Chemosphere 221 (2019) 758e767

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Removal of Cr(VI) from synthetic wastewater by adsorption onto

coffee ground and mixed waste tea
Wachiraphorn Cherdchoo a, Srisuda Nithettham a, b, Jittima Charoenpanich a, c, *
a
Bioengineering Program, Faculty of Engineering, Burapha University, Bangsaen, Chon Buri 20131, Thailand
b
Department of Chemical Engineering, Faculty of Engineering, Burapha University, Bangsaen, Chon Buri 20131, Thailand
c
Department of Biochemistry, Faculty of Science, Burapha University, Bangsaen, Chon Buri 20131, Thailand

h i g h l i g h t s

Recycle of mixed waste tea and coffee ground as alternative adsorbents for Cr(VI) removal.

Both adsorbents completely removed 30 mg L1 Cr(VI) within 180 min and could be reused for four times.

Carbon and oxygen functional groups on the surface of both adsorbents involved in Cr(VI) adsorption.

Kinetic study matched well with the Freundlich and pseudo-second-order model for the 10-250 mg L1 concentration range.

A 100 L of reactor containing mixed waste tea showed the breakthrough time of adsorption as 30 min in 100 mg L1 Cr(VI).

a r t i c l e i n f o a b s t r a c t

Article history: We attempted to recycle mixed waste tea and coffee ground as alternative low-cost adsorbents for Cr(VI)
Received 21 August 2018 removal. The adsorption parameters optimized were: initial Cr(VI) concentration (10e30 mg L1), contact
Received in revised form time (180 min), adsorbent dose (2.0 g L1), initial pH (2.0), temperature (30e50  C), and agitation speed
12 January 2019
(250 rpm). Freundlich isotherm was found better fitted with a high correlation coefficient (R2 ¼ 0.97 for
Accepted 16 January 2019
Available online 18 January 2019
mixed waste tea and 0.92 for coffee ground) than to Langmuir model (R2 ¼ 0.89 for mixed waste tea and
0.86 for coffee ground) for the 10e250 mg L1 concentration range. Analysis of kinetic studies indicated
Handling Editor: Y Yeomin Yoon that Cr(VI) adsorption by both adsorbents was consistent with the pseudo-second-order kinetic model
with a good R2 and Marquardt's present standard deviation (MPSD) values. Experimental data demon-
Keywords: strated a sorption capacity of 94.34 mg g1 of mixed waste tea and 87.72 mg g1 of coffee ground.
Cr(VI) removal Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Energy dispersive X-
Adsorption isotherm ray spectroscopy (EDS) revealed the noticeable chromium accumulation on the adsorbent surfaces after
Adsorption kinetics adsorption. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS)
Beverage wastes
studies showed that carbon and oxygen functional groups on the surface of both adsorbents involved in
Cr(VI) adsorption. The adsorbents could be reused four times. Large-scale operation using 100 L of
packed-bed reactor showed the breakthrough time of adsorption for mixed waste tea of 30 min in
100 mg L1 Cr(VI) concentration. These results suggested that mixed waste tea and coffee ground be
considered as alternative adsorbent for Cr(VI) removal.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction Pittman, 2006). It is mainly present in the environment as triva-

lent, Cr(III) and hexavalent, Cr(VI) stable oxidation states. The Cr(III)
Chromium is one of the major heavy metals released to the is an essential element in human, plant and animal metabolism
environment by various industries such as leather production, (Pressman and Buff, 2000). It is much less toxic than the Cr(VI)
electroplating, wood preservation and textiles etc. (Mohan and form, which is recognized as a carcinogenic and mutagenic agent
(IARC, 1987; Whitacre, 2012; Yao et al., 2008). The Cr(VI) is
remarkably hazardous and being listed by the United States Envi-
* Corresponding author. Department of Biochemistry, Faculty of Science, Burapha ronmental Protection Agency (USEPA) as one of the 129 most
University, Bangsaen, Chon Buri 20131, Thailand. critical pollutants (Krishnani and Ayyappan, 2006). Human toxicity
E-mail address: jittima@go.buu.ac.th (J. Charoenpanich).

https://doi.org/10.1016/j.chemosphere.2019.01.100
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
 W. Cherdchoo et al. / Chemosphere 221 (2019) 758e767 759

of Cr(VI) is ranged from skin irritation to lung cancer, as well as using a packed-bed reactor was monitored.
kidney, liver, and gastric damages (Cieslak-Golonka, 1995). The
liberated wastewaters from the industries pose a major risk to 2. Materials and methods
environment as they are very persistent. The USEPA has announced
the maximum permissible limit of Cr(VI) to 0.05 mg L1 (EPA, 1990), 2.1. Synthetic wastewater characteristics
while total chromium, including Cr(III), Cr(VI), and its other forms is
regulated to below 2 mg L1 (WHO, 2004). Therefore, to reduce the Synthetic wastewater used in this study had similar character-
environmental risk of the chromium in industrial wastewater, istics as that of municipal wastewater. It consists of tap water
Cr(VI) should be treated before releasing to the environment. together with relative trace concentrations of suspended dissolved
Various treatment technologies have been suggested for the organic and inorganic solids: 29.1 g of sucrose, 9.1 g of CH3COONa,
removal of Cr(VI) from wastewater. These include chemical pre- 10 g of NH4Cl, 1.8 g of MgCl2, 0.9 g of CaCl2$2H2O, 18.18 g of NaHCO3,
cipitation, membrane-based separation, ion-exchange resins, 1.19 g of K2HPO4 and 0.59 g of KH2PO4 in 40 L of tap water. The
adsorption, and solvent extraction (Barrera-Díaz et al., 2012; resulting characteristics were pH between 6.5 and 7.5, total
Rengaraj et al., 2001; Song et al., 2004). Adsorption, in comparison chemical oxygen demand (TCOD) 812.3 mg COD L1, soluble
with the other methods, is being used extensively for removing chemical oxygen demand (SCOD) 721.8 mg COD L1, mixed liquor
heavy metals from aqueous solution. The usefulness of this method suspended solids (MLSS) 98 mg MLSSL1 and ammonia nitrogen
lies in the benefits of cleaner and easy controlled process, more (NHþ 4 eN) 53.2 mg NL .
1

