Accepted Manuscript

Preparation and application of a tyre-based activated carbon solid phase extraction of

heavy metals in wastewater samples

K. Mogolodi Dimpe, J.C. Ngila, P.N. Nomngongo

PII: S1474-7065(16)30083-3
DOI: 10.1016/j.pce.2018.02.005
Reference: JPCE 2651

To appear in: Physics and Chemistry of the Earth

Received Date: 30 May 2016

Revised Date: 9 August 2017
Accepted Date: 7 February 2018

Please cite this article as: Dimpe, K.M., Ngila, J.C., Nomngongo, P.N., Preparation and application of a
tyre-based activated carbon solid phase extraction of heavy metals in wastewater samples, Physics and
Chemistry of the Earth (2018), doi: 10.1016/j.pce.2018.02.005.

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 ACCEPTED MANUSCRIPT

Preparation and application of a tyre-based activated carbon solid phase extraction of

heavy metals in wastewater samples

K. Mogolodi Dimpe, J.C Ngila P.N Nomngongo*

Department of Applied Chemistry, University of Johannesburg, Doornfontein Campus, P.O. Box

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17011, Johannesburg, 2028, South Africa

Abstract

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In this paper, the tyre-based activated carbon solid phase extraction (SPE) method was
successfully developed for simultaneous preconcentration of metal ions in the model and real

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water samples before their determination using flame atomic absorption spectrometry (FAAS).
The activation of carbon was achieved by chemical activation and the tyre-based activated
carbon was used as a sorbent for solid phase extraction. The prepared activated carbon was

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characterized using the scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET),
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and Fourier Transform Infrared spectroscopy. Moreover, optimization of the proposed method
was performed by the two-level full factorial design (FFD). The FFD was chosen in order to
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fully investigate the effect of the experimental variables (pH, eluent concentration and sample
flow rate) that significantly influence the preconcentration procedure. In this model, individual
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factors are considered along with their interactions. In addition, modelling of the experiments
allowed simultaneous variation of all experimental factors investigated, reduced the required
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time and number of experimental runs which consequently led to the reduction of the overall
required costs. Under optimized conditions, the limits of detection and quantification (LOD and
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LOQ) ranged 0.66–2.12 µg L-1and 1.78–5.34 µg L-1, respectively and the enrichment factor of 25
was obtained. The developed SPE/FAAS method was validated using CWW-TM-A and CWW-
TM-B wastewater standard reference materials (SRMs). The procedure showed to be accurate
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with satisfactory recoveries ranging from 92 to 99%. The precision (repeatability) was lower
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than 4% in terms of the relative standard deviation (%RSD). The developed method proved to
have the capability to be used in routine analysis of heavy metals in domestic and industrial
wastewater samples. In addition, the developed method can be used as a final step (before being

*
Corresponding Author Tel +27115596187; Fax +27115596154; Email: pnnomngongo@uj.ac.za;
nomngongo@yahoo.com

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discharged to the rivers) in wastewater treatment process in order to keep our water bodies free
from toxic metals.

Keywords: Heavy metals; Wastewater; Activated carbon, solid phase extraction; Waste tyre,
FAAS

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1.0 Introduction

Heavy metals are classified as a distinctive type of environmental toxicants due to their

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persistence non-degradable nature. However, several metals and metalloids are significantly
beneficial to human beings, plants, animals and aquatic species (Bahadir et al., 2014; Shahtaheri

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et al., 2007). These metals include Cu, Zn, Fe, Co, Ni, Se and Mn, among others. However, all
these metals are toxic when they exceed their maximum allowable limit. Metals such as arsenic,

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cadmium, mercury and lead, among others are not essential for living organisms and they are
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toxic even at trace levels (Marahel et al., 2011; Yildiz et al., 2011). Heavy metals apart from
being non-biodegradable, they also tend to bio-accumulate in organisms (Yildiz et al., 2011).
Nowadays, the liberation and determination processes of trace metal ions from a variety of
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matrices particularly aqueous samples have become of interest and have raised more attention
(Kassem and Amin, 2013). However, the majority of the studies are focused on surface water
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samples and only a portion of the abundant literature reports on complex wastewater samples
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such as untreated influents (Robles-Molina et al., 2013).

