Journal of Environmental Chemical Engineering 8 (2020) 103691

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Journal of Environmental Chemical Engineering

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Regeneration of activated carbon by applying the phenolic degrading fungus T

Scedosporium apiospermum
Yesid Sneider Murillo Acevedoa, Laura Tatiana Morales Mancerab,
Juan Carlos Moreno-Pirajána,*, Martha Vives Flórezb
a
Porous Solids and Calorimetry Research Group, Department of Chemistry, Universidad de los Andes, Bogotá, Colombia
b
Department of Biological Sciences, Universidad de los Andes, Bogotá, Colombia

A R T I C LE I N FO A B S T R A C T

Keywords: The regeneration of activated carbon (AC) is an important step for the industry because it reinstates its ad-
Bioregeneration sorption capacity with negligible changes in its original textural parameters. Thus, it allows the re-use of AC at a
Activated carbon low cost. Different methods have been used to achieve regeneration, most of them failing in reinstating its
Scedosporium apiospermum original adsorption properties and raising the cost of the process. In this study, we propose to combine two
Biological activity
methods for the removal of phenol: adsorption using AC and bioremediation. The use of the Scedosporium
apiospermum HDO1 fungus allowed the removal of the residual concentration of phenol from the solution, and
reinstated 98 % of the original textural parameters of AC. This level of bioregeneration has never before been
obtained using the common methods such as thermal treatment or solvent extraction.

1. Introduction that may reduce porosity [8]. However, in thermal regeneration, the AC
can also adsorb inorganic impurities, for example, in wastewater, such
Activated carbon (AC) is considered a universal adsorbent and is as alkaline and alkaline earth metals that affect thermal regeneration.
generally used in water purification and residual water treatment [1]. The alkaline earth metals catalyze the gasification reaction between the
The adsorption capacity of AC depends mostly on its surface area, AC and the regenerating agent (F. E. water vapor) causing the de-
porous structure, and chemical surface [2], and it is considered the best struction of micropores and the reduction of the adsorption capacity
adsorbent to use in the capture of inorganic and organic compounds [8,9]. Regeneration with solvent consists in passing an affine dissolvent
and toxic metal ions that contaminate water resources [3]. One of the into the contaminating adsorbate through the adsorbent bed or by using
principal limitations for the use of AC in the decontamination process is a dissolvent affine to the surface, in which the adsorbate moves from
the reduction of its adsorption capacity over time [4]. Because of this, the surface and dissolves in the solvent. Given its high cost, the dis-
current research is focused on its regeneration during the adsorption solvent is recovered for re-use [10].
process, as this might reduce the global process cost and will determine In recent decades, the capacity of several microorganisms (MO)
the viability of the effluent depuration process. In this sense, the ob- such as bacteria, microalgae, and fungi has been studied in order to
jective of the regeneration is to reinstate the adsorbent material's ori- contribute to environmental decontamination [11–19]. This process is
ginal adsorption capacity, removing the compounds adsorbed into the known as bioremediation and consists in the transformation of the or-
surface [5], with minimal changes to its textural properties and very ganic contaminants to less harmful or innocuous forms with reduced
little additional cost. use of energy, chemical substances, and time [20,21]. This technique is
AC is usually regenerated by thermal regeneration, in which tem- considered environmentally friendly, inexpensive, versatile, and easily
peratures between 600−800 °C are used in the presence of inert and/or constructed, operated, and maintained. It also, offers a wide spectrum
oxidant gases [6,7]. An inert atmosphere is sought to generate the de- of alternatives for combined applications [22]. For instance, several
composition and partial volatilization of the adsorbate, while the pur- MOs have been used to regenerate AC in a process known as bior-
pose of using the oxidizing atmosphere is to burn any pollutant residue egeneration [23–28], where the AC is renovated prior its saturation

Abbreviations: AC, activated carbon; NLDFT, non-local density functional; QSDFT, quenched solid density functional theory; BAC, biologically activated carbons;
BET, Brunauer, Emmett and Teller; DA, Dubinin-Astakov; MO, microorganism; MSM, minimal salt medio; TG, thermogravimetry; PSD, pore size distribution
⁎
Corresponding author.
E-mail address: jumoreno@uniandes.edu.co (J.C. Moreno-Piraján).

