Water Air Soil Pollut (2016) 227:62

DOI 10.1007/s11270-016-2760-z

Oak (Quercus robur) Acorn Peel as a Low-Cost Adsorbent

for Hexavalent Chromium Removal from Aquatic Ecosystems
and Industrial Effluents
Saranya Kuppusamy & Palanisami Thavamani &
Mallavarapu Megharaj & Kadiyala Venkateswarlu &
Yong Bok Lee & Ravi Naidu

Received: 7 October 2015 / Accepted: 12 January 2016

# Springer International Publishing Switzerland 2016

Abstract The efficiency of low-cost, abundantly avail- dose of 5 g L−1 and pH 7. Uptake of Cr by OP was
able local forestry waste, oak (Quercus robur) acorn described by pseudo-second-order chemisorption mod-
peel (OP), to remove toxic Cr(VI) from aqueous solu- el. ICP-OES, LC-ICPMS analysis of the aqueous and
tions was studied in a batch system as a function of solid phases revealed that the mechanism of Cr(VI)
contact time, adsorbate concentration, adsorbent dos- removal is by ‘integrated adsorption and reduction’
age, and pH. In an equilibrium time of 420 min, the mechanism. ESEM-EDX and XRD analysis of OP be-
maximum Cr removal by OP at pH 2 and 10 was 100 fore and after adsorption also confirmed that both ad-
and 97 %, respectively. The sorption data fitted well sorption and reduction of Cr(VI) to less toxic Cr3+ forms
with Langmuir adsorption model. Evaluation using followed by complexation onto the adsorbent surface
Langmuir expression presented a monolayer sorption contributed to the removal of Cr(VI). Consistent with
capacity of 47.39 mg g−1 with an equilibrium sorbent batch studies, OP effectively removed (>95 %) Cr from
the real water samples collected from lake and sea. The
results of this study illustrate that OP could be an eco-
S. Kuppusamy : Y. B. Lee nomical, green, and effective biomaterial for Cr(VI)
Institute of Agriculture and Life Science, Gyeongsang National removal from natural aquatic ecosystems and industrial
University, Jinju 660-701, South Korea
effluents.
S. Kuppusamy : M. Megharaj : R. Naidu
Centre for Environmental Risk Assessment and Remediation Keywords Oak residue . Biosorption . Hexavalent
(CERAR), University of South Australia, Mawson Lakes, SA
5095, Australia
chromium . Reduction . Trivalent chromium .
Wastewater treatment
S. Kuppusamy (*) : P. Thavamani : M. Megharaj :
R. Naidu
Cooperative Research Centre for Contamination Assessment and
Remediation of Environment (CRC CARE), PO Box 486, 1 Introduction
Salisbury South, SA 5106, Australia
e-mail: saran.miles2go@gmail.com Toxic heavy metals in natural water bodies are hazard-
P. Thavamani : M. Megharaj : R. Naidu ous to environment and living organisms due to their
Global Centre for Environmental Remediation (GCER), Faculty persistence and bioaccumulation through food chain
of Science and Information Technology, The University of (Rao and Rehman 2010; Kuppusamy et al. 2016b).
Newcastle, Callaghan, NSW 2308, Australia Various chronic diseases are caused by zinc, copper,
K. Venkateswarlu and chromium (Cr) which are considered to be the most
Formerly Department of Microbiology, Sri Krishnadevaraya dreadful heavy metals. Several industrial activities like
University, Anantapur 515055, India electroplating, leather tanning, steel fabrication, dyeing,
62 Page 2 of 11 Water Air Soil Pollut (2016) 227:62

