Fanta et al.

BMC Chemistry (2019) 13:44

https://doi.org/10.1186/s13065-019-0563-1 BMC Chemistry

RESEARCH ARTICLE Open Access

Copper doped zeolite composite

for antimicrobial activity and heavy metal
removal from waste water
Feleke Terefe Fanta1, Amare Aregahegn Dubale1*, Dawit Firemichael Bebizuh1
and Minaleshewa Atlabachew2,3* 

Abstract 
Background:  The existence of heavy metals and coliform bacteria contaminants in aquatic system of Akaki river
basin, a sub city of Addis Ababa, Ethiopia has become a public concern as human population increases and land
development continues. Hence, it is the right time to design treatment technologies that can handle multiple
pollutants.
Results:  In this study, we prepared a synthetic zeolites and copper doped zeolite composite adsorbents as cost
effective and simple approach to simultaneously remove heavy metals and total coliforms from wastewater of Akaki
river. The synthesized copper–zeolite X composite was obtained by ion exchange method of copper ions into zeolites
frameworks. Iodine test, XRD, FTIR and autosorb IQ automated gas sorption analyzer were used to characterize the
adsorbents. The mean concentrations of Cd, Cr, and Pb in untreated sample were 0.795, 0.654 and 0.7025 mg/L
respectively. These concentrations decreased to Cd (0.005 mg/L), Cr (0.052 mg/L) and Pb (bellow detection limit, BDL)
for sample treated with bare zeolite X while a further decrease in concentration of Cd (0.005 mg/L), Cr (BDL) and Pb
(BDL) was observed for the sample treated with copper–zeolite composite. Zeolite X and copper-modified zeolite X
showed complete elimination of total coliforms after 90 and 50 min contact time respectively.
Conclusion:  The results obtained in this study showed high antimicrobial disinfection and heavy metal removal
efficiencies of the synthesized adsorbents. Furthermore, these sorbents are efficient in significantly reducing physical
parameters such as electrical conductivity, turbidity, BOD and COD.
Keywords:  Wastewater, Copper-doped zeolite X, Adsorption, Heavy metals, Disinfection, Akaki river

Introduction persistent heavy metals (like Pb, Cr and Cd), which are
Rapid population growth and the consequent increase in harmful to humans when they exceed permissible limits.
anthropogenic activities have resulted in high demand As per the World Health Organization’s (WHO) guide-
for scarce water resources, generation of large volumes line, the maximum permissible limits of these pollutants
of wastewater requiring treatment technologies capa- in drinking water are 0  CFU/mL for faecal coliforms,
ble of removing multiple pollutants [1]. Major pollut- 0.003  mg/L for Cd, 0.01  mg/L for Pb and 0.05  mg/L for
ants of concern include pathogenic microorganisms and Cr [2–4].
Addis Ababa, the capital city of Ethiopia, has many riv-
ers and tributaries. Among which, Akaki Rivers (Little
*Correspondence: [email protected]; [email protected]
1
Department of Chemistry, College of Natural and Computational Akakki and bigger Akaki rivers) are those rivers which
Science, Energy and Environment Research Center, Dilla University, 419, receives polluted water from several tributaries such as
Dilla, Ethiopia
2
Kebena, BancheYeketu, Kortame, Bulbula, LequSoramba,
Department of Chemistry, College of Science, Bahir Dar University,
P.O. Box 79, Bahir Dar, Ethiopia kotebe and Fincha rivers etc. [5]. These river tributaries
Full list of author information is available at the end of the article are becoming an environmental concern in Addis Ababa

© The Author(s) 2019. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License
(http://creat​iveco​mmons​.org/licen​ses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium,
provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license,
and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creat​iveco​mmons​.org/
publi​cdoma​in/zero/1.0/) applies to the data made available in this article, unless otherwise stated.
Fanta et al. BMC Chemistry (2019) 13:44 Page 2 of 12

