Journal of Water Process Engineering 35 (2020) 101187

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Journal of Water Process Engineering

journal homepage: www.elsevier.com/locate/jwpe

Utilization of alum sludge as adsorbent for phosphorus removal in municipal T

wastewater: A review
Norah Muisaa,*, Innocent Nhapib, Walter Ruziwac, Mercy M. Manyuchid
a
Department of Environmental Science and Technology, Chinhoyi University of Technology, Zimbabwe
b
Department of Environmental Engineering, Chinhoyi University of Technology, Zimbabwe
c
Department of Fuels and Energy, Chinhoyi University of Technology, Zimbabwe
d
Department of Quality and Operations, University of Johannesburg, South Africa

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

Keywords: Aluminium sulphate is the commonest and most widely used coagulant for water treatment worldwide.
Adsorbent Aluminium is a well-known adsorbent for phosphorous (P), a nutrient highly associated with eutrophication in
Alum sludge most water bodies. Thus, this paper provides a review on P adsorption from aqueous media using alum sludge
Phosphorous removal waste material generated by water treatment plants that use aluminium sulphate as sole coagulant. A meta-
Wastewater treatment
analysis of data on characteristics of various alum sludges was done. The hindrance factors and adsorption
Eutrophication
capacities, under varying operating conditions are presented, including future direction. It is evident from lit-
erature survey that there is the emerging shift from reuse and recycling of raw alum sludge towards synthesis of
value-added alum sludge based adsorbents. Possibilities to improve efficacy as both filter media and adsorbent
but at the same time reducing metal leaching are highlighted. Value-added products may also offer an added
advantage of acting as source of phosphorous for possible reuse in agricultural soils.

1. Introduction
Phosphorous is regarded as the key element causing eutrophication
in freshwater bodies [1–3]. The major sources of phosphorus in surface
waterbodies are municipal wastewater, industrial discharges and
manure from livestock production as well as runoff from agricultural
lands [2,4,5]. Eutrophication is characterized by algal blooms and nu-
merous other problems for example; clogging of water treatment pro-
cess filters; bad odour and taste to drinking water; animal and human
health issues, ecological and economic challenges [2,3]. Effective con-
trol of phosphorous additions to waters is thus a fundamental step to-
wards controlling eutrophication and its effects on the environment,
economy and people.
Biological, chemical and physical methods are currently being used
to reduce or remove phosphorous from wastewater prior to discharges
from municipal wastewater treatment plants [6,7]. Biological methods
such as the enhanced biological phosphorous removal (EBPR) have
wide usage and can achieve almost 100 % P removal, albeit incon-
sistently [8]. Biological methods are also less effective at low influent P
concentrations as the metabolism of responsible microorganisms be-
comes starved. Biological treatment operations require strict control to
ensure optimum aeration and tend to be land and energy-intensive [8].
Chemical treatment is also widely used and includes the use of metal
salts such as iron (Fe), calcium (Ca) and aluminium to act as coagulants
that precipitate the phosphorous. Major drawbacks with chemical
treatment methods include possible secondary pollution, excessive
amounts of resultant sludge, the need to neutralize pH and high oper-
ating costs due to variable dosing [9]. Physical methods that can be
employed include reverse osmosis, membrane bioreactors, and elec-
trodialysis but these are either too expensive or inefficient [5]. Mem-
brane bioreactors have smaller ecological footprint and are able to
achieve low P discharge limits [10]. Nevertheless, membrane fouling is
a critical challenge which reduces the lifespan of the filters and increase
energy requirements for sludge recirculation; making the whole process
inefficient. Physical adsorption is also another method. Findings from a
review by Huang et al. [11] indicate that several authors agree that
physical methods are more effective than the former. This is because of
inherent low costs, high adsorption capacity or removal efficiency, fast
adsorption rates especially at low P levels, renewability, ease of op-
eration and no secondary pollution [11]. Accordingly, P adsorption has
been tried for P recovery and reuse as will be shown in this paper.
However, adsorption of P can be hampered by the effect of solution pH
as well as the characteristics of the adsorbent, among other challenges
to be highlighted in the following sections. Therefore, it is important to

⁎
Corresponding author.
E-mail address: norahmuisa@gmail.com (N. Muisa).