photography, and manufacturing of paints, pigments, subsequently sorbed by the negatively charged surface
canning, fertilizers, and cement have released Cr into functional groups. Park et al. (2007) provided a reliable
the environment. In general, Cr exists as Cr(VI) and evidence of adsorption-coupled reduction by 16 natural
Cr(III) in the environment. Cr(III) is less toxic and is biomaterials. More recently, pH-dependent integrated
essential in human nutrition. However, Cr(VI), which is reduction or oxidation reactions and sorption process
the most dominant oxidation state in the natural system, for Cr(VI) removal from aqueous solutions using a
is harmful even when present at negligible concentra- microalga, Laminaria digitata, was delineated by
tions (50 μg L−1) in drinking water. Generally, Cr(VI) Dittert et al. (2014).
associates with oxygen in such oxyanions as chromate Oak (Quercus robur) acorn is one of the notable tree
and dichromate. These two divalent oxyanions are high- residues found globally. Often, the damaged oak acorns
ly water-soluble and are poorly sorbed by soil organic are considered as trash. One of the options is to collect
matter, making them more mobile in soil and ground- the peel of the disposed oak acorns (shell of the oak nut)
water (Dittert et al. 2014). Both the anions are extremely and explore its utility, particularly as a sorbent for pol-
toxic, mutagenic, carcinogenic, and terotogenic, and lutant removal (Kuppusamy et al. 2015). This waste peel
their exposure causes respiratory diseases (bronchial being available at no cost will help to reduce the cost of
asthma), nasal irritation, skin ulceration, and lung can- wastewater treatment in attempts towards transforming
cer. The maximum permissible limit for Cr(VI) in inland Bwaste to resource^ and provide an alternative to the
and potable water are 0.1 and 0.05 mg L−1, respectively existing commercial activated carbon. In this direction,
(Saha et al. 2011; Sreenivas et al. 2014). Due to serious the main purposes of the present study have been (a) to
environmental and health impacts, industrial effluents evaluate the efficiency of oak acorn peel (OP) to remove
containing Cr(VI) are required to be treated before they Cr(VI) from aqueous systems at different operational
are let into the environment. conditions such as solution pH, hexavalent Cr con-
Many technologies adopted for Cr removal from centration, and biomass concentration, (b) to describe
industrial wastewaters include ion exchange, reduction, Cr removal process using kinetic and sorption iso-
(electro)chemical precipitation, membrane separation, therm models, (c) to study the mechanism of Cr
evaporation, foam formation, solvent extraction, activat- removal in aqueous solutions using OP, (d) to explore
ed carbon adsorption, and several biological processes the potential of OP to remove Cr(VI) in synthetic
(Rao and Rehman 2010). However, high chemical and wastewater samples, and (e) to determine OP’s re-
energy requirement, generation of toxic by-products, generation potential.
low removal efficiency for low Cr concentration, pro-
duction of large chemical wastes, and incomplete re-
moval limit the wide applicability of these treatment
techniques (Saha and Orvig 2010). Biosorption process 2 Materials and Methods
has, therefore, been considered as a highly effective and
economical alternative (Kuppusamy et al. 2016a) to 2.1 Materials
remove Cr(VI) from wastewaters. Thus, there is a need
to search for new, effective, low-cost adsorbents for Acorns that had fallen off from oak trees were collected
affordable larger-scale Cr(VI)-contaminated wastewater from the premises of Adelaide Botanical garden, South
treatment. A variety of natural biomass such as ground- Australia, during April 2012, washed with Milli-Q water
nut husk (Dubey and Gopal 2007), olive pomace (18 Ω cm−1, Milli-Q, ELGA LabWater, UK) to remove
(Malkoc et al. 2006), soya cake (Daneshvar et al. adhering soil particles, and air-dried for 3 days. Peels
2002), carrot waste biomass (Bhatti et al. 2010), tea were grounded and passed through a 0.5-mm sieve, and
factory waste (Malkoc and Nuhoglu 2007), neem leaf the powdered sections were stored in a desiccator with
powder (Venkateswarlu et al. 2007), etc., have been polythene sealing and used for experiments as needed.
used for Cr(VI) removal from synthetic wastewater. It Stock solution of potassium dichromate that served as
has been reported that apart from absolute adsorption, model Cr(VI) compound was prepared in Milli-Q water.
Cr(VI) can be reduced to Cr(III) using different solid NaOH (0.1 mol L−1) and HCl (0.1 mol L−1) were used to
biomaterials such as oat processing by-product (Gardea- adjust the pH. All the chemicals used were of analytical
Torresdey et al. 2000), where the reduced form of Cr is grade purchased from Sigma-Aldrich.
Water Air Soil Pollut (2016) 227:62 Page 3 of 11 62

