Accepted Manuscript

Combined magnetic field and adsorption process for treatment of biologically

treated palm oil mill effluent (pome)

Rafie Rushdy Mohammed, Mohammad Reza Ketabachi, Gordon McKay

PII: S1385-8947(13)01665-3
DOI: http://dx.doi.org/10.1016/j.cej.2013.12.084
Reference: CEJ 11622

To appear in: Chemical Engineering Journal

Received Date: 23 September 2013

Revised Date: 25 December 2013

Please cite this article as: R.R. Mohammed, M.R. Ketabachi, G. McKay, Combined magnetic field and adsorption
process for treatment of biologically treated palm oil mill effluent (pome), Chemical Engineering Journal (2014),
doi: http://dx.doi.org/10.1016/j.cej.2013.12.084

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 COMBINED MAGNETIC FIELD AND ADSORPTION PROCESS FOR TREATMENT
OF BIOLOGICALLY TREATED PALM OIL MILL EFFLUENT (POME)

Rafie Rushdy Mohammed1, Mohammad Reza Ketabachi2, Gordon McKay3*

1 Department of Chemical Industries, Mosul Technical Institute, Al-Majmoa’a Al-Thaqafiya, Mosul Iraq
2 Department of Chemical and Environmental Engineering, Faculty of Engineering, University of
Nottingham Malaysia campus, 43500 Semenyih, Selangor, Malaysia
3 Department of Chemical and Biomolecular Engineering, Hong Kong University of Science and
Technology, Clear Water Bay, Kowloon, Hong Kong Special Administrative Region
* Corresponding author. Tel.: +852 2358 8412; fax: +852 2358 0054.
E-mail address: kemckayg@ust.hk (G. McKay).

ABSTRACT

The production of palm oil, however, results in the generation of large quantities of polluted
wastewater commonly referred as palm oil mill effluent (POME). There is an actual need to seek
factors intensifying the treatment processes of POME. The new methods which not required
extension of existing plants or building very expensive bioreactors are still searching. In recent
years increasing attention has been directed to the possibility of improvement of waste water
treatment by static magnetic field. The aim of our study was to determine the impact of constant
magnetic field as well as the integration of this technique with the famous technique used for
wastewater treatment which is adsorption by activated carbon as a novel method for POME
treatment. This new method has been found to be a useful method for removing colour, TSS and
COD from biologically treated POME.

1
 1. INTRODUCTION

Palm oil, the most important commodity, and its industry are a significant contributor to the
Malaysian economy with over 4.9 million hectares of planted area with a production of 17
million tones of palm oil. Malaysia is the largest exporter of palm oil and exported to more than
100 countries with export earnings of RM 62 billion [1]. Extraction of palm oil involves a
number of processes that require large quantities of water. It usually requires an estimated 1.5m3
of water to process a ton of fresh fruit bunch, and half of this amount becomes palm oil mill
wastewater (POMW) [2]. Due to the high production rates, a large quantity of polluted
wastewater, (POMW) is generated. Palm oil mill effluent consists of water soluble components
of palm fruits as well as suspended materials like oil residues, short palm fiber, cell walls,
organelles, a variety of lipids and carbohydrates ranging from cellulose to simple sugars, Phenol
and phenolic compounds, a range of nitrogenous compounds from proteins to amino acids, free
organic acids and assembly of minor organic and mineral constituents. Nutrients contain in
POME according to are nitrogen, phosphorus, potassium, magnesium and calcium [3]. If the
effluent is discharged untreated, it can cause significant environmental impact due to its high
biochemical oxygen demand (BOD), chemical oxygen demand (COD), oil and grease, and total
solids. Therefore, a cost-effective treatment of POME to an acceptable level for discharge
continues to be a big challenge to the industry. In the last decade, several treatment methods have
been studied for POME treatment such as: anaerobic digestion [4-6], Aerobic oxidation based on
an activated sludge process [7], aerobic and anaerobic digestions [8-10], ultrafiltration
Membrane separation [11], up-flow anaerobic sludge fixed film (UASFF) reactor [12], chemical
coagulation and flocculation [13, 14], Solvent extraction [15], Electrocoagulation [16],
Electroflotation [17], Adsorption [18], and Hydrolysis [19].
The current treatment system, which is based mainly on biological treatments of anaerobic and
aerobic systems, is quite inefficient and this unfortunately leads to the environmental pollution
issues [19].
Liquid-phase adsorption processes have been proven to be highly efficient for removal of colors,
COD, suspended solids, and organic and inorganic pollutants from industrial processes.
Activated carbon is the most effective and widely used adsorbent for wastewater treatment [18].
More frequently the technological systems are introduced with physical factors. For instance,
positive results can be obtained when treating wastewater with a periodical field of external