https://doi.org/10.1016/j.jwpe.2020.101187
Received 8 October 2019; Received in revised form 19 January 2020; Accepted 12 February 2020
2214-7144/ © 2020 Elsevier Ltd. All rights reserved.
N. Muisa, et al.
find optimal and suitable adsorbents that can remove phosphorous from
wastewater effectively and efficiently, cost-effectively and in an en-
vironmentally-friendly manner.
Aluminium (Al) as an element is well-known to possess a strong
affinity for phosphorous [12,13]. Most water treatment plants in the
world use aluminium sulphate, or just alum (Al2 (SO4)3.14H2O), for
water clarification. This is because alum is the cheapest and simplest
aluminium-based flocculent available [14]. Alum sludges are the in-
evitable resultant waste product generated from the water treatment
processes that use alum as sole coagulant [15]. It follows then that alum
sludges are the most widely generated and locally-available water
treatment waste around the world at low or no cost at all but are
normally thrown away [16–18]. It is now widely acknowledged that
aluminium in alum sludge can be beneficially reused to remove phos-
phorous from wastewater [16,17,19,20]. As a result, alum sludges
present a big source of aluminium, in the form of aluminium hydroxide,
Al (OH)3, [18,21,22]. The reuse of alum sludge is in line with the
current research focus in the world on finding low-cost alternative
adsorbents for pollutant removal in the environment [9,13,18,20,23].
Historically, alum sludges were perceived to be inert waste material
with little value for reuse [24]. As a result, alum sludges have tradi-
tionally been discharged into aquatic systems [25,26]. Later, the wastes
were deemed toxic to aquatic life owing to the inherent high amounts of
aluminium and so, lately they have been landfilled or incinerated after
drying [16,17]. Where they are landfilled, the related costs are thus
factored into the tap water costs and, ultimately, borne by the con-
sumers such that tap water costs become exorbitant [27]. Landfilling is
also constrained by land use, public concerns and more stringent en-
vironmental regulations [28]. Incineration is also expensive, produces
greenhouse gases and other toxic compounds like dioxins and furans.
Ash tends to be laden with heavy metals, while its disposal entails extra
costs and generally, incineration is poorly acceptable to the public and
only works efficiently for sludges with low moisture content [28].
Measures to deal with alum sludges have been evolving over the
years. In a review by Babatunde and Zhao [29], three broad categories
of the past and present uses of drinking water treatment sludges were
identified as their use in wastewater treatment processes, use as
building and construction materials and for land application. Reviews
have been done for each of these three possible applications but gen-
eralizing on the type of water treatment sludge. The reviews have been
on all kinds of drinking water treatment sludges, including those from
water treatment plants that use Fe or Ca or other forms of coagulants
other than aluminium sulphate [19,30,31]. The review by Ippolito et al.
[30] looked at phosphate adsorption by various adsorbents that also
included alum sludge albeit no specification as to the source of Al
coagulant. Dassanayake et al. [19] focused on the use of alum sludges
for agriculture not for wastewater treatment. This present review is
focusing specifically on 1) alum sludge but with special emphasis on its
capacity as adsorbent for phosphorous removal from aqueous systems
such as water and wastewater; and 2) on aluminium sulphate coagulant
-based alum sludges only. The other Al salts, for example poly-
aluminium chloride (PAC) are not as common as aluminium sulphate. It
is important to note that the term alum sludge is also loosely used to
denote waste from water treatment plants that use Al salts other than
alum [16,17,32]. This review paper uses the term alum sludge referring
to aluminium sulphate-based drinking water treatment wastes.
In terms of applications, this present review is focused only on the
use of aluminium sulphate coagulant-based alum sludge in aqueous
wastewater systems. Previous reviews on alum sludges have been
looking at applications as adsorbent for phosphorous contained in soil,
surface runoff, and biosolids applied on land for agricultural reasons
[19,30]. The review by Haynes [31] looked at the use of various in-
dustrial wastes, water treatment sludges included, as media and filter
bed in constructed wetlands to remove phosphorous and metals. Ba-
batunde et al. [33] and Yang et al. [18] reviewed the use of dewatered
alum sludge in constructed wetlands as substrate and filter and how
2
Journal of Water Process Engineering 35 (2020) 101187
these kinds of emerging constructed wetlands can be a sustainable
move for wastewater treatment. Babatunde et al. [33] was focusing on
Ireland alone such that the findings do not reflect a global perspective
while Yang et al. [18] also looked at other kinds of substrates besides
alum sludge. This current review thus focuses on the control of phos-
phorous (P) emissions in various aqueous wastewater systems using
alum sludge from water treatment plants that use aluminium sulphate
as sole coagulant.
2. Materials and methods
The review was conducted by way of literature search from scho-
larly databases mainly Google scholar® and ScienceDirect in August
2017, finalized and consolidated in August 2018. The study was fo-
cusing on alum sludges from water treatment processes that use alu-
minium sulphate and not some other kinds of Al-based coagulants such
as PAC. The terms alum sludge, drinking water treatment residual, alum
residuals/residues were used repeatedly in combination (using Boolean
“AND” “OR”) with a variety of search terms that included: phosphorous
adsorption; phosphate adsorption; phosphate/phosphorous adsorption
mechanism; morphology; phosphate/phosphorous adsorption char-
acteristics; phosphate/phosphorous desorption; regeneration/recovery;
kinetics, thermodynamics, factors affecting AND phosphate/phos-
phorous adsorption; applications/uses AND wastewater treatment. The
Boolean operator “AND” was also used to search for other issues: eu-
trophication repeated using different terms (nutrients; phosphorous
“OR” phosphates) activation of alum sludge OR residual; calcination of
alum sludge OR residual; composite materials AND synthesis AND
phosphate/phosphorous adsorption. Eutrophication is an old and
widely researched problem from years back, hence there was no re-
striction to the year of publication especially looking at factors con-
tributing towards its occurrence. There was no restriction to the year of
publication or geographic location of studies done on reuse of alum
sludges to ensure that different kinds of this waste product are eval-
uated. The only critical selection criteria for papers to incorporate were
those researches on P adsorption in aqueous solutions using alum
sludges generated from water treatment plants that use aluminium
sulphate as coagulant. About 22 papers specifically on alum sludge as
an adsorbent for P in aqueous solutions were accessed. However, re-
searches looking at aluminium hydroxides were also used to allow for
comparison as well as those from other kinds of adsorbents or materials
such as ferric sludges, activated carbons, among others. Papers that also
incorporated alum sludge for adsorbing phosphates but in different
media for example soil, were also used for comparison or inference. Up
to 195 papers were accessed using the above search terms but around
135 papers were actually used in the development of this review paper.
3. Characteristics of alum sludges
3.1. Physical structure
Although sludge quality varies from plant to plant, the basic con-
stituents are the same [24,34]. Table 1 gives the general characteristics
of alum sludges from various water treatment plants from around the
world. The wide standard deviations indicate the variations in alum
sludges of alum sludges generated by individual water treatment plants.
Thus, it would be misleading and difficult to conclude or give typical
umbrella figures for such parameters without specifying the water
treatment plant being referred to. In the same vein, the removal effi-
ciencies of different water treatment plant sludges for various pollu-
tants found in the environment will differ. It will be equally difficult to
recommend universal beneficial reuse applications for water treatment
sludges before evaluation of the characteristics and phosphorous ad-
sorption capacity for a specific sludge.
Alum sludges are bulky and gelatinous, particularly before dewa-
tering [35]. Dewatered alum sludge has an amorphous structure and
N. Muisa, et al.
Table 1
Some biophysico-chemical characteristics of water treatment alum sludges.
Parameter Units
TOC g/kg
Surface area g/m2
Total P g/kg
Oxalate P g/kg
Ca g/kg
Total Al g/kg
Oxalate Al g/kg
Total Fe g/kg
Oxalate Fe g/kg
SiO42− g/kg
Cl− g/kg
SO42− g/kg
Fig. 1. The box and whisker plot includes the median, the first and third
quartiles and range of total Al mean given in Table 1, excluding the two out-
liers, displayed with the scatter plot of the raw data.
rough surface according to observations using powder X- Ray Diffrac-
tion (PXRD) and scanning electron microscopy techniques
[21,25,36–41]. Oxalate aluminium is a characteristic that represents
amorphous-structured aluminium hydroxide which is strongly related
with phosphorous immobilization [35,42]. The average oxalate-alu-
minium and total-aluminium values calculated by this research from
the three studies that determined oxalate-Al, in addition to total-Al,
were almost the same- total Al-102.8 ± 13.3 vs. oxalate Al- 95.7 ± 4.9-
[38,39,43]. This further confirmed that alum sludges are pre-
dominantly amorphous. This probably explains why most researchers
thereafter have focused on just total Al instead of adding the oxalate
form since results from the three studies done in 2007 have turned out
to be almost the same.
Other studies confirm that the amorphous nature of alum sludges is
a result of the inherent non-crystalline aluminium hydroxide which
gives the alum sludge an increased specific surface area and the sub-
sequent increased chemical affinity for phosphorous [12,46]. Using the
standard nitrogen Brunauer Emmett Teller (BET) surface area, the
average of the surface area results in literature gave an average specific
surface area of 121.8 ± 95.3 m2/g for alum sludge (Table 1). A surface
area less than 10 m2/g indicates a non-porous structure [23]. The
specific surface area of alum sludge is directly related to the number of
hydroxide sites available for adsorption [53]. This implies that in order
to increase efficacy of alum sludges as an adsorbent, it is important to
boost its hydroxide sites as one measure to improve specific surface
area. High specific surface area is a prerequisite for a good adsorbent
[54–57]. Haynes [31] explained that size, shape and porosity of parti-
cles determine surface area and the larger the surface area the greater
the surface for adsorption to take place [31].
Most alum sludges have been found to be dominated by fine parti-
cles [18,27,47]. Fine particle sizes are good as they render a greater
surface area for adsorption but they also present the challenge of pos-
sible clogging in practice when used as a filter media given that
Journal of Water Process Engineering 35 (2020) 101187
Mean ± SD Ref.
120,0 ± 33,8 [25,35,39,43,44,45,46,47]
134,1 ± 131,5 [20,23]
1,8 ± 1,1 [27,39,41,43,48,49,50]
2,4 ± 0,6 [39,43,49]
23,8 ± 64,2 [20,23,48,27,35,40,41,43,44,45,46]
161,2 ± 120,2 [20,22,46,48,49,50,51,23,27,39,40,41,43,44,45]
86,1 ± 12,8 [39,43,44,52]
6,5 ± 5,7 [27,35,50,39,40,41,43,44,45,46,48]
6,2 ± 2,3 [27,29,39,43]
10,3 ± 9,4 [27,41,44,45,46]
16,1 ± 0,2 [27,44,46]
8,8 ± 0,8 [27,44,46]
wastewater will contain a myriad of solids. Research would be neces-
sary to develop alum sludge-based materials that balance between sizes
of particles for adsorption and improved hydraulic conductivity that
aids in the passage of water and other materials without risk of clog-
ging. Although alum sludges are comparable to conventional com-
mercial adsorbents such as activated alumina and activated carbon in
terms of dominant particle and pore size, surface area greater than 10
m2/g and amorphous morphology, measured average specific surface
area is considerably low (121.1 ± 98.3 m2/g) than that of either of the
commercial adsorbents. Activated alumina has a surface area ranging
200−300 g/m2 while activated carbons’ can range from 600−2000 g/
m2 [54,58,59].
3.2. Chemical properties
Elemental analysis is widely done using Inductively Coupled
Plasma-Atomic/Optical Emission Spectrometer (ICP-AES/OES), X-Ray
Energy Dispersive Spectroscopy (EDS) [1,34,60–62]. Total aluminium
in alum sludge accounts for about 16 % of the proportion of chemical
composition, widely distributed across studies and averaging
161.2 ± 120.2 g/kg (Table 1; Fig. 1). Other elements inherent in alum
sludge that influence its adsorption of phosphorous include; Ca, SiO42−,
Fe, Cl-, SO42− and humic acids measured as total organic carbon, TOC
and also exhibit wide variations. These organic and inorganic elements
are those removed from the raw water as well as contained in the
coagulants.
Despite the dominance of Al in alum sludges, a study by Gibbons
and Gagnon [50] revealed that in comparison to other residuals such as
lime- or ferric-based, alum residuals contained the least concentration
of the primary element on a molar basis. This finding implied that alum
residuals may not be the best and efficient residual for use as adsorbent
for phosphorous on a commercial basis. However, it should be em-
phasized again that aluminium sulphate, being the most widely used
coagulant in the world for water treatment, gives rise to alum residuals
which inevitably become the commonest waste product available
compared to these other residuals. The research focus is now moving
towards the synthesis of value-added products with superior qualities
compared to the parent raw materials [28,60,62].
4. Characteristics of phosphorous adsorption by alum sludges
4.1. Adsorption capacity of alum sludges for phosphorous
Results in Table 2 show that adsorption capacity for phosphorous is
noticeably different and wide-ranging (2–43 mg P/g alum sludge) from
one treatment plant to another or from one experiment to another.
Other previous reviews also noted this pattern [19,30]. Most re-
searchers agree that adsorption capacity and removal efficiency of
phosphorous by drinking water treatment residuals depends on the
chemical and physical characteristics of the adsorbents used as well as
3
 Table 2
Maximum P adsorption capacities of alum sludges tested under different experimental procedures and conditions.
Max. P adsorption capacity (mg pH Initial [P] (mg/ Sludge particle Type of Test conditions Remarks Ref.
N. Muisa, et al.

