Accepted Manuscript

Title: Removal of perchlorate from drinking water using

granular activated carbon modified by acidic functional group:
Adsorption kinetics and equilibrium studies

Authors: Rekha Krishnan G., R. Radhika, T. Jayalatha, Salu

Jacob, R. Rajeev, Benny K. George, B.R. Anjali

PII: S0957-5820(17)30080-0
DOI: http://dx.doi.org/doi:10.1016/j.psep.2017.03.014
Reference: PSEP 1005

To appear in: Process Safety and Environment Protection

Received date: 21-10-2016

Revised date: 30-1-2017
Accepted date: 8-3-2017

Please cite this article as: Krishnan G., Rekha, Radhika, R., Jayalatha, T., Jacob,
Salu, Rajeev, R., George, Benny K., Anjali, B.R., Removal of perchlorate from
drinking water using granular activated carbon modified by acidic functional group:
Adsorption kinetics and equilibrium studies.Process Safety and Environment Protection
http://dx.doi.org/10.1016/j.psep.2017.03.014

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Removal of perchlorate from drinking water using granular activated carbon modified by
acidic functional group: Adsorption kinetics and equilibrium studies
Rekha Krishnan G., R. Radhika, Jayalatha T., Salu Jacob, Rajeev R., Benny K. George, Anjali B.R.*,

Analytical and Spectroscopy Division, Analytical Spectroscopy and Ceramic Group,

Propellants, Polymers, Chemicals and Materials Entity
Vikram Sarabhai Space Centre, Thiruvananthapuram – 695 022, India
* Department of Chemistry, University of Calicut, Malappuram, India
The corresponding author of the Paper is Rekha Krishnan G. not Anjali B R. Please remove the * it is not
required

1
Graphical abstract

2
Highlights

1. A cost effective method with high adsorption capacity was developed

2. The maximum adsorption capacity of 44.0 mg g-1 was obtained for GAC-PH
3. Acid modification increased the positively charged sites on the adsorbent
4. The microcrystalline and interlamellar pores increase the adsorption

3
Abstract

Granular activated carbon was treated with different types of acids in order to improve its capability for the removal
of perchlorate from drinking water. The characteristics of acid treated granular activated carbons were examined by
SEM, XRD, Raman spectrum and FTIR spectroscopic analysis. The effect of various adsorption parameters such as
contact time, initial perchlorate concentration, pH of the solution, temperature and presence of co-existing anions on
the efficiency were studied. Maximum adsorption capacities were observed as 20.1, 37.5 and 44.0 mg g -1 for GAC,
GAC-AA and GAC-PH respectively at 303K. Equilibrium adsorption isotherms and kinetics for the process were
investigated and found that the process follows Langmuir adsorption isotherm. The adsorption of perchlorate could
be well described by pseudo-second-order kinetic model. Thermodynamic parameters, ΔG o, ΔHo and ΔSo were also
evaluated.

Key words: Perchlorate, Activated carbon, Adsorption, Kinetics, Langmuir isotherm.

1. Introduction

Perchlorate has become a major inorganic contaminant in drinking water and has been detected in a number of
public drinking water systems throughout the world (Lin et al., 2014). It is commercially available in the form of
perchloric acid and salts such as ammonium, potassium and sodium perchlorate. Perchlorate is widely used as an
oxidizer in solid rocket propellants, explosives, missiles and also in various commercial products like air bag
inflators, matches, safety flares, fireworks and pharmaceuticals, which contribute to its presence in the environment
(Jackson et al., 2010; Eva Kumar et al., 2010). Perchlorate is an anthropogenic and naturally occurring chemical
substance (R. Renner 1999). Perchlorate presence in water is of increasing concern because of its toxicity. It inhibits
the iodine uptake by the thyroid gland, affecting/altering the production of thyroid hormones and subsequently
causes malfunction of the metabolic processes resulting in neurological damage, and anemia (Wilkin et al., 2007)
Since its health effects, USEPA set an interim health advisory level of perchlorate at 15 ppb in 2009 and has
declared a decision to regulate perchlorate under the Safe Drinking Water Act in 2011 (US Environmental
Protection Agency 2011). Due to its characteristics of high mobility, high stability, non volatility and non- reactive
nature, perchlorate is commonly viewed as a persistent water pollutant (Roy and Bickerton, 2012) and hence
effective removal of perchlorate from water is very important.