city and its vicinity areas, where (more than 40% of large However, there is no report showing the simultaneous
and medium scale manufacturing industries are located heavy metal and microbial removal efficiency of unmodi-
and some of these industries discharge their effluents to fied and modified synthetic zeolite.
these rivers without being properly treated [5, 6]. As a Thus, this study was aimed to demonstrate the simul-
result, Akaki river is believed to be highly polluted chem- taneous removal effect of copper doped and unmodified
ically, physically and bacteriologically, and as a result the synthetic zeolite for decreasing the heavy metals, bio-
river water is unfit for domestic, industrial, commercial logical load and some physical parameters (BOD, COD,
and agricultural uses [5]. Therefore, those industries dis- turbidity and electrical conductivity) in wastewater treat-
charging their effluents to this river and river tributar- ment processes.
ies require more treatment technologies that can handle
multiple pollutants [7]. Methods/experimental
Among the various treatment technologies, ion Chemicals and reagents
exchange and adsorption are feasible and cost effective All chemicals used were analytical grades. Two kilogram
to remove heavy metals using an exchanger/sorbent with of Kaolin sample was collected from Hadiya zone Balesa
high selectivity for the target metal [8]. In the last few district, Ethiopia. ­CuSO4 as precursor for loading cop-
decades, sorbents for the treatment of heavy metals con- per, deionized water for washing the adsorbent, ­HNO3
tamination have been investigated. Numerous waste bio- and NaOH for pH adjustment, ascorbic acid as reductant
mass sources such as rice husk, saw dust, tea and coffee were used in the experiment.
waste, orange peel peanut shells, activated carbon, dry
tree leaves and barks, papaya seed, egg shell and coco- Instruments and apparatus
nut leaf powder were used as adsorbent for the removal Inductively coupled plasma atomic emission spectrom-
of heavy metals from various waste water sources [9–12]. etry (ICP-AES) Perkin Elmer 4300 DV model from USA
However, these adsorbents have several limitations such was used to quantify the mass of copper dissolved in the
as stability, reusability and others. leach liquor after adsorption experiment. Flame atomic
An alternative to the natural products, low-cost zeolite absorption spectroscopy (FAAS) equipped with deu-
sorbents, which have unique ion exchange and sorption terium background corrector and air-acetylene flame
properties, have been investigated as candidates for cost- system was used to quantify the heavy metals before
effective removal of heavy metals from waste solution. and after absorption; X-ray diffraction (XRD), Fourier-
Synthetic, natural and modified zeolites have been tested transform infrared radiation (FTIR) and autosorb IQ
[1, 8, 13]. However, the modified and synthetic zeolites automated gas sorption analyzer were used to character-
were found to be advantageous in terms of purity, uni- ize the adsorbent; pH meter, turbidity meter (VSI-13N
form pore size and better ion exchange abilities as com- NEPHELOMETER), conductivity meter (1153 JENWAY)
pared to natural zeolites [8]. were used to measure physico-chemical parameters of
Regarding microbial disinfection, several physical and the effluents.
chemical methods (chlorination, UV treatment, treat-
ment with ozone, membrane filtration etc.) have been Waste water sampling and study area description
reported. Although these techniques provide water of The Akaki catchment is located in central Ethiopia along
high microbiological quality, they have several limita- the western margin of the Main Ethiopian Rift. The catch-
tions such as expensiveness, formation of byproducts, ment is geographically bounded between 8°46′–9°14′N
requirement of pre-treatment step, and/or being resisted and 38°34′–39°04′E. Composite samples were collected
by some microbials [14]. Thus, as an alternatives strategy, in 2 weeks interval during September–October 2017 and
the application of metal nanoparticles for water disinfec- analyzed for biochemical oxygen demand (BOD), chemi-
tion and treatment had been reported by many research- cal oxygen demand (COD), temperature, turbidity, con-
ers. The metallic nanoparticles are most promising for ductivity, pH and total coliforms. The concentrations of
disinfection as they exhibit high anti bacterial properties the heavy metals, Cd, Pb and Cr were determined using
due to their large surface area to volume ratio. Copper FAAS before and after treatment. The large particles
in the form of nanoparticle has good bactericidal activ- from the effluent sample were removed through sedi-
ity [15]. Hence copper has been immobilized on different mentation and stored at 25  °C in a dark place in acidic
inorganic support materials for a wide range of antimi- medium pH 2 using 1.0 M HCl solution.
crobial applications including water and wastewater
disinfection [15–18]. There is also a report showing the Digestion of waste water sample
bactericide effect of the Mexican natural zeolites modi- Waste water samples were digested with ­ HNO3 and
fied with silver ions in the treatment of wastewater [13]. ­HClO4 in the ratio of 3:1. The samples were digested on
Fanta et al. BMC Chemistry (2019) 13:44 Page 3 of 12