2
oscillations, e.g. an acoustic, temperature field with defined parameters, as well as ultrasounds or
UV radiation [20].
One of the most important physical factors is the magnetic field. Since several decades,
researchers have found that magnetism is a unique property that independently helps in water
purification by influencing the physical and chemical properties of contaminants in water [21].
For a long time now, in numerous research centers investigations have been made in order to
discover the mechanism of changes occurring in solutions under an impact of this physical
factor. However, the optimal conditions for magnetic activation of liquids are sought, and
attempts made to determine the favourable technological effects of such treatment. Among
different physical and chemical methods of water and wastewater treatments; magnetic methods
attract a special attention due to their ecological purity, safety, simplicity and less operating
costs. Until now, there has been no unequivocal explanation about the modifications mechanisms
in the magnetically-treated wastewater.
Magnetic field-exposed methods have gradually drawn attention to improving the adsorption and
separation. Some researchers described the impacts of magnetic exposure on nonmagnetic
colloidal particles in aqueous solutions and the comparison of physiochemical properties before
and after magnetic exposure [22]. Magnetic exposure on the water changed water properties and
the interface between water and solid surface by magnetic-field-induced adsorption and
desorption [23]. There are only few studies that use magnetic field for wastewater treatment
processes, and in most of them, magnetic field is used only for separation of solids or attached
microorganisms from effluent. However, there is an important observation here, which is the
increased biological activity with the magnetic field application [24]. Yulan Ji et al. [25], found
that using magnetic field enhanced the biological treatment of wastewater. Maria Łebkowska et
al. [26], deduced that the static magnetic field had a positive effect on formaldehyde
biodegradation in wastewater by activated sludge. Duan et al. [27], demonstrated that the
adsorption ability, including adsorption amount and adsorption rate of Pb(II) using modified
chitosan could be enhanced with a suitable magnetic field. However, until recently, there is some
lack of knowledge about magnetic effects on adsorption and the mechanism of magnetic
exposure on adsorption characteristics. Till now the effect of magnetic field exposure and the
enhancement of magnetic field to adsorption process for the treatment of palm oil mill effluent
have not been investigated.

3
Static magnetization is convenient, simple, of little cost, and may be an alternative by itself or to
improve the adsorption. This paper aims to provide basic experimental findings of magnetic and
magnetic assisted adsorption and to guide the application of the magnetic chemistry on
adsorption process and palm oil mill effluent treatment.

2. EXPERIMENTAL

2.1 Materials
Biologically treated POME samples were collected from a palm oil mill in Dengkil -Malaysia.
Sample was stored in a cold room at 4oC prior to use. Biologically treated POME was analysed
for colour, total suspended solids (TSS), chemical oxygen demand (COD) and pH, the results are
shown in Table 1. The table also lists the POME standard discharge limit of Environmental
Quality Act (EQA) 1974, Department of Environment (DOE), Malaysia [28]. It can be observed
from Table 1 that the biologically treated POME exceeded the standard discharge limit.
Commercial activated carbon with a mesh size of 30 was supplied by GlobeChem (Malaysia).
Distilled water was used for any dilution.
Table 1. Properties of biologically treated POME and the regulatory discharge limits

2.2 Methods
In this study, a separate and combined process concept of activated carbon adsorption, and
magnetic field were applied for the treatment of biologically treated POME. It was proposed that
the substantial removal of colour, TSS, and COD from wastewater by adsorption to activated
carbon enhanced by magnetic field would significantly facilitate the POME treatment process.
According to the studies of Oshitani et al. [29] and Gaoke et al. [30], solutions can be
magnetized within a strong field such as the magnetic apparatus we used generated. The
magnetic field of the apparatus was adjustable and permanent, and the magnetic flux density was
high, up to 0.5 T.
Optimum conditions were examined for each process separately. Then these processes were
carried out consecutively. At the last stage a combination of the two processes was examined
simultaneously.

4
2.2.1 Adsorption experiments
To select the optimal adsorption condition without magnetic field, we varied the adsorbent
(commercial activated carbon) dosage from 5 g/100 ml to 25 g/100 ml, and the range of contact
time from 0.5 to 6 hr. A batch adsorption studies were conducted by adding different amounts (5,
10, 15, 20 and 25 g) of activated carbon, into a 250 ml flasks each containing 100 ml of
biologically treated POME. The conical flasks were then covered with glass stoppers and placed
on a shaker at shaking speed of (150 rpm) and at constant temperature of (25ºC) for a certain
period of (30, 60, 120 180, 240, 300 and 360 min). The samples were then withdrawn at
appropriate time intervals using glass pipette, the sample then filtered and the filtrate was used to
determine the residual concentrations of colour, TSS and COD.
The amounts of colour, TSS and COD adsorbed at time t, qt (mg/g) and at equilibrium, qe (mg/g)
were calculated using Eqs. (1) and (2).
 

 = (1)


 

 = (2)

The percentage of removal (%R) of each parameter and the amount that adsorbed by the
adsorbents were calculated by the following equations:
 
%  = × 100 (3)


where Co, Ct and Ce (mg/L) are the liquid-phase concentrations at initial, time t and equilibrium,
respectively. V (L) is the volume of the solution and M (g) the mass of activated carbon
adsorbent used. Each experiment was conducted in triplicate and the average values were
reported.