2.2 Adsorbent Characterization Biosorption isotherms were examined by adding

5 g L−1 adsorbent with Cr(VI) solution at various
Specific surface area of OP was measured on a Gemini initial concentrations (0 to 500 mg L−1) and pH 7.
V Surface Analyzer (Micrometrics Instrument Corp., The percent Cr(VI) removal (R) and amount of Cr
USA). The biomaterial was analyzed for total carbon sorbed by the biomaterial (qe) was calculated using the
(C) and nitrogen (N) by dry combustion with a TruMac following equations:
CN analyzer (LECO® Corporation, USA).
C o −C e
Subsequently, macro- and micro-elemental contents of Rð%Þ ¼  100 ð1Þ
Co
OP were analyzed using diluted extracts of the digest
(0.5 g sample digested in a microwave reaction system
with 5 mL of conc. HNO3) in an Agilent 7500c (Agilent
C o −C e
qe mg g−1 ¼ V ð2Þ
Technologies, Japan) Inductively Coupled Plasma M
Mass Spectrometer (ICP-MS). Total polyphenolic where Co and Ce (mg L−1) are the initial and equilib-
(Singleton and Rossi 1965) and flavonoid rium Cr(VI) concentrations, V (L) is the volume of
(Khomdram and Singh 2011) contents in hot water the metal solution, and M (g) is the mass of the
extracts of OP were determined. Antioxidant poten- adsorbent used.
tial was investigated by following 1,1-diphenyl-2- As OP was rich in polyphenols and possessed
picrylhydrazyl (DPPH) radical scavenging activity reducing potential, we tested whether Cr(VI) remov-
(Blois 1958) and determining ferric reducing power al by OP was an integrated adsorption and reduction
(Oyaizu 1986). Surface structure and chemical com- process. In order to explore the mechanism of
position of the peel before and after adsorption were Cr(VI) removal, additional batch study was conduct-
investigated using FEI Quanta 450 FEG ESEM ed at a wide ranging pH (2 to 10) under optimized
(Environmental Scanning Electron Microscope) conditions. After 2 h of incubation, the aqueous
equipped with an EDAX Apollo X SDD Energy- suspensions were centrifuged (3000 rpm for
Dispersive X-ray (EDX) detector at an acceleration 10 min), filtered and analyzed for (a) total Cr by
voltage of 15 kV and magnification ranging from Inductively Coupled Plasma + Optical Emission
150- to 60,000-fold. OP sample after Cr treatment Spectrophotometer (ICP-OES, PerkinElmer, Optima
was pressed in a stainless steel sample holder, and XRD 5300V, Japan) and (b) Cr(VI) species separated by
pattern was obtained on a LabX XRD-6000, Shimadzu high-performance liquid chromatography (Agilent
diffractometer (Shimadzu Corporation, Japan). 1100, Japan) equipped with a guard column and
separation column (Hamilton PRP-X100), and quan-
2.3 Batch Adsorption Experiments tified by ICP-MS (Agilent 7500C, Japan).
Concentration of total Cr(III) was calculated by
Batch biosorption experiments were carried at ambi- deducting the concentration of Cr(VI) from that of
ent temperature in a set of centrifuge tubes containing the total Cr.
20 mL of Cr(VI) solution to investigate the effects of
initial pH (2–10), contact time (0–7 h), biosorbent
dosage (1.25–5.0 g L−1), and initial Cr(VI) concen- 2.4 Cr(VI) Removal from Synthetic Wastewater
tration (0 to 500 mg L−1). After each biosorption Samples
experiment, samples were centrifuged (3000 rpm
for 10 min) and absorbance of the residual Cr(VI) Potential of OP to remove Cr(VI) (250 mg L−1) in
concentration was determined spectrophotometrical- synthetic wastewater samples was tested using lake
ly (Synergy™ Multi-Detection Microplate Reader, and sea water collected from Adelaide following the
Bio-Tek R Instruments, Inc., Vermont, USA) at same procedure (sorbent dose, 5 g L−1; solution pH,
517 nm using diphenylcarbazide method (Sarkar 7, and incubation time, 3 h) as used in the batch
et al. 2010). Optimum conditions for the biosorption adsorption study. Desorption was carried out with
of Cr(VI) were determined. Biosorption kinetics were 10 mM phosphate buffer (20 mL, pH 6.4), and data
investigated using 250 mg L−1 initial Cr(VI) concen- values were recorded after different time intervals
tration, 5 g L−1 sorbent dose, and solution pH 7. until equilibrium.
62 Page 4 of 11 Water Air Soil Pollut (2016) 227:62