a hot plate at a temperature of 93 °C for 2 h following a in KBr was scanned (64 times) from 4000 to 400  cm−1
method reported by Idera et al. [19]. with a resolution of 4  cm−1. The copper content in the
zeolite, copper modified zeolite and leach liquor samples
Instrument calibration was measured using ICP-AES Perkin Elmer 4300 DV
Calibration curves were prepared to determine the con- model from USA. The specific surface area of the zeo-
centration of the metals in the untreated and treated lite X and copper doped zeolite X were obtained from
effluent sample solution. The FAAS instrument was cali- ­N2 adsorption/desorption data measured at 77.4 K using
brated using four series of working standards (0.1, 0.5, autosorb IQ automated gas sorption analyzer. The sam-
1.0, 1.5  mg/L). For the three metals, a correlation coef- ples were degassed at 50 °C for 3 h prior to ­N2 adsorption.
ficient of 0.9998 was obtained. The specific surface area of the sample was calculated by
using the multiple-point Brunauer–Emmett–Teller (BET)
Synthesis of zeolite and copper doped zeolite method in the relative pressure range (P/Po) of 0.05–0.3
Zeolite X was synthesized following the method which [20].
was originally optimized in our research group. In brief, The loading extent of copper into zeolite X was stud-
the kaolin was washed with distilled water several times ied using ASTM D4607-94 method. Iodine number was
to remove the impurities and dried in an open air for calculated by investigating the adsorption of iodine from
about a week. The dried kaolin sample was ground with solution using 0.1  N standardized iodine solution and
mortar and pestle and then sieved with 0.25  mm mesh the titrant sodium thiosulfate (0.1  N). The milligrams
size sieve. Metakaolin was synthesized by calcinations of iodine adsorbed by 1.0 g of zeolite X when the iodine
of kaolin in muffle furnace at 900 °C for 2 h. About 20 g concentration of the filtrate is 0.02 N was calculated.
of the synthesized metakaolin was treated with 15  mL
of concentrated HCl and allowed to settle for 6  h. The
metakaolin suspension was added to NaOH solution Batch adsorption experiment
to 250  mL borosilicate flask to form a gel, and shaken Batch equilibrium experiments were carried out to find
on an orbital shaker at 270  rpm until equal distribution the optimum adsorbent dose, contact time and initial
of NaOH solution was obtained. To develop the zeolite metal concentration. About 0.5–3.0 g of adsorbent (zeo-
framework, the homogenized sample was allowed to lite X and copper-doped zeolite X) was added into syn-
crystallize at 50 °C for 24 h in water bath and then dried thetic solution of each metal and stirred for 4 h and then
in the oven. The dried sample was washed with deionized kept for 24 h until equilibrium could achieve and filtered.
water to bring the pH 9, dried, powdered and crushed The experiment was carried out in duplicate. The opti-
to uniform pore size. The copper doped zeolite was pre- mum mass of adsorbent was obtained by plotting the
pared by ion-exchange method. About 10 g of the synthe- percentage removal versus the mass of adsorbent. The
sized zeolite X was treated with 0.1 M of copper sulphate effect of contact time in removal of Cd, Cr and Pd using
­(CuSO4) followed by treatment with 0.2 M ascorbic acid. zeolite X and copper doped zeolite X is studied in a con-
The resulting Cu–Zeolite was dried at 70  °C overnight, tact time range of 30 to 105 min. Removal of metal ions
ground using mortar and pestle and characterized for was also carried at different initial concentration of met-
adsorption experiment. Here after, for clarity, the synthe- als (1–25 mg/L).
sized zeolite and copper doped zeolites are named as Z
and CuZ.
Determination of Cd, Cr and Pb in waste water
Characterization before and after treatment with zeolite X and copper
The prepared zeolite X and copper doped zeolite X doped zeolite X
were characterized by X-ray diffraction (XRD), Fourier- Following the optimized procedure, 2  g of bare zeolite
transform infrared radiation (FTIR), inductively coupled X or copper doped zeolite X was added to 50 mL of the
plasma atomic emission spectrometry (ICP-AES) and composite waste water containing the Cd (0.795  mg/L),
autosorb IQ automated gas sorption analyzer. X-ray dif- Cr (0.658 mg/L) and Pb (0.696 mg/L) metals (at pH 7.5).
fraction (XRD) patterns were acquired with a D2 phaser The solution was shaken for 60 min, filtered using What-
XRD-300  W, with measurements taken using Cu Ka man filter paper, acidified to pH < 2 and stored in refriger-
radiation at 40  kV and 100  mA. The X-ray patterns was ated prior to AAS analysis.
recorded a linear silicon strip ‘Lynx Eye’ detector from % metal removal efficiency = [(Ci − Cf )/Ci ] × 100
­ in−1. An FT-IR spec-
10° to 70° at a scan rate of 0.1° m
where ­Ci and C
­ f are the initial and final metal concentra-
trometer (model: Nicolet NEXUS-670) with transmission
tions respectively.
mode was used to obtain the FTIR spectra. Each sample
Fanta et al. BMC Chemistry (2019) 13:44 Page 4 of 12

Bacteriological analysis spiked samples were digested and analyzed in similar

The adsorbent’s microorganism removal efficiency was conditions. Thus, the efficiency of the optimized pro-
tested by taking 100 mL of the river water sample before cedure was checked by spiking 1.0  mL of 100  mg/L of
and after treatment. The number of total coliform was Cr, 12.5 mg/L of Cd and 50 mg/L of Pb into a 50 mL of
counted by using a magnifying glass lens. Total coliform river water sample. As shown in Table 1, the results of
count of waste water samples were determined by plate the percentage recovery for the studied metals in Akaki
count method using Methylene Blue Agar and coliform river sample lie within the acceptable range. Therefore,
colonies were enumerated and expressed as total coli- this verifies that the optimized digestion procedure was
form/100 mL of water samples. valid for the analysis.

Turbidity reduction test

Turbidity of the waste water sample was tested by using Copper loading into zeolite X
portable turbidity meter. Turbidity removal efficiency of Copper doped zeolite X was prepared by ion-exchange
the zeolite X and copper–zeolite X composite were eval- method. Iodine adsorption number is the most funda-
uated and compared. Turbidity of the water samples was mental parameter used to identify pore size of most
measured relative to the turbidity of distilled water hav- adsorbents. It is used to measure the activity level
ing turbidity 2NTU. The turbidity reduction was calcu- (higher degree indicates higher activation), often
lated by the following formula [21].

