All rights reserved.
M. El Gamal et al.
Fig. 1. Mechanism of surface coverage, adapted from [12].
high specific surface area, wetting characteristics and adsorption ca-
pacity, all of which can be adjusted by controlling the chemical and
physical activation steps. To overcome the high cost of available com-
mercial ACs, numerous studies focus on developing new low-cost ACs
with properties comparable to that of commercial ones [10,11].
The volume of the adsorption pores in ACs can be measured using
the Brunauer-Emmett-Teller (BET) method. The total pore volume is
usually estimated to be larger than 0.2 ml/g, while the pore-width
varies from 3 Å to several thousand angstroms, and the internal specific
surface area is typically more than 400 m2/g. In addition to different
diameters, the pores usually have different shapes. In their cross-sec-
tion, the pores can to be cylindrical, rectangular or irregular shapes.
There are some pores which are open only to the smaller molecules
while blocking larger ones. A simple illustration of different pore shapes
in ACs containing adsorbate molecules is presented in Fig. 1 [12]. Pores
may also have constrictions or bottlenecks. Macropores depend mainly
on the nature of the carbonaceous raw material employed and the
preliminary manufacturing process. They usually contribute only very
little to the total specific surface area of AC. Their major function is to
serve as transport arteries that make the internal parts of the carbon
granules readily accessible to the molecules being adsorbed. The tran-
sitional pores account for about 5%, and the micropores for about 95%
of the internal surface area. The micropores are largely the result of the
activation process [13].
2. Types and properties of activated carbon
For broad application purpose, ACs are generally classified based on
their physical appearance into:
(i) Powdered AC (PAC), which has a particle size below 100 mm and a
diameter from 15 to 25 µm. It has high specific surface area and
higher diffusion resistance of adsorbed molecules.
(ii) Granulated AC (GAC), which is larger in particle size, lower in
specific surface area and lower gas/liquid diffusion resistance
compared to the PAC. It is therefore preferred for many industrial
applications.
(iii) Spherical AC, which is made up of small spherical particles, and
has higher mechanical strength and lower diffusion resistance
compared to PAC or GAC.
(iv) Impregnated AC, where, the porous carbon is impregnated with
elements such as iodine or cations of Ag, Al, Mn, and Zn. Such
elements or ions are used for the removal of specific contaminants
that are not predominantly adsorbed by the carbon.
(v) Polymer coated carbon [14], where the surface of the porous
carbon is coated with biocompatible polymers. They can be ap-
plied in homoperfusion [15].
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Separation and Purification Technology 197 (2018) 345–359
3. Application of activated carbon
The adsorption capacity of ACs depends on both their physical and
chemical properties of AC [16]. Recently, the effects of surface func-
tional groups on the adsorption phenomenon were investigated
[14,17–19]. The surface chemical structure and functional group play
important role in the extent of substrate adsorption from the liquid
phase. For example, the oxygenated functional groups improved the
adsorption and removed methylene blue from wastewater [20]. Func-
tional groups such as carboxylic act as centers of water vapor adsorp-
tion, they are thus used in humidity removal [21]. It has been shown
that the selectivity of ACs for adsorption is dependent on their surface
chemistry. The distribution of functional groups changes the structure
of AC and hence modifying the AC surface functional groups to induce
changes on the AC’s surface structure by creating or eliminating certain
interactions. For instance, the presence of sulfur-philic functionalities
improves the adsorption of volatile sulfur containing molecules
[16,22,23]. Likewise, the surface functional groups of ACs can be tai-
lored to enhance the removal of volatile organic compounds [24].
4. Methods of regeneration of activated carbon
Although AC is used in the industrial application, its cost is a major
barrier to its more widespread application. Once AC is saturated with
the adsorptive species, the carbon is mostly discarded in the landfills.
Regeneration of saturated AC is indispensable to minimize the opera-
tional costs and product wastage [25]. Regeneration allows stabiliza-
tion of the exhausted AC which in turn reduces the amount of solvents
and adsorbents used in the process [26]. Several methods have been
developed to regenerate AC. These include chemical [27,28] super-
critical carbon dioxide [29], electrochemical [30], microwave [31] and
thermal [32]. Usually an appropriate technique is selected depending
on the nature of the contaminant, the recovery cost and process con-
ditions.
4.1. Steam regeneration
Steam regeneration of AC has been shown to be effective and eco-
nomical [33]. It has been used for the regeneration of adsorbents in
industry for years [34]. In steam regeneration, the steam rapidly heats
up the bed be , allowing a faster desorption of the contaminant from the
adsorbent; the desorbate, however, is only removed out of the bed when
the latter is hot enough such that at least some steam remains in gas-
eous form and can satisfactorily remove the adsorbate. During the
steam regeneration of consumed GAC from a wastewater treatment
plant, five steps take place: the thermal decomposition of AC, oxidiza-
tion of AC with steam, vaporization of adsorbate, thermal decomposi-
tion and carbonization of the contaminants, and the oxidative decom-
position of carbonized waste matter with the steam [35].
4.2. Thermal regeneration
Thermal regeneration involves the use of rotary kilns, fluidized-
bed/fixed-bed furnaces, etc. In thermal oxidation using kilns, extensive
amounts of CO2, contaminants in partially oxidized and reactive states
and particulate matter are released into the environment. The process
includes drying at 105 °C, pyrolysis under inert atmosphere, and gasi-
fication of the organic contaminants using an oxidizing gas. Some low-
volatilty hydrocarbons are thermally decomposed [36]. Furthermore,
some AC undergoes oxidation and is lost in the process. Thermal re-
generation can also affect the mechanical strength of ACs.
High temperature regeneration of spent AC is characterized by
complex physical and chemical processes that depend on many para-
meters. The processes directly affect carbon regeneration efficiency,
thereby affecting the ability of AC to regain its adsorbing capacity. The
adsorption of different chemical compounds and their mutual reactions
M. El Gamal et al.
during thermal treatment, as well as different conditions associated
with the production and origin of AC, make it difficult to predict the
behavior of AC during high temperature regeneration [37]. Adsorption
capacity, mass loss, and regeneration granular strength of the re-
generated GAC offer the main basis of evaluating the thermal re-
generation method. However, the three indicators are closely related.
Achieving more adsorption capacity leads to more mass loss of GAC,
and hence higher cost. However, to restore the adsorption properties of
AC and fully recover its adsorption capacity, the regeneration condi-
tions should be supported. This often leads to a reduction in carbon
intensity and size, and increase in regeneration mass loss. The total
mass of the added AC usually accounts for 20 to 40% of the regenera-
tion cost [38]. It is possible to achieve 100% recovery of the adsorption
capacity of spend AC; consequently, the loss of regenerated carbon is
vast. Considering a whole adsorption-regeneration system used in the
water treatment process, the recovery rate of adsorption in a certain
range should be controlled to maintain the balance of the whole system.
Thermal regeneration is a simple regeneration method, but it is an
energy and time-consuming method and causes a significant amount of
carbon loss. Hazardous by-products are also produced and there is al-
ways the tendency to introduce negative effects on the natural prop-
erties of the product [39].
4.3. Chemical regeneration
In chemical regeneration of AC, certain specific chemical reagents
are used to desorb or decompose the adsorbates [40,41]. The chemical
regeneration typically leads to zero carbon-attrition and results in re-
covery of the adsorption capacities [27]. Acidic and alkaline reagents,
when used dissolve the adsorbed substances based on their affinity for
the reagents. The efficiency of this type of regeneration therefore de-
pends on the solubility and the reactivity of the adsorbents with the
chemical reagents. The efficiency of chemical regeneration depends
also on the type of contaminant in the spent AC. Once the contaminants
are removed chemically, the reagents themselves have to be removed to
recover the regenerated AC. [42] An example of chemical regeneration
of granular AC is the removal of phenol from granular ACs using Lewis
base and electrochemical oxidation but it is difficult to have the re-
generation efficiency above seventy percent [43].
4.4. Microwave regeneration
Exposure of spent ACs to microwaves (MW) is another technique for
carbon regeneration [44]. The improvement of AC regeneration via this
method is due to the heating mechanism which proceeds through
thermally activated reactions [43,45–47]. In the regeneration process,
carbon materials must be a good microwave absorber, where the sup-
plied energy directly penetrates the carbon bed. The microwave energy
is converted into heat within the AC matrix. Microwave regeneration
requires less energy compared to conventional regeneration processes
and leads to better recovery of the spent carbon in terms of adsorption
capacity [45–50].
4.5. Wet oxidation regeneration
In this process, toxic contaminants are decomposed in aqueous
media to form less-toxic species. The oxidation regeneration is suitable
for ACs used in wastewater treatment under moderate temperature and
pressure conditions [51,52] During wet oxidation regeneration, the
consumed AC is suspended in an aqueous solution and is heated to
150–200 °C and 10–50 bar oxygen is fed into the solution. The me-
chanism of carbon regeneration involves desorption of the con-
taminants which are replaced by water. The desorbed contaminants
which become available in the bulk aqueous phase are oxidized by the
oxygen gas. The second step shifts the equilibrium of the contaminant
to right which causes further desorption. Studies of wet air oxidation of
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Separation and Purification Technology 197 (2018) 345–359
contaminants phenol and substituted phenols in aqueous solution in-
dicated phenol removal efficiencies above 99.9% [53]. The regenera-
tion of AC containing paracetamol using this process has also been
studied over several cycles, the work showing the AC surface area and
catalytic performance to be diminished by regeneration [54].
4.6. Electrochemical regeneration
Electrochemical regeneration of AC has some advantages such as
moderate temperatures and avoding chemical addition. During the
process, organic contaminants adsorbed on the ACs are cracked in-situ
while the structural integrity and characteristics of the carbon are not
affected [55]. The electro-adsorption/desorption on AC for industrial
effluent wastewater treatment has been studied with reference to
phenol [56], the process regenerating the carbon with an efficiency of
more than 95%. No carbon loss was observed during the electro-
chemical regeneration [57]. Likewise, Zhang observed more than 80%
efficiency when AC containing phenol was regenerated electro-
chemically [43]. The mechanisms of electrochemical regeneration of
ACs which have been studied include electro-oxidation [58], electro-
reduction [59], and electro-sorption [60] . The imposed electric field in
the process removes the polar ions or molecules from the electrolyte
which are then adsorbed onto the surface of the electrodes. The con-
taminants are then either oxidized or reduced on the electrodes de-
pending on the charge and polarity of the species [61,62]. The Arvia
processprovides electrochemical regeneration for the removal of or-
ganic pollutants from water in a commercial scale [63]. The electro-
chemical regeneration has been performed after adsorption and gravity
settling of contaminants in the water. In this process, the electro-
chemical oxidation at the anode converts the contaminants to carbon
dioxide and water.
4.7. Bio-regeneration
Bio-generation of spent ACs involves the use of microbial colonies to
regenerate the capacity and surface of the carbon. Several studies
available in the literature report the microbial removal of en-
vironmentally relevant contaminants, such as phenolic organics from
the spent ACs [64–66]. Bio-regeneration occurs when the organic
contaminant species can be easily desorbed. The concentration gradient
of the organic contaminants between the adsorbent and the bulk liquid
aids the bio-regeneration. This two-step process of desorption and
biological removal of the adsorbed organics has been demonstrated in a
closed-loop re-circulating batch system [65]. In biological AC (BAC)
mediated wastewater treatment system, the bio-regeneration of spent
carbon takes place during the wastewater treatment [65]. Owing to the
complexities of BAC bio-regeneration in wastewater treatment systems,
many studies quantify the performance of bio-regeneration using off-
line systems. These comprise a column containing the spent AC from
which the contaminants are desorbed, and a closed batch system where
the contaminants are bio-degraded with a mixture of suspended or
immobilized microbial colonies, oxygen and nutrients [67]. The effi-
ciency of bio-regeneration depends on several factors such as the con-
taminant biodegradability, the strength of contaminant-carbon inter-
action and, physico-chemical characteristics of AC and process
configuration [65].
Regeneration can also be accomplished by powdered AC treatment
(PACT) or biological AC (BAC) or by making use of bacteria along with
saturated AC. Bio-regeneration can be conducted offline, where bio-
degradation and adsorption take place simultaneously [67,68]. PACT
presents a wastewater purification method based on combined ad-
sorption and biodegradation [69,70]. Studies have shown that there are
two different PACT mechanisms, the first being the interrelated impact
of the bacterial cells and the PAC. Since liquid-solid surfaces arise due
to the existence of PAC, the microbial metabolism is sustained by ad-
sorption of microbial cells, enzymes, organic materials and oxygen.
M. El Gamal et al.
Kalinske has shown that the AC surface physico-chemical reaction plays
a role in bio-regeneration [71]. The second mechanism is the repeated
adsorption process using microorganisms. This mechanism creates a
steady decline in the purging process of organic substances, which is
revealed as PAC surface saturates. This indicates the absence of bio-
regeneration of core substances [72–74] Moreover, there are three main
processes for BAC treatment that have been identified [75]. The first
phase is characterized by the high rate of adsorption over the de-
gradation rate. The second is characterized by the similarity of both
rates, and in the last phase the biodegradation rate exceededs the ad-
sorption rate [65]. BAC can be achieved either by concurrent waste-
water treatment and microbe-mediated decomposition as in PACT and
BAC systems or by batch-wise process of adsorption followed by the
microbial decomposition of the organic contaminants [76]. Certain pre-
requisite microbiological and physico-chemical conditions are neces-
sary for BAC [77]:
i. Microbes utilize only the adsorbate/contaminant as the source of
carbon;
ii. Availability of mineral components, such as nitrogen, phosphorus,
and sulfur for the microbial metabolism of the adsorbate;
iii. Optimum growth and metabolic conditions including pH, oxygen
and temperature for vital activities of microorganisms;
iv. Optimum ratio of the concentrations of the microbes and the con-
taminants.
5. Mechanisms of bio-regeneration of activated carbon
5.1. Bio-regeneration through concentration gradient
In the bio-regeneration systems the concentration gradient of the
target compounds between the AC and bulk solvent results in the fur-
ther desorption of the contaminants. This concentration gradient causes
desorption of organics into the bulk solvent. When microbes metabolize
adsorbed contaminants, the equilibrium is shifted resulting in further
desorption. This regeneration continues untill all contaminants are
consumed by the microbes. The microbial population, the strength of
carbon-contaminant interaction, and other factors control the efficiency
of the biodegradation [78].
The Gibbs free energy difference between the adsorbed phase and
bulk liquid phase is an important thermodynamic attribute that controls
the efficiency of bio-regeneration. Fig. 2 represents the mechanism of
bio-regeneration due to the change of substrate concentration across
the liquid and biofilm in the surface of AC. When the substrate con-
centration reaches a minimum value, at the plane of zero gradient
(PZG), the concentration gradient (DSf/dr) is zero. With decreasing
concentration of the contaminant in the bulk liquid, the PZG moves to
the liquid film. This inverts the change of substrate; the substrate
changes direction from the carbon surface to the solvent. The result is
Fig. 2. Concentration profile of a contaminant during bio-regeneration, adapted from [79].
348
Separation and Purification Technology 197 (2018) 345–359
the bio-regeneration of the spent AC. When the concentration of the
contaminants in the bulk liquid increases, the PZG moves toward the
solid AC surface and limits the bio-regeneration [73].
5.2. Bio-regeneration due to exoenzymatic hypothesis
In this method, the bio-regeneration system comprises desorption of
the contaminants through the enhanced exoenzymes reaction [80]. The
desorption due to the concentration gradient plays a similar role as
discussed before, while the contaminants that are desorbed remain
unbiodegraded [81]. According to the exoenzymes theory, bacteria
having sizes of few micrometers cannot diffuse into the pores of AC due
to their size. However, the microbes secrete some enzymes which dif-
fuses into the pores and react with the organic contaminants. The
exoenzymes co-adsorb on the carbon before reacting with the organic
contaminants [82]. The reaction leads to the hydrolytic degeneration of
adsorbate. The interaction of the organic matter with the AC may be
decreased after the reaction and this leads to desorption of the con-
taminant. The rate of desorption increases with the time and the ad-
sorption rate correspondingly decreases. It is suggested that under
specific conditions, the system enters an equilibrium state (desorption
rate equals to adsorption rate). However, Xiaojian et al.instead sug-
gested that adsorption declines continuously after the reaction product
with exoenzymes are desorbed by the carbon [74]. If the bio-re-
generation and exoenzymes theory is valid in all cases, then all organic
contaminant in the AC pores would be biodegraded during bio-re-
generation. The exoenzymes are likely to be too small to engage with
the micropores, but are able to react with the material adsorbed on the
mesopores and macropores [76].
5.3. Biodegradation following desorption
Reversibility of the adsorption process is the major determining
factor for the bio-generation of AC [77]. When equilibrium is reached,
the adsorbable material is dispersed between the solution and the
surface of the powdered AC (PAC). This balance is influenced when
microorganisms degrade the adsorbable material, eventually resulting
in desorption. Such a mechanism may continue until degrading all
adsorbed and non-adsorbed material. Loading the AC with non-deso-
rbable substances may impede the process of bio-regeneration. This
concept of irreversibility is generally known as hysteresis or non-sin-
gularity [65].
It has been proposed that the amount of the Gibbs free energy varies
between the molecules in the free solution and those of the adsorbed
particles in the porous structure and such difference in energy is a
major factor influencing bio-regeneration [83]. During the initial stages
of the process, a large amount of the organic substance is adsorbed.
Subsequently, this leads to diffusion and biodegradation of organic
contaminants. A crucial factor affecting adsorption and biodegradation
M. El Gamal et al. Separation and Purification Technology 197 (2018) 345–359