3 Results and Discussion

3.1 Characteristics of the Adsorbent

OP had a BET surface area of 0.99 m2 g−1 and was rich

in macronutrients, viz., C (480.5 mg g − 1 ), N
(5.7 mg g−1), K (4.0 mg g−1), Mg (1.7 mg g−1), P
(0.6 mg g −1 ), and Na (2.1 mg g −1 ). Among the
micronutrients, Mn (24.7 μg g−1), Fe (9.2 μg g−1), and
Al (3.2 μg g−1) constituted the maximum with consid-
erable amount of Cu (7.8 μg g−1), Ni (2.5 μg g−1), and S
(2.1 μg g−1) which are useful for extracting pollutants
from water (Mallampati and Valiyaveettil 2012). Cr was
not in detectable concentrations in OP by the method
employed (ICP-MS). The total polyphenolic content of
OP extract accounted for 66.7 mg gallic acid g−1 with
flavonoids being 9.2 mg quercetin g−1 dry extract. The
iron reducing power was 24.7 mg g−1 ascorbic acid.
Notably, OP had an antioxidant potential of about
96.2 % (based on DPPH radical scavenging activity),
which highlights the suitability of OP as a valuable
natural antioxidant (Moure et al. 2001), and its use in
food and pharmaceutical industries can be considered
for future research. Since OP is witnessed to be one of
the rich sources of natural polyphenols that are most
recently used in green nanoparticle synthesis (because
natural polyphenols act as a reducing or stabilizing
agent) (Moulton et al. 2010), we recon the green syn-
thesis of nanoparticles using OP extract to detoxify
Cr(VI)-contaminated water and industrial effluents in Fig. 1 Effect of contact time on percent adsorption of Cr at a
the near future. varying initial Cr(VI) concentrations (sorbent dose, 5 g L−1; tem-
perature, 24 °C; pH, 7) and b different adsorbent doses (initial
Cr(VI) concentration, 250 mg L−1; temperature, 24 °C; pH, 7)
3.2 Optimization of Cr(VI) Adsorption

The data in Fig. 1a depict the effect of contact time on of 420 min. It is important to note that, as the Cr(VI)
Cr(VI) removal at various initial concentrations (200, concentration increased from 200 to 250 mg L−1, the
250, 300, and 400 mg L−1). The percent Cr adsorption adsorption capacity of OP also increased from 39.0 to
increased with increase in contact time before equilibri- 48.94 mg g−1. Similar observation was reported by
um (420 min) was reached for all initial concentrations. Anandkumar and Mandal (2009) for Cr(VI) removal
The rate of adsorption increased sharply with increase in using bael (Aegle marmelos correa) fruit. This might
time for the first 45 min, indicating that there are plenty be due to the fact that the increased Cr(VI) concentration
of readily accessible sites for Cr(VI) adsorption. provides the maximum driving force to overcome all the
Thereafter, the amount of Cr removed almost became mass transfer resistances of metal ions from the aqueous
insignificant owing to a quick exhaustion of the adsorp- phase to solid phase resulting in higher probability of
tion sites. The effect of initial Cr concentration on per- collision between metal ions and active sites
cent adsorption by OP can also be witnessed in Fig. 1a. (Anandkumar and Mandal 2009).
The percent adsorption decreased from 99.0 to 59.7 % The results presented in Fig. 1b show the effect of
as the initial concentration of Cr(VI) increased from 200 adsorbent dosage, wherein increase in Cr(VI) removal
to 400 mg L−1 for 5 g L−1 adsorbent at equilibrium time was observed with increase in rate of sorbent dose from
Water Air Soil Pollut (2016) 227:62 Page 5 of 11 62