https://doi.org/10.1016/j.jece.2020.103691
Received 12 November 2019; Received in revised form 26 December 2019; Accepted 13 January 2020
Available online 14 January 2020
2213-3437/ © 2020 Published by Elsevier Ltd.
Y.S.M. Acevedo, et al. Journal of Environmental Chemical Engineering 8 (2020) 103691

with the contaminant, therefore increasing its useful life and decreasing Where N(P/P0) is the experimental adsorption isotherm data, W is the
the cost of the decontamination process [29]. pore width, N(P/P0,W) is the isotherm on a single pore of width W and f
Bioregeneration studies have been focused on the use of bacteria (W) is the pore size distribution function.
[30], and even on the study of the bacteria and protozoa population The difference between Vt and VN2, is considered the mesopore
[31]; but despite the good degrading capacity of fungi, in the literature, volume (Vmeso).
there are very few studies that use these MOs for AC bioregeneration
[32]. Fungi have certain advantages over bacteria: they can oxidize a 2.2. Minimal salt medium
greater diversity of organic compounds, they have greater tolerance to
high concentrations of the contaminants and to the oxidative stress of The Minimal Salt Medium (MSM) has the following composition:
the environment, and their production of extracellular enzymes during NH4NO3 2 g/L, MgSO4*7H2O 500 mg/L, HK2PO4 600 mg/L, H2KPO4
the colonization process accelerates degradation [33]. Therefore, in this 500 mg/L, CaCl2 100 mg/L, CuSO4*5H2O 0,4 mg/L, MnCl2*H2O,
study, we worked with a filamentous fungus to take advantage of these 0,09 mg/L, H3BO3 0,07 mg/L, NaMoO4*2H2O 0,02 mg/L, FeCl3 1 mg/L,
benefits and evaluate its performance in the bioregeneration of the AC. ZnCl2 2,5 mg/L, and thymine (C5H6N2O2) 0,1 mg /L. This medium is
Phenol is one of the most common pollutants in wastewater. It is using for degradation’s assays because it not has any carbon source that
involved in environmental damage and in human health issues. Phenol can be use by the fungus.
has been classified as one of the “priority pollutants” by the EPA
(Environmental Protection Agency), due its toxicity, making its removal 2.3. Phenol solutions
an important task for governments, various agencies, and researchers.
The use of AC to remove phenol has been widely reported with good A stock solution of 1000 ppm was prepared by weighting the pure
results, especially in the treatment of low concentrations of this pollu- crystal solid and by dissolving it in MSM. For the adsorption kinetics
tant at large volumes [34–36], in comparison with other types of car- assays and adsorptions isotherms in liquid phase, the obtained dilutions
bons [37]. Many methods have been used for the regeneration of AC were prepared with MSM solution.
saturated with phenol such as microwaves [38,39], electrochemical
[40], thermal, with ozone [41], and bioregeneration [42,43]. 2.4. Adsorption kinetics
Scedosporium apiospermum is a fungus belonging to the Ascomycota
phylum, which has been isolated from several environments such as An amount of AC (10 mg) was mixed with 4 mL of phenol solution
estuaries, frog intestines, a fertilizer, and environments influenced by following up on the concentration change in intervals of 1 min during
human activity [44]. This fungus has also been reported as a hydro- the first 30 min (n = 30) and subsequently taking experimental data
carbon degrader MO [29,45,46], able to degrade complex compounds every 30 min for 24 h (n = 47) at 20 °C. The determinations were made
such as polycyclic aromatic hydrocarbons, long chain-aliphatic hydro- by UV spectroscopy at a wavelength of 271 nm.
carbons, and contaminant mixtures [47]. The complete characteriza-
tion of the genome of the S. apiospermum and pathways involved in the
2.4.1. Reaction-based models
degradation process was analyzed to understand the ability of this
The kinetic reaction models most commonly used in batch experi-
fungus to degrade hydrocarbons in our research group [48].
ments are the pseudo-first-order model (Eq. (3)), the pseudo-second-
In this study, we intended to regenerate the adsorbent and textural
order model (Eq. (4)), and the Elovich model (Eq. (5)) [50,51]:
properties of AC saturated with phenol, using the S. apiospermum HDO1
fungus isolated as contaminant from assays on bacterial strains able to qt = qe (1 − e−k1 t ) (3)
grow in crude oil.
qe2 *k2*t
qt =
2. Experimental 1 + qe *k2*t (4)