PO/g alum sludge) L) size (mm) experiment

25 4 30 <2 Batch 3 g air-dried alum sludge; synthetic P The major part of reactive Al and adsorbent was in amorphous [25]
Reduction from 30 mg P/l to Flow through phase, adsorption reduced at pH < 4 or > 8; orthophosphate
< 1 mg P/l ∼90 % removal Column adsorbed the most.
130 g alum sludge, Flow rate of synthetic P of 3 ml ortho- pH 3 most favourable; Al dissolution detected;
P/min at 250 pore volume at pH 4 or 200 pore volumes at
pH of 5; residence time of influent was 32 min
12.5 300 0.3-1.0 Batch Air dried alum sludge (0.1-0.3 mm size); 20 g sludge (dry P bound to alum sludge will not readily desorb; P is associated with [36]
weight basis), synthetic P used the Al fraction of alum sludge not Ca
10.2 4 14.7 ortho-P < 2.36 Batch Alum sludge (< 2.36 mm size), synthetic P used Ortho-P was the most adsorbed P species [63]
> 80 % removal efficiency (∼40 6.8- 50.8 < 2.36 Continuous flow 500 g alum sludge to a height of about 80 cm (90 cm Hydraulic rate of 2.96 m3/m2/d and ortho-P loading of 210.6 g/m2/
mg ortho-P/g) in 30 days 7.2 column long*7.4 cm columns), Hydraulic loading of 2.79 m3/m2/ d; dewatered alum sludge bed used as filter medium remained stable
d, P loading of 210.5 g/m2/d for over 60 days. and did not reach saturation for 60 d
4.5 4 5.4 1.18 Batch 1.18 mm size alum sludge, synthetic P, 48 hr shaking Condensed phosphate used; a significant amount of P can be [47]
adsorbed but up to a certain saturation point
90 % removal or 2.66 mg P /g Not specified Continuous flow 1 kg alum sludge to a height of 50 cm (1 m long*7.4 cm 90 % removal at condensed phosphate-P loading rate of 3.9 g/ m2/d
Column columns), hydraulic loading of 2.32 m3/m2/d and P and about 70% removal at loading rate of 16.5 g/ m2/d; Hydraulic
loading of 3.9 g/m2/d rate of 2.32 m3/m2/d and initial residence time of 3 hr; Al leaching
remained below 0.1 mg Al3+/l; alum sludge bed remained fairly
stable although porosity decreased after 40 days of experiment.
31.9 4 0-360 <2 Batch 1.0 g alum sludge, synthetic P solution, 48 hr shaking P removal increased only up to 10 g alum sludge dosage thus higher [27]
adsorbent dosage per mass of adsorbate only results in inefficient
adsorption.
22.4* (Ballymore-Eustace sludge) 4.3 100 < 0.063 Batch Alum sludge, synthetic P solution, agitation at 200 rpm There is need to evaluate the adsorption capacity of individual alum [79]

4
& 20.1 (Leixlip sludge) for 48 hr sludge before decision on large scale application can be made as the
P adsorption capacity of any particular alum sludge will be
influenced by the raw water source; P adsorption possibly reduced
by inherent P and Ca content of alum sludge.

Max. P adsorption capacity pH Initial [P] Sludge particle size Type of Test conditions Remarks Ref.
(mg P/g alum sludge) (mg/L) (mm) experiment

1.11 (synthetic P) and 1.59 6.04 & 6.0, 1.50 & 1.75, 0.3-1.18 Batch Oven-dried alum sludge (24 hr), synthetic P The alum sludge adsorbed less P per mass of Al compared to ferric or lime [50]
(wastewater) resp. resp. and wastewater used sludges hence a weaker adsorbent for P than the other two adsorbents
Up to 85 % 10 2.36 Fixed bed Higher initial phosphate concentration reduces the time to saturation, i.e.,
Column the breakpoint; fine particle sizes and higher bed depth increases P removal
efficiency; residence time more important than flow rate to improve
efficiency of P removal in columns
1.13 4 10 < 2.36 Batch Synthetic P, oven-dried alum sludge (24 hr at none [21]
105 °C)
15.57 4 150 < 1.18 Batch Alum sludge dried at 50 °C for 5 days, P adsorption rate decreased with increase in particle size of alum sludge; [22]
synthetic P solution higher temperatures (40 °C) speeded up adsorption process by 21 % than
lower temperature (30 °C); adsorption rate was also high (0.174 mg P/g/
min)
29 6.8 1-1.8 Not specified Batch Secondary wastewater, alum sludge used, 50 Recycling already-used alum sludge adsorbent reduced alum dose used in [80]
rpm chemical P removal process with age of the sludge having no effect
32.27-42.67 6 50 0.15-0.6 Batch Synthetic P solution and secondary The alum sludge could remove P from secondary effluent wastewater [61]
wastewater used, oven-dried alum sludge
(24−48 hr at 105 °C)
4.86 (sludge A) 4 55 1.65 and 1.98 Batch Alum sludge air-dried then oven-dried (103 Both sludges achieved higher removal efficiencies (> 95 %) for [20]
5.5 ± 2 °C), synthetic P solution orthophosphates than condensed phosphates; metal leaching risks minimal
1.58 (sludge B)
2.06 -6.06 Not specified 100 Not specified Batch Alum sludge, synthetic P solution [65]
(continued on next page)
Journal of Water Process Engineering 35 (2020) 101187
N. Muisa, et al. Journal of Water Process Engineering 35 (2020) 101187

external conditions of the experiments [40,63–65]. This is also typical

Ref.
of adsorption reactions in general [66] and also explains the differences
depicted in Table 2. External conditions for actual sludges include the

capacity followed the order of inherent Al content in the sludges; inherent P

quality of the sludges produced which depend on the raw water quality
and properties of the coagulant and coagulant aid used. Physical and
Different sludges produced different adsorption capacities; adsorption

chemical characteristics of the sorbent itself include its particle size,

surface functional groups, specific surface area, metal content and
possibly decreased P adsorption capacity of the alum sludges

stability. External or environmental conditions are those that surround

the adsorption components and these comprise the solution pH, tem-
perature, presence of competitors, dosage of sorbent, and initial phos-
phorous solution concentration. These factors have been shown to af-
fect the phosphorous adsorption capacity or removal efficiency in the
studies given in Table 2 and others not given.
Phosphate adsorption capacities that have been recorded in litera-
ture include; 14.49 mg/g by iron hydroxide eggshell [67], 8.21 mg/g
for iron oxide tailings [68], 6.42 mg/g by goethite [69], and 2.15 mg/g
by natural zeolite [70]. In comparison to other low cost adsorbent
materials, oven-dried alum sludges adsorbed about 98 % of initial 2.5
mg/l synthetic phosphates which was highest comparing to other tested
adsorbents such as cement kiln dust, bone char, blast furnace slag or
limestone [71]. Orthophosphate adsorption by alum sludge in the same
Remarks

study was better than that of a reference coal-based granular activated

carbon (GAC) of 1.25 mm particle size, d60. In contrast, a coconut shell-
based granular activated carbon had the best phosphorous removal
capability than alum sludge due to its higher surface area average 1000
m2/g vs. 191 m2/g oven-dried alum sludge) in a study by Mohammed
and Rashid [59]. These differences were attributed to variations in the
qualities of the alum sludges used in the studies. Mortula et al. [71] did
not indicate the surface area of the activated carbon they used whilst
Mohammed and Rashid [59] did not give the d60 particle size of the
GAC used to allow for a complete evaluation of their findings.
Test conditions