0.5 to 5 g L−1. This is due to the greater availability of lower pH, Cr(VI) species is mainly in univalent form
the exchangeable sites or surface area at higher concen- (HCrO4−) and thus requires one exchangeable site for
tration of the adsorbent. This observation also reveals one molecule of Cr(VI) species, making biosorption
that within a certain range of initial metal concentration, more rapid and easier. However, with increasing pH,
the percentage of metal adsorption on OP is determined the divalent forms of Cr(VI) species (Cr2O72− and
by its sorption capacity. Our results are in agreement CrO42+) are abundantly present, necessitating two ex-
with the findings of Dubey and Gopal (2007), Acar and changeable sites for adsorption to occur, thereby
Malkoc (2004), and Venkateswarlu et al. (2007). delaying the process of metal removal (Deng and Ting
Among various adsorbent dosages, 5 g L−1 could re- 2005). The high performance under wide-ranging pH is
move a maximum of 97.89 % Cr(VI) and was selected thus providing OP for a far ranging remedial
as the optimum dose for all our studies. application.
The effect of pH on percent adsorption of Cr is shown
in Fig. 2. Though a slight increase in Cr(VI) removal
with decreasing pH (from 10 to 2) was observed, the 3.3 Adsorption Isotherm
differences were not that significant after 420 min (equi-
librium time). Previous researchers reported that the To examine the type of interaction between the adsor-
optimum pH was 1–2 for maximum Cr(VI) removal— bate and adsorbent at equilibrium and determine the
for instance, using Brazilian pine (Araucaria maximum sorption capacity of adsorbent, Langmuir
angustifolia) fruit coat (Vaghetti et al. 2008), pine needle and Freundlich isotherms were tested for this study.
(Dakiky et al. 2002), and olive pomace (Malkoc et al. Langmuir isotherm model fitted well (R2 = 0.99) and
2006). In this study, the adsorbent had a relatively higher hence was chosen to estimate the maximum adsorption
and broader working pH and removed as high as 96.66 capacity corresponding to complete monolayer cover-
to 100 % of Cr(VI) between pH ranges of 10 to 2. This age on homogenous adsorbent surface without any in-
performance may be associated with the functional teraction between adsorbed ions. The Langmuir equa-
groups on the adsorbent surface which can be protonat- tion is given as:
ed even at varying pH, thus allowing Cr(VI) adsorption Ce 1 Ce
to occur through electrostatic attraction (Luo et al. ¼ þ ð3Þ
qe qm K qm
2011). We observed complete removal of Cr(VI) within
45 min when the initial pH of the solution was acidic where Ce is the equilibrium Cr(VI) concentration
(pH 2); however, as the pH increased (5 to 10), the time (mg L−1), qe is the amount of Cr(VI) adsorbed at equi-
taken to achieve maximum Cr(VI) removal prolonged librium (mg g−1), qm is a measure of adsorption capacity
up to 420 min. This might be because of the fact that at of the adsorbent (mg g−1), and K is the Langmuir
constant which is a measure of adsorption (L−1 mg).
The experimental data were fitted into Eq. (3) for line-
arization by plotting Ce against Ce/qe (figure not shown).
The Langmuir parameters were obtained from the slope
and intercept of the straight line for Cr(VI) removal and
are elucidated in Table 1. Since OP adsorption data fit
well to this model, it is clear that the active sites of OP
surface are homogenous for Cr(VI) binding. Also, high
value of correlation coefficient (R2 = 0.99) indicates a
good agreement between the parameters and confirms
the monolayer adsorption of Cr(VI) onto the adsorbent
surface. The constant qm, which is a measure of the
adsorption capacity to form monolayer, was
47.39 mg g−1 at initial pH 7. The constant K which
denotes adsorption energy was equal to 1.33 L g−1.
Fig. 2 Effect of pH on percent adsorption of Cr(VI) (sorbent dose,
5 g L−1; temperature, 24 °C; contact time, 7 h; initial Cr(VI) The qm value for OP at pH 7 is comparable only with
concentration, 250 mg L−1) that observed by Venkateswarlu et al. (2007) who
62 Page 6 of 11 Water Air Soil Pollut (2016) 227:62

Table 1 Isotherm and kinetic constants for adsorption of Cr(VI) RL remained between 0.002 and 0.008 (0 < RL < 1)
onto OP
(Table 1) consistent with the requirement for a favorable
Constant Unit adsorption process.

Pseudo-second-order kinetic model 3.4 Adsorption Kinetics

qe exp. (mg g−1) 48.23
K (g mg−1 min−1) 0.005 Several investigators showed that Lagergren pseudo-
qe pred. (mg g−1) 50.25 second-order kinetic model can well describe the
h (mg g−1 min−1) 13.05 Cr(VI) adsorption by natural biomass-based adsorbents
R2 0.99 (Anandkumar and Mandal 2009). Hence, pseudo-
P <0.0001 second-order model was tested for this study which is
Langmuir constants expressed as:
qm (mg g−1) 47.39
t 1 1
K (L g−1) 1.33 ¼ 2þ ð5Þ
qt kqe qe
R2 0.99
P <0.0001 where qe and qt (mg g−1) are the amounts of Cr(VI)
Langmuir separation factor (RL) adsorbed at equilibrium and time t, respectively, and k
100 0.008 (g mg−1 min−1) is the pseudo-second-order kinetic rate
200 0.004 constant. Pseudo-second-order kinetic parameters, elu-
250 0.003 cidated in Table 1, were obtained from the slope and
300 0.003 intercept of the plot of t against t/qt. The initial adsorp-
400 0.002 tion rate (h) (mg g−1 min) is calculated if t = 0 from the
equation:

reported a qm value of 7.4 mg g−1 for neem leaf powder. h ¼ kq2e ð6Þ
All the other studies that are reported so far in the The results indicate that the calculated qe value is
literature describe the Cr(VI) removal by natural mate- close to the experimental data. Attainment of faster
rials under acidic pH of 1–3 (as listed in Table 2). The adsorption equilibrium is supported by the calculated
present result is thus attributable to the superiority of the pseudo-second-order rate constant (k) which was
unmodified OP over the existing adsorbents and high- 0.005 g mg−1 min−1. In addition, the initial adsorption
lights its cost-effectiveness because of no preparation rate (h) was 13.05 mg g −1 min. High Bh^ value is
cost and higher implicability in treating metal- expected due to the presence of more cationic active
contaminated divergent aquatic environments. adsorption sites that can readily hold Cr(VI) anion. After
Moreover, OP holds promise over other adsorbents as exhaustion of the active sites, the adsorbate anions need
it is an abundantly available forestry waste. to migrate into the inner pores of the biomaterial, thus
A further analysis of the Langmuir equation can be resulting slower adsorption at latter stages. The best
made on the basis of a dimensionless equilibrium pa- fitness of the pseudo-second-order model describes the
rameter, RL (Babu and Gupta 2008), also known as presence of chemisorption mechanism.
separation factor which is commonly represented as:

1 3.5 Mechanism of Cr(VI) Removal

RL ¼ ð4Þ
1 þ KC o
Earlier studies in the literature claimed that Cr(VI) re-
where K (L−1 mg) is the Langmuir adsorption constant moval from aqueous solutions by natural biomass is
and Co (mg L−1) is the initial Cr(VI) concentration. RL through an adsorption process, where anionic Cr(VI)
values indicate the isotherm shape whether or not the binds to the positively charged groups of the adsorbent.
system is favorable. If RL > 1, sorption is unfavorable; However, recently, it has been explained by Park et al.
RL = 0, sorption is irreversible; RL = 1, adsorption is lin- (2007) and few others (Dittert et al. 2014; Anandkumar
ear; and 0 < RL < 1, adsorption is favorable. In this study, and Mandal 2009) that these findings were
Water Air Soil Pollut (2016) 227:62 Page 7 of 11 62

Table 2 Cr(VI) adsorption capacities of unmodified natural adsorbents with present study: a comparative overview

Adsorbent Optimum pH Concentration of Adsorption Reference

Cr(VI) (mg L−1) capacity (mg g−1)

Brazilian pine (Araucaria angustifolia) fruit coat 2 0–1000 154.7 Vaghetti et al. (2008)
Pine needle 2 20–1000 21.50 Dakiky et al. (2002)
Eucalyptus bark 2 250 45.0 Sarin and Pant (2006)
Gular (Ficus glomerata) fruit 2 50 46.73 Rao and Rehman (2010)
Groundnut husk 3 50 7.0 Dubey and Gopal (2007)
Olive pomace 2 50–200 12.15 Malkoc et al. (2006)
Soya cake 1 34.25 0.28 Daneshvar et al. (2002)
Beech (Fagus orientalis) sawdust 1 200 16.13 Acar and Malkoc (2004)
Carrot waste biomass 1 100 88.27 Bhatti et al. (2010)
Tea factory waste 2 400 54.65 Malkoc and Nuhoglu (2007)
Rubber wood sawdust 2 200–500 4.87 Akmar Zakaria et al. (2009)
Neem leaf powder 7 25–125 7.43 Venkateswarlu et al. (2007)
Bael (Aegle marmelos correa) fruit shell 2 50–125 17.27 Anandkumar and Mandal (2009)
Oak acorn peel powder 2-10 100–400 47.39 This study

misinterpreted due to errors in measuring the concentra-

tions of different Cr species in aqueous phase over time
and had briefed the occurrence of integrated reduction/
oxidation reactions and sorption processes in Cr(VI)
removal using biomaterials. Hence, to obtain a clear
understanding of the Cr(VI) removal process by OP,
we analyzed the fractions of Cr species (hexavalent,
trivalent, and total) in the aqueous and solid phases after
treatment (Fig. 3a, b). Removal efficiency of total Cr by
OP was not related with the rate of Cr(VI) removal.
Though LC-ICPMS confirmed the removal of nearly
97.27–99.84 % Cr(VI) (0.4–6.8 mg L −1 Cr(VI)
remained) from the aqueous solution at a pH range of
2 to 10, ICP-OES analysis of the aqueous fractions
revealed the existence of nearly 8.31–14.56 mg L−1 of
total Cr (Fig. 3a). The existence of total Cr in the
aqueous phase implies the occurrence of Cr(VI) reduc-
tion to Cr(III) when brought into contact with the bio-
material. The mechanism of Cr(VI) removal by OP can
be either by direct or indirect reduction-coupled adsorp-
tion. Direct mechanism is absolute reduction or
reduction-coupled adsorption. In case of direct
reduction-coupled adsorption process, complete reduc-
tion of Cr(VI) to Cr(III) by interaction with surface
electron-donor groups of the adsorbent might occur,
Fig. 3 a Total Cr, Cr(VI), and Cr(III) remaining in the solution at
followed by complexation of the reduced Cr, which different pH (sorbent dose, 5 g L−1; temperature, 24 °C; incubation
either remains in the aqueous phase or get sorbed to time, 7 h; and initial Cr(VI) concentration, 250 mg L−1). b Total Cr
the adsorbent. Another possible mechanism is indirect, (mg) sorbed by 100 mg powder after 7 h at different pH
62 Page 8 of 11 Water Air Soil Pollut (2016) 227:62