turbidity of source waste water − turbidity of treated waste water

Turbidity removal (%) = ×100%
turbidity of source waste water

Dissolved oxygen, biochemical oxygen demand

reported in mg/g (with typical range of 500–1200 mg/g)
and chemical oxygen demand test
and the micropores content of the copper doped zeo-
Organic pollutants in wastewater in general consist of
lite X (values > 0 to 20 Å, or up to 2 nm) by adsorption
proteins, carbohydrates and fats and oils; at approxi-
of iodine from solution. The loading extent of copper
mately 50, 40 and 10%, respectively. Priority pollutants,
into zeolite X and their corresponding iodine number
surfactants, and emerging contaminants represent trace
was shown in Table 2. Zeolite X doped with 6.3 g cop-
organic pollutants in wastewater. Dissolved oxygen (DO),
per provided maximum iodine value (641.7 mg/g) indi-
biochemical oxygen demand (BOD) and chemical oxygen
cating good adsorption capacity with high porosity and
demand (COD) considered as the most practical indica-
high surface area. Adsorption capacity of copper doped
tors of water organic pollutants quality [22]. The treated
zeolite increases with increasing the amount of copper
and untreated wastewater samples were analyzed for
loaded from 0.63 to 6.3  g. However, further increase
DO, COD and BOD, according to standard methods for
in copper loading beyond 6.3  g, the adsorption iodine
examination of water and wastewater [23].
value decreases, indicating the presence of less active
sites for adsorption. Thus, based on the determined
Conductivity and pH test iodine value above and in Table 2, the optimum amount
Conductivity and pH of the source river water and the of copper loading into the zeolite framework was 6.3 g.
treated water through zeolite X and copper doped zeolite Therefore, we fully characterized both undoped zeolite
X were measured using conductivity meter and pH meter X (i.e. just zeolite X) and copper doped zeolite X (zeo-
respectively. lite X loaded with 6.3 g of copper).

Results and discussion
Method of detection limit (MDL) and method validation Table 1 Recovery test for  the  optimized procedure
Before quantifying the metals in the water samples, for heavy metals analysis
the method detection limit of the FAAS was evaluated
Elements Conc. Amount Conc. in spiked Recovery (%)
by analyzing six blank samples. It was found that the in sample added sample (mg/L)
method detection limit of Pb, Cd and Cr was 0.07 mg/L, (mg/L) (mg/L)
0.03 mg/L and 0.04 mg/L respectively. The efficiency of
Pb 0.696 2.00 2.57 93.7
the digestion procedure and analytical method (FAAS)
Cd 0.795 0.25 1.03 94.0
was checked by adding known concentration of each
Cr 0.658 1.00 1.65 99.2
metal in waste water sample. The spiked and the non
Fanta et al. BMC Chemistry (2019) 13:44 Page 5 of 12

Table 
2 Iodine value and  mass of  copper loaded nature. The overall finding from XRD pattern suggests
in modified zeolite the incorporation of copper into the zeolite X framework.
Sample Loaded copper (g) Iodine The surface area of the prepared zeolite X and copper
value doped zeolite X samples were investigated by measur-
(mg/g) ing the nitrogen adsorption and desorption isotherms.
1 0.63 478.4 Figure 2a shows the nitrogen adsorption–desorption iso-
2 6.3 641.7 therms of prepared zeolite X and copper doped zeolite X
3 63 584.4 samples. The shape of the isotherms for both samples can
4 126 552.9 be categorized to type V isotherm (i.e. based on IUPAC
5 189 426.2 recommendation) with H4 hysteresis loop, indicating the
existence of mesopores character of the samples. Another
uptake appears at high relative pressure (P/P0 > 0.85) for
both samples are attributed to the filling of macropores
Crystallinity studies of adsorbent
formed by the packing of aggregated particles [24]. The
To investigate the crystal structure and phase transfor-
determined BET surface area of the zeolite X was found
mation of the synthesized zeolite X and copper doped
to be 460 m2/g, which is comparable to that of literature
zeolite X, we carried out XRD measurements of the sam-
reported before [25]. However, the BET surface area of
ples. Figure 1 shows XRD patterns of zeolite X and cop-
zeolite X was decrease to 435 m2/g after copper loading
per doped zeolite X. As clearly seen in Fig.  1a, a strong
(i.e. ­SBET for copper doped zeolite X sample), indicating
diffraction peaks located at 2 Theta values of 14.3, 22.4,
the successful incorporation of copper into the zeolite X
24.5, 31.9, 35.3 and 43.5 are characteristics and match-
frameworks. The decreased in surface area is attributed
ing well with the diffraction patterns of zeolite X peaks
to the fact that Cu are embedded in the pores of zeolite
(JCPDS card number: 01-070-2168), indicating the pro-
resulting partial blocking of the zeolite pore access by
found crystalline nature of the prepared zeolite X. The
copper, leading to a reduction in total specific surface
XRD patters of copper doped zeolite X, shown in Fig. 1b,
area. The textural properties of the samples are summa-
revealed a slight shift in the peak positions to lower
rized in Table  3. Cu loading did not brought significant
degree or higher d-spacing (e.g. peak at 2θ = 29.4, 32.7
effect on pore volume compared with zeolite X. However,
and 41.8) and appearance of new emerging peaks (e.g. at
the effect of Cu loading is more pronounced in decreas-
2θ = 41.8 and 57.1) compared with XRD patterns of zeo-
ing the micropore volume. That is, for zeolite X sample,
lite X (Fig. 1a). The weak intense peaks at 2θ = 14.3 was
the micropore volume represents 94% of pore volume,
disappeared while the more intense peak at 2θ = 24.5
while the value drops to 81% for the copper doped zeolite
becomes broader after incorporation of copper into the
X sample.
zeolite X. A decrease in the intensities of some diffrac-
To determine the structural information of the pre-
tion peaks can be also observed, but the XRD analysis of
pared zeolite X and copper doped zeolite samples, we
the copper doped zeolite X shows excellent crystalline
also carried out measurement of FT-IR spectra of the