2.2.2 Magnetic field experiments

The effective of magnetic field on POME treatment as colour, TSS and COD removal was
investigated at different magnetic field intensity ranged from 5 mT (weak magnetic field) to 500
mT (strong magnetic field), and different periods of exposure time from (15 to 180 min).
A separate set of experiments have been done using magnetic field exposure followed by
adsorption at the optimum conditions stemmed from the above experiments. Combined

5
adsorption enhanced by magnetic field experiments were performed in well-tight polyethylene
50 ml bottles at 25ºC. Samples of activated carbon, 20 g/100 ml dry weight, were suspended in
the biologically treated POME. The magnetic treatment of the solution was performed by placing
the samples between magnets for 15–180 min at 25ºC. The intensity of the magnetic field is 200
mT. Each experiment was conducted in triplicate. The average values were reported. The
experimental diagram is depicted in Fig. 1.

Fig. 1. Graphical representation of adsorption with magnetic field experimental apparatus

2.3 Adsorption isotherm models
To investigate the magnetic field enhanced adsorption mechanism, commercial activated
carbon was used as adsorbent with 200mT magnetic field in biologically treated POME with
different initial concentrations of colour, TSS and COD. The acquired data from adsorption
isotherm experiments were analyzed using the Langmuir equation [31] (Equation (4)) and the
Freundlich equation [32] (Equation (5)) utilizing correlation method.
 

 = (4)




 =   (5)
where Q0 is the maximum amount of sorbate per unit weight of cell to form a complete
monolayer on the surface bound at high Ce (mg/g), and b is a constant representing the affinity of
the binding sites. Q0 stands for a practical limiting adsorption capacity when the surface is fully
covered with sorbate molecules and assists in the comparison of adsorption performance,
particularly in cases where the sorbents do not reach their full saturation. Values of Q0 (mg/g), b
(L/mg), and KF, and 1/n were calculated from the linear plot of Ce/qe vs. Ce, the intercept of
linear regression, and the plot of log qe vs. log Ce, respectively.

2.4 Adsorption kinetic models

The study of adsorption dynamics with magnetic treatment describes the solute uptake
rate and evidently this rate controls the residence time of adsorbate uptake at the solid-solution
interface. The kinetics of colour, TSS and COD adsorption on the activated carbons were
analysed using pseudo first-order [33], pseudo second-order [34], intraparticle diffusion [35, 36]
and Elovich [37, 38] kinetic models, Table 2.

6
Table 2. List of Kinetic models used.

2.5 Error analysis

In the isotherm and kinetic studies, the optimization procedure requires an error function
to be defined in order to be able to evaluate the fit of the model to the experimental data. In this
study, linear coefficients of determination and a nonlinear Chi-square test, as described in the
literature [39], were used.
Coefficient of determination, which represents the percentage of variability in the
dependent variable (the variance about the mean) is employed to analyze the fitting degree of
isotherm and kinetic models with the experimental data. Its value may vary from 0 to 1. The
nonlinear chi-square test is a statistical tool necessary for the best fit of an adsorption system,
obtained by judging the sum squares differences between the experimental and the calculated
data, with each squared difference is divided by its corresponding value (calculated from the
models). The equivalent mathematical statement is:
! , #$ ! .,&'(& )
  = ∑*
+, (10)
! ,&'(&

If data from the model are similar to the experimental data, χ2 will be a small number; if they are
different, χ2 will be a large number. Therefore, it is necessary to also analyze the data set using
the Chi-square test to confirm the best-fit isotherm or kinetic for the sorption system.

2.3 Analytical procedure

Colour, TSS and COD detection were carried out with standard methods. HACH
Spectrophotometer DR2800 was used according to the procedure 8025 Platinum-Cobalt standard
method. Method No. 8006 was used to determine COD concentration of the sample carried in
COD vials (HR 20-1500 mg/L) by APHA potassium dichromate method using HACH
spectrophotometer DR2800 and DRB 200 reactor. TSS was determined in conformity with the
standard method no. 8000 using HACH spectrophotometer DR2800.
The magnetic field intensity was measured by a magnetic field meter (microteslometer)
(CLASS TOUCHSTONE-10). The field homogeneity was measured in different horizontal
sections in the zone of the exposed reactor. In accordance with the readings the experimental set-
up provides a homogeneous field in 25 ml of the reactor volume placed between the poles. The

7
homogeneous field of the reactor volume has a maximum deviation from the average value of
±10.

3. RESULTS AND DISCUSSION

3.1 Adsorption only

To select the optimal adsorption condition without magnetic field, we varied the dosage of
activated carbon from 5 g/100 ml to 25 g/100 ml. It was found that as the dosage of adsorbent
was increased, the percentage of colour, TSS and COD removal also increased, as shown in Fig.
2.