i.e., adsorption-coupled reduction, where the anionic between the positively charged groups of the adsorbent
Cr(VI) binds to the positively charged groups present and the surface-bound Cr(III). Similar mechanism was
on the surface of the adsorbent. The adsorbed Cr(VI) described by Anandkumar and Mandal (2009) for
then gets reduced to Cr(III) by adjacent electron-donor Cr(VI) removal by bael fruit. Relatively more fractions
groups of adsorbed sites, and a part of the reduced Cr is of Cr(III) species at pH 2 indicate that the mechanism is
released into the aqueous phase by electronic repulsion more of a direct reduction-coupled adsorption, where

Fig. 4 a Scanning electron micrograph of OP: 1 before and 2 after Cr adsorption; b SEM-EDX spectra of OP: 1 before and 2 after Cr
adsorption; and c XRD pattern of Cr sorbed OP
Water Air Soil Pollut (2016) 227:62 Page 9 of 11 62

most fractions of Cr(VI) are directly reduced to Cr3+ Table 3 Cr(VI) removal by OP in real environmental water
samples
form which is not fairly adsorbed. With increase in the
reaction pH, reduction is less and hence the Cr(III) Sample In aqueous solution (mg L−1) Total Cr (mg) sorbed by
fractions in the aqueous phase decreased steadily as 100 mg OP powder
has been observed by Dakiky et al. (2002) The reducing Cr(VI) Total Cr Cr(III)
property of OP could be attributed to its constituents like
W1 4.24 11.09 6.85 2.84
Fe (Zhang et al. 2011) and polyphenols (Scalbert and
W2 6.1 13.42 7.32 3.61
Williamson 2000), which are regarded as the most ef-
fective reducing agents. Finally, the Cr(VI) removal by Sorbent dose, 5 g L−1 ; temperature, 24 °C; and initial Cr(VI)
concentration, 250 mg L−1
OP can be described exclusively as a combination of
adsorption and reduction process. W1 lake water, W2 sea water
The mechanism of adsorption-coupled reduction by
OP was further confirmed by examining the Cr-sorbed was 2.84 and 3.6 mg, respectively. The Cr(VI) removal
biomaterial under SEM-EDX against untreated sample. efficiency witnessed in this study is far superior as it
It is clear from Fig. 4(a1, a2) that the pores and surfaces achieves almost complete removal of Cr(VI) (initial
of adsorbent are covered and hence became smooth by Cr(VI) concentration of 250 mg L−1) in real environ-
adsorbate. EDX analysis of OP revealed the presence of mental samples which is in accordance with the initial
carbon, nitrogen, potassium, sodium, magnesium, alu- batch studies. Thus, this first evidence on the remarkable
minum, silica, chlorine, and calcium on its surface be- potential of Q. robur acorn peel for the detoxification
fore interacting with Cr(VI) ions (Fig. 4(b1)), whereas a and removal of Cr(VI) in real water samples can be
new Cr peak was observed with the surface bearing implied for wastewater treatments. As this biomaterial
groups of carbon, nitrogen, potassium, sodium, magne- has higher metal removal potential and works well in
sium, aluminum, silicon, chlorine, and calcium wide ranging pH, it can be further investigated for its
(Fig. 4(b2)), which confirmed the Cr adsorption onto implication in the removal of toxic heavy metals like As,
OP. Pb, Zn, Cu, etc., in real samples.
The XRD pattern of OP after Cr adsorption (Fig. 4c) Only about 49 out of 230 mg L−1 of the sorbed Cr
was recorded to acquire information regarding the type was extractable. This indicates the strong complexation
of Cr species that are sorbed over the biomaterial. XRD and immobilization of Cr by OP. Of the total Cr
patterns showed that both trivalent (as chromium oxide) desorbed (20 mg L−1), the most toxic Cr(VI) species
and hexavalent (as dipotassium chromate) forms of Cr constituted only about 1.5 mg L-1. It is thus evident that
exist on the surface of the biomaterial after the treat- most form of the Cr bound on OP surface exists in
ment. It can thus be concluded that integrated reduction reduced form, i.e., less toxic trivalent Cr, and hence
and adsorption contributed to the removal of Cr(VI) OP is a potential natural detoxifier of Cr(VI).
from aqueous solution by OP.

