Removal of metals (copper, manganese, nickel and zinc) from waters by activated

unsaturated sand filter (AUSF)

Sugihhartati Dj Rachmawati1,2, Chedly Tizaoui1, Nidal Hilal1

Abstract

Activated unsaturated sand filter (AUSF) is one among the few of the filtration
technologies utilized to treat waters that use unsaturated filter media. It employs sand
coated by potassium permanganate, operates with naturally flowing air and without a
sedimentation unit. It was previously proved efficient in removing iron and
manganese; however, there are very limited studies on AUSF. This research was thus
done to study the performances of AUSF in removing copper, manganese, zinc and
nickel from waters. Sieve, BET, SEM/EDX, acid/alkali resistance, point of zero
charge, porosity, acid digestion analysis and tracer studies were done to characterize
sand particle and bed. Plug flow characteristic with low dispersion was obtained
which validated the model used to describe the experimental results. The coated sand
was proven effective to remove the metals as shown by column studies. pH theory
was assumed to be best applied in the removal of individual metal in artificial water.
Precipitation, electrostatic attraction, adsorption/ion exchange and complex ion
formation were proposed as the mechanisms for the metal removals. The AUSF
performance in removing the studied metals followed the order of Cu > Mn > Zn >
Ni.

Keywords: Metals removal, Activated unsaturated sand filter, Manganese,

Electrostatic attraction, Precipitation, Adsorption, Complex formation

1. Introduction

High concentrations of heavy metals were found globally in ground (Vaaramaa and
Lehto, 2003; Halim et al., 2009) and surface waters (Neal and Robson, 2000; Chen et
al., 2007; Wang et al., 2007). Heavy metals are not biodegradable and tend to
accumulate in living organisms. Copper occurs naturally as un-combined metal and
in many minerals (Eisler, 2007). Manganese is an inorganic naturally occurring
element (WHO, 2006; USASTDR, 2009). Nickel is seldom found naturally in its
elemental form (Alley, 2007); it is generally occurred in nature as oxide and sulphide
ores (Wentz et al., 1998). Zinc occurs as a sulphide, oxide or carbonate naturally
(Eisler, 2007).

Zinc is released to the environment largely from human activities (Eisler, 2007;
Perez-Quintanilla et al., 2009). Copper, nickel (Eisler, 2007) and manganese
(USASTDR, 2009) discharge to the environment naturally and from human activities.

Nickel is reportedly vital for normal growth of several species of microorganisms,

plants, animals and humans (Eisler, 2007; Fu et al., 2007); but, there is no proof that
nickel is vital for humans. Copper (Kotz, 2006; Eisler, 2007; Zhou et al., 2009) and
zinc are important trace elements for all living organisms (Kotz, 2006; Eisler, 2007;
Bojic et al., 2009). Manganese is an essential trace element for the human body
(USASTDR, 2009; Winter, 2009; Hernandez-Bonilla et al., 2011). However, excess
exposure to copper in drinking water may cause vomiting, diarrhoea, stomach
cramps and nausea (Eisler, 2007), and may severely affect the brain and liver of
people with Wilson’s disease (Eisler, 2007; Bojic et al., 2009); excess exposure of
manganese, can lead to neurological disorders (USASTDR, 2009; Hernandez-Bonilla
et al., 2011) similar to Parkinson’s disease (Atsushi, 2003) and was linked to lower
children’s cognitive performance (Hernandez-Bonilla et al., 2011); and excess
exposure of zinc, may produce induced copper deficiency, harmed immune function
and impaired blood lipid profiles (Eisler, 2007). Adverse effects of nickel to humans
are identified for gastrointestinal, dermal, neurological and reproductive systems, to
name a few (Eisler, 2007). It is thus important to treat the metals so as it is safe to
consume the waters.

Conventional methods to treat metals in water mainly employ the alkaline

precipitation process. However, this process generates huge amounts of sludge which
needs further disposal (Lee et al., 2004). In recent years, metal oxides have been
applied to adsorb heavy metals from waters. Nevertheless, most metal oxides are
only available as fine powders or are formed in aqueous suspensions, as hydroxide
floc or gel, thus require separate sedimentation or filtration units, and hence
solid/liquid separation is quite difficult. In addition, metal oxides alone are
inappropriate as a filter medium due to their low hydraulic conductivity (Hu et al.,
2004; Han et al., 2006).