efficient and cost-effective technology (Atar et al., 2012; Pintor

et al., 2015). However, economical operating cost from the use of 2.2. Preparation and morphological characterization of adsorbents
low-cost adsorbents is a major concern for a practical deployment.
Many by-products of agriculture like sawdust, rice husk, nut and Two adsorbents, coffee ground and mixed waste tea were kindly
walnut shells, eucalyptus bark, and wheat bran have been investi- received from a coffee shop in Burapha University, Chon Buri,
gated as potential adsorbents for the removal of Cr(VI) from Thailand. They were dried in an oven at 60  C for 3 d and kept in
wastewater (Ghasemi et al., 2015; Hegazi, 2013; Kaya et al., 2014; desiccators until used.
Sugashini and Begum, 2015; Sumathi et al., 2005; Xavier et al., Morphological characterization of the adsorbents was con-
2013). Moreover, Cr(VI) removal using modified biomaterials such ducted by SEM-EDS (Leo, Eindhoven, Netherlands) and TEM-EDS
as activated carbon from tamarind wood and coconut shell, phos- (JEM-2100, JEOL, Japan) techniques. The SEM samples were cross-
phate treated sawdust, coconut husk and palm pressed fibers, oil section cut and dried under vacuum. Then, the samples were
palm endocarp, and Leucaena leucocephala waste sawdust were fixed on the stub and sputter-coated with gold particle. The analysis
documented (Acharya et al., 2009; Ajmal et al., 1996; Babel and parameters were pressure 1.3  102 Pa and resolution ˂10 nm at
Kurniawan, 2004; Malwade et al., 2016; Marrugo et al., 2015; Tan 115 kV. For TEM, the samples were isolated by ultrasonically
et al., 1993). However, many of these readily available adsorbents treating the adsorbent in ethanol and drying the residual solvent on
showed a limit of adsorption capacity and could not be reused carbon-coated copper TEM grids. TEM images were taken using a
(Table 1). Therefore, it is always of interest to search for new low- JEOL JEM-2100 at 200 kV. EDS analysis was done with an Oxford
cost adsorbents, which is suitable for a practical application in PentaFetx5 probe. The specific surface area of the adsorbents was
large-scale operation. estimated using a surface area and pore size analyzer (Autosorb
Coffee and tea are one of the worldwide-consumed beverages 1 MP, Quantachrome) with N2 and the Brunauer-Emmett-Teller
with the average of many billion cups daily, and hence liberating (BET) method. The total pore volume was determined as the vol-
considerable waste. Some waste can be recycled into cosmetic ume of nitrogen that was kept in the sample at relative pressure, p
production with remainder unused and, in many occasions, posing p1
0 of 0.99.
a disposal problem. One solution to recycle these wastes is to use FTIR (Specac GS01160, USA) was analyzed to investigate the
them as alternative useful materials. Owing to the facts that coffee interaction between adsorbent and chromium. The adsorbents
ground and waste tea contain oxidizing organic chemicals mainly were initially dehydrated at 80  C for 3 h and grinded by agate
rich of oxygen and hydroxyl, carboxyl, amino, sulfonic and phenolic mortar and pestle. Then, the adsorbents were mixed separately
functional groups, which are the basic materials involved in with spectroscopic grade of KBr powder for preparing powder
adsorption of heavy metals (Ballesteros et al., 2014; Yashin et al., samples and pressed for pellet formation using a 10 tons pressure.
2015). To overcome the disposal problem, this study aims to The KBr-sample pellets were 13 mm diameter and 1 mm thickness.
apply coffee ground and mixed waste tea as alternative low-cost Finally, the samples were analyzed in the diffuse reflectance mode
adsorbents for Cr(VI) removal from synthetic wastewater. The at a resolution of 4000e400 cm1 under a 4 cm1 resolution. The
optimal condition for Cr(VI) adsorption was investigated using baseline of raw data was adjusted, and modified data were
batch experiments. Equilibrium isotherms and adsorption kinetics normalized using OMNIC 8.0.342 software (Thermo Scientific,
were studied. Finally, adsorption efficiency in large-scale operation USA). A change in chemical composition of the adsorbent surface

Table 1
Adsorption capacity of mixed waste tea and coffee ground compared to the other published low-cost adsorbents for Cr(VI) removal.

Adsorbent Maximum Cr(VI) concentration (mg L1) pH Adsorption capacity (mg g1) Reference

Mixed waste tea 250 2 94.34 This study

Coffee ground 250 2 87.72 This study
Peanut shell 100 4 8.31 Al-Othman et al. (2012)
Coconut shell charcoal 25 4 10.88 Babel and Kurniawan (2004)
Treated waste newspaper 50 3 59.88 Dehghani et al. (2016)
Walnut shell 100 2 40.83 Ghasemi et al. (2015)
Fertilizer industry waste 100 4 15.24 Gupta et al. (2010)
Rice husk 100 2 13.1 Sugashini and Begum (2015)
Tamarind hull-based 50 2 81 Verma et al. (2006)
760 W. Cherdchoo et al. / Chemosphere 221 (2019) 758e767

was investigated using an XPS (AXIS ULTRADLD, Kratos analytical,

Manchester, UK.) The base pressure in the XPS analysis chamber ðVdes  cdes Þ  100
Desorptionð%Þ ¼
was ~5  109 Torr. The samples were excited with X-ray hybrid ðci  ce ÞVads
mode 700  300 mm spot area with a monochromatic Al Ka 1,2 ra-
diations at 1.4 keV. X-ray anode was run at 15 kV, 10 mA and 150 W. where “Vdes” is the volume of desorbent used (25 mL), “cdes” is the
The photoelectrons were detected with a hemispherical analyzer final concentration of Cr(VI) in solution after desorption (mg L1),
positioned at an angle of 90 with respect to the normal to the “ce” is the equilibrium Cr(VI) concentration after adsorption (mg
sample surface. The spectra were calibrated using the VISION II L1), “ci” is the initial Cr(VI) concentration before adsorption (mg
software included with the instrument and all spectra were charge L1), and “Vads” is the volume of Cr(VI) solution used for adsorption
corrected by means of the adventitious carbon signal (C1s) and (25 mL).
oxygen signal (O1s) at 285 eV and 533 eV, respectively.
2.5. Adsorption isotherms