Commercial, physically activated coconut shell AC was used. The 1

qt = ⎜⎛ ⎟⎞ ln (αβt + 1)
technical sheet of this material is presented in Table 6. The AC was ⎝β⎠ (5)
sieved to a particle size between 1−2 mm, washed with distillated
Where qe (mg/g) is the amount of phenol adsorbed at equilibrium, qt
water and dried for 24 h at 90 °C.
(mg/g) is the amount of adsorbate adsorbed at time t, k1 (min−1) is the
adsorption rate constant of pseudo first order, k2 (g*mg−1*min−1) is
2.1. AC characterization the adsorption rate constant of pseudo second order, α (mg g−1 min) is
the initial adsorption rate and β (g mg−1) is related to the extent of
The Brunauer, Emmett and Teller (BET) superficial area and the surface coverage and the activation energy for chemisorption.
pore distribution for the adsorbents were evaluated by means of N2 The kinetic models were evaluated with different error functions
adsorption at −196 °C. The samples were previously degassed at 250 °C (Table 1). The solver add-in with Microsoft’s spreadsheet, Excel, was
for 8 h. The data of N2 isotherm were used to determine: (I) pore total used for calculations (method GRG non-linear).
volume (Vt) at relative pressure of 0.95; (II) BET apparent superficial
area (SBET), obtained by applying the BET equation to the N2 adsorption
2.4.2. Diffusion-based models
data, in the P/P:0.01-0.05 interval (Eq. (1)) [49]
The intraparticle diffusion model is based on the Weber theory,
p / p0 1 C−1 which consists of a common empirical relationship in adsorption pro-
= + (p / p0 )
a (1 − p / p0 ) am C am C (1) cesses, where the adsorption process varies proportionally with time t1/
2
, according to (Eq. (6)) [52]:
where P is the saturation pressure, C = exp[(ΔHA- ΔHL)/RT], ΔHA is
0

the adsorption heat, ΔHL is the liquefaction heat, n is the adsorbed qt = kpi t 1/2 + Ci (6)
quantity and nm is the quantity of adsorbed molecules in te monolayer. 1/2
Where kpi (mg/g*min ) corresponds to the rate of each stage i, cor-
(III) micropore volume (VN2), pores < 2 nm, by applying the DFT
responding to the slope of the graph qt versus t1/2, where the intercept
method (Eq. (2))
Ci gives an idea of the thickness of the boundary layer.
Wmax The Bt values were determined by Eqs. (7 and 8), and it is plotted
N (p / p0 ) = ∫Wmin N (p / p0 , W ) f (W ) d (W ) (2) against t [53].

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Y.S.M. Acevedo, et al. Journal of Environmental Chemical Engineering 8 (2020) 103691

Table 1 48 h. The phenol was measured using the 4-aminoantipyrine method

Explanation of different error functions. [54] at 510 nm.
Definition/expression
2.6.4. Bioregeneration with S. apiospermum HDO1
¯ )2
(qexp − qcal
r2 = The MO used was the environmental strain S. apiospermum HDO1,
¯ )2 + (qexp − qcal )2
(qexp − qcal
which was previously isolated from bioremediation assays using crude
n
SSE = ∑n = 1 (qcal − qexp )i2 oil (API gravity 33) as the only carbon source; this MO was char-
2
HYBRID =
100
∑
n ⎡ (qcal − qexp ) ⎤ acterized at the genomic and phenotypic level [53]. 50 mg of AC were
n − p i=1 ⎢ ⎥
⎣
qexp
⎦i placed in 100 mL of MSM with 100 ppm of phenol in 250 mL flask and
ARE =
100 n
∑i = 1
qcal − qexp the AC was allowed to saturate for 48 h; then, three plugs of fungus
n qexp
i were placed in the system previously grown during 5 days in PDA
1 n qcal − qexp
2 culture medium. Measurements of phenol in the medium were made
MPSD = 100 ∑ ⎛
⎜
⎞⎟
n − p i=1
⎝ qexp
⎠i using the 4-aminoantipyrine method at days 1, 2, 3 and 5. The ex-
n
SAE = ∑i = 1 |qcal − qexp |i periment was carried out at 30 °C and 100 rpm.