In order to solve these problems, currently some techniques were developed to coat
metal oxides onto the surface of sand. The studies found that these metal oxides
coated sand were effective to remove heavy metals (Lee et al., 2004; Han et al.,
2006). Recent study done by the authors showed that manganese coated sand
employed in an activated unsaturated filter (AUSF) could remove copper effectively
from water (Tizaoui et al., 2012). Although AUSF is basically a filter that uses an
activated granular media (e.g. sand), it is different with other filters. Many filtration
technologies employ filter media that are fully saturated in the water being treated
(Cho, 2005; AmericanPlanningAssociation, 2006; Devi et al., 2008). Few used un-
saturated filter media (Shimojima and Sharma, 1995; Jin et al., 2000; Kuechler and
Noack, 2007). This AUSF is one of those few technologies which operate under
unsaturated conditions (i.e. water does not occupy all the media pores). Since solid
metal species formed are removed by the filter (sand) media in AUSF; it thus also
offers the advantage of not requiring a separate sedimentation unit.

The research described here was done to investigate the characteristics of the
manganese coated sand, and of the sand bed, and the removals of metals (i.e. copper,
manganese, nickel and zinc) by AUSF. BET, SEM/EDX, acid and alkali resistance,
acid digestion, and point of zero charge analysis were done to characterize the
manganese coated sand. Tracer studies were executed to obtain the hydraulic
performance of the AUSF. Copper, manganese, nickel and zinc were then studied as
individual element. Finally, the processes that might occur within these metals in
AUSF are proposed.

2. Materials and methods

All chemicals were purchased from Fisher Scientific, UK, and were of reagent grade.
All metals solutions of desired concentrations were prepared by dissolving the
appropriate mass of solid metals (copper (II) nitrate (Cu(NO3)2.3H2O, manganese (II)
nitrate (Mn(NO3)2.4H2O), zinc (II) nitrate (Zn (NO3)2.6H2O), and nickel (II) nitrate
(Ni (NO3)2.6H2O)) in Milli-Q water (Q-H2O, Millipore Corp. with resistivity of
18.2mΩ_cm). KMnO4 solutions were also prepared in the same way.

All solutions were prepared at initial pH and metal concentrations so that the
solubility products of the metal hydroxides (pcKso) at 25oC = 19.66, 16.70, 15.00,
12.80 for Cu(OH)2, Zn(OH)2, Ni(OH)2, and Mn(OH)2 respectively were not
exceeded to avoid precipitation. Manganese coated sand was made as in the previous
studies done by the authors (Tizaoui et al., 2012; Rachmawati et al., 2013).

2.1 Analytical Measurements

The concentration of metals was determined using Varian AA240FS Fast Sequential
Atomic Absorption Spectrometry (Varian AA240FS AAS) equipped with Varian
SPS3 Autosampler and connected to Varian SpectAA Worksheet Oriented AA
Software Version 5.1 Pro.
The wavelength, slit width and lamp current of Varian AA240FS used to analyze
copper was 324.8nM, 0.5nM, and 4 mA respectively. The air flow, acetylene flow
and burner height were 13.50 L/min, 2 L/min and 13.5nM respectively. The standard
calibration method was linear. The correlation coefficient limit was 0.998 and
instrument detection limit was 0.0030 mg/L.

BET, SEM/EDX, acid and alkali resistance, acid digestion, point of zero charge and
trace studies analysis were done as in the previous studies done by the authors
(Tizaoui et al., 2012; Rachmawati et al., 2013).

2.2 Activated Unsaturated Sand Filter (AUSF)

A schematic diagram of the AUSF is depicted in Figure 1. The filter was made of a
QVF glass column of 40 mm internal diameter and 610 mm height as is used in the
previous study done by the authors (Tizaoui et al., 2013).

Top perforated plate

Perforated spray

Plastic hose

Sand

Bottom perforated plate

Influent tank Pump

Effluent beaker

Figure 1 A schematic diagram of the AUSF

3 Results and discussion

3.1 Mineralogy of the sand

SEM image of uncoated and coated sand were shown in Figure 1 (a) - (c), similar to
those shown in the previous study done by the authors (Tizaoui et al., 2013). SEM
images of the coated sand that was used to treat individual copper, manganese, zinc
and nickel appeared as fractures and some clusters which were likely those of the
newborn metal complexes, occurred on the surface of the sand (Figure 1 (c) – (f)).
The form of the cluster is unique for each metal. Complexes clusters of copper, had a
long shape with blossomed wings (Figure 1 (c)); of manganese, had rounded shapes
(Figure 1 (d)) and were seemed much smaller than the clusters shown in Figure 1 (b);
of zinc, had a big head shape with a long thin tail (Figure 1 (e)); and of nickel, had an
almost square shape (Figure 1 (f)).
 (a) (b)
(c)