Adsorption isotherms are expressed in terms of a relationship

2.3. Cr(VI) analysis between the concentration of non-adsorbed Cr(VI) and the amount
of adsorbent at a constant condition. These explain the adsorption
The Cr(VI) concentration was estimated using a spectropho- process by providing essential information of the adsorption
tometer at 540 nm after complexation with 1,5-diphenylcarbazide mechanisms. They are fundamentally required to evaluate the
under acidic condition (pH 2.0 ± 0.5) (APHA, 1989). The standard equilibrium data with different important isotherm models. In this
curve of Cr(VI) was constructed under different concentration of study, two parameter isotherm models, Langmuir and Freundlich
K2Cr2O7 (0e1 mg L1). The R2 value is 0.9998. The percentage of models were selectively tested with the experimentally obtained
removed Cr(VI) was calculated using the following equation: equilibrium data (Freundlich, 1906; Langmuir, 1916).
Adsorption capacity of Cr(VI) at equilibrium, qe (mg g1) was
ci  ce
CrðVIÞ removal ð%Þ ¼  100 calculated using the mass balance as shown in the equation:
ci
ðci  ce Þ
where “ci” is the initial Cr(VI) concentration (mg L1) and “ce”is the qe ¼ V
m
Cr(VI) concentration after the adsorption reaches equilibrium (mg
L1). All experiments were done in triplicate and the averages are where “ci” and “ce” are the initial and equilibrium Cr(VI) concen-
reported with standard deviation (SD) values. tration (mg L1), respectively, qe is the equilibrium adsorption ca-
pacity (mg g1), m is the mass of adsorbent (g), V is the volume of
solution (L).
2.4. Adsorption experiments
2.6. Adsorption kinetic studies
Adsorption of Cr(VI) onto the adsorbents was done in a batch
mode of operation. The experiments were initially performed in In this study, two kinetic models were tested to describe the
25 mL of synthetic wastewater (pH 7.0) containing 10 mg L1 of reaction in order of Cr(VI) adsorption. There are pseudo-first-order
Cr(VI) at 30  C and 150 rpm for 1 h. Physical parameters affecting kinetic and pseudo-second-order kinetic models (Qiu et al., 2009).
the adsorption efficiency of Cr(VI) by the adsorbents were studied Moreover, an intra-particle diffusion model was also analyzed
by varying any one of the parameters and keeping the other pa- (Hameed and Ahmad, 2009). The experiments were conducted by
rameters constant. The parameters studied were adsorbent dosage adsorption of Cr(VI) on mixed waste tea and coffee ground at
(0e6 g L1), solution pH (2.0e11.0), initial Cr(VI) concentration optimal condition: pH 2.0, agitation speed 250 rpm, 30  C, 2 g L1 of
(5e100 mg L1), agitation speed (50e350 rpm with 50 intervals), the adsorbent, contact times in the range of 20e360 min with
temperature (15e80  C with 5  C intervals) and contact time different initial Cr(VI) concentrations.
(20e360 min). The effect of common anions present in wastewater The best fit of kinetic model to the experimental data was
(OH, SO2 
4 , and Cl ) on adsorption of Cr(VI) was also tested. The
estimated according to regression coefficient values (R2) obtained
study was performed separately with each anion of varying from a linear plot of the equation model and the MPSD value
strength (0e10 mM) in synthetic wastewater (pH 2.0) containing developed by Marquardt (1963). The MPSD value was calculated
50 mg L1 of Cr(VI) at optimal condition. Control was done in the using the following equation:
same manner without other ions. Each experiment was carried out 0v
u
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
" #2ffi 1
in triplicate and the averages ± SD reported. u 1 X p
q  q
MPSD ¼ 100@t
t ;exp t ;calc A
Reusability of the adsorbents for Cr(VI) adsorption was tested p  n i¼1 qt ;exp
using batch system. The experiments were conducted in 25 mL of i
synthetic wastewater supplementing with 50 mg L1 of Cr(VI) at
optimal condition for 2 h. After adsorption, each adsorbent was where “p” is the number of the experimental data point and “n” is
washed with 25 mL of distilled water and collected by centrifuga- the number of parameters of the model equation. “qt,exp” and
tion. Then, the 0.1 M NaOH solution (pH 10.0) was added for “qt,calc” are referring to experimental and calculated values from
desorption of Cr(VI) by shaking at 150 rpm for 1 h. The adsorbents model equation, respectively.
were recovered by centrifugation and the residual concentration of
Cr(VI) ions in the solution was measured. The fresh Cr(VI) solution 2.7. Packed-bed reactor
was added to adsorbents for next adsorption-desorption cycle.
Each cycle of Cr(VI) adsorption was performed for 2 h at the same Packed-bed reactor was constructed as column using empty-
condition and Cr(VI) removal was expressed in percentage relative refillable water filter cartridge (size; 2.500  1000 ). Two hundred
to the original adsorption. Desorption amount was calculated using grams of mixed waste tea was packed in the reactor. Fig. S1 shows
the following equation: the model of packed-bed reactor used in this study. The adsorption
 W. Cherdchoo et al. / Chemosphere 221 (2019) 758e767 761