4.2. Mechanism of phosphorous adsorption

The mechanism of P-adsorption by alum sludges is best described

using sorption kinetics, equilibrium and thermodynamics. The process
kinetics for phosphorous adsorption by alum sludge is biphasic, being
constituted by a fast initial phase followed by a slow phase [1,27,65].
This is the same pattern for all forms of phosphates [1,47]. The rapid
experiment

phase is characterized by phosphorous adsorption onto the exterior,

Type of

easily accessible sites such as macropores as well as on surface func-

tional groups in a ligand exchange mechanism [27,40]. These surface
functional groups include hydroxyl groups (−OH), chlorides (-Cl),
Sludge particle size

sulphates (-SO4), acidic organic carbon groups from humic substances

(C]C and CO]) as given by Yang et al. [40], Yang et al. [46], Baba-
tunde and Zhao [72], and Liu et al. [73]. In a study by Yang et al. [40],
(mm)

the P concentration in solution decreased while the levels of sulphates,

chlorides and humic substances, as TOCs, increased as pH dropped to
4.3 from 9. These results indicated the replacement of these functional
Initial [P]

groups from the alum sludge surface, hence the ligand exchange me-
(mg/L)

chanism. One characteristic feature of P-adsorption by hydrous Al hy-

droxides is the release of hydroxyl group into solution [74]. These
hydroxyl functional groups play a critical role in the ligand exchange
mechanism that explains most of the P adsorption onto the surface of
alum sludge in the rapid phase [46]. In line with these findings, studies
have found that P-adsorption capacity increases with increase in the
pH

alum sludge dosage though up to a certain limit [1,27,47]. Different

dosages of alum sludge effecting maximum P-adsorption capacity have
Max. P adsorption capacity

been established by the studies possibly due to varying Al metal content

contained in the alum sludges. An increase in the Al metal content of
(mg P/g alum sludge)
Table 2 (continued)

the alum sludge appeared responsible for the increasing P adsorption

capacity in some studies [75,65]. Aluminium content means more hy-
droxyl and other functional groups to act as binding sites and for che-
mical reaction with the phosphate ions.
Yang et al. [40] found a simultaneous decrease in the phosphate and
alumininum concentrations from solution indicating the occurrence of