of the absorbed material is the ability of repeatedly reproducing the CA1 for the organic contaminants [81].
adsorptive feature of the PAC adsorbent and maintaining the adsorption ACs can be prepared from lignocellulosic residues through pyrolysis
sites [84]. The hypothesis of desorption-dependent bio-regeneration and by activation (physically or chemically). Activation has been de-
has been corroborated de Jonge et al., via extensive leaching experi- monstrated for coconut shells, olive stones and walnut shells, with three
ments under environments correlating to the bio-regeneration experi- phases (the char, tars and gases) being generated [89].
ment [81]. In 1984, DiGiano and Speitel utilized small amounts of
radio-labelled phenol to demonstrate the process of bio-regeneration by
6.2. Carbon particle size
checking CO2 in the effluent stream. This illustrated that the original
particles were initially desorbed and then biodegraded in the biofilm
Another factor that affects the bio-regeneration is AC particle size.
[85].
Applying common physical characteristics between PAC and GAC will
The relationship between bio-regeneration and biodegradation has
create a slightly similar reversible adsorption and minorly similar bio-
been illustrated in research studies utilizing 2-chlorophenol with the
regeneration [65,76]. Table 1 shows some of the carbon types together
aid of batch reactors operating concurrently [65]. The design of the
with their physical form and whether they are activated thermally or
study involved Plexiglas batch reactors of 2 L capacity. These batch
chemically, in addition to the reversibility of adsorption and bio-re-
reactors were optimized to avoid vortex formation via the addition of
generation efficiency. The PAC, which is activated thermally and che-
four baffles. Temperature control was achieved as the reactors were in a
mically, shows more hysteresis than GAC. Accordingly, with the further
hood with water jacket in the surrounding environment for the reactors.
macro-pore formation, the GAC shows higher desirability than PAC.
Conic lids were used to cover the tops of the reactors. Excess spent air
However, PACs show faster process for desorption than GACs and this
was eliminated. A compressor provided sufficient oxygenated air.
can be attributed to the advanced spread and prevalence in carbon. BAC
Mixing was carried out magnetically by special stirrers, mainly to
filters have proven to be more consistent with the bio-regeneration
minimize the loss of 2-chlorophenol through vaporization. The tem-
hypothesis than in the PAC [76]. This is attributed to the GAC which
perature in the batch reactors was maintained at the range of 22 and
provides appropriate attachment sites for microorganisms and offers a
25 °C. The amount of dissolved oxygen was always higher than 4 mg/l.
close relationship between AC pores and the used bacteria in the bio-
Essential nutrients for microorganisms were provided by the addition of
logical treatment. With respect to bio-regeneration by exoenzymes in-
mineral salts solution to the reactors. Constituents of this mineral salts
side the AC pores, the pore size of the carbon must be at least 3 times
solution containing (NH4)2SO4, KH2PO4, K2HPO4, MgSO4·7H2O, Ca-
greater than the radius of the enzyme [74].
SO4·2H2O, FeSO4·7H2O, and NaHCO3. The concentration of the mi-
nerals was used between 200 and 5000 mg/l. This solution was suffi-
cient for wastewater with a chemical oxygen demand (COD) of 6.3. Carbon porosity
10,000 mg/l and was made less concentrated in 2-chlorophenol batch
reactors in suitable concentrations to provide the nutrients required Depending on the range of diameter of the pores in a porous ad-
[65]. sorbent, such as AC, the pores are classified into micropores of less than
20 A, mesopores of 20–500 A and macropores of greater than 500 A,
based on the International Union of Pure and Applied Chemistry
6. Factors affecting bio-regeneration of activated carbon (IUPAC) classification [13].
The extension and degree of bio-regeneration largely depends on
6.1. Carbon activation type the porosity of AC [83]. In the bio-regeneration process the mesopores
are energetically over the mircropores in AC. Most of the toluene that
AC from coal is the most preferred option than any other type of ACs remained post-regeneration in AC was found to be bound to the mi-
[86]. Table 1 shows the physico-chemical properties of AC from dif- cropores [77,90]. Generally, the activation creates many pores in the
ferent sources. The method adapted to activate carbon is as important carbon structure. Macropores and micropores in the AC material are
as the type of AC. As mentioned previously, the two main methods used created under different conditions and have different physical char-
in regenerating AC were either thermal or chemical. PACs from peat acteristics, the former having diameters over 500 Å and the latter under
and coal showed more irreversible adsorption from thermal than che- 50 Å. Macropores are larger in size and strongly assist penetration of the
mical activation of wood [87]. The work indicated that a PAC that was AC by organic particles, but are not directly and mainly responsible for
based on wood showed high level of reversibility of adsorption and bio- adsorption. On the other hand, micropores are situated inside the
regeneration when chemically activated than one based on thermally carbon element and are directly responsible for adsorption.
bio-regenerated peat [88]. The authors also revealed a high extent of The porosity of AC controls the rate and degree of bio-regeneration
bio-regeneration when the PAC was chemically activated using CA1 [83], and the extent of regeneration is determined by the low range
from Norit. Thermal activation of SA4 PAC (Norit) embedded with o- pore size (5–50 nm), since such pores are accessible to exoenzymes
cresol and 3-chlorobenzoic acid showed a lower extent than the former [91,92]. Mesopores are the most useful part of AC internal structure for
compound, in spite of SA4 showing a higher absorptive capacity than sorption of large-sized molecules, including those of surface active
substances. It has been reported that mesoporous AC is more efficiently
Table 1 biogenerated than microporous AC sorbed with large-sized molecules
Properties of ACs derived from different biomass sources, [86]. [77]. It has been found that diffusive transport resistance in GAC filter
Property Coconut AC Coal AC Lignite AC Wood AC
is the rate limiting step in bio-regeneration. However, diffusivity con-
(powder) trols only the desorption rate, but not the total desorbability [93]. Bio-
regeneration might be reduced by the obstruction of pores due to
Micro pore High High Medium Low bacterial growth in the case of commercial AC that has a narrower pore
Macro pore Low Medium High High
Hardness High High Low n/a
size distribution compared to the mesoporous materials [94]. Li et al.
Ash (%) 5 10 20 5 determined the bioregeneration of the char produced from low-grade
Water soluble ash High Low High Medium coal briquettes loaded with p-nitrophenol [95]. Bio regeneration was
Dust Low Medium High n/a also determined for phenol-loaded natural zeolite. In this case, only 2%
Reactivation Good Good Poor None
of the adsorbed phenol was metabolized to carbon dioxide; the re-
Apparent density (g/ 0.48 0.48 0.4 0.35
cc) mainder was presumed to be either converted to dissolved products and
microbial mass and/or irreversibly adsorbed.