studies were carried out with a working volume of 100 L synthetic was performed. The infrared spectra of the adsorbents are illus-
wastewater. The initial Cr(VI) concentrations supplementing in the trated in Fig. S3. The more intense spectra frequencies are reported
synthetic wastewater were varied in the range of 40e100 mg L1. in Table 2. Both mixed waste tea and coffee ground have consid-
System was operated at optimum pH and room temperature erable numerous functional groups where there was good possi-
(28e30  C). The initial flow rate of water feeding was fixed at bility for Cr(VI) to be adsorbed. For examples, the functional groups
300 mL min1 by Diaphragm booster pump (DEW, Italy) and OH, NH and CH stretching in alcohol or amine or alkyl existed in
running time was 4 h. mixed waste tea and coffee ground at wavenumber 3445 cm1 or
3446 cm1. The CH stretching in alkane was also detected in both
3. Results and discussion adsorbents at wavenumber 2852-2915 cm1 for mixed waste tea
and 2848-2923 cm1 for coffee ground while amino groups were
3.1. Adsorbent characteristics found at wavenumber 2339-2360 cm1. These are similar with the
results of Gorzin and Ghoreyshi (2013) and Mulani et al. (2013)
Waste tea and coffee ground are big deposit beverage wastes, which the OH groups and CH stretching of alkanes were pre-
liberating global disposal problem. In this study, mixed waste tea sented in waste tea and coffee ground used for Cr(VI) adsorption.
and coffee ground from coffee shops in Burapha University were The C]O groups and CeH bending (in plane) were identified at
selected as alternative adsorbent for investigation of Cr(VI) wavenumber 1465-1645 cm1 for mixed waste tea and 1460-
removal. The mixed waste tea contains 47.36% carbon, 44.03% ox- 1700 cm1 for coffee ground. The CeO stretching for aliphatic
ygen, 4.68% potassium, 2.13% calcium and trace levels of magne- amines (1070 cm1) and NeH bending (1558-1645 cm1) were also
sium, aluminium and chromium (Fig. S2a). SEM image indicates noticed in the adsorbents. There were reports about the involve-
smooth surface and compose of the agglutinative flakes of original ment of C]O groups and eNH group in Cr(VI) adsorption by many
waste tea. In the same way, the EDS analysis of coffee ground modified biomaterials (Bai and Abraham, 2002; Levankumar et al.,
(Fig. S2c) mainly represented the percentage of carbon and oxygen 2009; Teymouri et al., 2013; Xining et al., 2015). Thus, it can be
as 35.48% and 58.06%, respectively. Other atomic components noted here that mixed waste tea and coffee ground would be
showed percentage by weight <2.5%. The smooth and thin layer applicable candidate adsorbent for the Cr(VI) removal.
surface was also detected as shown in the SEM image. Trace levels
of chromium found in both mixed waste tea and coffee ground are 3.2. Optimization of adsorption condition
possibly due to the original contamination occurred during tea or
coffee growth, transportation, packaging, and processing. Many 3.2.1. Effect of adsorbent dosage
documents confirmed the presence of chromium in tea and coffee Various factors affecting the adsorption as well as the
(Amin and Kassem, 2012; Mandiwana et al., 2011; Seenivasan et al., complexation of chromium ions were investigated. Removal of
2008; Zaleschi et al., 2012). Based on the results for the BET surface Cr(VI) at the initial concentration of 10 mg L1 was firstly tested in
area, mixed waste tea and coffee ground has an area of 13.86 m2 g1 synthetic wastewater (pH 7.0) for 1 h at 30  C and 150 rpm, with
and 13.01 m2 g1, respectively. Total pore volume of mixed waste different doses of the absorbent used. This examination is vital to
tea was 0.0173 cm3 g1, which is similar to the total pore volume in get the trade-off between the adsorption capacity and the per-
coffee ground (0.0177 cm3 g1). The average pore diameter of centage removal of Cr(VI) resulting in an optimum adsorbent
mixed waste tea and coffee ground was 4.99 nm and 5.44 nm, dosage. As shown in Fig. S4a, the %Cr(VI) removal are similar (~30%)
respectively, suggesting a mesoporous structure (Zdravkov et al., when 0.5e2 g L1 of coffee ground were applied. Then, the removal
2007). efficiency was gradually increased by increasing the coffee ground
Although the adsorption mechanism of heavy metal especially dose and seemed to be constant at the dosage between 5 and
Cr(VI) by waste tea and coffee ground is still not documented. There 6 g L1. For mixed waste tea, the %Cr(VI) removal was continuously
are some reports suggesting biosorption of heavy metal by these increased and reached maximum (~70%) when 5e6 g L1 was used.
materials uses carboxyl and amine groups for binding (Ahluwalia These can be explained because for a fixed initial Cr(VI) concen-
and Goyal, 2005). Also, some reports described cellulose and tration, an increase in the amount of adsorbent had provided a
hemicellulose, lignin and condensed tannins as responsible func- greater surface area (Khosravi et al., 2014). Overlapping and unsa-
tional groups for metals adsorption by waste tea (Nandal et al., turation of adsorbent sites limited the adsorption potential at
2014). Thus, to investigate the possibility of waste tea and coffee higher amount of the adsorbent used (Jain et al., 2009). Of these,
ground as alternative adsorbent for Cr(VI) adsorption, FTIR analysis dosage at 5 g L1 of both adsorbents seemed to be optimum.

Table 2
FTIR adsorption frequencies of mixed waste tea and coffee ground after Cr(VI) adsorption compared with before adsorption.

Mixed waste tea Coffee ground Assignment

Main observed bands (cm1) Main observed bands (cm1)

Before Cr(VI) After Cr(VI) Differences Before Cr(VI) After Cr(VI) Difference

adsorption adsorption adsorption adsorption

3445 3446 1 3446 3446 0 OH, NH, CH stretching in alcohol or amide or alkyl
2915 2923 2919 4 CH stretching in alkane
2852 2848 2846 2
2360 2360 0 2360 2360 0 Amino groups
2339 2341 2 2340 2339 1
1700 1700 1700 0 C¼O groups, CeH bending and NeH
1645 1649 4 1653 1653 0 bending
1558 1558 0 1558 1560 2
1465 1445 20 1460 1463 3
e e e 1070 1074 4 CeO stretching for aliphatic amines
762 W. Cherdchoo et al. / Chemosphere 221 (2019) 758e767