Wastewater treatment plants (WWTPs) are designed to manage and purify wastewater in
order to safeguard the environment and human health (Muga and Mihelcic, 2008). Over the
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years, industrialization and increased inhabitants have resulted in the dilapidation of diverse
environmental systems on which human beings are dependent on (Chan et al., 2009).
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High levels of heavy metals in water bodies are as a result of releasing poorly treated
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industrial and domestic effluent wastewater into rivers and oceans. This phenomenon shows that
most of the WWTPs are unable to completely remove these contaminants from wastewater
(Chan et al., 2009). The use of effluent wastewater in the environment should not be hazardous
to humans and animals (Kacprzak et al., 2005). Therefore, accurate determination of metal ions
(even for trace amounts) in wastewater is significant in the perspective of environmental
protection and for keeping an eye on environmental pollution (Jamshidi et al., 2011; Soylak and
Erdogan, 2006; Tavallali et al., 2013; Xu et al., 2013; Yildiz et al., 2011). In addition,

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quantification of trace metals in the environmental samples such as natural waters needs to be
thoroughly performed to eliminate health problems (Marahel et al., 2011).
Analytical techniques such as atomic spectrometric methods have been utilized in various
studies for the quantification of heavy metals (Ghaedi et al., 2009; Karadas et al., 2013; Soylak
and Erdogan, 2006;). The accuracy of determining trace metals is the significant part of

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analytical chemistry studies (Yildiz et al., 2011). Different instrumentation in analytical
chemistry including electrothermal atomic absorption spectrometry (ETAAS), flame atomic

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absorption spectrometry (FAAS), inductively coupled plasma-mass spectrometry (ICP-MS) and
inductively coupled plasma-optical emission spectrometry (ICP-OES), have been utilized for the

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quantification of analytes in environmental samples (Bahadir et al., 2014; Behbahani et al.,
2014a; Ghaedi et al., 2009; Porreza and Naghdi, 2014; Soylak and Erdogan, 2006; Urus et al.,

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2013). Among other analytical techniques, FAAS has been the most extensively applied for the
quantification of metal ions in different sample matrices. This is because FAAS displays a
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number of advantages, namely; robust interface, selectivity, relatively easy to operate, few
interferences and low capital costs, among others (Karadas et al., 2013; Marahel et al., 2011;
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Porreza and Naghdi, 2014; Yildiz et al., 2011). However, direct quantification of trace metals by
FAAS is restricted due to poor sensitivity (high detection limits) for some elements and the
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elevated complexity of the sample matrices (Behbahani et al., 2014b; Ghaedi et al., 2009;
Jamshidi et al., 2011; Karadas et al., 2013; Soylak and Erdogan, 2006; Tavallali et al., 2013; Xu
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et al., 2013). To overcome these difficulties, it is of utmost importance to carry out a separation
and preconcentration step before the FAAS detection (Xu et al., 2013) in order to increase the
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concentration of the analyte within the detectable range (Ghaedi et al., 2009; Soylak and
Erdogan, 2006; Tavallali et al., 2013). Sample preparation is a vital analytical procedure to
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achieve the desirable sensitivity and enhanced selectivity in the analysis of complex liquid and
solid samples, particularly for trace level metals (Ganan et al., 2014; Song et al., 2014).
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Therefore, sample preparation procedures are required to simplify analytical approaches thus
lowering the cost of analysis. The extraction of heavy metals has been accomplished by various
sample preparation techniques such as solvent extraction, liquid-liquid extraction,
coprecipitation, flotation as well as solid phase extraction (SPE). Sample preparation technique
such as solvent extraction presents advantages including the use of small volumes of the
extracting solvents and greener solvents that are less harmful to the environment (Dimpe and

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Nomngongo, 2016). Whereas in LLE methods, novel extraction solvents such as supramolecular
solvents and ionic liquids have an advantage of extracting various pollutants such as heavy
metals and amphiphilic compounds including drugs, pesticides, and bioactive compounds
(Dimpe and Nomngongo, 2016). These methods except for SPE are tedious procedures and
recoveries achieved from such methods are not reproducible and always necessitate large

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amounts of highly purified organic solvents, which are harmful to the environment (Bahadir et
al., 2014; Behbahani et al., 2014b; Ghaedi et al., 2009; Kassem and Amin, 2013; Marahel et al.,

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2011; Porreza and Naghdi, 2014; Shahtaheri et al., 2007;Soylak and Erdogan, 2006; Tavallali et
al., 2013; Xu et al., 2013). Solid phase extraction is a well known technique that has

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demonstrated to be an useful technique for sample preparation attributable to its flexibility,
simple application, environmental friendliness, simplicity, fast separation of phases, less reagents

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utilization, the use of different adsorbents and high preconcentration factor (Behbahani et al.,
2014a; Ganan et al., 2014; Jamshidi et al., 2011; Karadas et al., 2013; Robles-Molina et al.,
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2013; Xu et al., 2013; Zwir-Ferenc and Biziuk, 2006; Yildiz et al., 2011). The SPE method has
been also applied for the extraction of organic pollutants such as personal care products,
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pharmaceuticals and endocrine disrupting compounds such as pesticides (Dimpe and