Fig. 2. Effect of contact time on percentage removal of (a) colour, (b) TSS and (c) COD for
different amount of adsorbent dosage for adsorption process only
It could be noticed from the figure that the best results were obtained on 20 g of adsorbent for
colour, TSS and COD. The removal efficiencies, at equilibrium, increased from 28.35, 29.02 and
65.9% to 68.05, 93.71 and 100% by increasing the dosage from 5 to 20 g/100 ml for colour, TSS
and COD respectively. This can be attributed to increased adsorbent surface area and availability
of more adsorption sites with more functional groups resulting from the increase adsorbent
dosage. These findings are agreed with Igew et al. [40], who investigated the use of boiler fly ash
for the reduction of biochemical oxygen demand (BOD), (TSS) and colour from (POME).
However, the amount adsorbed per unit mass of the adsorbent decreased considerably (Fig. 3).
The decrease in unit adsorption with increasing dose of adsorbent is basically due to adsorption
sites remaining unsaturated during the adsorption [41]. Suspended and dissolved particles in
water influence color. The dark brown color of palm oil mill effluent consisted of many organic
compounds such as anthrocyanin and carotene pigment that was extracted from fresh fruit
bunches in the sterilization process. Moreover, it included polyphenol compounds, tannin,
polyalcohol and melanoidin [42]. From the previous facts, it is obvious that colour removal is
strongly dependent on the removal of total suspended solids and other soluble organic
compounds.

8
 Fig. 3. Effect of adsorbent dosage on the quantity adsorbed of Colour, TSS and COD on
activated carbon
The influence of contact time on percentage removal of studied parameters is also shown in Fig.
2. By increasing contact time, the residual adsorbate concentrations have a longer residence time
for adsorption on the activated carbon surface area. Initially there is strong adsorption and then
reaches to equilibrium after around 300 minutes. At equilibrium, the surface of the activated
carbon was covered with adsorbate molecules; therefore a longer mixing time does not increase
the percentage removal from POME.
3.2 Magnetic field
The present study attempts to determine the impact of the magnetic treatment on biologically
treated POME. The effectiveness of the technological systems consisting of different-strength
magnetic fields generated by a lab-scale device of static magnets was applied. The parameters
whose concentration clearly varied were colour, TSS and COD. These parameter’s values were
systematically decreasing in the examined POME, along with the time of the experiment
duration (Fig. 4).

Fig. 4. Effect of different magnetic field intensity and contact time on the percentage removal of
(a) colour, (b) TSS and (c) COD
It is thought that modifications to the properties of solutions exposed to stagnant magnetic field
resulted from changes in the molecular structure of liquids, polarization and arrangement of
particles, and finally from changes of the electric potential [43-45]. Most of the technological
effects of magnetic water can be attributed to a decrease in surface tension of the water and
decreased wetability of the solid phase due to a larger contact angle of the solid/liquid phase
boundary. The practical result of these phenomena is accelerated flocculation and improved
settling of suspended solids [46].
The study found that magnetic treatment reduced colour, TSS and COD effectively, a maximum
degradation of 16.13% of colour when magnetic intensity was 200mT; for TSS, a maximum

9
degradation of 34.34% was obtained, while 44.29% COD removal were achieved for the same
magnetic field intensity.
The reason for the reduction may have been degradation at the contribution of atmospheric
oxygen. A confirmed effect of water and wastewater magnetic preparation is the modification of
the contained gases concentration. Magnetized solutions are characteristic among others of the
diminished surface tension and in contact with the atmosphere adsorb the paramagnetic particles
of oxygen; eventually their concentration in water solutions increases. High concentrations of the
molecular oxygen in the analyzed wastewater may have accelerated the processes of organic
matter degradation, especially since the compounds resistant to degradation were absent in that
case [32, 33].
Another phenomenon which occur under the impact of magnetic field is the intensification of
free radicals formation. For these reasons, this physical factor is thought to be the element
responsible for generating hydroxyl radicals OH• [47]. High reactivity and high oxidation
potential of those chemical compounds may have effectively reduced the concentration of
organic matter contained in the analyzed liquids. The process of water molecule disintegration
with the formation of free radicals takes place when sufficient energy has been provided [43].
The precise mechanism for COD removal by magnetization was still obscures [48]. Based on
theories of energy changes in mass reaction as well as the kinetics of magnetic field [49–52], the
magnetizing mechanism for COD removal may be interpreted as: The organic molecules in
wastewater would absorb the energy when the wastewater exposed to magnetic field. Some
energy enhanced molecules were then induced to an excited state, which was unstable relative to
the ground state; this increased the rate of chemical reactions for the degradation of organic
substances in the magnetizing process [53]. Reference data would suggest that magnetic field
supports reduction of the surface tension and thus enables introduction of numerous oxygen
particles to the wastewater mass. This phenomenon should influence positively the
biodegradation process and limit the concentration of organic substances in the wastewater and
the COD value in the effluent [54].
It is also found that the adsorbed layer is thickened by the magnetic exposure [29]. The efficient
coagulation induced by the magnetic field may also have positively influenced the bonding and
removal of sorbates, also the suspended particles carry a surface charge, and this charge is
affected by the imposed magnetic fields. It has been proven that the physical factor modifies the

10
electro-kinetic potential [45] and influences the coagulation process [55]. 0ne may conclude that
the coagulation process in solutions can be initiated by magnetic waves having the effect on a
liquid without the application of any supporting chemical agents [20]. It has been also evidenced
that it is possible to initiate the coagulation process in water solutions without chemical
substance application, but only with the use of magnetic field forces. Studies of the magnetic
treatment influence on the physico-chemical properties of municipal sewage have revealed that
the settlement time of sewage prepared with magnetic field decreased considerably in
comparison to the settlement time of non-prepared sewage. Additionally, a tendency was
detected to coagulate fine particles of sludge in the magnetically prepared sewage, which
eventually accelerates sedimentation and increases dewatering susceptibility [54].
These results suggest that magnetic effects play an important role in the conformational change
of the water molecules around an ion or on a solid surface.
3.3 Magnetic field followed by adsorption
After the pretreatment of wastewater by magnetization, the removal of colour, TSS and COD in
subsequent adsorption process was performed and the results were shown in Fig. 5. Results
deduced that the primary exposure to magnetic field highly affect the adsorption process through
the high rates of percentage removal of sorbates.