However, high chemical oxygen demand (COD) values 3.2.5. Effect of temperature
(>2000 mg L1) were detected in effluent after adsorption when Adsorption experiments were performed in the temperature
>2 g L1adsorbents were used. Thus, to overcome this unsatisfied range of 15e80  C (Fig. S4f). Using of mixed waste tea as the
problem, 2 g L1of both adsorbents should be a sufficient dose for adsorbent revealed similar percentage of Cr(VI) removal at all
Cr(VI) removal and were selected as optimum dosage for the next studied temperature except at beyond 25  C and above 65  C that
studies. the efficiency was 10e20% decreased. These could be concluded
that there is no internal bond breakage near the edge of the
3.2.2. Effect of pH adsorbent active surface sites (Ucun et al., 2008). Adsorption effi-
Solution pH is another significant parameter influence on the ciency of Cr(VI) using coffee ground was rapidly increased with
adsorbent surface charge and degree of ionization. Adsorption of further increase of temperature from 15  C to 45  C. These suggest
Cr(VI) on both adsorbents gave a similar pattern which strongly the Cr(VI) adsorption process is endothermic in character (Kara and
depends on the initial pH (Fig. S4b). Maximum Cr(VI) removal Demirbel, 2012). Maximum adsorption (~95%) was observed at
(95.08% for mixed waste tea and 85.25% for coffee ground) was 50e65  C and then slightly decreased but still >80% removal. High
achieved at pH 2.0. Increase in the solution pH had progressively removal percentages of Cr(VI) at wide temperature range recom-
decreased the removal efficiency. This could clarify by the fact that mends the potential of these wastes as alternative adsorbent for
Cr(VI) has different ionic forms (H2CrO4, HCrO 2 2
4 , CrO4 and Cr2O7 ) decontamination of Cr(VI) from industrial effluents.
in the aqueous solution and the stability of these ions mainly de-
pends on the solution pH. At strong acidic pH, HCrO 4 is the
dominant Cr(VI) species easily bound to the positive charged ad- 3.2.6. Effect of initial Cr(VI) concentration
sorbents by means of electrostatic interaction. But at higher pH, Almost complete adsorption of Cr(VI) was observed for initial

competitiveness of CrO2 4 and OH ions interfere the binding site Cr(VI) concentration up to 40 mg L1 and 35 mg L1 for mixed
on the adsorbents (Baral et al., 2006; Suksabye and Thiravetyan, waste tea and coffee ground, respectively (Fig. S4g). As expected,
2012). Thus, pH 2.0 was selected as optimum pH for next studies. the removal efficiency decreased when initial concentration of
Maximum adsorption efficiency at acidic pH recommends the po- Cr(VI) continuously increased. These might due to limited of sur-
tential of these adsorbents for decontamination of Cr(VI) from face area to be adsorbed (Owalude and Tella, 2016). However, high
wastewater, especially the effluent from chrome tanning that pH percentages of Cr(VI) removal (80e90%) were still recorded at the
3.5 was recorded (Islam et al., 2014). concentration up to 80 mg L1. At 100 mg L1 of Cr(VI) concentra-
tion, coffee ground showed a better performance of adsorption
3.2.3. Effect of agitation speed than mixed waste tea ~20%.
In this study, agitation speed was varied between 50 and
350 rpm and keeping adsorbent dosage and pH constant. As shown
in Fig. S4c, the %Cr(VI) removal by both adsorbents increased by
increasing of agitation speed and seemed to be constants at the 3.2.7. Effect of other ions
speed >250 rpm. Using of mixed waste tea gave adsorption effi- Three anions, OH, SO2 
4 and Cl , commonly found in waste-

ciency ~95% at 200e350 rpm while the Cr(VI) removal >80% was water with varying strength were tested along with a control
obtained from coffee ground at the speeds 250e350 rpm. These (without anion). Two of them (Cl and SO2 4 ) did not show any

might due to improvement of the degree of physico-chemical inhibitory effect on Cr(VI) adsorption (Table S1). The %Cr(VI)
interaction between Cr(VI) ions and negatively charged of the ad- removal decreased by 10% possibly due to desorption effect of OH
sorbents as well as higher diffusion of the chromium ions towards (Gorzin and Abadi, 2018).
the adsorbent surface (Babel and Kurniawan, 2004). Throughout
the results, the speed at 250 rpm was recommended as the opti-
mum agitation speed for Cr(VI) adsorption and used in further 3.3. Reusability of the adsorbents
experiments.
The potential of adsorbent to be reused is the key factor for
3.2.4. Effect of contact time practical uses of the adsorbent with cost effective. Studies were
The effect of contact time on Cr(VI) adsorption by mixed waste performed in synthetic wastewater containing 50 mg L1 Cr(VI) at
tea and coffee ground was investigated over the time. Almost optimal condition. After adsorption, the adsorbents were washed
complete adsorption (~97%) was detected after 80 min for both with 0.1 M NaOH and dried at 60  C for 24 h before being used in
adsorbents (Fig. S4d and Fig. S4e). A quick removal of Cr(VI) was the next cycle. As shown in Fig. S5, a slight drop of %Cr(VI) removal
found in the early stages of the adsorption process. Then, the per- was recorded in the second cycle for both mixed waste tea and
centages of Cr(VI) removal were slowly increased and tended to coffee ground. More than 50% of Cr(VI) removal remained in the
attain equilibrium at 100 min and 120 min for mixed waste tea and third and fourth cycle while 20e30% of Cr(VI) removal was detected
coffee ground, respectively. It can be noted that during the initial in the fifth cycle. These results support the fact that adsorption
stage of the adsorption process, the higher concentration of Cr(VI) process of Cr(VI) is reversible (Tytłak et al., 2015) which desorption
ion provide the diving force to facilitate ion diffusion from solution of Cr(VI) occurred by the action of NaOH (Gorzin and Abadi, 2018).
to surface of adsorbent. Moreover, increase of contact time pro- Moreover, the results showed that 10e15% of desorbed chromium
motes sufficient time for Cr(VI) ions attached with the adsorbent was in the form of Cr(VI). These indicate conversion of Cr(VI) to
surface. Slower rate of Cr(VI) adsorption before equilibrium other valence forms after adsorption. The decrease in %Cr(VI)
possibly due to occupation of the adsorbent surface and the removal possibly due to a progressive saturation of the binding
decrease of Cr(VI) ion concentration, leads to a decrease in uptake Cr(VI) ions with negative charge of functional group in active site of
rate until equilibrium is achieved. Another reason might be the the adsorbent or extreme pH conditions might destroy textural
electrostatic hindrance or repulsion between the adsorbed Cr(VI) characteristics of the adsorbent. In addition, impurities from the
ions and the adsorbent surface (Nemr, 2009; Verma et al., 2006). reaction process such as salts from synthetic wastewater and heavy
Hence, according to the results, the contact time as 120 min was metal contaminants of untreated adsorbent probably block the
selected for further studies. active surfaces of the adsorbent (Kyzas, 2012).
 W. Cherdchoo et al. / Chemosphere 221 (2019) 758e767 763