3. Results
for F values > 0.85 Bt = −0.04977 − ln (1 − F ) (7)
3.1. Textural properties of virgin commercial AC
for F value < 0.85 Bt = ( π − π − (π 2F /3) )2 (8)
where F is the fractional attainment of equilibrium at different times t According to the N2 isotherm at −196 °C which is deduced quali-
(qt/qe) and Bt is a function of F. tatively based on the IUPAC classification, the isotherm obtained is I
type corresponding to solids with micropores. The pore size distribution
2.5. Adsorption isotherms in liquid phase (PSD) calculated with the QSDFT model for the kernell slit/cylinder./
Sphere pores, presented the lowest adjustment error of 0.034 (Fig. 1). In
To determine phenol adsorption, 0.1 g of AC were placed in amber this case, the PSD profile shows a distribution with pore sizes smaller
glass bottles, and 40 mL of each phenol solution. The samples were than 2 nm corresponding to a microporous material. However, the
mechanically shaken at room temperature (20 °C) over a period of 24 h. peaks of higher contribution in the microporosity are found with a pore
The adsorption isotherms were analyzed using Langmuir and size of 0.46 (a), 0.56 (b) and 1.08 nm (c).
Freundlich models: The textural parameters of the AC are shown in Table 6, obtaining
The Langmuir model (Eq. (9)) is defined as: qe the amount of solute an apparent surface area of 842 m2/g, micropore volume 0.38 cm3/g,
adsorbed per unit weight of the adsorbent at equilibrium (mg*g−1), Ce mesopore volume of 0.03 cm3/g and total volume of 0.41 cm3/g, i.e.,
concentration at equilibrium of the solute (mg*L−1), qm the maximum the AC presents a percentage of microporosity of 92.7 % and meso-
capacity of adsorption (mg*g−1), and b the constant related to the porosity of 7,32 % in relation to the total volume determined.
adsorption free energy (L*mg−1).
3.2. Kinetics of phenol adsorption on AC
KL Ce ⎞
Qe = ⎛ ⎜ ⎟

⎝ 1 + aL Ce ⎠ (9) 3.2.1. Reaction based models

Meanwhile, in the Freundlich model (Eq. (10)), Kf is a constant that The kinetics of phenol adsorption describes the adsorption rate, at
indicates the relative adsorption capacity of the adsorbent (mg1−(1/ which the equilibrium time is determined. We can see that the adsorbed
n)
*L1/n*g-1) and n is a constant that refers to the intensity of the ad- amount of phenol as a function of time (Qt) depends on reactions-based
sorption. The Freundlich equation is an exponential expression that and/or diffusions-based models. The error functions corresponding to
assumes that when the concentration of adsorbate increases, the con- the minimum deviation between the experimental data and the theo-
centration of this on the surface of the adsorbent also increases. retical data determined by each function suggest that the best fit is
obtained with the pseudo first order model, followed by the pseudo
Qe = Kf Ce1/ n (10)

2.6. AC regeneration

2.6.1. Phenol desorption of AC in aqueous phase

Phenol desorption was conducted by air-drying the phenol-satu-
rated AC for a day and washing it with water (50 mL) under agitation
for 8 days.

2.6.2. Thermal regeneration of AC

The mass loss in function of temperature was determined for the
saturated and regenerated AC by Thermogravimetry (Hitachi STA
7200). The analysis conditions used were: temperature interval be-
tween 30−800 °C, N2 flow of 100 mL/min, and heating rate of 10 °C/
min.

2.6.3. Determination of residual phenol concentration

After 48 h of AC saturation in a 100 ppm phenol solution, the re-
sidual phenol concentration in MSM was determined using different
amounts of AC, 100 mL of MSM with phenol 100 ppm. 20, 50 and
100 mg of AC were added, and measurements were taken at 24 and Fig. 1. Pore size distribution for the granular AC (QSDFT).

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Y.S.M. Acevedo, et al. Journal of Environmental Chemical Engineering 8 (2020) 103691

Fig. 2. Kinetic of phenol adsorption on AC. (a) kinetic model of pseudo first order (b) kinetic model of pseudo second order, and (c) Elovich model.