Fig. 5. Effect of magnetic field followed by adsorption on the percentage removal of (a) colour,
(b) TSS and (c) COD for different intervals of time and different magnetic field intensity

It is clear that the percentage removals of all sorbates are higher than that obtained from
adsorption only experiments; moreover equilibrium state had been reached faster. This
consolidates that the main role of magnetization was to improve the physical and chemical
characteristics of the POME so as to enhance the capacities of subsequent adsorption process and
the adsorption behavior of the activated carbon. Jun Oshitani et al. [29] demonstrated that the
magnetic effect remains for at least 3 days but disappears completely at 6 days. It is quite
mysterious that the magnetic effects are memorized in the samples for such a long period after
the magnetic exposure, but the same kind of memory effect is found in all other researches
experiments although the duration time is different [56, 57]. So it is hypothesized that the

11
magnetic exposure forms a quasi-stable structure of water molecules, and the effect remains until
the structure is destroyed by external disturbances [58].
3.4 Combined magnetic field and adsorption
Under magnetic field exposure, the properties of adsorbate and adsorbent would change, e.g.
magnetized water [29], and the surface morphology of the adsorbents may become less
homogeneous under magnetic exposure [59] which would increase the surface area of activated
carbon particles to enhance the adsorption of sorbates. On the other hand, the exposure to the
magnetic field could influence more the activated carbon particles than the sorbate molecules;
because of some components in the activated carbon were magnetic sensitive, which would
enhance the adsorption under magnetic field exposure.
After the treatment of biologically treated POME by combined magnetization and adsorption
process the results were shown in Fig. 6. This Figure presents the effects of magnetic field
intensity and contact time on colour, TSS and COD removal efficiency.

Fig 6. Effect of magnetic field intensity combined with adsorption on percentage removal of (a)
colour, (b) TSS and (c) COD on activated carbon for different contact time
Fig. 6 shows that the percentage removal was first increased by increasing the magnetic field
strength and reached a maximum at 200 mT then decreased with the further increases. At higher
magnetic field strength more free radicals are formed and these free radicals may combine with
each other forming hydrogen peroxide which could consider less reactive compared to the free
radicals and hence the suitable magnetic effect on degradation could not be achieved [20]. In
general the application of such combination of magnetic field and adsorption may greatly affect
the content of organic compounds in POME, and resulted in increasing the capacity of adsorbent.
Fig. 7 represents a condensed comparison between the different types of treatment processes.
Positive integration of adsorption and constant magnetic field are confirmed by the results of the
treatment of biologically treated POME. Adsorption process improved by constant magnetic
field resulted in limitation of the amount of used adsorbent at the same effectiveness of
pollutants’ removal from POME. The process was fast and the impact of constant magnetic field
was shown after shorter time of exposure to POME. The experiment revealed that there is a
possibility of application of lower doses of adsorbent at the same effectiveness of POME
treatment when constant magnetic field was introduced.

12
Fig. 7. Comparison of efficiency for different treatment processes as percentage of removal of (a)
colour, (b) TSS and (c) COD for different contact time
Fig. 7a showed the effect of magnetization followed by adsorption on removal of colour
gradually approached to its maximum (69.78%) and the maximum was obtained at 4 hrs,
whereas the un-magnetized wastewater obtained its maximum at 6 hrs. However, by applying
magnetic field simultaneously with adsorption the colour removal efficiency reaches its
maximum (79.303%) after 3 hrs only. Figure 7b shows that, a better TSS removal was obtained
during adsorption with magnetic field compared with adsorption without magnetic field. At
magnetic field strength of 200 mT and 120 min contact time, the TSS removal is as high as 98.45
% for the combined process, but only 61.33 % for adsorption without magnetic field and 87.66
% for magnetic field followed by adsorption process. As it is depicted in Figure 7c, during
adsorption combined with magnetic fields at field strength of 200 mT and 60 min contact time,
the COD removal efficiency is as high as 98.99 %, but only 67.87 % for adsorption process
without magnetic field, and 89.45% for magnetic field followed by adsorption. This result
indicated that the magnetization process accelerated the removal of colour, TSS and COD in
adsorption process. At the same contact time, the pretreatment of biologically treated POME by
magnetization would enhance the capacity of adsorbent for removal of colour, TSS and COD.
This emphasizes that with the exerting of magnetic field, the adsorption capacity was improved.
Therefore, applying magnetization technology is an important factor for further application of
magnetic field assisted adsorption on POME treatment.
Based on the mentioned above, it could be concluded that the use of magnetization in POME
treatment would be beneficial to the removal of the colour, TSS and COD substances as well as
the cut of the costs in engineering applications.
3.5 Adsorption isotherms
Adsorption isotherms were employed to illustrate how the adsorbate molecules distribute
between the liquid phase and the solid phase and are important for the design of the adsorption
system. In this work, the adsorption equilibrium data were modeled to the Freundlich isotherm
and Langmuir isotherm.
The linear models of Langmuir and Freundlich isotherms for the data obtained from colour, TSS
and COD adsorption on activated carbon for adsorption process only and for magnetic field