3.4. Morphological and physical changes of the adsorbent after waste tea after Cr(VI) adsorption (Fig. 1a) shows the shift of
Cr(VI) adsorption component peaks corresponding to graphitic carbon (CeC) or
carbogen (CeH, B.E. ¼ 285.06 eV, 73.7%) and hydroxyl/ether groups
After adding the mixed waste tea or coffee ground in synthetic (CeO, B.E. ¼ 286.15 eV, 10%). Similarly, after Cr(VI) adsorption, the
wastewater containing 50 mg L1 Cr(VI) at optimal condition, both shift of peaks corresponding to graphitic carbon (CeC) or carbogen
adsorbents became shiny and coarse surface (Fig. S2c and Fig. S2d). (CeH, B.E. ¼ 284.98 eV, 76.6%), hydroxyl/ether groups (CeO,
These results are in well agreement with that of the SEM-EDS B.E. ¼ 286.00 eV, 8%), and carbonyl/carboxy groups (C]O/OeCeO,
analysis representing chromium accumulation on adsorbent sur- B.E. ¼ 286.85 eV, 8%) were found in coffee ground (Fig. 1c). For XPS
faces. The percentage of chromium as 24.79% and 23.91% was O1s spectrum (Fig. 1b and c), the shift peaks of carbonyl/carboxy
detected on the surface of mixed waste tea and coffee ground, groups as well as hydroxyl/ether groups were also displayed for
respectively after adsorption. By combining the results with TEM both adsorbents after adsorbed with Cr(VI). These can be noted
images and EDS analysis, it is clearly shown that chromium can be here that both adsorbents use carbon and oxygen functional groups
accumulated on the adsorbent surface after adsorption (Fig. S6). on the surface for Cr(VI) adsorption.
The FTIR spectra of mixed waste tea and coffee ground after
adsorption are illustrated in Fig. S3c and S3d. Comparisons of 3.5. Time-course monitoring of Cr(VI) adsorption with different
intense frequencies before and after adsorption are summarized in initial concentrations
Table 2. The FTIR spectrum of mixed waste tea shows that some
peaks were shifted or disappeared (2915 cm1 and 2852 cm1) and The adsorption of Cr(VI) by mixed waste tea and coffee ground
new peaks were detected (1700 cm1). These changes suggest the were time-course studied in synthetic wastewater containing
possible stretching vibrations of CH groups on the surface of mixed different initial Cr(VI) concentrations (10e250 mg L1) at optimal
waste tea after Cr(VI) adsorption (Ahmad et al., 2013; Kaya et al., condition and 30  C. Similar pattern of adsorption efficiency was
2016). However, no significant changes on either the position or observed from both adsorbents (Fig. S8). The removal efficiency of
intensity during Cr(VI) adsorption by coffee ground could be Cr(VI) increased parallel with the increase of contact time. At low
detected. Then, XPS analysis was performed in parallel to identify concentrations of Cr(VI), mixed waste tea showed complete
the chemical change. adsorption within 80 min and 180 min of contacting time when
The XPS survey spectra (Fig. S7) indicates that carbon and ox- 10 mg L1 and 20e30 mg L1 of Cr(VI) was used, respectively
ygen are main elements on the adsorbent surface. However, there is (Fig. S8a) while coffee ground totally adsorbed 10 mg L1 Cr(VI)
no chromium signal in the spectra after adsorption. This implies after 140 min (Fig. S8b). Maximum removal level was constantly
binding of Cr(VI) to the surface of adsorbents possibly occurred via detected after 180 min for mixed waste tea and 240 min for coffee
the carbon and oxygen functional groups (Li et al., 2008; Sawalha ground when higher initial Cr(VI) concentrations were used. These
et al., 2007). The XPS spectra corresponding to the C1s and O1s times were considered as the equilibrium response time which
narrow scan region of the adsorbents before and after adsorption of indicates that the adsorption was saturated with Cr(VI) ions. The
Cr(VI) were compared (Fig. 1). The XPS C1s spectrum of mixed rapid rate of adsorption in the initial stages of the process probably

Fig. 1. Comparison of XPS spectra of mixed waste tea and coffee ground before and after Cr(VI) adsorption. High-resolution spectra of (a) C1s of mixed waste tea, (b) O1s of mixed
waste tea, (c) C1s of coffee ground, and (d) O1s of coffee ground.
764 W. Cherdchoo et al. / Chemosphere 221 (2019) 758e767

Table 3
Isotherm parameters for Cr(VI) adsorption onto mixed waste tea and coffee ground.