Various materials and treatment technologies have been reported for the removal of perchlorate from water. Ion
exchange resins appear to be the most sensible technology for removing perchlorate present at trace level (<50ppb)
in water (Darracq et al., 2014). The exchange capacity, stability, selectivity and regeneration capacity of a particular
resin will influence the removal capacity. However, this ion exchange technology is not found to be economically
viable due to its high cost and disposal of concentrated brine solution (Ye et al., 2012). In addition to that, presence
of co-existing anions like sulphate, nitrate, and chloride also affect the available sites on a particular resin and
accordingly perchlorate adsorption capacity will be reduced (Bardiya and Bae, 2011; Venkatesan and Batista,
2011). Biological treatments are eco-friendly and efficient technological solution for removing perchlorate. Some
bacteria produce two cell-bound enzymes, perchlorate reductase and chlorite dismutase, which minimize the
activation energy required for perchlorate reduction. However, the disadvantage is the least public acceptance since
microorganisms are involved during treatment process (Nadaraja et al., 2013). Granular activated carbon has been
widely used in water treatment process to remove perchlorate. Even though activated carbon could remove
perchlorate, its efficiency which is strongly affected by solution pH, base material, and organic constituents, is found
to be low. However, activated carbon offers the advantage of having large surface area and it has been shown to be a
probable candidate for perchlorate removal after proper surface modifications. Surface tailoring of activated carbon
with ammonia (Chen et al., 2005) and cationic surfactants have resulted in significant increase in perchlorate
removal capacity (Parette et al., 2005). Due to efficient adsorption of perchlorate, activated carbon has been used as
a catalyst support for surface mediated hydrogenation reduction of perchlorate (Hurley et al., 2007; Mahmudov et

4
al., 2008). Activated carbon on modification by several cationic surfactants showed the maximum adsorption
capacity up to 29.59 mg g-1 (Lin et al., 2013). Rovshan et.al studied the effect of surfactant type and surfactant
loading on two types of activated carbon for perchlorate removal. Significant improvement in perchlorate removal
over plain activated carbon was achieved for both modified activated carbons studied (Rovshan et al., 2015).

In recent years, adsorption of perchlorate using acid-washed zero-valent aluminum and aluminum hydroxide was
examined in batch method and approximately 90-95% perchlorate removal was achieved at acidic pH 4.5 (Lien t al.,
2010). Similarly, some other modified adsorbents were found to remove perchlorate from the aqueous solutions.
Granular ferric hydroxide was successfully used to adsorb perchlorate and the maximum adsorption capacity of
granular ferric hydroxide was 20 mg g-1 at pH 6.0-6.5 at 25°C (Eva Kumar et al., 2010). Another study showed that
cross-linked Fe(III)-chitosan composite can be used for removing perchlorate from the aqueous solution and a
maximum adsorption capacity of cross-linked Fe(III)-chitosan composite was observed as 29.85 mg g-1 at 25°C
and adsorption process exhibited almost independent of pH ranging from 3.0 to 10.2 (Lv et al. 2014). Ferric oxide
nano particles showed a good adsorption capacity towards perchlorate. Though, direct addition of nano particles into
water is not feasible in drinking water treatment, as their health effects are uncertain (Xu et al., 2013). The
adsorption capacities of calcined layered double hydroxide were also examined. The maximum adsorption capacity
was obtained with Zn/Al ratio of 2 at a calcined temperature of 500 °C and the adsorption process was followed to
be endothermic in nature (Wu et al., 2010). Recently, wood derived biochar produced at 500-700°C effectively
adsorbed perchlorate and maximum adsorption capacity was obtained as 10.55 mg g-1. Organosilicas and composites
of rice husk with MCM-48 were also explored for perchlorate uptake (Komarneni et al., 2010; Seliem et al., 2010;
Wanga et al., 2015)