Fig. 1  XRD patterns of a zeolite X and b copper doped zeolite X

Fanta et al. BMC Chemistry (2019) 13:44 Page 6 of 12

Fig. 2  a ­N2 adsorption–desorption isotherms and b FTIR spectra of as prepared zeolite X and copper doped zeolite X

Table 3  Textural properties of zeolite X and copper doped lower frequency by copper doped zeolite, indicating the
zeolite X samples successful loading Cu into zeolite frameworks. This is in
Sample SBET ­(m2/g) Pore volume Micropore good agreement with our XRD and BET results.
­(cm3/g) volume
­(cm3/g)
Optimization parameters for removal of metals (using
Zeolite X 460 0.214 0.201
synthetic solution)
Copper doped 435 0.202 0.164
Optimization of absorbent dose (zeolite X and copper doped
zeolite X
zeolite X)
The effects of zeolite X and copper doped zeolite X dos-
ages on the removal of metal ion are illustrated in Fig. 3.
prepared zeolite X and copper doped zeolite X in the The adsorbent dosage was varied from 0.5 to 3 g/25 mL
region from 400 to 4000  cm−1 in KBr using FTIR spec- for both adsorbents. The concentration of Pb, Cd and Cr
trometer. Figure  2b displays the FTIR spectra of zeolite before treatment were 0.696, 0.795, 0.658  mg/L respec-
X and copper loaded zeolite X. As clearly seen in Fig. 2b, tively. At the same operating conditions (stirring speed,
the IR spectra of zeolite X and copper doped zeolite X initial pH and temperature), the concentration of Pb, Cd
are quite similar to each other except that shifts of most and Cr were decreased to 0.214, 0.029 and 0.063  mg/L
vibrations to slightly lower frequency after Cu loading. using zeolite X treatment while to BDL (bellow detection
The presence of a broad band at 3430  cm−1 in zeolite limit), 0.012 and BDL mg/L using copper doped zeolite
X sample can be ascribed to the O–H stretching, and treatment. It is observed from Fig.  3, that the removal
the band shifted towards a slightly lower frequency of efficiency of adsorbents generally improved with increas-
3428 cm−1 for copper doped zeolite X sample. This might ing the amount of zeolite X and copper doped zeolite X.
be due to a decrease in O–H bond strength. The bend- This was as expected because the higher dose of adsor-
ing vibrations of the O–H at 1640  cm−1 showed insig- bent in the solution, the greater availability of exchangea-
nificant change in position by both samples. The peaks ble sites for the ions. At the same adsorbent dose, copper
located at 1446 and 1372 cm−1 are assigned to the O–NO doped zeolite X has better removal efficiency for Pd,
stretching vibrations. The T–O asymmetric stretching Cd and Cr metals (Fig.  3). In this finding, the optimum
are observed at 938  cm−1 whilst the symmetric stretch- adsorbent dose of Pb, Cd and Cr were 2  g, 1  g, 2  g for
ing of T–O (T=Si or Al) due to the internal vibrations zeolite X and 2  g, 1.5  g and 1  g for copper doped zeo-
of the zeolite X framework are observed at 728  cm−1. lite respectively (Fig.  3). At optimum adsorbent dosage
The absorption bands located at 598 and 487  cm−1 are the percent removal efficiency for Pd, Cd and Cr met-
assigned to the vibrations associated with the double six als using zeolite X is (69.5, 96.4 and 90.4%) and for cop-
rings (D6R) that connect the sodalite cages and the inter- per doped zeolite X is (100, 98.5 and 100%) respectively.
nal vibrations due to the bending of the T–O tetrahedral, As shown in Fig.  3a, at low dosage, zeolite and copper
respectively. We observed a slightly shift in vibrations to modified zeolite showed similar performance towards
Fanta et al. BMC Chemistry (2019) 13:44 Page 7 of 12

Fig. 3  Dose effect of zeolite X and copper doped zeolite X for removal of Pb (a), Cd (b) and Cr (c)

removal of lead. This might be due to scarcity of available This indicates, copper doped zeolite X had more active
enough active sites, further indicating copper modifica- sites than bare zeolite X.
tion did not bring significant change in performance at
low dosage. Effect of the initial metal ion concentration
To investigate the effect of initial concentration on the
removal efficiency of heavy metals, we also carried out
Optimization of absorbent contact time intensive optimization experiments revealing the effect
The effect of contact time on the percentage removal of of initial metal concentration. To different 50  mL size
each metal was also studied in duplicate analysis by using Erlenmeyer’s flask, 25 mL sample of 1, 5, 10, 15, 20 and
optimum adsorbent dosage (zeolite X and copper doped 25 mg/L concentrations of Pb, Cd and Cr were added. To
zeolite X). The applied time intervals were 30, 45, 60, 75, each of the above metal concentration, optimum dose of
90, and 105 min. As shown in Fig. 4, increasing the con- zeolite (2 g, 1 g, 5 g) and copper doped zeolite (2 g, 1.5 g
tact time increases the percentage removal of each metal and 1 g) for Pb, Cd and Cr were added, and the mixture
until the system reaches the adsorption equilibrium. were mechanically stirred for their optimum time. After
From this study, it is found that the optimum contact filtration the concentration of Pb, Cd and Cr were ana-
time revealing maximum percentage removal of Pd, Cd lyzed using atomic absorption spectroscopy. The effects
and Cr were 75, 105, 90 min and 45, 45, 60 min for zeolite of initial metal concentration on the % retention of Pb,
X and copper doped zeolite respectively. In all the cases, Cd and Cr by zeolite X and copper doped zeolite X is
copper doped zeolite X provided maximum percentage shown in Fig.  5. As shown in Fig.  5, except for Cr, the
removal of Pd, Cd and Cr (100, 98.4 and 100%) in short percentage removal efficiency Pb and Cd increases with
period of time than bare zeolite X (69.7, 96.3 and 90.4%). increasing metal concentration in the aqueous solutions,
Fanta et al. BMC Chemistry (2019) 13:44 Page 8 of 12