Adsorbent Langmuir parameters Freundlich parameters

KL (calculated) (L mg1) RL (L mg1) qm (mg g1) R2 Kf (calculated) (mg g1) 1/n n R2

Mixed waste tea 0.10 0.037e0.082 0<RL < 1 97.09 0.8905 20.05 0.31 2.06 0.9723
Coffee ground 0.12 0.031e0.072 0< RL < 1 87.72 0.8600 23.15 0.39 3.24 0.9233

due to the availability of abundance adsorption site of the adsor- under study condition.
bents used for Cr(VI) binding. In the same way, slow rate of
adsorption comes from limited of adsorbent capacity at the equi- 3.6.2. Freundlich model
librium (Kumar et al., 2008). Thus, the equilibrium adsorption at The linear form of Freundlich model equation is reported in
360 min was used to calculate the isotherm and kinetic adsorption. Fig. S9. A good correlation (R2 > 0.9) between the experimental data
and Freundlich adsorption models for Cr(VI) suggests that both
3.6. Adsorption isotherm mixed waste tea and coffee ground possess high sorption capacity
and high affinity for Cr(VI) (Table 3). As 1/n indicates type of
The Langmuir and Freundlich isotherm models were used to adsorption process: 1/n ¼ 0 is irreversible process, 0 < 1/n < 1 is
describe the equilibrium relationship between Cr(VI) and adsor- optimum adsorption state and 1/n > 1 non-optimum adsorption or
bents (mixed waste tea and coffee ground). cooperative adsorption. Our result showed 1/n ¼ 0.31 for mixed
waste tea and 1/n ¼ 0.39 for coffee ground which lies between
3.6.1. Langmuir model 0 and 1 indicates favorable adsorption. The Freundlich isotherm
The linear Langmuir isotherm plots of mixed waste tea and constant (Kf) were calculated as 20.05 mg g1 for mixed waste tea
coffee ground are shown in Fig. S9. Moderate values of correlation and 23.15 mg g1 for coffee ground. Thus, from the results, the
coefficient (R2 ¼ 0.89 for mixed waste tea and R2 ¼ 0.86 for coffee adsorption of Cr(VI) onto mixed waste tea and coffee ground fitted
ground) as presented in Table 3 indicate that Langmuir isotherm well with the Freundlich isotherm model, which indicates that
was unsuitable for Cr(VI) adsorption onto these adsorbents. Cr(VI) uptake occurs on heterogeneous surface by multilayer
Maximum adsorption capacities (qm) of 97.09 mg g1 for mixed adsorption (Malik, 2004; Owalude and Tella, 2016).
waste tea and 87.72 mg g1 for coffee ground were exhibited.
The main characteristic of Langmuir equation is a dimensionless 3.7. Adsorption kinetic studies
constant called equilibrium parameter (RL) which indicates the type
of isotherm. RL > 1 is unfavorable and used for non-optimum The study of adsorption kinetics which describes the rate of
adsorption, RL ¼ 1 is linear adsorption, 0 < RL < 1 is favorable and adsorption is the key factor used for designing a process. The
used for optimum adsorption and RL ¼ 0 is irreversible adsorption. adsorption kinetic depends on the physical and chemical charac-
According to the obtained results, mixed waste tea showed teristics of the adsorbent as well as on the mass transfer process
0.037e0.082 RL values and the RL values of 0.031e0.072 were found (Wang et al., 2005). Experimental data were used to predict the
by coffee ground. These indicate optimum adsorption of Cr(VI) kinetics chromium adsorption. In this study, the adsorption data

Fig. 2. Kinetic plots for adsorption of Cr(VI) onto (aec) mixed waste tea and (def) coffee ground at 100e250 mg L1 Cr(VI) concentrations. (a, d) Pseudo-first-order model, (b, e)
Pseudo-second-order model, (c, f) Intra-particle diffusion models. Symbols represent the experimental data and linear/dot/dash lines imply theoretical data fitting of the model.
Experimental conditions were pH 2.0, agitation speed 250 rpm, 30  C, 2 g L1 of adsorbent.
 W. Cherdchoo et al. / Chemosphere 221 (2019) 758e767 765

was analyzed with two kinetic models, i.e., pseudo-first-order and gave a larger correlation coefficient (R2 > 0.99) and close in values
pseudo-second-order kinetic models as well as the intra-particle between qe, exp and qe, cal. The smallest correlation coefficient in
diffusion model. The conformity between experimental data and this case was 0.991, which is still better than the pseudo-first-order
the model predicted values was expressed by the correlation co- kinetic model. The MPSD values < 10 indicate a closeness of qe,exp
efficients (R2 values closeness to 1) as well as closeness of values and qe, cal. These data recommended the adsorption of Cr(VI) onto
between experimental and calculated adsorption capacity values as mixed waste tea and coffee ground was consistent with the pseudo
indicate as MPSD values. second-order kinetic model. Hence, it can be concluded that
chemical adsorption (chemisorptions) is the rate-limiting step. A
3.7.1. Pseudo-first-order model similar conclusion has been documented for the adsorption of
This model is based on the fact that the change in Cr(VI) ion Cr(VI) by tamarind wood (Acharya et al., 2009) and cereal by-
concentration with respect to time is proportional to be power one. products (Arris et al., 2016). The adsorption of heavy metals onto
The results of the pseudo-first-order adsorption kinetic are plotted waste tea was also consistency reported (Ghasemi et al., 2017).
in Fig. 2 and Fig. S10. It has been found that the amount of adsorbed
Cr(VI) ions onto both adsorbents increase slightly at all studied 3.7.3. Intra-particle diffusion model
times. The adsorption uptake, qt (mg g1) increases with increased Since transportation of Cr(VI) ions to the surface of the adsor-
initial concentration and the adsorption rate declines and reaches bent might occur in several steps: film or external diffusion, pore
the equilibrium position over time. However, the experimental data diffusion, surface diffusion and the adsorption on the pore surface,
are far from the theoretical data. The linear form of the model was or a combination of more than one step. Also, in a rapidly stirred
used for model prediction. Values of k1 (pseudo-first-order rate batch adsorption, the diffusive mass transfer can be related by an
constant) are calculated from the plots of log (qe-qt) versus t apparent diffusion coefficient. The Morris-Weber equation is
(Fig. S11 and S12). The R2 values obtained for mixed waste tea and generally applied to evaluate the intra-particle diffusion rate con-
coffee ground are shown in Table 4. These values are relatively stant (kid). Fig. 2 show a plot qt against time of the diffusion model.
small and the experimental qe values do not agree with the values The linear portion of the plot qt vs t0.5 (Fig. S11 and Fig. S12) for a
calculated from the linear plot. High MPSD values confirming a big wide range of contact time between Cr(VI) ions and adsorbents
gap of qt values between experiments and theories were also found. (mixed waste tea and coffee ground) do not pass through the origin.
These suggest the pseudo-first-order kinetic model is not well This might due to difference in the rate of mass transfer between
fitted to the data obtained from the studies. the initial and final stages of adsorption. Furthermore, such devi-
ation from the origin indicated that the intra-particle diffusion is
3.7.2. Pseudo-second-order model not only the rate-limiting step. Although the correlation co-
The pseudo-second-order model, an indication of a chemi- efficients (R2) for this model (Table 4) are higher than those ob-
sorptions mechanism was also analyzed. Nonlinear plots of the tained from pseudo-first-order kinetic model, the R2 values of
model are shown in Fig. 2. The plots showed good agreement be- pseudo-second-order kinetic model are more closeness to 1. Thus,
tween theoretical and experimental data of the pseudo-second- the experimental data fit better to the pseudo-second-order kinetic
order model. The kinetic rate of adsorption can be predicted us- model than the other two models.
ing a linear form equation of the model. The plot t/qt against t as From all results, the mechanism of Cr(VI) adsorption by both
shown in Fig. S11 and S12 presented straight line with slope of 1/ adsorbents can be proposed. At first, the Cr(VI) attaches to adsor-
k2q2e and intercept of 1/qe, the constants (qe and k2) as experi- bent using chemical interaction, possibly by the carboxyl/carbonyl
mentally determined from the plot are summarized in Table 4. groups on the adsorbent surface. Then, multilayer adsorption as
According to the results, the pseudo-second-order kinetics model film covering the adsorbent surface occurred before reduction to