Nomngongo, 2016).
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However, the application of a solid phase material is the most important aspect of SPE as it is
advantageous in allowing a full interaction with the sample (Latorre et al., 2012). Thus various
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sorbents such as ion exchange resins, carbon nanotubes, cellulose, alumina, amberlite, and
activated carbon, among others, are used for extraction of heavy metals (Latorre et al., 2012).
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Activated carbon is the widely used sorbent due to its porous structure, large surface area, high
thermal resistance, low cost and selective adsorption (Zhang et al., 2010; He et al., 2010).
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Activated carbon is defined as a hydrophobic solid material which adsorbs non-polar or slightly
polar substances in aqueous solutions and can be made highly selective and specific to any
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analyte of interest (He et al., 2010). The sources of carbon are abundant in nature and nowadays,
the conversion of waste material into useful adsorbents in trying to remediate the environmental
pollutants is the route in which most scientists are following (Betancur et al., 2009). The
commonly known waste material used to produce low-cost sorbents include sawdust, paper mill
sludge, fly ash, agricultural by-products and the recently discovered waste tyres (Acevedo et al.,
2015; Gupta et al., 2014; Mina and Harris, 2006). Among the above-mentioned waste materials,

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waste tyres are abundant in the environment due to its non-recyclability and it is one of the major
sources of carbon that is manufactured in huge amounts, yearly (Mina and Harris, 2006). Waste
tyres do not pose a threat or danger to the environment instantaneously. However, eventually
hazards associated with waste tyres can cause both health and environmental problem (Belgacem
et al., 2013). Stockpiling of waste tyres can represent a significant fire hazard, and fires in tyre

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deposits are not easy to control (Li et al., 2010). Used tyres are possible sources for breeding
quite a number of smaller animals and insects such as mosquitoes, mice and rats which can be in

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turn become sources of diseases that affect human health (Miguel et al., 2002). Therefore, due to
their easy accessibility of waste tyres, their conversion into carbonaceous material makes them to

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be an alternative way of producing carbon-based sorbents that can be used for separating and
preconcentrating heavy metals.

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This paper reports the procedure of separation and preconcentration employing the tyre-
based activated carbon for determining metal ion such as As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn
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in wastewater samples by FAAS. The preparation of activated carbon was carried out by
activating the carbon using hydrogen peroxide (chemical activation) after the pyrolysis process
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that used to extract carbon from the waste tyre. One of the major objectives of this work was to
develop an efficient method for the separation and preconcentration of metal ions (As, Cd, Cr,
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Cu, Fe, Mn, Ni, Pb and Zn) and the factorial design was used to optimize the preconcentration
system, focusing on parameters such as the sample flow rate, sample pH, and eluent
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concentration. The optimal method will then be applied in wastewater samples obtained from the
domestic and industrial WWTP.
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2.0 Materials and methods

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2.1 Instrumentation
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The digital hot plate (DigiBlock ED36S, LabTech Africa, South Africa) was used as a
heating source for the activation of the carbon powder in this study. The concentration of heavy
metals in solution was analyzed by Flame Atomic Absorption Spectrometer (GBC-902 scientific
equipment, USA). Appropriate hollow cathode lamps (HCL) of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb
and Zn were used in these experiments. The wavelengths used for monitoring As, Cd, Cr, Cu, Fe,
Mn, Ni, Pb, and Zn were 189.0, 228.8, 357.9, 324.8, 248.3, 279.48, 221.47, 283.3, and 213.9 nm,

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respectively. Detailed operating factors of FAAS are listed in Table 1. The pH meter with an
electronic glass electrode (Mettler-Toledo FE20, Switzerland) was used to determine pH values.
VacMaster-24 sample SPE station (Biotage®, Uppsala, Sweden) was used for SPE experiments.
The tubular electric furnace was used to perform the pyrolytic process under inert conditions
using nitrogen.

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Table 1: FAAS operating factors

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Operational factors
Slit width 7.0 mm

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Lamp current 8.0 mA
Spectral band passes 0.2 nm

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Flow rate gas 1.8 L min-1
Sample flow rate 4.5 mL min-1
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Fuel Air-acetylene
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2.2 Reagents, solution, and samples

The water used throughout the experiments for preparing solutions and rinsing of glassware
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was double distilled water and soaked overnight in 5% HNO3 (traceSELECT 69%, Sigma–
Aldrich, St. Loius, MO, USA) solution. Hydrogen peroxide (H2O2, traceSELECT 30%, Sigma–
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Aldrich, St. Loius, MO, USA) was used as a chemically active agent. Polyethylene containers
were utilized to store sample solutions. The acrodiscs (0.45µm) syringe filters (Pall Corporation,
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USA) were used to filter the wastewater before passing it through the column to avoid clogging.
A solution of 100 mg L-1 multi-elemental standard containing the elements of interest (As, Cd,
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Cr, Cu, Fe, Mn, Ni, Pb, and Zn) was supplied by SpexCertiPrep (Industrial Analytical (Pty) Ltd,
South Africa) and utilized for preparation of calibration standards. The developed method was
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verified using the wastewater standard reference material (SRM) CWW-TM-A and CWW-TM-B
(Trace Metals in Certified Wastewater from High-Purity Standards, Charleston, SC, USA).The
model solutions (50 µg L-1) for SPE were prepared from a spectrascan stock solution (100 mg L-
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) of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn (Teknolab A/S, Dröbak, Norway). Working
solutions were freshly prepared as per the experimental requirements for each experimental run.
The pH of the model solutions (3, 6.5 and 10) were adjusted with 1.0 mol L-1 HNO3 and NaOH.