(d) (e) (f)

Figure 1 SEM micrographs for : (a) uncoated (b) coated sand; (c) copper (d)
manganese (e) zinc (f) nickel bearing coated sand (dsand = 0.710mm, qMn/qsand =
0.0709 mg Mn/g sand, Cin = 20 mg/L)

3.1.2 SEM/EDX analysis

Previous study done by the authors (Tizaoui, et al., 2013) showed the attachment of
Mn oxide to the surface of sand through the EDX spectra of the coated sand. Figure 3
(a) – (c) depict the EDX spectra for manganese, zinc and nickel bearing coated sand.
Besides the elements occurred in the coated sand, the figure clearly shows the
appearance of each metal signal. These metal signals specify that the coated sand
was effective in removing the metals which likely occurred through precipitation and
adsorption processes.

SEM/EDX elemental analysis (not shown here) also shows that the coated sand was
effective in removing the metals. This is supported by the SEM/EDX line mapping
(not shown here) and scanning that show that each metal was attached onto the
surface of the coated sand. Figure 4 (a) – (c)) show the metal cluster as clearly
supported by its peak. This supports the proposed theory of electrostatic attraction
between the negatively charged manganese oxides with the positively charged
cations as discussed later.
 2 (a) 2 (b)
1

5
3 4
3
5a 7 1a
5 6 1a 3a 5a 7a
4

1 2 (c)

5
4

1a
3a
9 6 5a
8
9a

Figure 3 EDX spectra for: (a) manganese (b) zinc and (c) nickel beraing coated sand (dsand = 0.710mm,
qMn/qsand = 0.0709 mg Mn/g sand, Cin = 20 mg/L): 1, 1a = Mn; 2 = Si; 3, 3a = C, Ca; 4 = Al; 5, 5a = Fe; 6 = K;
7, 7a = Zn; 8 = Mg; 9, 9a = Ni.

M S O O S
O C O
(a) (b) i C

Al
Si
Al Si

M
K Mn Zn
Ca Mn
A C O
(c)
Fe
Al Fe
Mg Zn

Si
K

M
Ca

Fe N

Figure 4 SEM/EDX line scanning for: (a) manganese (b) zinc and (c) nickel bearing coated sand
(dsand = 0.710mm, qMn/qsand = 0.0709 mg Mn/g sand, Cin = 20 mg/L)
3.1.3 Specific surface area

Results from the previous study done by the authors (Tizaoui et al., 2013) show that
surface area of sand increased (by 21%) after coating with Mn. This indicates that
coating the sand would result in increased adsorption sites hence giving better
removal. In contrast, for Cu bearing coated sand, the surface area was almost halved.
This reduction may be due to blockage of the adsorption sites by the adsorbed Cu
complexes.

3.1.4 Other results on sand particles characterisation

Previous study done by the authors also revealed that a careful control of pH > 4.5
assures high resistance to Mn (acid and alkali resistance tests); the pzc for the coated
sand occurred at pH=7.75; pH for uncoated sand = 7.3, for the coated sand = 7.81
(batch tests); and there was no manganese leaching from the coated sand (the acid
digestion analysis) as has been proved by AUSF results (Tizaoui et al., 2012;
Rachmawati et al., 2013).

4.2 Sand bed characterisation: Tracer studies

Tracer studies done by the authors recently, showed that the flow approaches plug
flow but with low dispersion, which validates the model used to describe the
observed experimental results; and that operating at lower flow rates gives better
removal percentages, and proved that when the flow was introduced at the top of the
column, the sand bed was not fully submerged in water, hence the system operated
under unsaturated conditions (Tizaoui et al., 2013).