5
N. Muisa, et al.
Table 3
Time needed to reach equilibrium in phosphorous (orthophosphate) adsorption by alum sludges.
Ref. Initial P Removal efficiency (%) Removal efficiency after 24
hrs (%)
[63] 73 within 2 hours ∼96
[89] 50 within 2 minutes 100
[59] ∼48 within about 12 hours 50 at 24 hrs and 85 on day 7
[22] 94 and 96 within 5 hours at 30 and 40 ∼99
°C, respectively
[80] 90 in first 1 minute, Equilibrium in 10 Not reported
min
[61] ∼85 in 8 hr Not reported
96 in 21 hr
[65] > 80 in 30 min Equilibrium nearly reached
chemical reactions as other mechanims. Using a cold-field emission
scanning electron microscope coupled with an energy dispersive X-ray
spectrometer (EMS-EDS), dot maps of cross sections of the WTR re-
vealed that P was evenly distributed within the particles which pointed
towards intra-particle diffusion/sorption mechanism [37]. A typical
adsorption reaction uses up 8–16 KJ/mol [77], but in the study by
Babatunde and Zhao [72], they found an average adsorption energy of
between 17 and 21 kJ/mol. The higher adsorption energy was a further
indication towards the presence of chemical adsorption (or chemi-
sorption) besides the physical surface process of ligand/anion exchange
and the electrostatic and chemical attractions. Diffusion into micro-
pores requires great activation energy. Liu et al. [78] also showed that P
adsorption was reduced by the accumulation of biofilm of activated
sludge on alum sludge pores. The biofilm acted to close the pores on the
surface of the alum sludge and surface active sites which reduced ad-
sorption by about 40 %. This finding supports the fact that mechanism
of P-adsorption is a result of surface active sites and inner pores.
Thus, when all surface sites have been occupied by the phosphate
anions, adsorption process occurs via intra-particle diffusion me-
chanism into meso-and micropores, precipitation and chemical reac-
tions [21,22,37,47,72]. These subsequent mechanisms constitute the
slow phase of the adsorption process of phosphates on alum sludges.
Babatunde and Zhao [72] further showed that particle diffusion me-
chanism was active under higher P concentrations. Higher P con-
centrations create a concentration gradient that pushes remaining
phosphates from the exterior into the interior pores for additional ad-
sorption, further supporting the intra-particle diffusion mechanism.
4.3. Adsorption kinetic models
Reaction kinetics are as important as specific adsorption capacity
studies as both the rate of adsorption and the amount adsorbed are
important to achieve an acceptable optimum performance [64]. Besides
porosity, polarity and high surface area, a good adsorbent should pos-
sess fast adsorption kinetics [54–56]. It is important that maximum
amount of adsorbate is removed in the shortest time possible for
practical application. More than 80 % of the studies reviewed that fitted
their P-adsorption data into sorption kinetic models found the pseudo-
second order model to give the best fit for alum sludge [1,21,61,65,72].
The mechanism of phosphate adsorption on other natural adsorbents
such as saw dust, rice husks has also been consistent with the pseudo
second order model [81]. In their review paper on metal hydr(oxides),
Li et al. [64] also highlighted that kinetic data of phosphate adsorption
on most metal hydr(oxides) adsorbents are usually better represented
by the pseudo second order model. Devi and Saroha [28] did a review
on sludge-based adsorbents for several pollutants and found that ad-
sorption by these kinds of adsorbents also follows the pseudo second
order model. The second order model points towards the dominance of
chemical adsorption (also called chemisorption) as rate limiting step
Journal of Water Process Engineering 35 (2020) 101187
Test conditions
Rapid phase followed by gradual reduction, 5 g/l alum sludge, pH of 4, shaking at 200 rotations
per min (rpm) for 24 hr, synthetic P solution
1 g alum sludge and 25 mL of 10 mg/l P solution, shaking
No mechanical mixing; Initial P concentration of 5 mg/L; pH of 5; temperature of 25 °C, synthetic
particle size of 0.5 mm and oven dried alum sludge dosage of 50 g/L
pH 4, 2.50 ± 0.05 g fine alum sludge, alum sludge pre-dried at 50 °C, synthetic P solution (150
mg P/L in 10.5 mg/l NaCl at pH ∼7.2–7.3)
Removal % applies to soluble total phosphorous; secondary wastewater used; shaking at 50 rpm;
alum sludge (50 mL); 950 ml wastewater
Continuous stirring; initial P concentration of 50 mg/L; 5 g alum sludge dosage; solution pH of 6
Initial synthetic P concentration of 100 mg/L, alum sludge used
and hence the governing mechanism occurring through the formation
of new compound on the surface of the adsorbent [82]. Babatunde and
Zhao [72] also found that the pseudo first order model fitted their data
well along with the second order model. The intra-particle diffusion
model was also found to play a part but was not the rate limiting step
and was most prevalent under high initial P concentrations [72].
Chittoo and Sutherland [21] also found the diffusion-chemisorption
kinetic model to fit their data well after the pseudo second order model.
The assumption behind the pseudo first order kinetic model is that only
one adsorbate, in this case, phosphate (PO42−), may occupy one site on
the adsorbent surface. The diffusion-chemisorption model is based on
the assumption that both diffusion and chemisorption determine ad-
sorption. The implication of chemisorption is that the adsorbed pollu-
tant is almost irreversibly bound or cannot be easily desorbed [28].
Phosphate adsorbed onto alum sludge has also been shown to be almost
permanently attached and that it could remain so for a long time
[37,39]. Thus, chemisorption mechanism may be a positive or negative;
depending on the objectives for the adsorption application. For ex-
ample, if the goal is to remove pollutants from wastewater by adsorp-
tion or to remove phosphorous from a eutrophic water body then per-
manent attachment of the phosphate to the alum sludge would be
desirable. However, if the goal is to capture and reuse the phosphorous
pollutant then irreversible adsorption would be least preferred. The
issue with using alum sludge as adsorbent in wastewater is on the
disposal of the subsequent sludge. Thus, the trend in literature is to
reuse the P-containing sludge as a form of slow-release fertilizer to
offset P-deficiency in soils especially in tropical and subtropical regions,
and limit over-use of the natural reserves for this non-renewable re-
source as well as to avert eutrophication [2,83,84]. The recovered
phosphorous could also be used as a source of raw material in the
phosphate industry [2].
Various equilibration times have been reported in literature albeit
under varying test conditions as shown by the findings obtained from
selected studies given in Table 3. The optimum equilibration time for
phosphate adsorption on alum sludge is 24 h. The variations in the
equilibration times are due to differences in experimental conditions
that include; alum sludge dose, initial phosphate concentration, agita-
tion, solution pH, temperature of reaction, particle size of alum sludge
[20–22,27,59]. It is important to note the importance of shaking in
increasing the rate of adsorption from the results presented in Table 3.
The study by Mohammed and Rashid [59] is the only one that removed
phosphate as low as 50 % in 24 h with the rest in 7 days probably due to
the absence of shaking. The other studies involved shaking albeit at
different duration or intensities.
4.4. Adsorption equilibrium isotherm models
Adsorption isotherm represents the relationship between adsorbent
and adsorbate at a fixed temperature under equilibrium conditions and
6
N. Muisa, et al.
also represents the effect of initial adsorbate concentration as a function
of adsorbent dosage [85]. The majority of studies on phosphate ad-
sorption by alum sludges have found the Langmuir isotherm model to
provide the best fit [20,25,40,72,65,86], followed by the Freundlich
adsorption isotherm model [71,87]. This is also typical of other metal
hydroxide adsorbents [64]. The Temkin model was also good [87],
while the Langmuir-Freundlich model, the two-site Langmuir model
were a better fit than the Langmuir in studies by Mohammed and Ra-
shid [59] and Gao et al. [1], respectively. The Langmuir model assumes
that effective adsorption is monolayer in nature [20].
4.5. Thermodynamics of phosphate adsorption
Gibb’s free energy, enthalpy and entropy changes are critical vari-
ables when estimating the performance of an adsorption desorption
process and predicting the mechanism of this process and hence, basic
parameters to characterize and optimize an adsorption process [85]. To
further understand the mechanism of phosphate adsorption on alum
sludge, these thermodynamic parameters were calculated by Gao et al.
[1]. The positive value of the enthalpy change (ΔHo, kJ/mol) as well as
the pattern of increasing adsorption capacity with increase in tem-
perature confirmed the endothermic nature of the process. The me-
chanism of phosphate adsorption on alum sludges also involves diffu-
sion into micropores as mentioned before, which requires activation
energy as these narrow-sized pores present an energy barrier to the
adsorption process [37]. The positive values of entropy change (ΔSo,
kJ/mol K) were a further indication of disorder caused by the adsorp-
tion process taking place as temperature increased. The values of the
standard Gibb’s free energy (ΔGo, kJ/mol) were negative and decreased
with increasing temperature (range: -8.97 at 288 K to -19.99 at 328 K)
for all the phosphate species studied that include; ortho-P, hexameta-P;
phytate; pyro-P, glycerol-P, [1,88]. The negative Gibbs free energy
values indicated that the adsorption process of phosphate on alum
sludges is a thermodynamically feasible and spontaneous process.
4.6. Factors affecting adsorption of phosphates on alum sludge adsorbent
4.6.1. Effect of pH
Almost all adsorption studies on alum sludges that were accessed in
literature have found that adsorption is highly dependent on pH of the
solution and that highest adsorption capacity mostly happens in the
acidic pH range of 4–5.5 [1,20,21,25,30,36,40,50,63,71,72]. Although
most of these researches studied ortho-P, this trend has been found to
apply for all forms of phosphates [1]. A pH below 4 or above 8 de-
creases phosphate adsorption on alum sludge [25]. This trend is par-
ticularly so for orthophosphate-P which is an inorganic phosphate
species tested in most phosphorous adsorption studies by alum sludge.
Orthophosphate-P is the most easily and strongly adsorbed phosphate
species from aqueous solution by alum sludge [25,63,71,90]. Ortho-
phosphates have got a small molecular weight in comparison to the
other types of phosphates such that they quickly diffuse into the ad-
sorbent material and get adsorbed fastest.
Aluminium hydroxide, dominant in alum sludge, is amphoteric in
nature which results in acid-base dissociation of alum sludges [40]. As
aluminium dissolves back into solution, surface charge of aluminium
hydroxide which is mainly responsible for phosphorous adsorption is
reduced, either forming positive or negative charges depending on the
surrounding pH. When the pH is low, H+ ions dominate the surface of
the alum sludge which triggers a release of OH− ions into solution,
creating free active sites for phosphate adsorption. The presence of
hydroxyl group (−OH) active sites creates a better chance for phos-
phate−OH ligand/ion exchange to take place on the surface of the
sorbent providing for increased phosphorous adsorption capacity [64].
This ligand exchange mechanism was confirmed by Liu et al. [91] using
column tests and is the main mechanism explaining phosphate ad-
sorption on alum [40]. Likewise, under alkaline conditions (pH > 7),
7
Journal of Water Process Engineering 35 (2020) 101187