13
enhanced adsorption are shown in Fig. 8 a-c. Table 3 indicates the constants of the
aforementioned models for adsorption process without and with magnetic field respectively.
The plots, the R2 and Chi-squres values show that the Langmuir model gave a very good fit to
the sorption process without magnetic field for colour, TSS and COD. The values of the
Langmuir constants are show on Table 3. The fact that the Langmuir isotherm fits the
experimental data well may be due to homogeneous distribution of active sites on the activated
carbon surface; since the Langmuir equation assumes that the adsorbent surface is energetically
homogeneous [31]. A good fit of this equation reflects monolayer adsorption. The value of b
(L/mg) parameter of the Langmuir model is the constant representing the affinity of sorbate to
sorbent. Higher b values mean more affinity of sorbate to sorbent and so the higher the
adsorption rate [20].
From Table 3 according to R2 and Chi-square values, it could be seen that the Freundlich
equation gave a very good fit to the adsorption process combined with magnetic field. With R2
value of 0.9986 for TSS reduction, which is the highest, and Chi-square value of 0.051557 which
is the lowest, it means that the Freundlich isotherm fits the adsorption of TSS more, followed by
COD and then colour. KF the characteristic coefficient of adsorbate-adsorbent pair, a measure of
the adsorption capacity of the adsorbent, given by the influence of the different energies
associated with the heat of adsorption, n is an exponent. The constant (n) represents a measure
for surface sites energetic non-uniformity and the parameter (1/n) quantifies the intensity of
adsorption, in some studies being called “the intensity parameter” [60]. The Freundlich
exponents (1/n) are all less than one showing that significant adsorption takes place. Also, KF
and (1/n) determines the curvature and steepness of the isotherm [61]. Thus, the higher the KF
value, the greater the adsorption intensity. Hence the higher value of KF for TSS adsorption
followed by COD and then colour. Igew et al. [40], found that Freundlich isotherm gave a better
fit followed by Langmuir for the adsorption of BOD, TSS and colour from POME on boiler fly
ash.
The Freundlich isotherm does not exhibit a maximum number of adsorption sites. It fits well data
without physical meaning because Eq. (5) teaches that the adsorbed amount grows without
restriction as the bulk concentration C increases. However, despite this formal drawback, this
power-law relationship allows the surface heterogeneities to be taken into account, in away more

14
general than the Langmuir isotherm. Thus, the equation applies very well to solids with
heterogeneous surface properties and generally for heterogeneous solid surfaces [62].
Magnetic field may affect activated carbon by enhancing the high-adsorption of sorbent capacity
for reactivity towards a wide range of organic pollutants. This reactivity arises from the
complexity of its chemical surface groups compared to those of other surfaces.
Table 3. Constants for Langmuir and Freundlich isotherm for adsorption of colour, TSS and
COD on activated carbon without and with magnetic field

Fig. 8. Comparison between Langmuir and Freundlich model and experimental results for (a)
colour, (b) TSS and (c) COD

That difference in the adsorption caused by the use of magnetic fields can likely be explained by
the improvement in the orientation of the molecules of the adsorbate towards the activated
carbon pores, facilitating the adsorptive process, and resulting in a gain in the adsorption time
[63].

3.6 Adsorption Kinetics

In order to describe the adsorption kinetics for colour, TSS and COD on activated carbon,
pseudo first-order, pseudo second-order, intraparticle diffusion and Elovich model were applied
to the experimental data. The results of kinetic parameters are shown in Table 4 for adsorption
only process and for combined magnetic field and adsorption process. The conformity between
experimental data and the model predicted values was expressed by the correlation coefficients
R2 (R2 values close or equal to 1) and nonlinear Chi-square test. A relatively high R2 and low
Chi-square values indicate that the model successfully describe the adsorption kinetics. The R2
value of pseudo second–order is higher compared to R2 values of other kinetic models tested.
Moreover, the pseudo second order model exhibited very low χ2 values compared to other kinetic
models. Therefore, drawing conclusion from the non-linear Chi-square analysis, the pseudo
second order model was best fitting the kinetics.

Table 4. Parameters of the kinetic models for the adsorption of colour, TSS and COD on
activated carbon without and with magnetic field.