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The concentrations of HNO3 solutions were 0.5, 1.0, 1.75, and 3.0 mol L-1 which were prepared
from the concentrated HNO3 (traceSELECT 69%, Sigma–Aldrich, St. Loius, MO, USA) and
were used to flush down the analytes that were retained in the activated carbon.

2.3 Sampling and collection of samples

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Samples were collected at two full-scale municipal wastewater treatment facilities (Northern
(25056’39.8”S 27059’25.0”E) domestic plant and Goudkoppies (26016’20.5”S 27055’28.2”E)

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industrial plant works) which receive wastewater from the same city (Johannesburg, Gauteng)
but at different places (The north and the south). Wastewater (Influent and Effluent) samples

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were collected using a Bailer sampling scoop 1metre from the surface of the wastewater and
upon arrival, samples were refrigerated at 4 o C. The collected samples were acidified to a pH
that is less than 2 using 3 mol L-1 HNO3. The waste tyre was collected from the landfill in a

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stockpile in Gauteng (South Africa). Only the sides of tyres were cut from the whole tyre since
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the side-walls are thread-free.
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2.4 Pretreatment of waste tyre

The raw waste tyre was thoroughly washed with a detergent and rinsed with deionised water to
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ensure that there is no detergent or soil particles’ remaining on the surface of the tyre. Thereafter,
the tyre material was dried in an oven for 24 h at 100˚C. Small pieces of tyres were cut using a
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sharp knife before inserting them into an electric tubular furnace to obtain a powder with
different particle sizes, under a continuous purging with nitrogen (Inert condition). The pyrolysis
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process was utilized to obtain the raw carbon powder at the temperature of 800 oC. The powder
was then made uniform by milling the particles into fine powder. This entire pyrolysis procedure
was a standard method for obtaining the raw carbon powder (char) that will be further activated
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using different conditions.

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2.5 Chemical activation of carbon

The preference of chemical activation over the physical activation has been well documented due
to the porosity, large surface area and the pore size of the material after activation (Fung et al.,
2012). The disadvantage of physical activation is that it is time and energy consuming for the
production of carbon. For this reason, the chemical activation process is considered an

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alternative process for the production of activated carbon from waste tyres. Chemical activation
has an advantage over physical activation because it allows both pyrolysis and activation to
occur in a single process (Fung et al., 2012). During the chemical activation, activating agents
such as KOH, NaOH, HCl, H2SO4 have been extensively used to enhance the activation process
(Mui et al., 2004) but in this study hydrogen peroxide (H2O2) was explored due to its

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environmentally friendly properties. Hydrogen peroxide that was used as an activating agent
played a vital role in obtaining the attractive properties of the adsorbent (activated carbon) that

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are suitable in adsorbing inorganic pollutants.
The chemical activation procedure was performed by fixing various factors such as

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temperature (200˚C), time (2 hours), the mass of carbon (1g). The most important aspect of
performing was to impregnate the raw carbon with a relevant functional group that will be

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helpful in absorbing heavy metals. The activation procedure was carried out using the digital
block digestor. After the activation process, the end product (activated carbon) was allowed to
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cool down for a few minutes and it was mixed with 10% HCl to completely remove the
inorganic impurities. The activated carbon was washed with cold water and dried at 110 oC for
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24 h and finally calcined at 500˚C.

2.6 Preparation of an activated carbon packed column

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The column was packed with the prepared activated carbon which was used throughout the
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entire study due to its ability to use an active functional group that is attractive to opposite charge
of ions in order to accomplish effective retention of the sample. The activated carbon was
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expected to separate species that are charged such as carboxylic acids, carbonyl, and hydroxyl.
The activated carbon is appropriate and suitable for this study because of the different matrices
that the wastewater entails and it acts as an alternative cleanup strategy. Supelco polyethylene
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columns (Supelco, PA, USA, 1.35 cm in diameter and 6.5 cm in length) with frits were
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employed for solid-phase extraction in a VacMaster-24 sample SPE station. Columns were
immersed in 5% HNO3 solution for rinsing before experimental use. Preparation of the SPE
column was prepared by modifying a procedure reported by Nomngongo et al. (2013). The
powdered activated carbon (750 mg) was packed into columns. Porous frits were placed at the
bottom and at the top of the column for the proper settling of the sorbent.