5. Removal of metals

The following definitions have been used in the calculations made in this study. The
mass of copper removed by the activated sand column (mr) at a time t was calculated
using Equation 1, which was derived from a mass balance over the volume of the
column and the trapezoidal rule was used to calculate numerically the integral part.
Besides the mass removed by the sand, Equation 1 accounts for a negligible mass of
copper accumulated within the filter voidage as well, which was found less than 4%
of the total as calculated by Equation 1. The removal capacity of AUSF, q, at a
particular time was defined as the mass of copper removed, mr, over the mass of sand,
ms, (q = mr/ms). The ratio of maximum metal adsorbed to the amounts of manganese
was defined as qMmax/qMn, where qMmax= the maximum metal adsorbed onto the sand
and qMn = the amounts of manganese on the sand.
t
 C    C   C  
mr  QCin  1  dt  QCin  0.5  t i 1  t i  2      
  Cin   i 
0 Cin  i  i 1  C in

(Equation 1)

5.1 Removal of copper, manganese, nickel and zinc

The removal of copper, manganese, nickel and zinc are shown in Figure 5 (a – c). Q,
H, msand, Cin, dsand, and manganese to sand ratio were kept constants at 25.01 mL/min,
450 mm, 869.77 g, 20 mg/L, 0.400 mm, and 0.0709 mg-manganese/g-sand
respectively.

Figure 5 (a-b) shows that mass metal retained and the removal capacity of AUSF for
each element after saturation (except for copper where these removals were
calculated at 480 min) was in the order of copper > manganese > zinc > nickel. The
order shows that AUSF had a stronger affinity for Cu2+ than Ni2+. This is in line with
Boujelben et al (2009) who studied the adsorption of nickel and copper (individually
and mixed) onto natural iron oxide-coated sand.

16 250 0.25 0.240

(a) (b)
Removal capacity, q (mg-
Mass metal retained (mg)

14
Mass copper retained (mg)

0.20
200
metal/g-sand)

12
0.15
10 150
8 0.10
Mn 100
6 Zn 0.05
4 Ni 0.017 0.011
Cu 50 0.002
0.00
2

0 0
0 100 200 300 400 500
Time (min)

Figure 5 AUSF performances for individual copper, manganese, nickel and zinc
(Cin = 20 mg/L, Qin = 25.01 mL/min, dsand = 0.400 mm, H = 450 mm, msand =
869.77 g, qMn/qsand = 0.0709 mg Mn/g sand) (a) mass metal retained (mg) vs time
(min) (b) removal capacity, q
Previous studies revealed that the adsorbent affinity towards metal ions will vary
depending on the pH value of the solution, ionic strength (Reddad et al., 2002),
hydration enthalphy of the cations (Ricordel et al., 2001), and electro-negativity of
the atom (Greenwood and Earnshaw, 1997).

The ionic strength theory cannot be applied in this study as the ionic strength was not
changed in this study. The hydration enthalpy and the electro-negativity of the atom
theory cannot also be used in this study as they would result in a different removal
order of the metal ions with that of the result. The pH theory, on the other hand,
would be more appropriate to be applied in this case, as it is more likely to affect the
removal order as discussed next.

5.2 Proposed processes for the removal of copper, manganese, nickel and zinc

Copper, manganese, zinc and nickel will form hexa-aqua complexes once they are
dissolved in water (Stumm and Morgan, 1996; Winter and Andrew, 2000). These
complexes donate a proton to a water molecule to produce the hydrated proton H3O +
as follows (Winter and Andrew, 2000):
[M(H2O)6] 2+ (aq) + H2O (l) → [M(H2O)5OH]+ (aq)+ H3O (aq) + ...(Equation 2)
where M = metal. Therefore, they are weakly acidic in water (pH values for input
copper, zinc, nickel and manganese are 5.58, 5.66, 5.71 and 5.64 respectively).
The process by which copper, manganese, zinc and nickel removed in the AUSF may
be best described as follows:

1. Precipitation

The occurrence of precipitation of metal hydroxide depends on the metal

concentration in and the pH value of the solution. Table 1 depicts the pH values at
which these metals will theoretically precipitate for metal concentration of 20 mg/L.
For copper, theoretically copper will precipitate as hydroxide at pH > 5.92 (pH
critical). By taking this pH critical into account and knowing that the pH value for
the 480 min operational period was decreasing from 8.48 to 7.06 (Figure 6 (a)), then
precipitation is assumed to be the dominant process during this period (0 ≤ t ≤ 480
min). Similarly for zinc and nickel, precipitation might be the dominant process
during 0 ≤ t < 80 min (Figure 6 (c)), and 0 ≤ t < 1 min (Figure 6 (d)) respectively. For
manganese, however, it is then believed that manganese would not precipitate in the
experiment (Figure 6 (b)).