Table 4
Kinetic constants for Cr(VI) adsorption onto mixed waste tea and coffee ground.

Adsorbent Experimental Kinetic model constants, R2 and MPSD

Pseudo-first-order model Pseudo-second-order model Intra-particle diffusion model

2 2
Cr(VI) (mg qe (exp.) (mg qe (cal.) (mg k1 R MPSD qe (cal.) (mg k2 R MPSD kid W R2 MPSD
L1) g1) g1) (min1) g1) (min1) (min1)

Mixed waste 10 4.99 10.41 0.0111 0.5234 95.64 5.02 0.1773 1.0000 1.01 0.0145 4.7661 0.7137 1.31
tea 20 10.00 1.05 0.0071 0.7398 125.83 10.04 0.0225 0.9998 2.07 0.0818 8.5673 0.8250 3.17
30 14.97 1.68 0.0150 0.9483 122.53 15.13 0.0195 0.9990 1.64 0.1080 13.2200 0.8146 2.55
50 24.97 5.60 0.0147 0.9483 125.19 25.32 0.0064 0.9990 6.77 0.2079 21.3030 0.8997 2.12
100 45.93 8.89 0.0064 0.8658 119.08 46.30 0.0313 0.9980 8.44 0.5144 36.0200 0.9538 1.71
125 53.78 8.89 0.0074 0.6092 128.37 54.35 0.0030 0.9990 2.61 0.3450 47.9350 0.8867 1.50
150 63.96 8.89 0.0039 0.9046 129.58 63.69 0.0148 0.9940 5.05 0.3024 57.5660 0.9205 0.92
175 72.81 1.62 0.0083 0.6092 133.04 72.99 0.0087 1.0000 0.39 0.0999 71.2930 0.7309 0.53
200 81.05 14.77 0.0345 0.9695 110.98 81.97 0.0028 0.9993 8.45 0.6671 68.4620 0.9409 0.14
250 94.22 15.78 0.0078 0.8738 110.05 94.34 0.0029 0.9992 6.79 0.9443 76.8730 0.9402 0.73
Coffee ground 10 5.00 5.60 0.0069 0.7180 60.83 5.05 0.0636 0.9990 3.10 0.0482 4.2358 0.7367 4.39
20 9.91 2.78 0.0048 0.6629 116.07 10.02 0.0174 0.9992 2.78 0.1191 7.8865 0.8623 3.84
30 14.97 1.48 0.1244 0.8737 120.59 17.36 0.0031 0.9970 18.52 0.0925 13.432 0.9175 1.95
50 23.98 4.00 0.0193 0.8167 115.12 24.04 0.0081 0.9930 5.07 0.2168 19.974 0.9175 2.04
100 45.78 6.09 0.0058 0.9199 124.51 45.87 0.0022 0.9910 9.44 0.3568 38.727 0.8949 1.86
125 53.63 6.80 0.0062 0.9588 124.62 53.76 0.0051 0.9940 7.14 0.3938 45.968 0.9691 0.98
150 60.44 5.12 0.1658 0.4665 122.69 60.61 0.0037 1.0000 0.57 0.1565 57.8570 0.7296 0.12
175 73.02 3.00 0.0299 0.5580 129.31 74.07 0.0272 0.9960 2.76 0.0506 72.2460 0.0536 1.82
200 77.42 5.39 0.0131 0.5958 127.19 78.74 0.0017 0.9998 2.72 0.6671 66.6760 0.8035 2.91
250 87.10 7.19 0.0064 0.8752 127.96 87.72 0.0014 0.9996 2.41 0.5973 76.9660 0.8196 1.95
766 W. Cherdchoo et al. / Chemosphere 221 (2019) 758e767

adsorbents can be reused four times with the remaining adsorption

efficiency >50%. Study on a 100 L of packed-bed reactor showed the
breakthrough time of adsorption for mixed waste tea as 30 min in
100 mg L1 Cr(VI) concentration.

Acknowledgements

We gratefully acknowledge research grants from the National

Research Council of Thailand through Burapha University (Grant
no. 37/2558, 70/2559, and 1/2560). We also thank Faculty of En-
gineering, Burapha University for the graduate research assistant
(GRA) scholarship awarded to W.C. We would like to thank Dr. P. Na
Nongkhai for the useful discussion about XPS results and Dr. N.
Fig. 3. Breakthrough curves for Cr(VI) adsorption onto mixed waste tea at different
Kurukitkoson for proofreading the manuscript.
initial feed concentrations.
Appendix A. Supplementary data
the other forms of chromium.
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2019.01.100.
3.8. Packed-bed reactor study
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