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2.7 Preconcentration procedure of trace elements

The preconcentration procedures were first optimized by using model solutions prior to the
application of real samples. Model solutions (1000 mL) containing 50 µg L-1 of As, Cd, Cr, Cu,

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Fe, Mn, Ni, Pb and Zn were adjusted to appropriate pH values. The solutions were passed
through the activated carbon packed column at an appropriate flow rate. Retained metals on the

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resins were flushed with 10.0 mL of various concentrations of HNO3. The end solutions (eluent)
were analyzed for heavy metal concentrations using FAAS. The blank solutions were treated

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with the same procedure just like the model solutions.

2.8 Characterization of tyre-based activated carbon

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The morphology of the prepared activated carbon was characterized by a high resolution
scanning electron microscope (Nano 2000 High ResolutionSEM (HRSEM), Jeol-Japan). The
surface properties of the sorbent such as surface area, pore volume, and pore size were examined
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using the Brunauer-Emmett-Teller (Micromeritics ASAP 2020). Lastly, the Fourier transform
Infrared spectroscopy, FT-IR (Perkin Elmer 100 Spectrophotometer, United Kingdom) was used
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to confirm the presence of oxygenated functional groups.

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2.9 Multivariate optimization of H2O2-activated carbon preconcentration system

For rapid analysis, the optimization of parameters affecting the preconcentration step was
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achieved by a two-level full factorial design. The significance of employing multivariate

chemometric approach as a statistical tool was to minimize the experimental runs, and to
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potentially assess the interactions among factors as well as the investigation of the most
influential effects (Soylak et al., 2005; Divrikli et al., 2009). The optimization process was
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carried out using a two-level (23) full factorial design. Experimental variables affecting the
preconcentration system were eluent concentrations, sample and eluent flow rates and pH.
Factors and levels (minimum, the central point and maximum) of experimental designs used for
the optimization of preconcentration system are presented in Table 2.

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Table 2: Factors and level used in the factorial design

Variables Minimum Central point Maximum
pH 3 6.5 10

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Eluent Concentration (mol L-1) 0.5 1.75 3
Sample Flow Rate (mL min-1) 1 3 5

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2.10 Application to real samples

The developed SPE technique was applied for the quantification of As, Cd, Cr, Cu, Fe, Mn,

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Ni, Pb and Zn in wastewater samples under optimal experimental conditions. The optimized
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method was first validated by analyzing the SRMs for wastewater (CWW-TM-A and CWW-
TM-B) and applied for the analysis of untreated (influent) and treated (effluent) samples of
wastewater, obtained from the domestic and industrial WWTP. The acrodisc (0.45µm) was used
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to filter off the particulates from the wastewater.

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3.0 Results and discussion

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3.1 Characterization of the sorbent

The prepared tyre-based activated carbon was characterized using SEM to examine the
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morphology of the raw carbon powder (not activated) and the activated carbon. According to
Fig. 1(a), it is observed that the morphology of the particles on the surface was not uniform with
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irregular shapes of the particles. The micrograph image (Fig. 1(b)) of activated carbon showed
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the uniformity of particles which are less than 200 µm in size. Furthermore, the pores of the
activated carbon were evident due to the activation of carbon as shown in the magnified image
(Fig. 1(c)). The use of H2O2 as an activating agent showed the presence of oxygen, which is
confirmed by the Energy dispersive X-ray spectroscopy (EDX) shown in Fig. 1(d). Overall, the
prepared material consisted of elements such as carbon and oxygen (Fig. 1(d)).

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Figure 1: SEM micrograph image of (a) raw carbon powder, (b) activated carbon, (c) magnified
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structure of an activated carbon particle and (d) EDX graph of the activated carbon
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Surface properties of the activated carbon were characterized with BET. The studied sorbent was
examined in terms of the surface area, pore volume and pore size of the raw and activated
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carbon. Table 3 listed the surface properties of the raw and activated carbon. The obtained BET
results showed very low surface area, pore volume and pore size of the raw carbon as compared
to the activated carbon. Raw carbon exhibited pore volume that is low with more or less closed
pores which make it to be less porous. The chemical activation of the tyre-based carbon
enhanced the surface of the activated carbon, therefore, it presented properties that are attractive
for the adsorption of heavy metals.

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Table 3: Surface structure parameters of raw and activated carbon

Pore size (nm)

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Sample Surface area (m Pore volume (cm Pore width Pore diameter
-1 -1
g ) g ) (nm) (nm)
Raw carbon 412.4 0.585 2.756 3.692

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H2O2-Activated 27.44 0.154 0.059 0.876
carbon

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The effectiveness of the use of H2O2 as an activating agent was investigated by using FT-IR

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spectroscopy to identify the presence of oxygenated functional group on the surface of the
activated carbon. The activated carbon was mixed with potassium bromide (KBr) at a ratio of
1:15 before characterization. The FT-IR spectrum is presented in Fig. 2. Major peaks were