Fig. 4  Effect of contact time on the removal of Pb (a), Cd (b) and Cr (c) by zeolite X and copper doped zeolite X adsorbent

and reached the saturation point at higher initial concen- doped zeolite X) and the metal ions; and decrease in the
trations. It is revealed that copper doped zeolite x exhib- available active sites for adsorption due their saturation.
ited efficient removal efficiency of Cd and Cr compared
with undoped zeolite x while comparable response for Pb Leaching test
particularly at higher initial concentration. At the same We conducted leaching tests to further evaluate the sta-
initial concentration of each metal (i.e. 5 mg/L), the max- bility of the adsorbent. The mass of copper dissolved in
imum retention of the zeolite X and copper doped zeolite the leach liquor after adsorption experiment was deter-
X were found to 93.7, 95.9 and 93.0% and 90.7, 97.7 and mined by elemental analysis in comparison with the orig-
100% for Pb, Cd and Cr respectively. inal one in the zeolite framework. After 1  h adsorption
The increase in adsorption or removal capabilities of experiment a very negligible (0.78 ppb) amount of copper
the adsorbents with increasing in metal ions concentra- was detected in the leach liquor for the prepared copper
tion could be explained by an acceleration of diffusion doped zeolite powder (Table 4). A low amount of copper
of metal ion into the adsorbents because of increase in detection in the leach liquor after adsorption test con-
concentration gradient with increase in initial metal ion firms relatively a good adhesion of copper with the adsor-
concentration. As a result, the extent of each metal ion bent material (i.e. zeolite).
uptake by the adsorbents increases significantly with
the increase of contact time. The slight decrease in the Application of zeolite X and copper doped zeolite X
removal capacity or being remain constant after the satu- into adsorption experiment (real water samples from Akaki
ration point of the adsorbents at higher initial metal ion river)
concentration could be due to higher probability of colli- Lead, cadmium and chromium removal efficiency of the
sion between the adsorbent particle (zeolite X and copper prepared adsorbents, zeolite X and copper doped zeolite
Fanta et al. BMC Chemistry (2019) 13:44 Page 9 of 12

Fig. 5  Effect of initial metal concentration on the % retention Pb (a), Cd (b) and Cr (c) by zeolite X and copper doped zeolite X

Table 4  ICP-OES test X, were tested on real water samples under optimized
conditions. As it is clearly seen from Table  5, the con-
Sample Concentration
centrations of Pb, Cd and Cr in the waste water samples
Initial raw material (i.e. zeolite) 0.00 mg/L before treatment were higher than the permissible level
Copper doped zeolite before adsorption experiment 80 mg/L (0.696, 0.795 and 0.658  mg/L respectively for Pb, Cd
Copper doped zeolite leach liquor after adsorption 0.78 µg/L and Cr). This concentration was reduced to BDL, 0.005
experiment and 0.052  mg/L after the treatment with the adsorbent

Table 5  Pb, Cd and  Cr removal from  the  real water samples (Akaki river) using zeolite X and  copper doped zeolite X
at optimized conditions
Metal Concentration After treatment with zeolite X After treatment with copper doped
before treatment (mg/L) zeolite X
Concentration (mg/L) Removal efficiency Concentration (mg/L) Removal
efficiency

Pb 0.696 BDL 100 BDL 100

Cd 0.795 0.005 99.37 0.005 99.37
Cr 0.658 0.052 92 BDL 100
Fanta et al. BMC Chemistry (2019) 13:44 Page 10 of 12

Zeolite X and BDL, 0.005 and BDL for samples treated zeolite X enables completely eliminating microbes after
with copper doped zeolite X, respectively. Zeolite X and 90 and 50 min contact time on average, demonstrating its
zeolite X doped with optimum copper loading have simi- effectiveness as a disinfectant respectively. Copper doped
lar removal efficiency for Pb and Cd. Whereas copper zeolite X with relatively high porosity and short contact
doped zeolite X has better removal efficiency of Cr than time had good efficiency in removing microbial from
bare zeolite X. bacterially contaminated water sources. When microor-
ganism in contact with zeolite X and copper doped zeo-
Microbial removal efficiency lite X, there might be strong suffocation on their path due
As indicated in Table  6 and Fig.  6, the concen- to the tortuosity of the path, and at the same time they
tration of total coliform before treatment was compete for feeding which reduce the number of micro-
5.45 × 104  CFU/100  mL and after treatment in the fil- bials after treatment.
trates runs was zero (CFU) per 100 mL of sample water.
This was however expressed in terms of percentage Properties of water samples before and after treatment
reduction of total coliform removal denoted the micro- Table 7 shows the physico-chemical parameters data of
bial removal efficiency of 100% both for zeolite X and the water sample before and after treatment. It can be
copper doped zeolite X. This is most likely obtained due concluded that most of the parameters were changed
to high porosity of the adsorbent because of the high per- after treatment towards the safe limit set by WHO.
centage of contact time. Zeolite X and copper-modified The reduction of COD and BOD might be the organic