349
M. El Gamal et al. Separation and Purification Technology 197 (2018) 345–359

6.4. Concentration gradient and carbon saturation
The amount of target compound is a major determining factor to the
extent of bio-regeneration of AC. Following its activation, the rate at
which the carbon bio-regenerates is proportional to the bulk con-
centration of the target compound, i.e. it's loading. A lower equilibrium
concentration within a BAC column has been ascertained to be more
favorable towards reducing the rate of bio-regeneration [90]. Further-
more, this relationship between bio-regeneration and a lower con-
centration of the contaminant compound was found to be linked to the
low loading on the AC surface. This is explained by the principles of
adsorption where a lower concentration of target compound results in
irreversible high energy binding of the compound to the AC [90].
6.5. Biomass concentration
The adsorbent and support in this instance are AC, rendered in a
granular form [68]. The rate of bio-regeneration is influenced by the
concentration of the carbon biomass. A 24-h study demonstrated a 50%
up increase in the bio-regeneration of AC when the mean concentration
of mixed liquor volatile suspended solid (MLVSS) was increased from
126 to 963 mg/l [67]. Adjusting the relative concentrations of biolo-
gical and ACC solids produced a notable shift in the equilibrium such
that bio-regeneration occurred. Increasing the concentration of MLVSS
also resulted in a higher bacterial presence on the carbon in a batch bio-
regeneration system [96]. Whilst leaving the final rate of bio-re-
generation unchanged, this increase in MLVSS concentration was linked
to a marked reduction in the time taken to reach equilibrium. Oh et al.
quantified the bio-regeneration efficiency of GAC loaded with 4-chlor-
ophenol and 2,4-dicholorophenol by comparing the amount of amount
of chlorophenols adsorbed onto GAC, under abiotic and biotic condi-
tions. Table 2 shows that the bio-regeneration efficiency for GAC loaded
with 4-CP increased from 42 ± 4% to 57 ± 2% as the GAC dosage
increased from 1.0 to 1.5 g/L and remained stable at 57 ± 2% for the
dosages of 1.5–3.5 g/L. For GAC containing 2,4-dichlorophenol, a stable
bio-regeneration efficiency of 48 ± 2% was observed at GAC dosing
1.0–2.0 g/L GAC [97].
availability of dissolved oxygen (DO). Therefore, the extent of bio-re-
generation is logically dependent on the presence of the DO. Chudyk
and Snoeyink found that the amount of available DO influenced the
efficacy of bio-regeneration, an initial concentration of 9 mg/l DO being
more effective at bio-generating GAC containing phenol than a DO
concentration of 4 mg/l [98]. It is thus clear that in bio-regeneration the
amount of DO in GAC columns should be taken into consideration.
When the adsorbed material is very rapidly exposed very rapidly to a
significant number of microorganisms, the amount of DO is increased
[90].
6.7. Type of micro-organisms
The type of the involved micro-organisms can influence the bio-
regeneration process. This explained by certain types of microbes being
utilized in degrading the target substance into so called ‘non-biode-
gradable’ material or thoese that biodegrade at a very slow rate. This
has been shown in a study by manipulating the insecticide atrazine; a
biorefractory substance, where an atrazine-degrading bacterium
showed the bacteria on the GAC to have a considerable extended bed
life via bio-regeneration of AC.
This impact of the nature of microorganisms on bio-regeneration
has been studied by Caldeira et al. Their study indicated that loading
the biorefractory substance, 4-chlorophenol (4-CP), on AC and then
colonizing GAC with the bacterium isolated from the rhizosphere of
Phragmitiscommunis, resulted in the degradation to take place.
Additionally, certain substances and compounds derived from the
Pseudomonas strains were utilized in isolating bio-resistant surface-
active compounds from AC [77]. Most studies on bio-regeneration focus
on the study of a single material. There are various constituents and
substances associated with wastewaters which could affect each other's
desorption and the biological degradation. Putz et al., explained that it
is challenging to treat combinations of organic materials due to the
different properties of these compounds [90]. Nath and Bhakhar re-
vealed that the percentage of bio-regeneration of AC loaded with var-
ious organic substrate varies with the different microorganisms such as
pure culture microbial consortium and acclimated or non-acclimated
biomass from activated sludge reactor, Table 3 [68].

6.6. Dissolved oxygen concentration 6.8. Desorption kinetics

In aerobic environments, biodegradation is affected by the Basically, chemical kinetics refers to the rates of chemical processes
by examining factors affecting the speed of a chemical reaction. The
Table 2
kinetics of desorption affects the extent of irreversibility of adsorption,
Bio-regeneration efficiencies of GAC loaded with 4-CP and 2,4-DCP; adapted from Oh
et al. [97]. which is reflected by the rate of adsorption. Organic compounds with
slow adsorption show slow rate of bio-regeneration [67,88,99]. The
Initial adsorbate GAC Final amount of Bio-regeneration absorption rate, therefore, depends on the following factors: fluid dy-
concentration (mg/ (g/L) chlorophenol efficiency (%) namics, metabolic activity of microorganisms, culture environments,
L) adsorbed (mg/g)
Abiotic Biotic
and the type and mass of carbon elements [84]. Bacterial activity in a
GAC bed has achieved high rates of bio-regeneration. It makes the rate
4-chlorophenol extents to the peak. This may be attributed to the surface portion of
100 1 104 ± 2 32 ± 1 69 ± 2 GAC that is accessible to microorganisms [100]. Kinetics are integrated
200 1 199 ± 1 64 ± 4 68 ± 2
with the mathematical models which play a vital role to generate im-
300 1 272 ± 1 96 ± 6 65 ± 2
400 1 289 ± 10 117 ± 1 59 ± 2 portant information for bio-regeneration of AC [100]. Two important
500 1 289 ± 0 139 ± 6 52 ± 3 processes are required to be revealed in favor of the bio-regeneration:
600 1 291 ± 3 169 ± 9 42 ± 4 the sorption kinetics of in the AC column, and the kinetics of bacterial
600 1.5 289 ± 1 123 ± 5 57 ± 2
growth and substrate degradation [101].
600 2 263 ± 3 119 ± 3 55 ± 1
600 2.5 230 ± 1 91 ± 4 60 ± 2
600 3 198 ± 1 83 ± 1 58 ± 1 6.9. Substrate-carbon contact time
600 3.5 172 ± 0 78 ± 7 54 ± 4

2,4-dichlorophenol The sequential role of adsorption and biodegradation steps is evi-

100 1 101 ± 2 32 ± 3 68 ± 3 dent in the offline bio-regeneration, where bio-regeneration is extended
200 1 201 ± 3 81 ± 2 59 ± 1 in a dispersed biological container after accomplishing the adsorption
300 1 295 ± 0 156 ± 5 47 ± 2
process [67]. Offline bio-regeneration uses closed-circulatory system as
300 1.5 200 ± 1 106 ± 6 46 ± 3
300 2 150 ± 1 73 ± 1 52 ± 1 shown in Fig. 3, to undertake and integrate desorption and biological
activity.

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M. El Gamal et al. Separation and Purification Technology 197 (2018) 345–359

Table 3
The efficiency of bio-regeneration when different microorganisms are used for regenerating AC contaminated with different organic substrates [68].

Organic substrate/contaminant Type of AC Microorganism used Type of reactor/ Maximum bio-regeneration, %

operation

2-Chlorophenol Granular Non-acclimated biomass from activated sludge Batch 12.9

reactor
Surface active substrate Powdered Psuodomonas rathonis, P. Alcaligenes TR, P. Batch 85–95
Aureofaciens
o-Cresol;3-Chlorobenzoic acid Powdered Pseudonomas B-13 Continuous flow gas lift o-Cresol:15% 3 Chlorobenzoic acid:
85%
Phenol Granular Microorganisms from activated sludge process Column 92–100
Phenol Powdered P. putida-ur:ATCC Batch 87
Phenol Powdered and P. putida Batch 47
Granular
Tetrachloroethylene Granular Pseudomonas sp., Rhodococcus rhodochrous BAC column 39.4
Toluene Granular Pseudomonas sp., R. rhodochrous BAC column 45.5
Phenol Powdered Acclimated to substrate Sequential 56 ± 6
Polyoxyethylene Granular Acclimated to substrate GAC filter 50–53