15
The values for the equilibrium adsorption capacity as predicted by the pseudo-second-order
model coincided well with the experimental uptake values. (Fig. 9). These findings revealed that
the pseudo second-order kinetic model provided a good correlation for the adsorption of colour,
TSS and COD onto activated carbon compared to other kinetic model used. This suggests that
the rate controlling step of adsorption was largely attributable to chemical sorption. The
applicability of the pseudo-second order model means the rat of adsorption was subject to a
second order rate law, with respect to the availability of adsorption sites on the surface of
adsorbent rather than adsorbate concentration in bulk solution [64]. The pseudo-second-order
rate constant, K2, for COD was higher than for TSS and colour, demonstrating that the
adsorption rate of COD was higher than that of TSS and colour. Compared to same process
without magnetic field, the adsorption rates with the enhancement of magnetic field were fast.
Hence, a practical advantage of using magnetic field enhance adsorption would be in its ability to
remove more colour, TSS and COD from biologically treated POME in a much shorter
adsorption time.

Fig. 9. Comparison of different kinetic models with experimental data for the adsorption of (a)
colour, (b) TSS, and (c) COD on activated carbon combined with magnetic field

Although the Elovich equation does not provide any mechanistic evidence, it has proved suitable
for highly heterogeneous systems [65] of which the adsorption of colour, TSS and COD on to
activated carbon is undoubtedly such a case.
Though the pseudo first order model and the pseudo second order model are widely applied to
study kinetic adsorption it is known that they are not suitable to explain the diffusion mechanism
occurring in the adsorption process, which is generally the rate determining step [64]. Thus the
intraparticle diffusion model was introduced to give the explicit information about the diffusion
mechanism. According to this model, the plot of uptake, qt, versus the square root of time, t1/2,
should be linear if the intraparticle diffusion is involved in the adsorption, and if these lines pass
through the origin, then intraparticle diffusion is the rate controlling step, otherwise this indicates
that two or more steps occurred in the adsorption process [66]. The plots (shown in Fig. 10)
presented multilinearity, indicating that three steps took place. As can be seen in Fig. 10, the first
sharper step was not observed and completed before 15 min, which may be considered as the
external surface adsorption. The second step described the gradual adsorption from 10 to 65 min,

16
where intraparticle diffusion was rate-controlling. The third step was attributed to the final
equilibrium stage, in which intraparticle diffusion started to slow down due to the decrease of
solute concentration in solution. The R2 values of the intraparticle diffusion model were lower
than that of the pseudo-second-order kinetic model, but this model indicated that the adsorption
of colour, TSS and COD onto activated carbon may be followed by an intraparticle diffusion
model up to 65 min. This implied that although intraparticle diffusion was involved in the
adsorption process, it was not the only rate-controlling step [67].

Fig. 10. Intra-particle diffusion plots for the removal (a) colour, (b) TSS and (c) COD onto
activated carbon

It was previously reported [62] that magnetic treatment could reduce the viscosity and surface
tension of solutions, an effect possibly concerned with resonance. When the magnetic field and
the oscillation frequency of the molecules were in tune, resonance could occur. This resonance
would then impart energy to the system for activation, changing the structure and nature of the
material in the magnetic field. Magnetic treatment could thus promote the adsorption of metal
ions. However, the mechanism of magnetic treatment remains to be clarified in an in-depth
study.
CONCLUSION
Based on the results presented above, the following conclusions can be drawn for the combined
magnetic field and adsorption process for treatment of biologically treated POME:
• From the adsorption only experiments it was found that the removal efficiencies increased
from 28.35, 29.02 and 65.9% to 68.05, 93.71 and 100% by increasing the dosage from 5 to 20
g/100 ml for colour, TSS and COD respectively. The best results were obtained on 20 g of
adsorbent and equilibrium was reached at 5 hrs.

• The results of this study concluded that, the combined magnetic field and adsorption process
has a vital role in treating biologically treated POME; the magnetic flux density increases the
removal efficiency of colour, TSS and COD. The percentage of colour removal was 79.303
compared to 57.111 without magnetic effect, so as TSS was 98.455 compared to 61.11, and
COD was 98.99 compared to 67.87, without magnetic field at the same contact time. This is

17
 one of the interesting findings in this field of research. This encourages more research in this
field.
• The adsorption ability, including adsorption amount and adsorption rate, could be enhanced
with a suitable magnetic field. For example, upon treatment with field strength of 200mT, the
adsorption equilibrium period for colour, TSS and COD on activated carbon shortened from
300 min to 120 min. In the future, the mechanism of magnetic treatment on ad- sorption will
have to be studied deeply.

ACKNOWLEDGEMENT

This work has been carried out during sabbatical leave granted to the author (Rafie R.
Mohammed) from Mosul Technical Institute, so the author thanks Ministry of Higher Education
/ Iraq and Foundation of Technical Education / Iraq, for their great support. We would like to
express the deepest appreciation to Mr. Shridharan Parthasarathy for his great support throughout
this work. This research has been supported by the University of Nottingham / Malaysia Campus
and Hong Kong University of Science & Technology as a research scholar fellowship.