Table 2
Comparison of the kinetic models of pseudo first order, pseudo second order, and Elovich model.
Seudo first order Seudo second order Elovich model

K1 Qe,Cal O.F K2 Qe,Cal O.F a B O.F

(min−1) (mg g−1) (g/mg min) (mg g−1) (mg/(g min)) (g/mg)

SSE 0.00509 40.3 349.3 0.00011 48.1 712.7 0.329 0.0811 1352.6
HYBRID 0.00253 44.6 106.6 2.68XE−5 64.7 129.8 0.110 0.0420 152.7
ARE 0.00085 64.9 25.54 4.09XE−6 115.9 25.90 0.0534 0.0181 26.19
MPSD 0.326 0.764 8.663 0.405 0.916 6.832 0.574 4.68 5.429
SAE 0.00578 39.7 110.3 0.00013 46.3 192.7 0.284 0.0778 275.6
R2 0.00560 38.5 0.9908 2.96XE−5 96.2 0.3758 0.9876 0.1225 0.9069

second order model and the Elovich model. Therefore, the best fit is the Boyd model applied for segment I corroborates this mechanism,
given for the pseudo first order model with the SAE error function, from since the intercept passes through the origin. In the case of linear seg-
which the best graphic adjustment is obtained. The pseudo first order ment II, we can see that the intercept does not pass through the origin
model is based on the fact that the adsorption process is limited by the hence it is deduced, according to the Weber model, that another me-
transport of molecules from the solution to the adsorbent (diffusion chanism different from the intraparticle diffusion is established.
film), given that transport does not limit the speed. The adjustments of Meanwhile Boyd's model allows us to affirm that in segment II, the
the experimental results and the estimated parameters are presented in mechanism that controls speed is film diffusion. In sum, the segment of
Fig. 2(a–c) and Table 2. intraparticle diffusion occurs in the 1−60 min period, after which the
speed is controlled by the diffusion film mechanism. In both models,
rupture times of 54.3 and 64.2 are observed for the Weber and Boyd
3.2.2. Diffusion-based model model respectively.
Fig. 3a–b show two linear segments from which the parameters In Fig. 3(a), Segment I correspond to the instantaneous adsorption
presented in Table 3 are obtained. According to the Weber model, or the external superficial adsorption; gradual adsorption occurs in
linear segment I, passes through the origin, where it follows that the Segment II, where the intraparticle diffusion is the limiting rate; finally,
mechanism controlling the speed is intraparticle diffusion. Accordingly,

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Y.S.M. Acevedo, et al. Journal of Environmental Chemical Engineering 8 (2020) 103691

Fig. 3. Diffusion models: (a) intraparticle diffusion (b) Weber and Boyd model.

the rate decreases due to the extremely low concentrations of residual

phenol, since 99.2 % of the adsorbate is adsorbed.
Segment I is completed at 60 min, at a rate of 0.20 mg/g*min1/2;
Segment II takes 144 min and the rate increases 22 times (4.4 mg/
g*min1/2). This is where the greatest amount of adsorption occurs
compared to the other regions.

3.3. Phenol adsorption isotherms

Subsequently, the adsorption isotherm was determined (Fig. 4) in

order to determine the maximum capacity by mathematical models
such as Langmuir and Freundlich. The Langmuir isotherm models and
Freundlich are used to adjust the experimental data on adsorption in
the phenol equilibrium. The Langmuir model assumes uniform ad-
sorption energies on the surface and non-transmigration of the ad-
sorbate in the plane of the surface.
In the first points, phenol was completely adsorbed (10, 25 and
50 ppm) by the AC. In the other concentrations, we obtained different
percentages of adsorption (99.2–78.8). For the 100 ppm concentration,
we can see from the kinetics and the adsorption isotherm that the re- Fig. 4. Phenol Adsorption Isotherm on AC.
sults obtained are in accordance with the saturation capacity, corre-
sponding to 39.5 mg of phenol/g of AC.
Table 4
The maximum adsorption capacity of the AC was determined ac-
Parameters of the Langmuir and Freundlich models of Phenol Adsorption.
cording to the Langmuir model obtaining a value of 120.9 mg / g. This
value allows us to estimate the amount of AC that must be added to the SSE MPSD
system in order to have a level of residue lower than 200 ppm. Table 4
Langmuir qm 147.3 120.9
shows the objective functions where the best object function is found b 0.12 0.34
for the Freundlich model that corresponds to 24.29. The assumptions of O.F 1178 210.1
this model are applied to heterogeneous surfaces, where there is in- Freundlich Kf 40.45 40.45
n 3.58 3.58
teraction between adsorbed molecules and the adsorption energy de-
O.Fa 40.64 24.29
creases exponentially.
a
Objective function for the minimum error distribution between experi-
3.4. Effect of MSM on the phenol adsorption on AC mental and predicted isotherms.