Offline generation uses the carbon column to recycle combination of
adapted bacteria, nutrients, and dissolved oxygen (DO) nutrients, to
contract exhausted AC and regenerating, increasingly, the adsorbed
organic will be biodegraded [67]. AC contacts with the adsorbates in
two forms, either continuous flow or in batches. Bio-regeneration extent
relies on the initial contact time. De Jonge et al. evidently stressed that,
increasing the contact time between the compound and the AC can
decrease the availability of the adsorbed compounds for bio-regenera-
tion [81]. The reversibility of adsorption shows various variable read-
ings and responses in relation to the contact time.
6.10. Conditions and applications
During biodegradation, organic compounds are degraded by mi-
croorganisms (e.g. bacteria, fungi, algae) into simpler chemical struc-
tures, often resulting in complete mineralization [103]. It has been
reported that decomposition of micro pollutants in biologically based
wastewater treatment systems is faster in aerobic, rather than anae-
robic, conditions [103,104]. However, even in anaerobic conditions in
a treatment system, aerobic environments may be present around an
algal bloom or near the surface. This coexistence of both aerobic and
anaerobic conditions in biological treatment systems allows for the
biodegradation of a range of different types of organic pollutants [104].
Microorganisms regenerate the surface of AC using sorbed organic
substrate as a source of food and energy. Aromatic hydrocarbons,
particularly phenols, including their chlorinated derivatives and in-
dustrial wastewater containing synthetic organic compounds and ex-
plosives-contaminated ground water are the major removal targets in
adsorption-bioregeneration process. Since AC has a high specific sur-
face area and highly developed pore structure, it is characterized by its
great effect on absorbing dissolved oxygen and organics in raw water.
For BAC technology, AC is used as a carrier, by accumulating or arti-
ficially immobilizing microorganisms under proper temperature and
nutrition conditions. The microorganisms will reproduce on the surface
of the AC and finally form BAC, which can exert the adsorption and
biodegradable roles simultaneously [105]. The BAC mechanism in-
cludes the interaction of AC particles, microorganisms, contaminants
and the dissolved oxygen, in water solution. Fig. 4, shows a schematic
model describing the 4 factors interact with each other [106]. The re-
lationship between the AC and adsorbed contaminants depends on the
properties of the AC and contaminants. In addition, the AC can adsorb
the dissolved oxygen (DO) and the microorganisms, which are adsorbed
on the surface of AC, will biodegrade the contaminants. The successful
interaction of these four factors will achieve the purpose for removing
contaminant from raw water. The free chlorine, contained in carbon
layer, inhibits the growth of the microorganism and prevents the ob-
servable biological activity in the carbon layer [107].
In BAC filters, biological treatability is enhanced through the ad-
sorption of inhibitory substances as in the PACT processes, but in ad-
dition, the GAC used in these filters serves as a supporting medium for
biofilm colonization [107]. It was recognized that the PACT or BAC
process protected the biological system from upsets caused by shock
loads of organic compounds [70]. Biological processes using AC as
carrier for biofilm attachment are efficient treatments for wastewater
[84]. However, in PACT systems the microbial attachment to surface is
less efficient than in fixed film or in fluidized bed reactors using GAC as
a biofilm carrier. This is because, in the latter, the retention time of
solids is generally much higher than in activated wastewater processes,
allowing more time for microbial attachment to GAC. On the other
hand, in suspended growth systems, the use of PAC is more advanta-
geous than GAC since PAC systems provide a uniform distribution of
solids with a minimum energy requirement for mixing [108].
7. Principle and target compounds for bio-regeneration
Organic molecules are readily adsorbed by the ACs because of the

Fig. 3. Closed-loop offline bio-regeneration systems

with pre-filtration of microorganisms; adapted from
[102].