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evident around 3400 cm-1, 1624 cm-1 and 1420 cm-1 were attributed to the OH group of phenols
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and C-O bonds (Zhang et al., 2010). The broad band that is observed at 3400 cm-1 is attributed
to the stretching of O-H vibration of the hydroxyl groups (Al-saadi et al., 2013) and the peak at
1624 cm-1 is associated with the C-O vibrations of the carboxyl groups in acidic oxygenated
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surface that take a huge role in adsorbing heavy metals (Al-saadi et al., 2013). The peak that is
observed at 1420 cm-1 represents the aromatic ring stretching vibrations (Li et al., 2014). The
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carbonyl band to an ester is affirmed by an absorption in the C-O stretching region at 1180 cm-1
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and other bands were observed between 1100 cm-1 and 1300 cm-1. Furthermore, the peak at
about 670 cm-1 is assigned to the bending mode of the C-H or O-H (He et al., 2010). The FT-IR
spectra confirmed that the activated carbon included the oxygen-containing functional groups
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that had additional sites that are active which gives the prepared material adsorption abilities for
the sorption of metal ions.
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Figure 2: The FT-IR spectra of the tyre-based activated carbon

3.2 Factorial design

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The SPE optimization using activated carbon as an adsorbent for preconcentration and
extraction of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn was achieved using a two-level factorial
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design. Various effects of influential factors such as eluent concentration (EC), sample flow rate
(SFR) and pH was studied. The sample volume for SPE studies was fixed at 50 mL. The design
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matrix (actual values) and analytical response (% recovery), are given in Table 3. According to
the results in Table 4, experiment 9, 10 and 11 were chosen as the best optimum conditions due
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to good recoveries obtained by simultaneous preconcentration of nine metal ions and were
ranging from 93-100%. The rest of the experiments (1-8) were not consistent in terms of
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recoveries since they showed fluctuations and far less recoveries for all metals. Hence,
considering the experimental conditions established for simultaneous extraction of all metals, the
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central point of variables including eluent concentration (1.75 mol L-1), pH (6.5), and sample
flow rate (3 mL min-1) were chosen as the optimum method for simultaneous preconcentration.
The statistical software was used to process the experimental data. The analysis of variance
(ANOVA) presented in terms of Pareto charts was used to evaluate the main effects and their
interactions. The ANOVA results (Figure 1) for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn demonstrated
that all factors studied were not significant at 95% confidence level, showing to have no

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influence in the analytical response. For arsenic (As) on the other hand, the results showed that
the interaction between pH and SFR factors are statistically significant. The bar for As on the
Pareto chart shown in Fig. 3 (a) exceeded a reference line, corresponding to a 95% confidence
interval is a significant values relating to the response (Ferreira et al., 2002). The negative effect
of the interaction of pH and SFR indicated that the recoveries as the response increased with the

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decrease in the interaction between pH and SFR.

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Table 4: The design matrix and the results of the two-level full factorial design
pH EC SFR Recovery (%)

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-1 -1
Experiment (mol L ) (mL min ) As Cd Cr Cu Fe Mn Ni Pb Zn
1 3 0.5 1 99 107 102 101 109 91 72 75 72

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2 10 0.5 1 110 81 106 84 103 93 76 75 86
3 3 3 1 89 93 90 83 93 96 96 74 77
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4 10 3 1 101 110 116 85 108 97 59 88 108
5 3 0.5 5 108 88 90.2 82 97 98 70 96 95
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6 10 0.5 5 98 108 114 74 92 104 71 91 99

7 3 3 5 106 84 107 80 102 96 76 81 90
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8 10 3 5 104 103 105 35 103 99 76 75 91

9 6.5 1.75 3 97 97 104 97 99 102 98 102 105
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10 6.5 1.75 3 97 99 99 96 93 105 96 110 101

11 6.5 1.75 3 98 104 98 97 97 100 97 109 106
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Figure 3 (a): Pareto charts of effects of heavy metals (A to D)
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Figure 3 (b): Pareto charts of effects of heavy metals (E to I)

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3.3 Effect of sample volume

In preconcentration procedures, sample volume is an important parameter hence, it is

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desirable to obtain high preconcentration factor especially when analyzing trace metals in real
samples. Therefore, under optimum condition, the effect of sample volume (50-600 mL) was
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investigated. In this study, quantitative recoveries were set to be >95%. The recoveries of metals
were quantitative only up to 250 mL, which was then taken as the optimum sample volume. It
was evident that after 250 mL a significant drop (graph not shown) in recoveries of metals were
experienced. The observed decrease in metal recoveries was most likely due to saturation of the
active sites of the adsorbents. The preconcentration factor was found to be 25 with the eluent
volume of 10 mL.