hydroxyl ions (OH−) become dominant in solution, which reduces the
release of the OH− ions from the alum sludge active sites. Instead, the
hydroxyl ions outcompete phosphates (PO43-) for the active sites on the
surface of the alum sludge by forming a counter ion layer surrounding
the aluminium ion that reduces P adsorption [20,40]. Yang et al. [40]
also found that the zeta potential of the alum sludge studied changed
from +75.8 to -33.7 mV, which corresponded to a pH change from
4.3–9.0. A positive zeta potential signifies a positive surface charge
which occurs when the pH of the suspension is low, indicating presence
of unsatisfied surface charge that needs to be neutralized by an anionic
adsorbate e.g., Cl−, SO42-, OH−, humic acids as TOC, PO42- ions. Thus,
effective use of alum sludges as adsorbent for wastewater treatment
would require pH maintenance within the acidic range of 4–6 to ensure
the availability of metal hydroxides and a positive surface charge in
order to attract anions.
Besides the stability of the functional groups present on the active
sites of the sorbent surface (that is, the surface potential), pH influences
the surface charge of the adsorbent [27,64,92]. The adsorption capacity
of the adsorbent surface and the type of active centres on the surface are
indicated by a significant factor called the point of zero charge (pHpzc).
The pH at the point of zero charge for alum sludge is 7.5 [40]. In the
range of pH 2–12, when solution pH > pHpzc, the phosphate adsorption
may be affected by the electrostatic repulsion and increasing competi-
tive effect of OH− ions for the active sites on the sorbent. When
pH < pHpzc, the sorbent surface is positively charged, favouring ad-
sorption of the anions. Adsorption process of anions onto alum sludge is
also facilitated by electrostatic and chemical attraction onto the posi-
tively-charged outer surface of the alum sludge [64]. This is the reason
why most studies on alum sludge have found the best phosphate ad-
sorption at a pH range of 4–5.5 as this is below the pHpzc of alum sludge
of 7.5.
The solution phosphate chemistry is also influenced by pH and also
determines adsorption capacity of alum sludges for the anion
[27,64,92]. Electrostatic repulsion is increased when a phosphate of
higher negative charge is dominant in the solution. For example, as pH
increases, more negatively charged phosphate ions become dominant in
solution, increasing the repulsion between the phosphate species in
solution and the adsorbent surface which is already predominantly
negative under these pH conditions. Adsorption capacity has been
noted to decrease at these alkaline pH ranges. The phosphate species
dominant at various pH values are: H3PO4 (pH ∼2.15); H2PO4− (pH
2.15–7.20); HPO42- (pH 7.2–12.33) and PO43- at pH > 12.34 [93–95].
The phosphate species, H2PO4−, requires lower energy for adsorption
than HPO42- such that the former is more easily adsorbed on the ad-
sorbent surface than the later species [95]. Besides increased compe-
tition between phosphates and hydroxyl groups or counter ion layer
formed by hydroxyl groups or electrostatic repulsion, higher energy
requirements for adsorption of the prevailing forms of phosphate under
alkaline conditions may also explain the reduced adsorption capacity of
alum sludge for phosphates as pH increases from acidic to alkaline
ranges.
4.6.2. Particle size
Although particle size ranges used by different studies are different
and difficult to compare, what is common is that much more phos-
phorous adsorption is favoured with small/fine particle size ranges than
with bigger sized particles in both batch and column tests
[22,42,59,91,96]. Yang et al. [40] also found that in addition to a
significant increase in adsorption of phosphorous, equilibrium con-
centration of phosphorous left in solution was also lowered which also
shows the extent of the adsorption process. In addition, Lee et al. [22]
found that the adsorption rate is also much more rapid with fine par-
ticles than with bigger particles. It took 7 h (size 1.18 mm-fine parti-
cles), 24 h (1.18 mm–4.0 mm) and more than 24 h (> 4.00 mm) for
alum sludges to remove 2.5 g of phosphorous to detection limit. At least
50 % of the particle size less than 1.18 mm contained particles of size
N. Muisa, et al.
below 0.30 mm. Ippolito et al. [30] reported that particle size of less
than 0.15 mm provides greater surface area compared to sizes greater
than 2.36 mm. Even smaller sizes to the nanoscale have been shown to
further increase surface area and adsorption capacity. For instance,
nanosized water treatment residue obtained through high-energy ball
milling yielded 30 times higher maximum adsorption capacity (50 mg
P/g) than the unmilled residue (1.7 mg P/g) [97].
Intraparticle diffusion of phosphorous in micropores has been re-
ported in literature [37,72]. It has been noted that the intrapore specific
surface area for adsorption is 24-times the average size of the adsorbent
particles [37]. Specific surface area also increased with increase in
micropore volume. This intra-particle diffusion mechanism explains the
significant increase in maximum PO43−-P adsorption when the particle
size is reduced in all of the abovementioned studies. Thus, fine particles
can significantly increase the intra-pore specific surface area and pro-
vide additional adsorption sites in the form of micropores, macropores
and mesopores. This acts to increase the effective area and/or contact
between adsorbent and adsorbate for PO43−-P adsorption than coarse
particles. Therefore, any change in the particle size and surface area of
alum sludge will also translate to variations in phosphorous adsorption.
The emerging trend in the world right now is the use of nanosized
materials with a high surface-to-volume ratio, that is, high surface area,
which is known to increase surface reactivity of the substance, among
other uses [92,98]. There is no doubt that particle size of alum sludge
can also be manipulated to increase its efficacy as an adsorbent. The
only difficulty is the lack of a standard size of particles that give the best
adsorption as different sources use different size ranges which makes
comparison inappropriate. However, in column experiments, there are
issues of impeded hydraulic conductivity and possible clogging of sus-
pended materials which can reduce effectiveness of alum sludge acting
as a filter substrate and adsorbent [99].
4.6.3. Retention time
This is also known as the contact time between the adsorbent and
the adsorbate, in this case the phosphorous-containing aqueous solu-
tion. Most researchers have found that increasing the retention time of
the adsorption process increases removal or adsorption capacity in
batch or in fixed bed column experiments [22,42,59]. Maximum P
adsorptions were achieved within 48 h [42] although equilibrium time
is mainly 24 h (Table 2). Makris et al. [52] amended poultry litter with
different rates of alum sludges and found that contact time was not a
significant factor for P adsorption. Bai et al. [13] also found phosphate
adsorption to be the same for hydraulic retention time of 2 h and 3 h,
such that 2 h was adopted for further studies, aided with stirring, as the
most efficient time for the process. Increases in hydraulic retention time
in a column study did not result in improvements in phosphate removal
in another study [27]. The results from Babatunde and Zhao [72] in-
dicated that contact time needed to achieve equilibrium might be af-
fected by the initial P concentration, with more time being required for
higher initial P concentration. Thus, even if there is little phosphorous
for adsorption it seems that surface adsorption will still prevail and
rapidly for that matter, regardless of contact time, so long other factors
are optimal such as the particle size of the alum sludge, the tempera-
ture, pH, agitation and presence of competing substances. As a result, it
appears that contact time may not necessarily be an important de-
termining factor alone but these other surrounding factors.
4.6.4. Competitive anions
Anions always occur together in the environment and the same
applies for phosphates and its competing anions in wastewater [18,95].
Being of the same charge, phosphates and its competing anions are
bound to compete with each other for the same sites on a metal cationic
surface. These competing substances thus interfere with the adsorption
of phosphates by alum sludges. Normally, adsorption will favour the
anion with a higher valence such as; PO42−, SO42− and CO32− com-
pared to single-charged ones that include; Cl-, F-or NO3- and the order
8
Journal of Water Process Engineering 35 (2020) 101187
of interference given was: SO42− and CO32− > F-, Cl- > NO3- [64].
Studies looking specifically on aluminium or alum sludges have given
somewhat contrasting results. There is consensus that NO3- and Cl-,
have an insignificant effect on phosphate adsorption [40,100]. In con-
trast to Li et al. [64], sulphates (SO42−) have also been found to have an
insignificant effect when it comes to aluminium or alum sludges, whilst
fluorides and hydroxide monovalent anions have a superior affinity for
aluminium or alum sludges [40,100]. The study by Li et al. [64] was a
review on phosphate adsorption onto various types and sources of
metal hydr(oxides). This pattern indicated replacement of these func-
tional groups from the alum sludge surface by phosphates. The order of
decreasing competitive strength or affinity for aluminium reported by
Diamadopoulos and Benedek [100] is: OH- > F-
> PO42− > SO42− > Cl-, NO3-. Humic substances also fall in the same
category with Cl- and NO3- in terms of competitive strength [40,69,91].
Phosphate adsorption from wastewater has also been shown to be
hampered by the presence of carbonates but insignificantly affected by
chlorides, nitrites (NO2-) and nitrates on other adsorbents such as iron-
modified biochar or Mg/Al LDH functionalized biochar [18,95]. Car-
bonates inhibit phosphate adsorption by increasing pH of solution
[101]. However, there is no consensus on the effect of sulphates. As
explained in section 4.6.1, phosphate adsorption decreases as hydro-
lysis of aluminium increases with increase in pH to the alkaline range.
This shows that hydroxyl ions, if present, have a greater tendency to
attract to aluminium than phosphates for aluminium, Al3+. Mortula
and Gagnon [102] found that phosphate removal in aquaculture pro-
cess water and deionized water spiked with orthophosphates was
comparable at pH of 6.48. This finding showed that the presence of
competing ions did not affect phosphate adsorption by alum sludges
tested but pointed towards the inferior competitive strength of most
anions present in the aquaculture wastewater. Conclusively, nitrates
and chlorides are weaker competitors whilst carbonates and fluorides
are stronger competitors than phosphates for aluminium. As given by Li
et al. [95], sulphates have a larger ionic radius than chlorides, nitrates
or nitrites such that they are strongly associated with the positively
charged aluminium ion along with the H2PO4- which induces compe-
tition. Fluoride has a strong electronegativity and so it is easily com-
bined with the protonated adsorbent surface than phosphate [95].
4.6.5. Dosage of adsorbent
Increasing the dosage of alum sludge can improve P-removal ca-
pacity [13,63]. This is because the quantity of active sites or total
surface area for adsorption to take place also increases. However, this
increase in P-removal capacity is only up to a certain dosage or limit
and variable from one study to another for instance, 5 g/L [47]; 10 g/L
[47]; 50 g/L [59]; 12 g/L [20]. The very high limit of 50 g/l might have
been due to the absence of shaking in the experiments. The same study
also had the longest equilibration time (Table 2). Shaking increases
mobility of the adsorbate on the surface of the adsorbent as well as