The precipitation process of the metals may be written as follows:

M2+ (aq) + 2OH- (aq) M(OH)2(s)....(3) (Tchobanoglous et al., 2004)
or
[M(H2O)6] 2+ (aq) + 2OH- (aq) [M(OH)2(OH2)4](s) + 2H2O (l)....(Equation 4) (Winter
and Andrew, 2000).
Where M = metal (copper, zinc or nickel)

The release of hydroxide ions is in line with the experiment done with pure water.
Indeed the pH of influent pure water was about 6.15 and after passing through AUSF,
its pH increased to 8.35 and as water passed through the column, the pH gradually
reduced to 6.47 in 60 minutes.

2. Electrostatic attraction

Electrostatic attraction results from the interaction between species having opposite
charges and since the charge of the surface is affected by pH, point of zero charge
(pzc) of the Mn-coated sand was determined. A value of pzc equal to 7.75 was
obtained. This indicates that at pH values above the pzc, the surface of the Mn-
coated sand is negative (i.e. MnO- predominates; Equation 5), which favours
removal of the positively charged hexaaquametal complex; while at pH values less
than pzc, the removal by electrostatic attraction is expected to be less significant
since positive surface predominates (i.e. MnOH2+; Equation 6). The electrostatic
attraction results in metal adsorption as illustrated by Equations 7 and 8. Adsorption
of metal may also take place on a neutral surface as illustrated by Equation 9.
MnOH MnO- + H+ ….(Equation 5)
MnOH + H +
MnOH2+ ….(Equation 6)
MnO- + M2+ MnOM2+ ….(Equation 7)
2(MnO-) + M2+ (MnO-) 2M2+ ….(Equation 8)
MnOH + M2+ M(Mn-OH)2+ ….(Equation 9)

As there was an increase in copper removal as the pH increases (pH = 8.48 – 7.75, 0
≤ t ≤ 65 min), it is then believed that at pH > 7.75, the coated sand is negatively
charged. This negative surface charge increased as the pH increased resulting in a
greater electrostatic attraction between the surface and the copper ions. Similarly for
zinc, nickel, and manganese, the period for electrostatic attraction is 0 ≤ t < 10 min,
0 ≤ t ≤ 150 min, and 0 ≤ t ≤ 270 min respectively.

3. Adsorption/Ion exchange and surface complex formation

The pH values of the solutions were decreasing from the beginning to the end of the
experiments (Table 1). This indicates that the mechanism by which metal was
adsorbed onto the coated sand might involve an exchange reaction of metal cations
(M2+) with H+ on the surface and surface complex formation.

Based on the principle of ion-exchange, the more metal adsorbed onto the coated
sand, the more hydrogen ions are released resulting in the decrease in the pH value.
The complex reactions of M2+ with manganese oxide may be written as follows
(Stumm and Morgan, 1996):
≡Mn−OH + M2+ ≡Mn−O-M2+ + H+ ….(Equation 10)
≡Mn−O- + M2+ ≡Mn−O-M2+ ….(Equation 11)
2(≡Mn−OH) + M2+ (≡Mn−O-)2M2+ + 2H+ ….(Equation 12)
2(≡Mn−O-) + M2+ (≡Mn−O-)2M2+ ….(Equation 13)
≡Mn−OH + M2+ + H2O ≡Mn−OMOH + 2 H+ ….(Equation 14)

Equation 10, 12 and 14 show that the hydrogen ion concentration increased with an
increasing amount of metal ions adsorbed onto the coated sand. Copper, manganese,
zinc and nickel would undergo adsorption/ion exchange and surface complexation
processes at 0 ≤ t ≤ 480 min, 0 ≤ t ≤ 270 min, 0 ≤ t ≤ 240 min, and 0 ≤ t ≤ 150 min
respectively when their pH values were decreasing (Figure 6 (a-d)). For zinc, after
240 min, there was no removal and the pH value decreased from 7.34 to 5.66.

The assumed metals (copper, zinc, manganese and nickel) speciation occurred in the
water at certain pH are as follows. The dominant species for pH ≤ pH critical of
metals, may be that of M2+ (aq) or M(OH)+ (aq) whereas for pH > pH critical, may be
that of M(OH)2 (s). Other species for pH ≤ pH critical of metals, may be that of
≡Mn−O-M2+ or (≡Mn−O-)2M2+ or ≡Mn−OMOH while for pH > pH critical, may be
that of M2+ (aq) or M(OH)+ (aq) or ≡Mn−O-M2+ or (≡Mn−O-)2M2+ or ≡Mn−OMOH.
The proposed reactions for the studied individual metals occurred in the AUSF are
depicted in Figure 7 (a-d).