Fig. 5 shows that the blank Phenol (100 ppm) in aqueous solution
has no variation in the absorbance after the principal peak at 271 nm.

Table 3
Constants of the intraparticle diffusion model and determination coefficients in the adsorption of phenol on AC.
Slope I Intercept I Slope II Intercept II Break Time (min)

Pore difussion plot 0.20 mg/g*min1/2 0.093 4.4 −30.6 54.3

mg/g*min1/2
Boyd plot 2.64 × 10−5 2.04 × 10−5 0.005 −0.31 64.2

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Y.S.M. Acevedo, et al. Journal of Environmental Chemical Engineering 8 (2020) 103691

Fig. 5. Effect of MSM and AC on the wavelength of phenol.

Fig. 6. Phenol desorption (%) in aqueous medium.

However, in the range of concentrations between 50 and 100 ppm with
AC, there is a shift of the maximum absorption peak from 1 to 301 nm;
the peak forms are usually associated with phenol oxidation. For con-
centrations between 400 and 500 ppm a peak of phenol absorption is
observed at 271 nm and another of lower absorbance at 301 nm.
The effect of MSM in the adsorption process favors the amount
adsorbed per gram of adsorbent as is shown in Table 5. The results show
an increase of 15.4 % and 2.10 % for concentrations of 400 and
500 ppm respectively.

3.5. AC regeneration: Desorption in aqueous medium and thermal

regeneration

The adsorbed carbons were taken, and desorption was conducted in

the aqueous phase, with a maximum desorption percentage of 6.4 %,
corresponding to concentrations of 450 and 500 ppm. This percentage
of desorption is proportional to the concentration (Fig. 6), and provides
evidence of the strong interaction between adsorbent-adsorbate.
Moreno-Castilla reported strong interactions between the surface and
aromatic compounds that involve electron donor-acceptor or charge Fig. 7. Thermograms- Thermal regeneration of AC saturated with phenol.
transfer mechanisms [2], which explain the difficulty in desorbing these
compounds even at high temperatures. To corroborate this, a thermo-
gravimetric analysis was carried out. Fig. 7 shows the thermograms of
the virgin AC (This carbon was never exposed to phenol),
AC + 100 ppm and AC + 500 ppm; the latter two are the AC assays that
were left in equilibrium with the respective solutions. The weight
change in the virgin AC is due to water desorption, and surface groups
decomposition. However, by the time the AC has adsorbed phenol at
different concentrations (100 and 500 ppm), it is found that maximum
phenol desorption process occurs (Fig. 8) at a temperature of 214 °C and
260 °C, desorbing between 8.31 and 6.51 % respectively. This result
correlates positively with the desorption results obtained in aqueous
phase and corroborates the strong interactions between the adsorbate-
adsorbent.

Table 5
Effect of MSM in the amount of adsorbed phenol.
AC + Phenol (Distilled water AC + MSM + Phenol (Qe mg/g)
without MMS) (Qe mg/g)
Fig. 8. DTG -Thermal Phenol Desorption from AC at different concentration (A)
400 ppm 129.3 149.2 Enlargement of the peaks that are between 100–400 °C.
500 ppm 147.9 151.0

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Y.S.M. Acevedo, et al. Journal of Environmental Chemical Engineering 8 (2020) 103691

Fig. 11. N2 isotherms at −196 °C.