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24
Figures

Fig. 1. Graphical representation of adsorption with magnetic field experimental apparatus

25
(a)

(b)

26
 (c)
Fig. 2. Effect of contact time on percentage removal of (a) colour, (b) TSS and (c) COD for
different amount of adsorbent dosage for adsorption process only

Fig. 3. Effect of adsorbent dosage on the quantity adsorbed of Colour, TSS and COD on
activated carbon

27
(a)

(b)

(c)

28
Fig. 4. Effect of different magnetic field intensity and contact time on the percentage removal of
(a) colour, (b) TSS and (c) COD

29
(a)

(b)

(c)

30
Fig. 5. Effect of magnetic field followed by adsorption on the percentage removal of (a) colour,
(b) TSS and (c) COD for different intervals of time and different magnetic field intensity

31
(a)

(b)

(c)
32
Fig 6. Effect of magnetic field intensity combined with adsorption on percentage removal of (a)
colour, (b) TSS and (c) COD on activated carbon for different contact time

33
(a)

(b)

(c)

34
Fig. 7. Comparison of efficiency for different treatment processes as percentage of removal of (a)
colour, (b) TSS and (c) COD for different contact time

35
(a)

(b)

(c)

36
Fig. 8. Comparison between Langmuir and Freundlich model and experimental results for (a)
colour, (b) TSS and (c) COD

37
(a)

(b)

(c)

38
Fig. 9. Comparison of different kinetic models with experimental data for the adsorption of (a)
colour, (b) TSS, and (c) COD on activated carbon combined with magnetic field

39
(a)

(b)

(c)

40
 Fig. 10. Intra-particle diffusion plots for the removal (a) colour, (b) TSS and (c) COD onto
activated carbon

Tables

Table 1. Properties of biologically treated POME and the regulatory discharge limits

Property Values Standard discharge limits [28] Units

pH 8.4 5-9
Colour 9900 --- PtCo/l
TSS 1800 400 mg/l
COD 4700 mg/l
BOD5 1350 100 mg/l

41
Table 2. List of Kinetic models used.

Model Name Model Equation Parameters

qe = the amount of solute
adsorbed (mg/g) at equilibrium
qt = the amount solute
Pseudo first order -.
 −
 = -.
 −  0 (6)
adsorbed at time t (mg/g)
k1 = the rate constant of the
adsorption process (min-1)
  
K2 = the rate constant of
Pseudo second
1 2= + 0 (7) pseudo second-order
order ! 3) ! ) !
adsorption (g· mg-1· min-1)
Intraparticle  Kp = Intraparticle diffusion rate
Diffusion
 = 5 0  (8) constant (mg.g-1.min-1/2)
α and βare model constants
Elovich
 = 6 + 7 -.0 (9)
(mg.g-1)

42
 Table 3. Constants for Langmuir and Freundlich isotherm for adsorption of colour, TSS and
COD on activated carbon without and with magnetic field
Langmuir Model Freundlich Model
Q0 b KF
R2 χ2 1/n R2 χ2
(mg/g) (L/mg) (mg/g)(L/mg)1/n
Without Colour 58.824 207.9×10-6 0.9938 0.091861 0.1869 0.5939 0.9811 0.426981
magnetic TSS 34.247 2.333×10-3 0.9913 0.217377 0.4219 0.5942 0.982 1.068192
field COD 63.694 285.2×10-6 0.993 0.050708 0.0654 0.7652 0.9869 1.134951
With Colour 87.719 156.5×10-6 0.9874 0.14199 0.1558 0.6643 0.9953 0.109748
magnetic TSS 42.735 2.573×10-3 0.9689 1.511188 0.9817 0.5001 0.9986 0.051557
field COD 76.923 427.3×10-6 0.9209 2.419764 0.3099 0.6135 0.9982 0.235606

43
 Table 4. Parameters of the kinetic models for the adsorption of colour, TSS and COD on
activated carbon without and with magnetic field.
Adsorption without magnetic field Adsorption with magnetic field
Colour TSS COD Colour TSS COD
K1 8.09×10-3 6×10-3 1.62×10-3 8.4×10-3 7.4×10-3 8.7×10-3
Pseudo first order model R2 0.9893 0.9931 0.9684 0.8819 0.8989 0.7751
χ2 0.4856 0.140671 2.370373 12.71623 0.028598 0.027146
K2 1.918×10-4 6.944×10-4 4.713×10-4 3.016×10-4 3.19×10-2 3.203×10-2
Pseudo second order
R2 0.993 0.9847 0.9701 0.9716 1 1
model
χ2 0.1765 0.028463 1.072847 0.839952 0.003224 0.001593
Kp 2.1022 0.4901 1.7207 3.2466 0.1336 0.1747
Intraparticle Diffusion
R2 0.9546 0.9719 0.8387 0.9112 0.8605 0.7879
model
χ2 1.9326 0.266308 5.495229 2.220499 0.024304 0.02207
α -27.128 6.6302 -16.368 -24.765 6.2663 19.977
β 10.747 2.5673 7. 602 12.814 0.5436 0.7256
Elovich model
R2 0.994 0.9968 0.9407 0.9615 0.95 0.9061
χ2 0.1978 0.054931 1.919106 1.011935 0.009204 0.009702

44
Highlights
• A novel method was introduced by integrating magnetic field exposure with adsorption
technique.
• Combined magnetic field and adsorption process has a vital role in treating POME.
• Adsorption performance and adsorption rate could be enhanced by magnetic field.
• Magnetization process accelerated the removal of colour, TSS and COD in adsorption
process.
• The new method increased the percentage removal of Colour, TSS and COD by 39, 61
and 46% respectively.

45