351
M. El Gamal et al.
Fig. 4. Basic interaction model of factors in biological AC process, adapted from [107].
similar non-polar and hydrophobic nature of adsorbate-adsorbent
system. If multiple organic contaminants are present, the one that is
least soluble in the water is the most strongly adsorbed. Also, smaller
organic molecules diffuse faster and adsorb in smaller pores. The ki-
netics of adsorption process is affected by the concentration of the
target components [109]. Before using AC filter for the removal of
specific contaminants, its performance for the selectivity and removal
of contaminants must be evaluated. Chemical reactions between the
adsorbate and surface functional groups in carbon releases forms of
chemicals that alter the pH and temperature of the solution. This fur-
ther improves the adsorption of many organic molecules [110]. In bio-
regeneration, microorganisms use the organic contaminants in the
spent AC as a source of food which they use in their metabolism to
produce energy. Major target compounds for adsorption–bio-regenera-
tion as follows;
7.1. Synthetic organic compounds
In public water sources, decaying plants release organic matter
which dissolves in water over time. These organic matters mostly
consist of high molecular weight organic acids. Due to the presence of
large hydrocarbon chains, they are usually non-polar. Another group of
synthetic organic targets compounds that are usually found in the spent
AC is aromatic hydrocarbons and phenols. These parent aromatics and
their derivatives including mono-chloro, dichloro and nitro-phenols
have been used extensively in industry. Subsequently, their residues are
found in water treatment systems. Most of the research that focuses on
bio-regeneration of AC uses a surrogate solvent mixture containing the
organic residues, such as phenol to simulate the target contaminants. As
phenol has good biodegradable characteristics and easily adsorbed on
AC, it can be used to benchmark the performance of AC bio-regenera-
tion. Moreover, phenol is toxic and is commonly found in the industrial
wastewater. In addition to phenols, many studies use phenolic deriva-
tives such as oxyethylated alkyl phenol, cresols, catechol, chloro-ben-
zoic acid, chloro- and nitrophenols, benzene, toluene, tri and tetra-
chloroethylene, and carbon tetrachloride [65]. Regeneration of ACs
saturated with synthetic surfactant mixture, non-ionic surfactant has
been studied [75]. Coelho et al. studied the BACs loaded with the
herbicide molinate loaded using consortia of microbes [22]. Walker and
Weatherley reported the bio-regeneration of activated bone char satu-
rated with an azo dye [111]. They used biological AC in fixed bed re-
actor to study the removal of azo dyes Tectilon Red B and Tectilon
orange 3G. Bio-regeneration of the desulfurization adsorbents con-
taining magnetic microbes are also reported [111]. Likewise, Li et al.
reported the removal of sulfur compounds via bio-regeneration of ad-
sorbents with the magnetic Pseudomonas delafieldii R-8 cells. They
found that up to 93% of the initial adsorption capacity was restored
after the AC was bio-regenerated [112].
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Separation and Purification Technology 197 (2018) 345–359
7.2. Industrial wastewater
AC is one of the main adsorbent used in the wastewater treatment
plants in the industrial and municipal facilities. AC is generally pre-
ferred over other adsorbents due to its ability to adsorb larger variety of
contaminants. Although most of the studies reported in the literature
uses simulated wastewater containing target organic contaminants, few
studies also report the bio-regeneration of AC used in actual industrial
effluent treatment. Biologically AC sorbents are used by Augulyte et al.
to study the treatment of wastewater containing petroleum residues.
Their study indicated that toxicities of effluents after the treatment with
BAC were reduced by up to 90% [113]. Vuoriranta and Remo used
pilot-scale fluidized AC bed to remove residual organic contaminants
from a secondary effluent from a bleached kraft mill. GAC has two
functions: as an adsorbent for organically bound halogens and as a
biofilm support medium. Over a period of 18 weeks, 57% reduction of
dissolved organic carbon was observed. The mean load of 0.9 g of
chemical oxygen demand (COD)/kg of AC/day was observed. They also
observed even better efficiency in removal of organic halogens between
70 and 90%. Biological granular AC was used by Vuiriranta and Remo
to treat bleach plant effluent from the pulp and paper industry. The
aerobic process could remove more than 50% COD and the color [114].
Granular bio-AC, likewise can remove nearly 100% of COD and 72% of
nitrogen compounds from oil refinery wastewater within 16.5 h of op-
eration. Suzuki et al. used biological AC to remove refractory organic
pollutants and heavy metals from wastewater from plating industries.
They found that bio-film thickness on the AC increased with the time,
indicating the growth of microbes. Their work showed a 50% reduction
in organic pollutants [115].
7.3. Explosives-contaminated ground water
Bio-regeneration, has been used to remove explosive contaminants
such as hexahydro-1,3,5-trinitro-1,3, 5-triazocine (RDX) and octahydro-
1,3,5,7-tetranitro-1,3,5, 7-tetrazocine (HMX) from contaminated
groundwater near military establishments and test sites. The bacterial
cultures isolated from Pantex Plant could biodegrade RDX and HMX.
Within 4 days of operations in sequencing batch reactors, the initial
RDX concentration was reduced from 1 mg/l to below detection
threshold. The reduction of HMX was somewhat less; from 0.6 mg/l to
0.4 mg/l. A coupled desorption and biodegradation was found to im-
prove the overall efficiency of the process to remove both RDX and
HMX [101].
7.4. Residual disinfectants
Chlorine and chloramine are typical residual disinfectants present in
the ground waters of municipalities. These residual contaminants can
be adsorbed by AC surface and can be degraded through catalytic re-
duction reactions. The reduction occurs through the electron transfer
from the ACs to the residual contaminants; subsequently chlorine is
reduced to chloride ion. At a flow rate of 3–5 gpm/cu.ft and bed depth
of 3 feet, the chlorine removal capacity is 1 lb/lb of AC. Contrary to the
quick reduction of chlorine, the reduction of chloramine is much slow.
The reduction of mono chloramine, which is the predominant con-
taminant in municipal water supplies is non-oxidative chloride [116].
The mechanism of the dechlorination in AC in aqueous medium
combines the hydrolysis if chlorine to form hypochlorite ion (Eq. (1)).
The AC adsorbs hypochlorite ion, which is catalytically decomposed to
from HCl and O [117] Different pathways of the chlorine removal by
AC are presented in Eqs. (1)–(3).
a- Hydrolysis of free chlorine in aqueous media
Cl2 + H2 O→ HOCl + HCl (1)
M. El Gamal et al.
b- The ionization of hypochloric acid
HOCl→H+ + OCl−
Low pH High pH
c- Catalytic decomposition of hypochloric acid
HOCl + C∗ → HCl + C∗O
∗ 3
where is an adsorption site on the AC surface.
8. Quantification methods of bio-regeneration
Direct and indirect methods are used to quantify the efficiency of
bio-regeneration. In direct measurement, the adsorption capacity of the
AC is determined while in indirect method, the contaminant con-
sumption is estimated by measuring the CO2 production. Different di-
rect and indirect methods used for the quantification of bio-regenera-
tion are presented below:
8.1. Degree of reversibility of the adsorption
Hysteresis of adsorption is a characteristic by which an adsorbent
does not desorb all the contaminant it adsorbed at a given condition.
The degree of hysteresis, therefore is a measure of the reversibility of
the adsorption. It is related to the amounts of contaminants adsorbed
and desorbed at similar conditions. The relation between these quan-
tities are given in Eq. (4).
1/ nads ⎞
w (%) = ⎛ ⎜ −1 × 100⎟
⎝ 1/ ndes ⎠
where ndes and /nads are the amounts of contaminants in the desorption
and adsorption paths. These are normally obtained by parametrizing
the experimentally measured isotherms using isotherm models such as
Freundlich model. Aktas and Cecen showed that higher dosage of ACs
decreases the degree of hysteresis. This is due to the fact that, the initial
substrate/carbon ratio affects the distribution of adsorption drives
among carbon pores. Spent AC can also be regenerated via abiotic
desorption, where the contaminants are leached by the exoenzymatic
reactions [76].
8.2. Adsorption isotherms
In this method, bio-regeneration is quantified using the isotherm
constants and equilibrium concentrations. These are obtained from
semi-empirical isotherm adsorption models, such as Freundlich ad-
sorption isotherms. To estimate this, AC is initially equilibrated with a
known concentration of adsorbate. Once the adsorption is completed,
the concentration of the contaminant in the supernatant liquid is
measured. The carbon sample is then subjected to bio-regeneration with
microbes and nutrients. The microbes can metabolize the contaminants
adsorbed in the AC. Finally, the AC is recovered by heating in an au-
toclave. This terminates the activity of microbes. The sterilized AC is
then subjected to adsorption of contaminants as in the first step [78]. To
calculate the contaminants adsorbed before the bio-regeneration, the
following relation is used [79].
q = (So−Se )·V / W = KF Se1/ n
where,
q = amount of a substance adsorbed per unit weight of carbon (Ms/
Mc),
S0 = initial concentration (Ms/L3),
Se = equilibrium concentration (Ms/L3),
V = total volume of sample (L3),
W = weight of AC (Mc).
Separation and Purification Technology 197 (2018) 345–359
The adsorption capacity and intensity in Eq. (5) are represented by
KF and 1/n. These are obtained from the measured isotherm. In the
units, s and c represent the substrate and carbon, respectively. After bio-