Fig. 9. Effect of the AC mass on the concentration of free phenol in the medium
as a function of time.
not detected by the 4-aminoantipyrine method at day 5.
3.6. Effect of degradation of phenol with HDO1 fungus and regeneration of The fungus was allowed to grow for two more days in order to
AC evaluate whether the HDO1 strain could use the phenol adsorbed to the
AC to conduct a bioregeneration process.
In order to determine the amount of AC necessary to adsorb half of
the phenol present in the medium and leave the other part as residue in 3.7. AC regeneration with HDO1 fungus: textural analysis
the MSM solution at a concentration not toxic to the fungus (not higher
than 200 ppm), tests were conducted with 25, 50 and 100 mg of AC and This process was assessed by N2 adsorption isotherm at −196 °C
the residual phenol was measured using the 4-aminoantipyrine method after treatment with the MO (Fig. 11), where the textural parameters
[29]. The results are shown in Fig. 9, in which we can see that using obtained for both virgin AC and bioregenerated AC are similar (dis-
50 mg of AC allows between 47 and 58 ppm of residual phenol, which is cussed below), while the AC saturated with 100 ppm of phenol showed
a completely tolerable and degradable concentration for the fungus. On a decrease of the textural parameters, probably due to the adsorbed
the other hand, when using 25 mg, only a small amount of phenol is phenol that partially blocks microporosity. That is, the HDO1 fungus is
absorbed and with 100 mg there is only 20 ppm of phenol free in the able to degrade the free phenol present in the medium as well as phenol
medium, resulting in a high concentration of phenol adsorbed on the adsorbed to the AC, thus allowing a high percentage of regeneration
AC that could affect viability, binding and regenerative activity of the compared to other methods such as thermic desorption and desorption
fungus. Considering that the objective of the work is to combine the in aqueous medium (Section 3.5).
adsorption capacity of the AC with the degradation capacity of the Pore size distribution (Fig. 12) shows how the saturated sample
fungus, a mass of 50 mg was chosen for the regeneration experiment. decreases the micropore volume by 70.3 % in relation to the virgin
As mentioned earlier, phenol removal tests were carried out with sample (Table 6). On the other hand, saturated AC with phenol can be
the HDO1 fungus with 50 mg of AC. Fig. 10 shows the results using the regenerated by 98 % in relation to the micropore volume. A 0.07 cm3/g
HDO1 strain, where the concentration of free phenol in the medium is increase in mesoporosity is also observed compared to the virgin AC,
and a widening of the ranges of microporosity of between 0.5–0.7 nm

Fig. 10. Phenol removal assay. Fig. 12. Pore Size Distribution QSDFT.

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Y.S.M. Acevedo, et al. Journal of Environmental Chemical Engineering 8 (2020) 103691

Table 6
Textural parameters determined by N2 isotherms at −196 °C.
SAMPLE Area (m2/g) Micro Vol., (cm3/g) Meso Vol. (cm3/g) Total Vol. (cm3/g)

VIRGEN AC 842 0.37 0.01 0.38

AC + PHENOL +HDO1+MMS (Regeneration) 858 0.38 0.08 0.46
AC + PHENOL + MMS (Saturated with phenol) 620 0.26 0.02 0.28