While there are many studies on the surface modification of different activated carbons, there is limited systemic
study on the effect of different types of acids modified activated carbon on the removal of perchlorate from drinking
water. The objectives of this study were (1) to prepare and characterize different acid modified activated carbon; (2)
to systematically monitor the effects of several adsorption parameters including contact time, adsorbent dosage,
initial perchlorate concentration, co-existing ions (sulphate, chloride and nitrate), temperature and pH values on
perchlorate removal and (3) to interpret the adsorption kinetic and isotherm patterns of perchlorate on the virgin and
modified GAC.

2. Materials and methods

2.1 Materials

The GAC used in the experiments was coconut shell based with particle size 0.40 mm to 1.0 mm obtained from
Active Char Products Pvt Ltd., Kochi. The following chemicals used for the study were purchased from Merck and
of ACS grade: hydrochloric acid, (purity >36-38%), sulphuric acid (purity >95-98%), phosphoric acid (purity >85–
89%), nitric acid (purity >67–71%), acetic acid, (purity >99%) and formic acid (purity >89-91%). Ammonium
perchlorate, (prepared in house), tartaric acid, GR (purity >99%), oxalic acid, GR (purity >99%) and citric acid, GR
(purity >99%) were purchased from Sigma Aldrich. Deionized (DI) water obtained from Millipore MilliPac 40
system with resistivity of ≥ 18 MΩ cm-2 was used for preparing analytical standards of perchlorate solutions.

2.2 Instrumental

A Dionex model ICS 2000 Ion Chromatograph equipped with AS16 column, AG16 Guard column, ASRS 300
Suppressor column and a conductivity detector was employed for the analysis of perchlorate using 35.0 mM NaOH
as eluent with a flow rate of 1 mL min-1. Chromeleon chromatographic software was used for the data analysis of
chromatograms by peak area and peak height methods. Before running a sample, the ion chromatography system
was calibrated using a standard solution. From the calibration plot and data obtained from the sample, concentration
of perchlorate in the sample was calculated.

5
2.3 Preparation of treated GAC

GAC (1g) was mixed with 100 mL of the acid solution (1M) and the mixture was agitated in a thermo-stated rotary
shaker for 1 hour at 27 ± 2°C. The excess acid was washed with distilled water to a pH of 7 and dried at 105°C in an
air oven. Finally the solid GAC was stored in sealed containers at constant temperature (30 ± 5°C).

2.4 Characterization of virgin and treated GAC

2.4.1 SEM analysis

Field emission scanning electron microscopy (FESEM) observations were performed to examine the morphology of
the samples using Carl Zeiss, Supra 55 model field emission scanning electron microscope equipped with an
energy-dispersive X-ray spectrometer (EDX).

2.4.2 XRD analysis

XRD measurements were carried out using a Bruker D8-Discover X-ray diffractometer operating with a Cu anode
(40 KV, 40 mA). Diffractograms were recorded using a solid state detector, LynxEye from 10 to 90° at a step size
0.02° and time/step 0.5sec. Samples were placed on top of a zero background silicon cup and diffractograms were
recorded.

2.4.2 FTIR analysis

Surface characteristics of the virgin and treated GAC were determined by Fourier Transform Infrared Spectroscopy.
The spectra were recorded using NICOLET iS50 FT-IR spectrometer in the region 4000 to 400 cm-1 with a
resolution 4 cm-1. Spectrum of the sample was taken by making a pellet with KBr powder.

2.4.3 Raman analysis

Raman spectroscopic analysis of the samples were carried out using WITec alpha 300R-Confocal Raman
Microscope. The samples were illuminated with an excitation wavelength of 532 nm. Spectrum was obtained by
accumulating five spectra with an integration time of 1 sec.