(2)
regeneration, the amount of adsorbed substrate left on AC (q′) was
determined by Eq. (6):
(3) q′ = KF Se′ 1/ n (6)
where Se′ = adsorbate concentration in the bulk liquid, (Ms/L ).
8.3. Adsorption capacities
In this method, the bio-regeneration is quantified by direct mea-
surements of adsorption capacities for the pristine and bio-regenerated
ACs as calculated by Eq. (7) [77].
% Bioregeneration = 100∗ ∝reg / ∝ (7)
where ∝reg and ∝ are adsorption capacities of regenerated and pristine
AC.
8.4. Solvent extraction
Bio-regeneration of GAC containing up to two contaminants in a
batch reactor was reported [118]. In this method, GAC was initially
equilibrated with a known concentration of contaminant. The super-
natant liquid was removed and the concentration of the supernatant is
noted. The temporal evolution of the amount of adsorbate that remains
in the GAC was measured. The percentage of bio-regeneration was
(4)
calculated as in Eq. (8):
% Bioregeneration = 100∗ (qi−qf )/ qi (8)
where,
qi = initial amount of adsorbate substance on GAC,
qf = amount of adsorbate remaining after contact with biomass.
8.5. Simultaneous adsorption-biodegradation
In this quantification method, the bio-regeneration can be de-
termined in batch systems where adsorption and biodegradation occur
concurrently [119]. The batch systems used can be with bacteria im-
mobilized on GAC (BAC system) or on sand, GAC without any microbes
or suspended free bacterial cells.
8.6. Biodegradation products
In this quantification method, the degree of bio-regeneration is
determined by the measuring the byproduct of biodegradation of or-
ganic species. Depending on the contaminants, the biodegradation
yields CO2, chloride, and methane. Fast and accurate determination of
CO2 from BAC system was reported [81]. Batch culture used in bio-
regeneration is made up of acclimated biomass, nutrient mineral salts
and PAC. The CO2 evolved due to microbial activity is determined
(5) usually with a gas chromatograph [100]. Isotopic or radiolabeled or-
ganic molecules are used in some studies to quantify the bio-degrada-
tion [120]. Biodegradation of chlorinated organics such as 4-chlor-
ophenol and trichloroethylene releases chloride ions into the solvent,
which can be measured indirectly [121,122]. This method is also sui-
table for contaminants with other halogens [14]. For AC systems with
anaerobic digestions, the degree of bio-regeneration can be determined
from the amount of biogas generated [123]. The use of isotopic labelled
contaminants leads to isotopic CO2 and methane in the effluent. These
can be quantified using gas chromatographs or mass spectrometers used
to monitor [73].
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M. El Gamal et al.
8.7. Respirometry method
Respirometric methods was used in the quantification of bio-re-
generation through monitoring the rate of oxygen consumed by mi-
croorganisms. The measurements are carried out using Warburg’s ap-
paratus or an isothermal manometric respirometer [124]. The removal
of substrate by biodegradation is determined by comparing the oxygen
consumption with and without adsorption. Bio-regeneration of AC
containing substituted phenols has been reported by measuring the
oxygen uptake in both simultaneous and successive adsorption-biode-
gradation processes [66].
8.8. Scanning electron microscopy (SEM)
Microorganisms use their essential strength for forming biofilms as a
part of their living strategy to survive in hostile, nutrient-limited,
aqueous environments such as lakes and streams [125]. Most bacterial
species occur in their planktonic state in bulk solution; once attached to
any abiotic or biotic material surface, they gradually develop into a
mature biofilm. The biodegradable organics are broken down by the
biofilms to biomass, carbon dioxide and waste products before these are
adsorbed on the GAC. This prolongs the carbon bed life for removal of
recalcitrant and non-biodegradable organics. These beneficial effects
have led to a growing trend of incorporating the BAC filters into the
treatment system [126].
SEM measure the morphology of the biofilm on the AC and regions
of biofilm attachment. Microbial colonies generally grow at the sites
where the organic contaminants are concentrated as microbes feed the
substrates during the metabolism. Microbial metabolism in the inner
surfaces and pores of the carbon results in the bio-regeneration of AC by
continuous removal of the adsorbate to the bulk liquid. SEM is used to
investigate if microbial biofilms attach to the outer surface or inside the
carbon. It is found that the biofilms attached to the inner side of carbon
are supposed to contribute more significantly to the assimilation of
adsorbed compounds and bio regeneration by inducing a progressive
desorption of adsorbate to the bulk solution [118]. Aktas and Cecen
also used SEM analyses and verified excreting extracellular enzymes
inside the AC pores. Also, they used Environmental SEM for in-
vestigation of PACs and they presented that microorganisms attached
on both the external surface and the internal pores [76] or by the re-
action with the exoenzymes within the AC pores. It has been reported
that bacteria (filamentous and rod-shaped) are only present inside the
holes and pores, but not on the surfaces of GAC particles in a fluidized
bed reactor [114] and that the bacteria are effectively colonized in the
macropore structure of GAC [127]. Another application of SEM analysis
showed that bacteria were attached on both the internal cavities and
outer surface of PAC particles [84].
9. Efficiency of bio-regeneration
The efficiency of bio-regeneration is expressed as a ratio between
the quantity of adsorption by the regenerated and fresh adsorbents,
both measured under identical conditions. Regeneration Efficiency (RE)
is expressed Eq. (9) [128].
Ar
RE (%) = × 100
A0 (9)
where Ar is the saturated equilibrium adsorption capacity of fresh ad-
sorbent and Ao is that of the regenerated one, both of which are mea-
sured per unit weight of the adsorbent. Isotherm models such as
Freundlich isotherm have been used by to determine the bio-re-
generation efficiency of ACs saturated with the 2-chlorophenol [65].
The time-dependent adsorption amount is determined using the Eq.
(10)
1 6
Q (t ) = KCe (t ) n (10)
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Separation and Purification Technology 197 (2018) 345–359
where Ce(t) is the concentration of 2-chlorophenol in the bulk liquid
(mg/l) at time t. Note that, to establish the equilibrium adsorption as
required by the Freundlich model, the experimental conditions should
consider the short contact time to reach equilibrium and time lag in
biodegradation stemming from the toxicity of the contaminant. It is
quite difficult to satisfy these conditions as the onset of biodegradation
commences before reaching the equilibrium. This is particularly for ACs
which are non-powdered [66]. The efficiency of AC regeneration de-
pends on the selectivity of the contaminants to AC as well as how easy it
for the microbes to decompose the contaminants [68].
10. Case studies of bio-regeneration
10.1. Bio-regeneration of activated carbon contaminated with
hydrocarbons
The effect of bacteria on the hydrocarbon was studied by Ameh
et al. who treated samples of hydrocarbon polluted soil with fresh GAC.
Before and after regeneration, the granular AC was characterized by
measuring the surface area, bulk density, pore volume, pH, moisture,
ash content and particle size [39]. The optimum degradation tem-
perature and total hydrocarbon concentration of the spent AC was de-
termined. The rate of hydrocarbon degeneration was measured at dif-
ferent intervals. The regeneration of the AC is indicated by the
reduction of the total hydrocarbon content (THC). The commercially
obtained GAC was characterized before and after use for the bio-re-
generation operation, the data is presented in Table 4.
The experiment results of the bio-regeneration showed that, by
varying the volume of bacteria of 10, 20, 30 and 40 ml, there was a
sharp decrease in THC after the first 24 h of the experiment. This can be
attributed to fast production of CO2 during the first phase of interaction
between the bacteria and the hydrocarbon pollutant. It is also indicated
that the volume of substrate as well as the kinetics of desorption of the
hydrocarbon decreases as the contact time between both increases [81].
Fig. 5 shows the effect of bacteria volume and contact time on the ef-
ficiency of bio-regeneration [39].
Fig. 6 shows clear drops in THC content at 25 and 35 °C and this was
consistent for the 21 days of the experiment [39]. Increasing the tem-
perature above the ambient of 27 °C led to improving the regeneration.
This could be attributed to chemisorption [26]. Final THC for the 25, 27
and 35 °C were 0.785, 0.599 and 1.535, respectively. There was need to
investigate the impact of temperature further considering that 25 °C
was below ambient and at ambient temperature, there was an un-
favorable impact on the bacteria for the first six days of lag phase [129].
10.2. Bio-regeneration of granular activated carbon loaded with aromatic
compounds
Bio-regeneration of PAC saturated with aromatic hydrocarbons was
studied [81]. The carbons used were chemically and physically acti-
vated and removal of two aromatic hydrocarbons, o-cresol and 3-
chlorobenzoic acid were tested. The results revealed that the extent of
bio-regeneration ranges between 15 and 85% of PAC loading. There are
Table 4
Results on the characterization of GAC before and after regeneration [39].
Sample No. Property Before After Standard
Regeneration Regeneration
1 Surface area 738 m2/g 730 m2/g 500–1500 m2/g
2 Bulk density 386 kg/m3 379 kg/m3 > 180 kg/m3
3 Pore volume 0.098 cm3/g 0.097 cm3/g 1.109
4 pH 6.0 6.4 6.0–7.0
5 Moisture 2.72% 2.71% < 5%
content
Ash content 3.69% 3.58% < 15%
M. El Gamal et al. Separation and Purification Technology 197 (2018) 345–359