helps to open up more sites for adsorption to take place [103]. After the
limit is reached, P-removal becomes constant, and then decreases and
this trend applied to all the initial phosphate concentrations in the
study by Babatunde et al. [27]. In addition, as alum sludge dose in-
creases, specific P uptake decreases [47]. Thus, increasing the alum
sludge dosage for the same initial phosphate concentration serves to
make the whole phosphate adsorption process inefficient per gram of
adsorbent [27]. The phosphate is only distributed on the available sites
and some sites are left unoccupied though overall P removal capacity is
increased or high. Also, the gradient of phosphate concentration is
lowered around the alum sludge particle surface which results in re-
duced specific adsorption on per mass of the water treatment sludge
[13,47]. Increasing dosage of alum sludge increased the Al ion content
which resulted in higher adsorption of phosphates [65]. Al ion content
affects adsorption because of ligand exchange mechanism as more Al
means more functional groups that can be exchanged for P on the
surface according to Yang et al. [40]. Hence, most studies have found
N. Muisa, et al.
that phosphate adsorption increases as dosage of alum sludge is in-
creased but these upper limit dosages are different probably because of
other confounding factors such as particle size of the alum sludge used,
contact time, initial phosphate concentrations, shaking duration, speed
and/or intensity, among others. Also, this could simply be due to some
of the studies not increasing the dosage to a point where further in-
creases do not effect any change in phosphate adsorbed. Therefore,
there is need for an optimization study to determine the optimum do-
sage of alum sludge-based adsorbent, of a particular optimum particle
size, Al content and form, to be used for a measured amount of phos-
phates to achieve effective and efficient phosphate adsorption from
aqueous solution.
4.6.6. Temperature
Adsorption capacity increases as temperature rises, and this applies
to all forms of phosphates [1,22,104]. Temperature also increases the
initial rate of adsorption reaction but after prolonged contact time,
removal efficiency becomes similar [22]. Generally, temperature also
reduces the time required to reach equilibrium in phosphate adsorption
by various adsorbents [92]. At a temperature of 30 ± 2 °C and 40 ± 2
°C, the maximum adsorption rate for P were 0.685 ± 0.084 and
0.870 ± 0.021 mg P/g alum sludge/min, [22]. More temperature levels
by Lee et al. [22] would have allowed for analysis in order to conclude
on the results. These two data points give a preliminary indication that
temperature speeds the initial rate of reaction but over prolonged time,
the different temperatures give similar results, typical of phosphate
adsorption reactions. All these results point towards the endothermic
nature of phosphate adsorption by alum sludges. The positive value of
the enthalpy change (ΔH°, kJ/mol) confirmed the endothermic nature
of the process [1]. As explained by Gao et al. [1], increasing tempera-
ture reduces the viscosity of the solution which then enhances the
diffusion of the adsorbate molecules across the boundary layer and into
the pores of the adsorbent rendering an increased adsorption capacity.
Devi and Saroha [28] also reported that increased temperature causes a
swelling effect in the internal structure of the adsorbent which makes it
easy for molecules to enter and so, increased adsorption capacity.
However, the effect of temperature on adsorption capacity should not
be overemphasized because this increase is most probably only de-
pendent on other adsorbent characteristics such as particle size and
whether the surface area for adsorption is high or not. Studies may be
needed to really ascertain the effect of temperature on adsorption ca-
pacity and the degree of this effect using both fine and coarse particle
sizes. In practice, energy-intensive processes may be undesirable due to
costs and issues of global warming, depending on the source of energy.
4.6.7. Age/storage time of alum sludge
Fresh alum sludge slurry was collected every 1−2 h from clarifiers
(constituting about 1 % of total sludge volume), aged for up to 5 days
by storing it at room temperature while mixing at 30 rpm [105]. Slow
mixing was so as to prevent breaking up of sludge particles and to
prevent anaerobic conditions and the changes that might accrue as a
result. The authors found that increasing the age of alum sludge from
day 0 to day 5 significantly reduced P sorption capacities especially for
orthophosphates [105]. Other authors also found this same pattern
[106,107]. Contrasting results are also present [46,100]. The study by
Yang et al. [46] was long-term (0 day up to 18 months) using actual
dewatered alum sludges, air-dried and specifically focusing on the ef-
fect of ageing on the structure of alum sludge and its P adsorption ca-
pacity and found marginal effects. There was insignificant change to the
structure and properties of the alum sludge and so, to its adsorption
capacity. The studies by Galarneau et al. [105], Georgantas et al. [106]
and Berkowitz et al. [107] were done using wet alum sludge (sludge
before drying). Maher et al. [104] also used wet alum sludge and found
that adsorption capacity for soluble reactive phosphorous decreased by
43 % by day 43 while total reactive phosphorous showed marginal
reductions. Hence, it can be concretely concluded that the age of actual
9
Journal of Water Process Engineering 35 (2020) 101187
dried alum sludge will not likely affect its P adsorption capacity.
However, a more solid comparative study done under same experi-
mental conditions is necessary to ascertain effect of age on the ad-
sorption of phosphorous under aqueous and dry sludge environment.
4.6.8. Initial phosphorous concentration
The majority of studies on phosphate adsorption by alum sludge
agree that maximum P adsorbed by alum sludge increases with in-
creasing initial P concentration [72,104,108]. This trend applies to all
the different P species that include; pyrophosphate, orthophosphate,
and glycerophosphate [109]. Further, there is higher adsorption rate at
higher initial P concentrations than at low concentrations. Babatunde
and Zhao [72] found the intraparticle rate constants to increase from
0.0075 mg P per gram per min at 5 mg initial P/L to 0.1795 mg P per
gram per min at 60 mg initial P/L. Intraparticle diffusion mechanism
was rate controlling step at high initial concentrations of phosphates
[72]. Hence, optimization studies should determine the best possible
and efficient combination of phosphate source to be mixed with a pre-
determined adsorbent dosage of a particular size and form.
4.6.9. Agitation/shaking speed
An increase in agitation speed (150–250 rpm) was found to increase
adsorption capacity, rate of adsorption and initial rate of adsorption
compared to an increase from 250−350 rpm [21]. Higher shaking
speeds (above 350 rpm) did not yield further changes to the above
parameters in the same study. This phenomenon had also been reported
by other authors, albeit looking at other kinds of adsorbents and ad-
sorbates [103,110,111] These findings indicate that the absence of
shaking prolongs the time to reach equilibrium as shown in Table 2
whereby the longest time to equilibrium was 6 days in a study by
Mohammed and Rashid [59]. It is clear that shaking/agitation/stirring
or mixing impact on the adsorption capacity and its rate of occurrence.
However, different shaking times and speeds are used in studies such
that, for practical application purposes, it is important to recommend
optimal shaking conditions factoring in other influencing factors. Agi-
tation would help in situations when there is high influent flow to a
wastewater treatment system, for example, during high rainfall events
when there is high stormwater runoff. Maximum phosphate adsorption
can be reached in the shortest possible time. Agitation can either be
hydraulic or mechanical but care should be taken to avoid flow patterns
that cause stratification and thus non-uniform mixing and reduced
contact between adsorbent and adsorbate. Baffled basins are some of
the most commonly used.
5. Desorption, regeneration and recovery
Desorption and regeneration of adsorbents are the most difficult and
expensive parts of an adsorption technology which can take up at least
70 % of the total costs for operation and maintenance of the system
[112]. The objectives of desorption/regeneration exercises are to re-
cover the adsorbent or adsorbate depending on their market demand
(desorption), restore the adsorbent back to its initial properties for ef-
fective reuse (regeneration) and so, reduce the overall process cost of
the adsorption process. Desorption can also help in the understanding
of the adsorption mechanism [28]. The exercises also allow for proper
disposal of either constituent.
Researches on P-saturated alum sludge desorption/regeneration is
very scarce. Of the few studies accessed in literature, they were mostly
looking at P availability and extraction from agricultural soils or lake
sediments amended with water treatment residues and even fewer from
alum sludge used as adsorbent in aqueous solutions or substrates. Alum
sludge can be desorbed of bound P by manipulating the pH conditions
[39,108,113]. An acid-base extraction experiment was performed by
Zhao and Zhao [114] for P extraction and found that all the acids tested
exhibited the highest desorption efficiencies at increased P concentra-
tions while the bases were effective at low concentrations. However,
N. Muisa, et al.
there was no significant difference between 0.075 M and 0.01 M con-
centrations of either base or acid. Sulphuric acid, H2SO4, was then
chosen as the most efficient agent for P extraction when factoring in
issues of cost, convenience and safety as well. The other acids tested
were hydrochloric acid (HCl) and nitric acid (HNO3) and the bases were
NaOH and KOH. Optimization studies found P extraction efficiency of
98 % under alum sludge dose of 5633.8 mg/l and H2SO4 concentration
of 0.063 M [114]. Other studies on oxyanions desorption from sludge-
based adsorbents have found the process to favour base extraction or
alkaline conditions, for example, a study by Zhou and Haynes [115]. It
appears only one desorption cycle was used to effect above 90 % and
around 65 % P extraction using the acids and bases, respectively. Stu-
dies are required to investigate the extent of regeneration for alum
sludge to make inference on the cost-effectiveness of its use for practical
application.
Alum sludges amended or composited with organic matter prior to P
adsorption resulted in a significantly greater release of P from the
cowshed wastewater amended-alum sludge than alum sludge alone
(yielding concentrations of 31.8 and 0.2 mg soluble reactive P/kg solid,
respectively) [108]. Organic matter probably inhibited the formation of
strong binding of phosphates to the adsorption sites making them easily
desorbed. Alum sludges contain large amounts of amorphous Al which
has been shown to be strongly correlated to high P sorption [27,96].
The results in a characterization study on 15 water treatment residuals
in South Africa showed elevated amounts of amorphous Al oxides and
also Ca [12]. The authors concluded that the sorbed P would be re-
tained in forms unavailable for plant uptake. The implication of these
findings is that phosphorous bound to alum sludges cannot be available
again in the environment naturally unless there are changes to the
surroundings, especially in terms of pH. Desorption occurred in the
presence of sulphuric acid to recover 97 % P and 99 % Al from a de-
watered alum sludge cake that was being used as substrate in a con-
structed wetland. The P and Al-laden leachate that was produced was