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3.4 Analytical Performances of the tyre-based activated carbon SPE method

The analytical performance of the tyre-based activated carbon SPE method was studied using
optimal conditions. Table 5 presents the analytical performance of the proposed method. The
correlation coefficients (R2) of calibration curves were in the range 0.9993-0.9998. The relative

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standard deviations (RSD) of the method were found to be < 4% for all metals of interest (As,
Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn). Thus, it can be confirmed that the recommended method
demonstrated good precision (repeatability) based on RSD values achieved. The limits of

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detection and quantification (LOD and LOQ) of all metals were determined under best possible
conditions of the experiment as 3.3SD/b and 10SD/b respectively, where SD is the standard

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deviation of analytical responses of fifteen independent measurements (n=15) of the blank
solutions and b is the slope of calibration curve. The LOD and LOQ were found to be ranging

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from 0.66–2.12 µg L-1 and 1.78–5.34 µg L-1, respectively.
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Table 5: Analytical figures for the determination of metal ions using the proposed method
(Method: SPE; model solution (sample volume): 50 mL; EC: 1.75 mol L-1; pH: 6.5 and SFR: 3
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mL min-1)
Analytes Linear range R2 LOD (µg L-1) LOQ (µg L-1) RSD (%)
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(µg L )
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As 12-140 0.9997 0.78 3.76 3.7

Cd 12-140 0.9996 1.73 4.65 3.1
Cr 12-140 0.9998 0.66 2.13 2.3
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Cu 25-300 0.9999 1.23 1.78 1.2

Fe 25-300 0.9995 2.12 5.34 1.7
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Mn 25-300 0.9997 1.06 3.11 2.9

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Ni 25-300 0.9996 0.98 2.96 3.8

Pb 12-140 0.9998 1.55 4.77 2.7
Zn 25-300 0.9997 1.35 5.15 3.6
SV: sample volume; EC: eluent concentration; SFR: sample flow rate

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3.5 Comparison of the current SPE/FAAS method with the reported methods

A comparison of the developed SPE/FAAS method with other reported preconcentration

methods is summarized in Table 6. In comparison with other methods (Table 6), the current
SPE/FAAS has a fairly low LODs and relatively low precision. These results were comparable

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with the documented in the literature and lower than most of the reported referenced studies.
Overall, the analytical figures of merit for the target proved that SPE/FAAS method is a
reproducible, sensitive rapid and simple. Therefore, this method is suitable for the

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preconcentration of metal ion species in water samples.

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Table 6. Comparison of the reported methods for the target analytes with the developed method. (Method: SPE; sample volume: 50
mL; eluent concentration: 1.75 mol L-1; pH: 6.5 and sample flow rate: 3 mL min-1)
Analytes Analytical method LOD (µg L-1) Preconcentration factor RSD (%) Ref.

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Pb, Cr and Cu Coprecipitation/FAAS 0.86-2.06 50 2.8-4.1 Bahadir et al.,
2014

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Ni and Ag SPE/FAAS 1.42-1.05 25 - Tuzen and
Soylak, 2009

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Cu and Ni SPE/FAAS 1.03-1.90 50 7&8 Tuzen et al., 2009
Cd, Cu, Cr, Co, SPE-ICP-AES 0.01-0.39 - 3 Nomngongo et
Fe, Ni, Pb and Zn al., 2013

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Pb SPE/FAAS 3.71 50 7 Soylak et al.,

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As, Cd, Cr, Cu, SPE/FAAS 0.16-2.12 25 4 Current study
Fe, Mn, Ni, Pb

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FAAS: Flame atomic absorption spectroscopy; ICP-AES: Inductively coupled plasma atomic emission spectroscopy; SPE: Solid
phase extraction; LOD: Limits of detection; RSD: Relative standard deviation

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3.6 Validation of the H2O2-activated carbon SPE method

The optimized analytical procedure was validated by analyzing the CWW-TM-A and CWW-
TM-B SRMs. The results are given in Table 7. The accuracy in terms of recovery values
obtained ranged between 90-99%, showing good concordance between certified and found

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values. The results of the SPE method employed were therefore satisfactory to be applied for
analysis of real samples to monitor and assess the amounts of heavy metals in untreated
(influent) and treated (effluent) wastewater.

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Table 7: Validation of the tyre-based activated carbon SPE method using SRMs. (Method: SPE;

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model solution (sample volume): 50 mL; EC: 1.75 mol L-1; pH: 6.5 and SFR: 3 mL min-1)
CWW-TM-A Wastewater CWW-TM-B Wastewater

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Element Certified Found Recovery Certified Found Recovery
(µg L-1) (µg L-1) (%) (µg L-1) (µg L-1) (%)
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As 1.0±0.02 0.97±0.6 97 5.0±0.1 4.7±0.3 94
Cd 1.0±0.02 0.92±0.2 92 5.0±0.1 4.6±0.2 92
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Cr 5.0±0.05 4.7±0.1 94 20±0.2 19.4±0.7 97

Cu 5.0±0.05 4.8±0.3 96 20±0.2 19.2±0.8 96
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Fe 5.0±0.05 4.6±0.2 92 20±0.2 19.7±0.4 99