Fig. 5. Bio-regeneration at various volume of

bacteria; adapted from [39].

several factors that control the efficiency of bio-regeneration. These Table 5

include the methods used for activating the carbon, the aromatic hy- Examples of bio-regeneration efficiencies and process conditions, adapted from [65].
drocarbon used and the contact time in the reactor. Better bio-re-
AC Major carbon features Efficiency (%)
generation is observed for PAC prepared by thermal activation, irre-
spective of the contact times used. The adsorption of 3-chlorobenzoic PAC Norit SA4 Thermally activated 58.1
acid is found to be larger than that of o-cresol for both chemically and PAC Norit CA1 Chemically activated 93.6
physically ACs. The extent of bio-regeneration depends on the rever- GAC Norit PKDA Thermally activated 66.6
GAC Norit CAgran Chemically activated 84.8
sibility of sorption in a way that before the bio-degradation of the
aromatics, the aromatics are desorbed from the carbons. The degrada-
tion of organics from the bulk solvent forces desorption and further tetrachloride acid in BAC column reactor were studied. Fig. 7 indicated
biodegradation. However, microorganisms were found not to directly that, the efficiency of GAC Calgon F-400 is comparable for different
influence the desorption [81]. compounds using the same Pseudomonas sp., Rhodococcus rhodo-
Aktas and Cecen, have used PAC Norit SA4, PAC Norit CA1, GAC chrous biomass [90].
Norit PKDA and GAC Norit CAgran to understand the effect of type of Table 6 compiles the bio-regeneration efficiencies of powder and
AC on sorption of 2-chlorophenol and the carbon bio-regenerability. granular ACs saturated with 7 aromatic hydrocarbons, [65]. They
Two of these samples were thermally activated while the rest were concluded that both the powdered and granular AC have similar sorp-
chemically activated. Although thermally ACs adsorbed more 2- tion characteristics. Both carbons are found to adsorb more 2-chlor-
Chlorophenol that that by the chemically activated ones, the adsorption ophenol than phenol. However, the carbons also desorb lesser amount
was found to be less reversible for the former ones. Table 5 compares of 2-chlorophenol than phenol. 2-Chlorophenol is not easily biode-
the efficiency of bio-regeneration on the carbons studied. Their study gradable. Therefore, desorption alone contributes to the regeneration.
recommends the application of thermally ACs, although the desorption Consequently, no further removal of 2-chlorophenol occurs.
is lower [65,76].
The bio-regeneration efficiencies of the GAC Calgon F-400 using
Pseudomonas sp., Rhodococcus rhodochrous biomass, for different
compounds like Tetrachloroethylene, Toluene, Benzene, Carbon

Fig. 6. Bio-regeneration at various temperatures,

adapted from [39].

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M. El Gamal et al. Separation and Purification Technology 197 (2018) 345–359

Fig. 7. Bio-regeneration efficiencies using different

compounds at the same process conditions, adapted
[65].

10.3. Bio-regeneration of granular activated carbon loaded with binary Table 7

mixtures Bio-regeneration efficiencies of GAC loaded with different ratios of phenol to 4-CP in two-
step method at a GAC dosage of 1 g/L; adapted from Oh et al. [134].