then precipitated using a base to form AlPO4. The AlPO4 can be a raw
material in the phosphate industry, or a fertilizer in agriculture. There
is need for more research using various alum sludges to ascertain the
production efficiency of the AlPO4, the optimized conditions for pro-
duction, its purity for use in agriculture and the cost- effectiveness if
applied at a large scale. Phosphorous (P) is a macronutrient essential for
all living organisms but it is also a finite resource which can get used up
from its main non-renewable source raw material, phosphate rock.
Coupled with increasing human population growth and no alternative
for phosphorous, the demand for phosphate rock to provide phos-
phorous will increase, probably even exceeding its supply. In addition,
P use efficiency is low with just between 15 and 20 % of applied
phosphorous being consumed by the plant or animal life and the rest
becoming lost in the waste generated thereof. The phosphorous present
in these wastes poses a threat to the environment for example, as eu-
trophication. Hence, the capture and slow release of phosphorous by
alum sludge-based fertilizers may offer a solution to these challenges.
6. Drawbacks of alum sludge use as adsorbent for phosphate and
counteracting measures
The specific surface area of alum sludge is considerably low
(121.1 ± 98.3m2/g – alum sludge) when compared to that of com-
mercial conventional adsorbents such as activated carbon (for instance,
200–300 g/m2 – activated alumina or 600-2000g/m2 – activated
carbon) as mentioned in section 3.1. This also applies to other sludge-
based adsorbents [28]. Surface area has been found to increase by ac-
tivation, reducing particle size to nanoscale and purification (that is,
removal of impurities) of the precursor sludge [28,58,97,116]. Al-
though some have found alum sludges, as well as other metal oxides or
hydroxides, to have significantly higher P removal relative to their
activated forms, for example, activated alumina, the adsorption reac-
tions tend to be highly pH-dependent and limited by adsorbent
10
Journal of Water Process Engineering 35 (2020) 101187
characteristics [95,117]. The bound phosphate ions cannot be easily
recovered from alum sludge for other environmentally sustainable uses
such as source of phosphorous-based fertilizer.
Activation of raw materials has always worked to increase surface
area of various adsorbents to more than double or triple the original
surface area [28,56,95,117,118]. Raw alum sludges calcined at 300 °C
removed organic/inorganic matter impurities that are normally ag-
glomerated to raw alum sludges and increased its surface area resulting
in a 5.4–8.7 times greater adsorption capacity for arsenate (V) than
unmodified alum sludge [118]. However, several studies have estab-
lished that calcination temperature is critical with high temperatures
reducing the surface area instead [95,119]. Jeon et al. [118] also found
that alum sludge structure changed from being amorphous to crystal-
line with temperatures above 300 °C which reduced its surface area for
adsorption. This phenomenon was also reported in a review of various
sludge-based adsorbents by Devi and Saroha [28], whereby an increase
in activation agent to sludge ratio beyond certain optimum levels re-
duced the surface area due to destruction of microporosity from pore
wall damage. Using thermal sol-gel method, activated alumina with
high purity was produced from raw alum sludge and successfully re-
moved 96 % fluoride from aqueous solution and the adsorption capa-
city was higher than commercial nano-alumina [120]. However, there
was no comparison made to the parent unmodified alum sludge ad-
sorption capacity in the study by Aghapour et al. [120]. Also, the yield
of activated alumina from the parent alum sludge was only 38.5 %.
Also, the yield of activated alumina from the parent alum sludge was
only 38.5 %. Thermal sol-gel is a chemical activation technique mostly
used to produce metal oxides of higher purity and abilities than the
parent materials. The method uses a chemical agent in a hydrolysis step
that yields a solution of the precursor that later becomes a gel. A poly-
condensation stage follows that is normally done using thermal means
to improve structural ability and mechanical properties. In the study by
Aghapour et al. [120], the process involved alum recovery by sulphuric
acid treatment then preparation of Al(OH)3 gel by addition of NAOH
solution followed by calcination for 2 h in air at 700 °C. It has been
determined that activated metal oxide product normally has a higher
point of zero charge which ensures that adsorption is optimal at a wider
pH range [95]. Jeon et al. [118] also found that the adsorption capacity
of alum sludge calcined at 300 °C did not change markedly across a
wider range of pH range than the uncalcined sludge.
Aluminium-based materials, other than alum sludge, have been
used as precursor raw material with other materials such as biochar,
chitosan, metal-doped mesoporous silica, metal-impregnated pre-
formed mesoporous silicas or as stand-alone mesoporous metal oxides
or hydroxides or sulphates to produce composite [11,95,118,121,122].
Wang et al. [60]and Zawrah et al. [62]successfully recycled alum
sludge for producing nano Al(OH)3 and iron oxy(hydroxide), FeO(OH),
and layered double hydroxides (LDHs). The synthesised alum sludge-
based LDHs have yet to be assessed for application in various uses.
However, Al-containing LDHs have been combined with biochar and
then used for phosphate adsorption [122,123]. These Al-containing
LDH-biochar composites have been found to reach equilibrium in 50
min to 1 h, achieve almost 100 % removal efficiency for phosphates,
reach adsorption capacity of 410 mg P/g with higher regeneration and
desorption capacity and greater selectivity for phosphate in the pre-
sence of competing ions than alum sludge alone [109,117]. This high
regeneration and desorption capacity implies that the adsorbents can
act as capture and release agents for the bound phosphate. This feature
is being exploited and explored so as to use these composites as a source
of phosphate in soils that are P-deficient as mentioned earlier. However,
no consensus has been reached yet on the structural stability of the
composites under various pH conditions.
It is highly difficult to separate out a powdered adsorbent from an
effluent at large scale to allow for commercial application of most ad-
sorbents. Alum sludge in constructed wetlands has been studied as a
source of low-cost substitute substrate to act as a filter media and
N. Muisa, et al.
phosphorous removal agent. Concerns were on metal leaching, natural
organic matter release and clogging by suspended solids. Clogging is an
issue because the best adsorption of alum sludge has been achieved
using fine particle size. Fine particle size is one parameter responsible
for clogging and reduced hydraulic conductivity resulting in surface
ponding and eventually normal operation is disrupted [124]. Hence,
there is a need to balance between high adsorption capacity and im-
proved hydraulic conductivity to ensure a longer lifespan of the con-
structed wetland. Modification by granulation shows great promise in
improving hydraulic conductivity in a filtration system to reduce
clogging and to allow for easy recovery of the adsorbents
[123,125–128]. Granulation also reduced bioaccessibility of heavy
metals [99]. However, granulated drinking water treatment residual
was shown to have a lower adsorption capacity than the parent pow-
dered form [99]. More research is required to explore the usefulness of
granulating alum sludge for wastewater treatment.
7. Summary, conclusions and recommendations for future
research directions
Most of the alum sludge adsorption studies were carried out as la-
boratory-based batch studies and few as fixed-bed or continuous flow-
through column experiments, mostly using synthetic phosphate solu-
tions and synthetic or actual secondary municipal wastewater. These
studies have mostly been performed under varying experimental and
environmental conditions which makes it difficult to adopt results from
one study and use them elsewhere. Also, the quality of the alum sludge
from different places is highly variable such that a use that is applicable
for a certain sludge may not be feasible for another. This scenario
makes it difficult to develop a crosscutting alum sludge based solution
that can be applied anywhere regardless of the alum sludge used or
conditions of application.
Alum sludge is a potentially good adsorbent for phosphates in
wastewater. Adsorption capacity ranges from 2 to 43 mg P/g alum
sludge. The adsorption kinetics follow the pseudo second- order model
while the Langmuir adsorption isotherm had the best fit in more than
80 % of the studies accessed. Equilibrium adsorption is generally
reached between 10 min and 24 h with shaking. Phosphate adsorption
by alum sludges occurs by ligand exchange mechanism, anion exchange
and electrostatic attractions in the rapid phase, followed by in-
traparticle diffusion and chemical precipitation in the slow phase. Its
efficacy for commercial large scale application is limited by several
drawbacks. Specific surface area of raw alum sludge is considerably low
(121.1 ± 98.3 m2/g). Phosphate adsorption by raw alum sludge is af-
fected by several hindering factors, especially pH, presence of in-
organic/organic material on its surface, particle size, sludge dosage. In
column applications, its use is affected by its particle size and form
which can cause clogging. Regeneration has been shown to be low as
well as phosphate desorption. Desorption of bound P can be improved
by prior binding of organic matter to alum sludge and pH manipulation,
otherwise phosphates can remain bound for years at pH range of 5–9.
The following areas are recommended for future research to im-
prove the efficacy of alum sludges, especially for practical application
in the near future:
• There is need to standardize the characteristics of a good adsorbent,
in general, for phosphate removal to allow for benchmarking and
future comparisons.
• Enhancing adsorption capacity of alum sludge by way of removing
impurities, concentrating the active ingredients, and increasing
surface area for adsorption.
• There may also be need to evaluate the water treatment plant pro-
cesses and chemicals so as to yield an alum sludge with higher po-
tential benefits for later reuse.
• Development of alum sludge-based materials that balance between
size of particles for adsorption and increased hydraulic conductivity
11
Journal of Water Process Engineering 35 (2020) 101187
to prevent clogging if used as filter media for practical application.
There is also need for an adsorbent with better characteristics and
structural stability under real-life conditions but can be produced at
reasonable costs with minimal adverse environmental effects.
Efficacy of granulation to prevent metal leakage from alum sludge
should also be studied.
• Research is needed to come up with either an optimal alum sludge-
based compound or synthesis method that can be effectively and
universally recommended for effective adsorption of phosphates and
other pollutants in wastewater for commercial application as a filter
media and/or adsorbent. This would allow easy replication and
large scale production anywhere regardless of alum sludge quality;
the way conventional adsorbents such as activated carbons are used.
• More desorption/regeneration studies of alum sludge adsorbents
used in wastewater treatment are required.
Declaration of Competing Interest
The authors declare that there are no conflicts of interest.
Acknowledgements
The authors give tremendous gratitude to some anonymous re-
viewers for their invaluable input that shaped the structure and scope of
this paper.
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