and 1.0–2.0 nm. For mesoporosity, a sacking is observed in the range adsorption isotherm at −196 °C (Fig. 11).
between 3−19 nm, which may be due to carbon consumption by the The percentage of regeneration obtained with the HDO1 fungus was
HDO1 fungus [45,46]. 98.0 %, while in the regeneration with solvent process, 6.4 % was
achieved (Fig. 6), and in thermal regeneration, only 14.8 % was
achieved at a temperature of 400 °C. Given the results of the textural
4. Discussion properties of the regenerated AC, it is possible that the phenol cannot be
desorbed completely due to the complex structure of AC.
AC adsorption is a commonly used method for the removal of However, in the case of the fungus used, it is difficult to immobilize
phenol form effluents. However, at concentrations higher than the MOs, since they produce spores, which cause the fungus to grow in
300 ppm, the percentage of removal decreases: at 100–300 ppm, re- the medium again. Also, it cannot be said that it is free since its hyphae
moval is 99 %; while at 500 ppm, it drops to 78 %. Therefore, at high also colonize the surface of the AC when placed in the medium.
concentrations, residual phenol in the effluent remains and the satu- We aimed to combine the adsorption properties of the AC with the
rated AC becomes a contaminating material. For this reason, many at- biodegradation abilities of S. apiospermum. The use of S. apiospermum
tempts have been made to find different techniques that allow the ad- for the degradation of phenol should improve the process of deconta-
sorbate to be removed from the adsorbent in order to regenerate the mination of such pollutants, since it has been reported that the species
adsorbent properties. possesses the necessary enzymes for its degradation through the ortho
Differences in phenol adsorption rates have been reported in pre- pathway to break the aromatic ring [45]. Biodegradation could guar-
vious studies. However, none had the characteristics we observed here. antee complete phenol metabolism and mineralization. The results
We found differences in the phenol AC adsorption rate, which can be presented show that it is possible to combine AC adsorption and bio-
divided into two segments (Fig. 3) where Segment II presented an ad- degradation for the efficient removal of phenol. AC showed a saturation
sorption rate 22 times higher than Segment I. This behavior indicates capacity of 39.5 mg of phenol/g of AC; when it is combined with the
that the adsorption mechanism is given by strong interactions that biological activity of the HDO1 fungus, the bioregeneration of the AC
occur in Segment I and II; these interactions are: adsorption in the adsorption capacity was demonstrated. For example, for 50 mg of AC
microporosity of AC, interactions π (graphene layers) -π (aromatic ring) previously saturated with 100 ppm of phenol, 100 % phenol removal
and adsorbate interaction with oxygenated surface groups of AC was achieved. However, the HDO1 fungus cannot survive in a high
[55,56]. However, adsorption also occurred in the first 60 min (Seg- concentration (upper to 200 ppm). In the adsorption process, it is pos-
ment I), although the adsorbed amount is lower compared to what is sible to use AC at high concentrations of phenol (higher than 500 ppm),
adsorbed in Segment II. This is explained by the adsorption of the because in the case of a solution with a concentration of 500 ppm, a
phenol on the surface of the AC [2]. residual of 100 ppm is obtained, and when the residual concentration is
There is an effect of the medium on the absorption of phenol below 200 ppm, the HDO1 fungus is capable of removing the residual
(Fig. 5), indicating that the MSM in combination with the AC has an phenol and start the regeneration process.
oxidation effect on the AC surface groups [2]. The AC in this system The bioregeneration of AC offers multiple advantages in comparison
may have two functions: (1) as a catalytic support, due to its large with other regeneration methods, including lower energy consumption,
surface area, allowing a greater dispersion of metals; and (2) as a whereas in thermal methods it is necessary to increase the temperature
phenol adsorbent, due to its textural characteristics. The MSM medium to over 700 °C in order to desorb the adsorbate from the surface with
also has an effect on the amount of phenol adsorbed to the AC; we think low yields and partial destruction of the textural parameters of the AC.
this might be due to the change in the pH. The Point Zero Charge (PZC) In addition, the solvent (water) regeneration process also showed low
of the AC is 5.4 and the pH of the MSM + Phenol solution is close to 7. yields due to the affinity between the adsorbate-adsorbent. In contrast,
On the other hand, the pKa of the phenol is 9.89, and, according to its all the tests with the HDO1 fungus were carried out at 30 °C with a
speciation diagram, the phenol species predominates at pH 7 in com- regeneration percentage of 98 %. The increase in porosity might be due
parison with phenolate ion, while the AC possesses negative surface to the action of the fungus on the AC (as an energy source), increasing
charges that are neutralized by the metals present in the MSM, thus the material's mesoporosity [57]. This hypothesis will require con-
increasing the AC phenol adsorption capacity. firmation. Finally, to eliminate the MO, it was only necessary to in-
These regeneration techniques involving treatments with dissolvent crease the temperature to 121.5 °C in an autoclave. It is also important
(water) and thermal treatment yields of between 6.47–8.13 % were to mention that this fungus has been reported as an opportunistic pa-
obtained respectively (Figs. 6 and 7). In the thermal treatment, high thogen [58] but this is common to other MOs with biodegradation
energy consumption is required and the elimination percentage ob- activity [59]. Additionally, in the context and the scope of the present
tained for solvent regeneration is low. The bioregeneration is a process investigation, this was not an issue to consider since no release to the
by which the AC is regenerated with the MO due to the symbiosis be- environment was envisioned as yet. A large-scale application must in-
tween adsorption and bioremediation. In the adsorption processes, the volve additional studies and safety considerations [27] (Fig. 13).
phenol can be found in the porosity of AC and as residual concentration
in aqueous medium [32]. That is, the adsorption equilibrium can be
temporarily shifted out by the MO to desorb phenol from AC to solu- 5. Conclusions
tion, but when the phenol is totally consumed the MO can use the AC
like a energetic source, for this reason, the bioregeneration can devel- Phenol removal by adsorption using AC can be combined with
opment some porosity. Thus, the MO can be used in the bioregeneration bioremediation processes, as complementary techniques. While most of
of saturated AC following an adsorption process, which was verified by the phenol is adsorbed, still the conditions allowed the growth of the
the measurements of free phenol in the medium (Fig. 9) and N2 fungus S. apiospermum, which degrades the residual phenol and phenol

8
Y.S.M. Acevedo, et al. Journal of Environmental Chemical Engineering 8 (2020) 103691

Fig. 13. Mechanism synergic adsorption-bioremediation.

desorbed due to the alteration of adsorption equilibrium. With this Comparison between thermal and ozone regenerations of spent activated carbon
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