9 9 10 20
8 8 9
7 7 8 16
(a) Copper
6 6 7

C (mg/L)
(b) Manganese

C (mg/L)
6 12
5 5

pH
5
pH

4 4
4 8
3 3
pH 3
2 2 pH
C (mg/L) 2 4
1 1 pzc
pzc 1
C (mg/L)
0 0 0 0
0 100 200 300 400 0 200 400
Time (min) Time (min)

20
8 9 20
8
7 16
7 15
6 (c) Zinc (d) Nickel
6
5 12

C (mg/L)
5
C (mg/L)
pH

pH

4 10
4
8
3 3
pH pH 5
2 2
pzc 4
pzc
1 1
C (mg/L) C (mg/L)
0 0 0 0
0 100 200 300 400 0 100 200 300 400
Time (min) Time (min)

Figure 6 pH for individual metal solutions in AUSF (H = 450 mm, Cin = 20 mg/L,
Q = 25.01 mL/min, msand = 869.77 g, dsand = 0.400 mm, qMn/qsand = 0.0709 mg
Mn/g sand) (a) Copper (b) Manganese (c) Zinc (d) Nickel
Table 1. pH values for hydroxide precipitation of the studied metals*
Metal hydroxide Theoretical pH Solubility products Experimental pH
(pcKs0) at 25oC
Cu(OH)2 > 5.92 19.66** 8.48 - 7.06
Zn(OH)2 > 7.41 16.70** 8.23 – 5.66
Ni(OH)2 > 8.23 15.00** 8.44 – 5.71
Mn(OH)2 > 9.32 12.80*** 8.81 – 5.64
Note:
* For metals concentration of 20 mg/L
** (Tchobanoglous et al., 2004)
*** (Snoeyink and Jenkins, 1980)

(a) (b) Adsorption/Ion Exchange & Surface Complexation,

0 ≤ t ≤ 240 min
Adsorption/Ion Exchange & Surface
Complexation, 0 ≤ t < 60 min

Electrostatic attraction,
Electrostatic attraction, 0 ≤ t < 10 min
0 ≤ t ≤ 65 min

Precipitation, 0 ≤ t < 80 min

Precipitation, 0 ≤ t < 4 min

pH 7.34 7.41 7.75 8.23

pH 7.06 7.75 8.48
(c) Adsorption/Ion Exchange & Surface
(d)
Adsorption/Ion Exchange & Surface
Complexation, 0 ≤ t ≤ 150 min
Complexation, 0 ≤ t ≤ 270 min

Electrostatic attraction, 0 ≤ t ≤ 150 min

Electrostatic attraction,
0 ≤ t ≤ 270 min
Precipitation,
0 ≤ t < 1 min

pH 7.79 8.81
pH 7.89 8.23 8.44

Figure 7 Proposed processes that occurred for individual metal removals in the
AUSF (H = 450 mm, Cin = 20 mg/L, Q = 25.01 mL/min, msand = 869.77 g, dsand =
0.400 mm, qMn/qsand = 0.0709 mg Mn/g sand) (a) copper (b) zinc (c) nickel (d)
manganese

According to Figure 7, the removal order for the studied metals based on the
precipitation, electrostatic attraction, and adsorption/ion exchange and surface
complexation processes is Cu > Zn > Ni > Mn; Mn > Ni > Cu > Zn; Cu > Mn > Zn >
Ni respectively. From Section 5.1, it is revealed that the order of mass retained and
removal capacity was Cu > Mn > Zn > Ni. Taking these ranking of order altogether,
it is then concluded that the order for individual metal removal in the AUSF is Cu >
Mn > Zn > Ni.

6.3 Conclusions

In this study a successful activated unsaturated sand filter (AUSF) was developed.
The BET and SEM/EDX results support the assumed mechanism of copper removal.
pH theory was assumed to be best applied in the removal of individual metals. The
order of removal for metals was Cu > Mn > Zn > Ni. This order was based on the
removals order with regard to the precipitation, electrostatic attraction,
adsorption/ion exchange and surface complexation processes; and the mass retained,
and removal capacity.

Acknowledgments

Sugihhartati Dj Rachmawati would like to thank Alex M. Lord (Swansea University)

for his help in conducting SEM/EDX analysis.