Table 6  Microbial removal efficiency of the adsorbents

Code Sample Total coliform (CUF) % removal

A Raw sample 5.45 × 104 CFU/100 mL –

B Treated sample with zeolite X (at its optimum time) 0 100
C Treated sample with copper doped zeolite X (at its optimum time) 0 100

Fig. 6  Total coliform counting after incubation of 2 days (48 h) of raw sample (a) and after treated with zeolite X (c); and before treated (b) and after
treated with copper doped zeolite X (d)
Fanta et al. BMC Chemistry (2019) 13:44 Page 11 of 12

Table 7  Properties of raw water before treatment and after treatment with adsorbents

Parameter Raw sample (A) Water sample treated with zeolite Water sample treated
(B) with copper doped
zeolite (C)

Temperature (°C) 22.45 22.12 22.42

pH 7.301 7.5 7.5
Conductivity (μS/cm) 585 13.6 27.6
Turbidity (NTU) 78.6 4.7 4.2
DO (mg/L)
 Before incubation (average) 4.8 6.2 5.8
 After incubation (average) 2.658 5.426 5.146
BOD (mg/L) 22.14 7.74 6.54
COD (mg/L) 219.2 6.8 7

compounds from the river’s wastewater trapped in the Authors’ contributions

FTF performed the experiments; AAD, DFB and MA designed the study; FTF
pores of zeolite and copper-doped zeolite adsorbents. collected the data and drafted the manuscript; AAD and MA edited the manu-
Hence, the oxygen needed to oxidize the organic sub- script. All authors read and approved the final manuscript.
stances becomes minimal and subsequently the COD
Author details
and BOD content decreased significantly. 1
 Department of Chemistry, College of Natural and Computational Science,
Energy and Environment Research Center, Dilla University, 419, Dilla, Ethiopia.
2
 Department of Chemistry, College of Science, Bahir Dar University, P.O.
Box 79, Bahir Dar, Ethiopia. 3 Blue Nile Water Institute, Bahir Dar University, P.O.
Conclusions Box 79, Bahir Dar, Ethiopia.
The use of copper-doped synthetic zeolite and bare
synthetic zeolite were investigated for their combined Acknowledgements
The authors are thankful to Dilla University and Bahir Dar University, Ethiopia
heavy metal removal, antibacterial activity and reduc- for the financial support and provision of laboratory facilities.
tion of physical parameters (BOD, COD, turbidity and
electrical conductivity). The synthesized materials Competing interests
The authors declare that they have no competing interests.
were characterized by X-ray diffraction (XRD), Fou-
rier-transform infrared radiation (FTIR), autosorb IQ Availability of data and materials
automated gas sorption analyzer and multiple-point The dataset used and/or analyzed during the current study are available from
the corresponding author on reasonable request.
Brunauer–Emmett–Teller (BET) method. The over-
all experimental results show that both bare zeolite X Funding
and the copper-doped synthetic zeolite X exhibited Not applicable.
good antibacterial properties and heavy metal as well
as physical parameters removal efficiency. However, the Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in pub-
later material showed complete removal of the heavy lished maps and institutional affiliations.
metals under the same condition and with complete
elimination of bacteria within 90 and 50 min of contact Received: 6 January 2019 Accepted: 20 March 2019
time respectively when bare zeolite X and the copper-
doped synthetic zeolite X used. Hence, this adsorbent
has very good potentials for simultaneous removal of
References
microbes, organic maters and toxic metals removal
1. Tabassum N, Rafique U, Ashraf MA (2016) Metal doped green zeolites for
from high-volume contaminated wastewaters. It also waste water treatment: a sustainable remediation model. J Chem Soc Pak
provides a substitute for the use of other expensive and 38:424–437
2. WHO (2011) Guidelines for drinking-water quality, 4th edn. World Health
less efficient materials as adsorbent.
Organization, Geneva
3. Lee CR, Cho I, Jeong B, Lee S (2013) Strategies to minimize antibiotic
resistance. Int J Environ Res Public Health 10:4274–4305
Abbreviations 4. Tripathi A, Ranjan MR (2015) Heavy metal removal from wastewater using
FTIR: Fourier-transform infrared spectroscopy; DO: dissolved oxygen; BOD: low cost adsorbents. J Bioremediat Biodegrad 6:1–5
biochemical oxygen demand; COD: chemical oxygen demand; XRD: X-ray dif- 5. Yohannes H, Elias E (2017) Contamination of rivers and water reservoirs
fraction; Z: zeolite; CUZ: copper doped zeolites; BET: Brunauer–Emmett–Teller; in and around Addis Ababa city and actions to combat It. Environ Pollut
MDL: method detection limit; BDL: bellow detection limit; ICP-OES: inductively Climate Change 1:1–12
coupled plasma optical emission spectrometry.
Fanta et al. BMC Chemistry (2019) 13:44 Page 12 of 12