3.6 Application of the Process to Synthetic Wastewater 4 Conclusion

Samples
The present work highlights the superiority of OP as a
In order to evaluate the applicability of the present biosorbent with its reducing potential that helps in the
process in natural ecosystems, the procedure of Cr(VI) efficient detoxification and removal of Cr(VI) from
removal by OP based on adsorption-coupled reduction aqueous solutions. OP is a rich source of essential
was applied to lake (pH 7.8) and sea water (pH 8.4) minerals, natural polyphenols, and flavonoids with high
samples. Fairly good removal efficiencies were obtained antioxidant activity indicating its great potential for
for Cr(VI) (Table 3). In 420 min, OP amendment wider industrial applications. Batch experiments
(5 g L−1) resulted in the removal of 98.3 and 97.6 % showed that the adsorption of Cr(VI) over OP was
Cr(VI) from lake and sea water samples, respectively. dependent on the adsorbent dose, contact time, and
Briefly, the aqueous solutions of lake and sea water initial dye concentration, and maximum sorption (100
samples contained only 11.09 and 13.42 mg L−1 of the to 96.6 %) was observed at varied range of pH from 2 to
total Cr, and the total Cr sorbed by the material (100 mg) 10 with an optimum adsorbent dose of 5 g L −1.
62 Page 10 of 11 Water Air Soil Pollut (2016) 227:62

Langmuir isotherm and pseudo-second-order kinetic Daneshvar, N., Salari, D., & Aber, S. (2002). Chromium adsorp-
tion and Cr(VI) reduction to trivalent chromium in aqueous
model parameters illustrated the biosorption capacity
solutions by soya cake. Journal of Hazardous Materials, 94,
of about 47.39 mg g−1. The mechanism of Cr(VI) re- 49–61.
moval by OP, as confirmed by ICP assays, SEM-EDX, Deng, S., & Ting, Y. P. (2005). Polyethylenimine-modified fungal
and XRD analysis, was found to be complex, involving biomass as a high-capacity biosorbent for Cr(VI) anions:
sorption capacity and uptake mechanisms. Environmental
adsorption and reduction processes. In particular, Cr(VI)
Science and Technology, 39, 8490–8496.
removal potential was fairly high in real environmental Dittert, I. M., de Lima Brandão, H., Pina, F., da Silva, E. A., de
water samples removing >95 % of total Cr and 97.6 % Souza, S., Ma, G. U., de Souza, A. A. U., Botelho, C.,
of Cr(VI) species, clearly suggesting that the selected Boaventura, R. A., & Vilar, V. J. (2014). Integrated
reduction/oxidation reactions and sorption processes for
biomaterial is suitable for treating environmental water
Cr(VI) removal from aqueous solutions using Laminaria
samples. Desorption studies revealed the strong ionic digitata macro-algae. Chemical Engineering Journal, 237,
interaction of Cr(III) molecules over the biomaterial 443–454.
surface. Majority of Cr species both in the aqueous Dubey, S. P., & Gopal, K. (2007). Adsorption of chromium (VI)
on low cost adsorbents derived from agricultural waste ma-
solutions and at the adsorbent surface were in less toxic
terial: a comparative study. Journal of Hazardous Materials,
form of Cr(III), highlighting the ability of OP to serve as 145, 465–470.
an efficient detoxifier of Cr(VI). Thus, the abundantly Gardea-Torresdey, J., Tiemann, K., Armendariz, V., Bess-Oberto,
available local forestry waste, OP, is a superior bioma- L., Chianelli, R., Rios, J., Parsons, J., & Gamez, G. (2000).
terial over the existing marketable adsorbents for con- Characterization of Cr(VI) binding and reduction to Cr(III)
by the agricultural byproducts of Avena monida (Oat) bio-
trolling water pollution due to toxic metal ions. mass. Journal of Hazardous Materials, 80, 175–188.
Khomdram, S. D., & Singh, P. K. (2011). Polyphenolic com-
Acknowledgments SK thanks the Australian Government, Uni- pounds and free radical scavenging activity in eight
versity of South Australia (UniSA), and Cooperative Research Lamiaceae herbs of Manipur. Notulae Scientia Biologicae,
Centre for Contamination Assessment and Remediation of the 3, 108–113.
Environment (CRC CARE) for the International Postgraduate Kuppusamy, S., Thavamani, P., Megharaj, M., & Naidu, R.
Research Scholarship (IPRS) and CRC CARE top-up fellowship (2015). Bioremediation potential of natural polyphenol rich
during PhD. green wastes: a review of current research and recommenda-
tions for future directions. Environmental Technology and
Innovation, 4, 17–28.
Kuppusamy, S., Palanisami, T., Megharaj, M., Venkateswarlu, K.,
& Naidu, R. (2016a). In-situ remediation approaches for the
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