Since industrial wastewater treated ACs contain more than one Initial f Qph Bio-
(QPh + Q4fCP )pris f
(QPh + Q4fCP )biots
contaminant, it is vital to study the bio-regeneration of ACs containing concentration −1 to regeneration
(mmol g ) (mmol g−1)
multiple contaminants. The bio-regeneration of AC containing a binary (mmol L−1) Q4CP Efficiency (%)
mixture of 2,4-dichlorophenol and phenol showed regeneration effi- ratio
phenol 4-CP
ciencies in range 43–48% [118]. Simultaneous removal of 2-chlor-
ophenol and 2-nitrophenol in the presence of phenol from ACs and the 3.19 0.78 2.21 ± 0.05 1.8 1.44 ± 0.02 65 ± 2
carbon regeneration was reported by Aktas and Cecen. The regenera- 3.19 1.56 2.15 ± 0.12 0.7 1.24 ± 0.04 58 ± 5
tion efficiencies were between 19.5 and 89.8% [132,133]. In 2016, Oh 3.19 2.33 2.33 ± 0.04 0.4 1.26 ± 0.12 52 ± 4
2.13 2.33 2.42 ± 0.09 0.3 1.27 ± 0.04 52 ± 3
et al., measured and compared the extent of bio-regeneration of GAC
1.06 2.33 2.29 ± 0.06 0.2 1.14 ± 0.05 50 ± 4
contaminated with phenol and 4-chlorophenol (4-CP) using the two-
step method as sequential and simultaneous adsorption and biode- Where (Qph + Q4-CP)biot and (Qf ph + Qf 4-CP)pris are the amounts of phenol and
gradation. These approaches were used to understand the degree of AC chlorophenol adsorbed in the bio-regenerated and pristine GAC.
regeneration and reusability, respectively [134].
Table 7 shows the effect of varying mixture of phenol and 4-CP Table 8
adsorbed (Qph to Q4CP) on bio-regeneration efficiency. It is found that Bio-regeneration efficiencies of AC containing varying fractions of phenol and 4-CP ratios
decreasing the phenol/4-CP ratio from 1.8 to 0.2 decreased the bio- under one-step approach at constant GAC dosage of 1 g/L; [134].

regeneration efficiency from 65 to 50%. This indicates easier re- Initial Ratio f Bio-
(QPh + Q4fCP )pris f
(QPh + Q4fCP )biots
generation of phenol adsorbed carbon sites as compared with that oc- concentration Ph to −1 −1 regeneration
(mmol g ) (mmol g )
cupied by 4-CP. Ng et al. suggests that 4-CP molecules undergo oxi- (mmol L−1) 4-CP Efficiency
dative coupling on the carbon surface, which leads to irreversible loss of (%)
phenol 4-CP
carbon’s active sites [66]. After the degradation of desorbable con-
taminants, the final efficiency of the GAC loaded with the individual 3.19 0.78 4.09 2.21 ± 0.05 0.54 ± 0.09 51 ± 5
components is limited by the adsorption irreversibility. The bio-re- 3.19 1.56 2.04 2.15 ± 0.13 1.19 ± 0.05 55 ± 5
generation efficiencies of granular carbon are 57 and 44, respectively 3.19 2.33 1.37 3.33 ± 0.04 1.03 ± 0.08 44 ± 4
2.13 2.33 0.91 2.42 ± 0.09 1.09 ± 0.12 45 ± 53
for single component adsorption of phenol and 4-CP. This confirms that
1.06 2.33 0.45 2.29 ± 0.06 1.01 ± 0.06 44 ± 4
4-CP is irreversibly bound to carbon as compared to phenol. Table 8
shows that the bio-regeneration efficiencies of granular AC containing
4-CP and phenol where the regeneration is performed in single-step contaminants in the single-step approach, which leads to enhanced ir-
combining desorption and degradation were lower compared to two reversibility.
stepped technique. This is attributed to the presence of residual Table 9 on the other hand, shows the effect of different GAC dosages

Table 6
Examples of bio-regeneration efficiencies and process conditions, adapted from [65].

[65] Compound AC Major carbon features Biomass Reactor type Efficiency (%) Reference

Phenol PAC Westvaco SA15 Chemically activated Acclimated to substrate Batch 100 [130]
Phenol GAC Calgon F-400 – Acclimated to substrate GAC column 17.7–75.2 [67]
p-nitrophenol (trace) GAC – Acclimated to substrate BAC column 5–22 [99]
Phenol GAC Sigma Lignite based Acclimated to substrate Batch 31.4 [78]
2,4-Dichlorophenol GAC Sigma Lignite based Acclimated to substrate Batch 14.3 [78]
2,4-Dichlorophenol GAC Sigma Lignite based Acclimated to substrate BAC-SBR 38–43 [131]
4-Chlorophenol GAC Sigma – Phragmitis communis acclimated to phenols Batch 21–75 [122]
Trichloroethylene GAC Calgon F-400 GAC column 82.5 [121]
Non-iogenic surfactant GAC SKT-3 – Acclimated to substrate BAC filter 20–24 [75]
Polyoxyethylene GAC SKT-3 Microporous Acclimated to substrate GAC filter 50–53 [75]

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M. El Gamal et al. Separation and Purification Technology 197 (2018) 345–359

Table 9
Bio-regeneration efficiencies of various GAC dosages saturated with varying fractions of phenol and 4-CP at under two-step approach, [134].

Initial Concentration (mmol L−1) GAC dosage (gL−1) f

(QPh + Q4fCP )pris (mmol g−1) ph to 4-CP ratio f
(QPh + Q4fCP )biots (mmol g−1) Bio-regeneration Efficiency (%)

phenol 4-CP

2.13 4.67 1.0 2.78 ± 0.05 0.20 1.28 ± 0.04 46 ± 2

1.5 2.58 ± 0.08 0.22 1.24 ± 0.06 48 ± 4
2.0 2.44 ± 0.03 0.24 1.25 ± 0.03 52 ± 2
4.25 3.11 1.0 2.90 ± 0.05 0.49 1.43 ± 0.05 49 ± 2
1.5 2.62 ± 0.04 0.56 1.37 ± 0.05 52 ± 3
2.0 2.45 ± 0.05 0.73 1.31 ± 0.06 53 ± 3
6.38 1.56 1.0 2.29 ± 0.05 1.17 1.42 ± 0.08 62 ± 5
1.5 2.25 ± 0.03 1.47 1.48 ± 0.07 66 ± 4
2.0 2.14 ± 0.03 1.86 1.36 ± 0.06 63 ± 4

on the bio-regeneration efficiency for two-step approach. It was found
that, the increase in GAC dosage increased the regeneration efficiency.
At lower dosage, more 4-CP was adsorbed due to its stronger interaction
with the carbon compared to phenol. This leads to lower phenol/4-CP
ratio. As with more GAC, many active sites become available for the
contaminants which reduce the competition between the components.
11. Summary and future prospective
As an adsorbent, AC is employed in several industrial applications,
including the removal of inorganic and organic pollutants. The costs
associated with its usage, however, are very high and often considered
major deterrent to its application as a common adsorbent. The types of
AC can be differentiated by their physico-chemical properties, such as
the effective size and uniformity coefficient, pore size distribution,
surface area and bulk density. Regeneration techniques for exhausted
AC include: steam regeneration, thermal regeneration, chemical re-
generation, microwaves regeneration, wet oxidation processes re-
generation, electrochemical regeneration, and bio-regeneration pro-
cesses. This paper presented a comprehensive review of bio-
regeneration with special emphasis on the mechanisms and factors af-
fecting bio-regeneration processes, principle and target compounds for
bio-regeneration, quantification methods of bio-regeneration and the
efficiency of bio-regeneration.
Bio-regeneration can be achieved by biological treatments or by
making use of bacteria along with saturated AC. Bio-regeneration is
characterized by restoration of adsorptive capacity of the carbons after
it is saturated with the contaminants. Microorganisms, use the organic
substrates in their metabolism to generate energy. A synergism between
the biodegradation of the organic matter by the microorganisms and
the adsorption by AC results in enhanced effects. Bio-regeneration can
be completed by contact of exhausted AC to microbial action successive
to adsorption or by instantaneous management.
Based on the studies on biological ACs, it is indicated that bio-re-
generation of carbon happens through the time sequence of wastewater
treatment processes. Several studies focus on the pathways of how
microorganisms renew the surface of ACs saturated with the con-
taminants. It is theorized that biodegradation occurs because of the
concentration gradient of the pollutant as one moves from the carbon
surface to the bulk solvent. As demonstrated in offline close-loop re-
circulating batch reactors with sequential desorption and biodegrada-
tion processes, the mechanism of bio-regeneration is facilitated when
organics are less strongly bound to the carbon. Bio-regeneration can
occur for compounds that readily desorb and it has been demonstrated
in offline systems, which involve desorption and biological removal of
adsorbed organic matter in a closed-loop re-circulating batch system.
Establishment of the optimum conditions for vital activities of micro-
organisms can be controlled by temperature, pH, dissolved oxygen
concentration, ratio of the concentrations of the microorganisms and
the adsorbate.
Bio-regeneration can certainly offer several benefits as compared to
other regeneration methods. It is a safer, less costly and more en-
vironmental friendly process than other common regeneration pro-
cesses such as steam and chemical regeneration, which are energy in-
tensive and often lead to deterioration of the AC structure. Although
there have been some good research efforts in bio-regeneration, there is
still a need for more research to better evaluate the factors affecting the
regeneration process. More research efforts are needed in such areas as
mechanisms and quantification of bio-regeneration, mainly the ad-
sorption reversibility, validity and the efficiency of bio-regeneration.
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