6. Mulu A, Ayenew T, Berhe S (2013) Impact of slaughterhouses effluent on 17. Harikumar PS, Aravind A (2016) Antibacterial activity of copper nanoparti-
water quality of Modjo and Akaki river in Central Ethiopia. Int J Sci Res cles and copper nanocomposites against Escherichia coli bacteria. Int J Sci
6:2319–7064 5:83–90
7. Akhigbe L, Ouki S, Saroj D, Lim XM (2014) Silver-modified clinoptilolite for 18. JankauskaitĿ V, VitkauskienĿ A, Lazauskas A, Baltrusaitis J, ProsyĿevas
the removal of Escherichia coli and heavy metals from aqueous solutions. I, AndruleviĿius M (2016) Bactericidal effect of graphene oxide/Cu/
Environ Sci Poll Res 21:10940–10948 Ag nanoderivatives against Escherichia coli, Pseudomonas aeruginosa,
8. Yuna Z (2016) Review of the natural, modified, and synthetic zeolites for Klebsiella pneumoniae, Staphylococcus aureus and Methicillin-resistant
heavy metals removal from wastewater. Environ Eng Sci 33:443–454 Staphylococcus aureus. Int J Pharm 511:90–97
9. Nguyen TAH, Ngo HH, Guo WS, Zhang J, Liang S, Yue QY, Li Q, Nguyen TV 19. Idera F, Omotola O, Paul UJ, Adedayo A (2014) Evaluation of the effective-
(2013) Applicability of agricultural waste and by-products for adsorp- ness of different acid digestion on sediments. IOSR J App Chem 7:39–47
tive removal of heavy metals from wastewater. Bioresour Technol 20. Ahmed IN, Yang XL, Dubale AA, Li RF, Ma YM, Wang LM, Hou GH, Guan
148:574–585 RF, Xie MH (2018) Hydrolysis of cellulose using cellulase physically immo-
10. Jayaweera HC, Siriwardane I, de Silva KN, de Silva RM (2018) Synthesis of bilized on highly stable zirconium based metal-organic frameworks.
multifunctional activated carbon nanocomposite comprising biocom- Bioresour Technol 270:377–382
patible flake nano hydroxyapatite and natural turmeric extract for the 21. Bulta AL, Micheal GAW (2019) Evaluation of the efficiency of ceramic
removal of bacteria and lead ions from aqueous solution. Chem Central J filters for water treatment in Kambata Tabaro zone, southern Ethiopia.
12:1–14 Environ Syst Res 8:1–15
11. Hegazi HA (2013) Removal of heavy metals from wastewater using agri- 22. Suleiman M, Mousa M, Hussein A (2015) Wastewater disinfection by syn-
cultural and industrial wastes as adsorbents. HBRC J 9:276–282 thesized copper oxide nanoparticles stabilized with surfactant. J Mater
12. Hussain AZ, Shariff KMM (2014) Removal of heavy metals from wastewa- Environ Sci 6:1924–1937
ter using low cost adsorbents. Arch Appl Sci Res 6:52–54 23. APHA (1998) Standard methods for the examination of water and waste-
13. Rivera-Garza M, Olguın MT, Garcıa-Sosa I, Alcántara D, Rodrıguez-Fuentes water, 20th edn. American Public Health Association, American Water
G (2000) Silver supported on natural Mexican zeolite as an antibacterial Works Association, Water Environment Federation, Washington, DC
material. Microporous Mesoporous Mater 39:431–444 24. Zhang X, Tang D, Zhang M, Yang R (2013) Synthesis of NaX zeolite: influ-
14. Milan Z, de Las Pozas C, Cruz M, Borja R, Sanchez E, Ilangovan K, Espinosa ence of crystallization time, temperature and batch molar ratio S­ iO2/
Y, Luna B (2001) The removal of bacteria by modified natural zeolites. J Al2O3 on the particulate properties of zeolite crystals. Powder Technol
Environ Sci Health Part A 36:1073–1087 235:322–328
15. DeAlba-Montero I, Guajardo-Pacheco J, Morales-Sánchez E, Araujo- 25. Hammoudi H, Bendenia S, Marouf-Khelifa K, Marouf R, Schott J, Khelifa A
Martínez R, Loredo-Becerra GM, Martínez-Castañón GA, Ruiz F, Compeán (2008) Effect of the binary and ternary exchanges on crystallinity and tex-
Jasso ME (2017) Antimicrobial properties of copper nanoparticles and tural properties of X zeolites. Microporous Mesoporous Mater 113:43–351
amino acid chelated copper nanoparticles produced by using a soya
extract. Bioinorg Chem Appl 2017:1–6
16. Rio L, Kusiak-Nejman E, Kiwi J, Bétrisey B, Pulgarin C, Trampuz A, Bizzini
A (2012) Comparative methods to evaluate the bactericidal activity of
copper-sputtered surfaces against methicillin-resistant Staphylococcus
aureus. Appl Environ Microbiol 78:8176–8182

Ready to submit your research ? Choose BMC and benefit from:

• fast, convenient online submission

• thorough peer review by experienced researchers in your field
• rapid publication on acceptance
• support for research data, including large and complex data types
• gold Open Access which fosters wider collaboration and increased citations
• maximum visibility for your research: over 100M website views per year

At BMC, research is always in progress.

Learn more biomedcentral.com/submissions