Mn 5.0±0.05 4.9±0.5 98 20±0.2 19.5±0.6 98
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Ni 5.0±0.05 4.5±0.3 90 20±0.2 19.1±0.3 96

Fe 5.0±0.05 5.1±0.4 102 20±0.2 19.4±0.5 97
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Pb 5.0±0.05 4.7±0.2 94 20±0.2 19.1±0.4 96

Zn 5.0±0.05 4.8±0.6 96 20±0.2 19.8±0.7 99
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SV: sample volume; EC: eluent concentration; SFR: sample flow rate and SRM: standard
reference material
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3.8 Analysis of real samples

The developed SPE method was applied for metal ion (As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn)
analysis in the influent (untreated) as well as effluent (treated) wastewater obtained from the
industrial and domestic WWTPs. The results are presented in Table 8. The industrial wastewater
had high concentrations as compared to domestic wastewater. As expected, the concentration

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levels of majority of heavy metals in the influent wastewater (both the domestic and industrial)
were found to be higher than the effluent wastewater. However, in the case of metals such as As,
Ni and Pb (domestic wastewater) and Mn (industrial wastewater) which showed more or less the
same level of concentrations, this can be attributed to the treatment process of wastewater which
does not release metals that are locked in different matrices. It was evident that the obtained

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results were above the maximum accepted levels especially for toxic metals such as Cd, Cr and
Pb. The different between metals found in the influent and effluent was minimal for most of the

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metals which suggest that the treatment system was not completely removing these inorganic
pollutants. In addition, the conventional way of the treatment system is not designed to treat or

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rather remove inorganic pollutants in wastewater. This analysis demonstrated that H2O2 activated
carbon as selective solid-phase extractant was suitable for the preconcentration of metal ions in

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real samples. AN
Table 8: Application of the optimized procedure in the domestic and industrial wastewater.
(Method: SPE; model solution (sample volume): 50 mL; EC: 1.75 mol L-1; pH: 6.5 and SFR: 3
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mL min-1)
Analytes Domestic wastewater Industrial wastewater
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Influent (mg L ) Effluent (mg L ) Influent (mg L-1) Effluent (mg L-1)
As 0.14±0.01 0.09±0.5 1.34±0.3 0.27±0.1
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Cd 11.9±0.3 10.0±0.4 13.6±0.7 11.2±0.6

Cr 0.23±0.05 0.18±0.8 2.78±0.9 1.43±0.6
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Cu 0.39±2.3 0.24±0.3 1.23±0.4 0.39±1.1

Fe 1.37±0.6 0.59±0.7 3.67±0.6 2.78±0.3
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Mn 0.36±0.4 0.25±0.9 5.02±1.3 4.62±0.7

Ni 0.31±1.5 0.27±0.2 2.48±0.8 1.24±0.6
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Pb 0.08±0.4 0.07±0.8 0.63±0.7 0.41±0.3

Zn 0.41±0.7 0.12±0.5 3.49±0.1 2.34±0.8
SV: sample volume; EC: eluent concentration; SFR: sample flow rate

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4.0 Conclusions

In this work, a tyre-based activated carbon SPE method was successfully optimized for
simultaneous preconcentration of metal ions in model and real (wastewater) samples before their
determination by FAAS determination. The SPE was made up of tyre-based activated carbon.

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Optimization of the proposed method was performed by the two-level full factorial design. The
prepared tyre-based activated carbon was characterized by SEM, BET and FT-IR to confirm the
modification of the raw carbon employing the chemical activation using the H2O2 as the

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activating agent. A decision was made from the detailed infrared spectrum, that the prepared
tyre-based activated carbon material includes oxygen-containing functional groups that provide

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additional active sites for the adsorption process. The use of multivariate optimization strategy
led to reduced number experiments thus reducing analysis time. The repeatability in terms of

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%RSD was lower than 4%. The prepared activated carbon was validated and successfully
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applied for the removal of heavy metals in influent and effluent wastewater collected from the
wastewater treatment plant. The quantification of metals ions by FAAS was enhanced by the
application of the tyre-based activated carbon SPE method since FAAS has high detection limits
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and cannot detect metals at trace levels. The developed method proved to have the capability for
use in routine analysis of heavy metals in wastewater obtained from domestic and industrial
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WWTP.
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Acknowledgements

The author (s) would like to thank National Research Foundation (NRF, grant nos.
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SFH14073184214 and 99270) for providing financial support and University of Johannesburg
for making this study possible by making laboratory facilities available.
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Highlights

• Heavy metals in wastewater are incorporated in complexed matrices

• Activated carbon is used as an alternative sorbent instead of traditional sorbents

• Used tyres are non-recyclable and are a source of carbon that is abundant in nature

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The SPE method was efficient in separating and preconcentrating heavy metals

• The activated carbon SPE was successfully applied in real wastewater samples

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