2.5 Batch Adsorption experiments

The batch adsorption experiments were carried out by adding 1g of virgin/treated GAC in 100mL of perchlorate
solution with different initial concentrations (0-7000 mg L-1) in 250 mL Erlenmeyer flasks. The mixture was kept in
a thermostated mechanical shaker (30±1°C) for 1 hour to reach equilibrium, filtered and the perchlorate
concentration in the filtrate was analyzed using IC. The perchlorate adsorption capacity at equilibrium q e (mg g-1)
was calculated by:

(C0−Ce ) V
qe = ………………………. (1)
W

Where, C0 and Ce are the concentration of perchlorate in the solution in mg L-1 at initial and equilibrium stages
respectively. V is the volume of the solution in liters and W is the mass of adsorbent used in grams.

Kinetic studies of adsorption were carried out by taking 1g of virgin/treated GAC samples in 100 mL of 100 mg L-
1
perchlorate solution. The solutions were shaken in 250 mL Erlenmeyer flasks at room temperature. Samples were
withdrawn at different time intervals (10 to 60 minutes) and the concentration of perchlorate was measured. The
amount of perchlorate adsorbed at time t, qt (mg g-1), was calculated by:

6
 (C0−Ct ) V
qt = ………………………………. (2)
W

Where, C0 and Ct (mg L-1) are the concentration of perchlorate at initial and at any time t, respectively. V is the
volume of the solution (L) and W is the mass of adsorbent used (g).

3. Results and discussion

3.1 Adsorption of perchlorate on treated Granular Activated Carbon (GAC)

Perchlorate adsorption capacities of acid treated GACs were measured and the results are given in Table 1. The
efficiency of organic acids is comparatively lower than that of inorganic acids. Among the inorganic acids,
maximum adsorption is observed for phosphoric acid treated GAC (GAC-PH) and the adsorption capacity decreases
in the order H3PO4 >HCl> H2SO4> HNO3. Among the organic acids, GAC treated with acetic acid and formic acid
showed the maximum adsorption capacity compared to tartaric acid, oxalic acid and citric acid. This may be due to
the smaller size of acetate and formate ions compared to tartarate, citrate and oxalate ions. Treatment with acetic
acid and formic acid showed comparable but lower adsorption capacity than that of inorganic acids. This may be due
to the greater dissociation and acidic strength of inorganic acids over organic acids. Among the acid treated GACs,
we have selected phosphoric acid treated GAC (GAC-PH) and acetic acid treated GAC (GAC-AA) for detailed
adsorption studies due to the better bio-compatibility of phosphate and acetate ions. It is also found that acid
treatment significantly changed the surface chemical properties due to the removal of impurities present in the
surface of virgin GAC.

Table 1-Effect of acid treatment on the adsorption of perchlorate

Sample Adsorption capacity (mg g-1)
GAC 3.5
GAC+ HCl 9.7
GAC+ H2SO4 9.1
GAC+ HNO3 7.7
GAC+ H3PO4 9.8
GAC+ Oxalic acid 5.1
GAC+ Citric acid 1.4
GAC+ Formic acid 9.1
GAC+ Acetic acid 9.2
GAC+ Tartaric acid 6.0
(Experimental conditions: Adsorbent dose - 1g in 100mL, ClO4- , concentration – 100 mg L-1,
Contact time - 1 hour, Temperature 30◦C)

3.2 Characterization

3.2.1 Physical properties of granular activated carbon

The physical properties of the virgin activated carbon used for the study were measured by following ASTM test
methods. The various parameters studied, the test method numbers, and the results obtained are indicated in the
Table 2.

Table 2-Physical properties of granular activated carbon (GAC)

Parameters Test Method Test Result Parameters Test Method
Moisture (%) ASTM-D-2867 3.0 0.23 0.29

7
 Apparent Density (g cm-3) ASTM-D-2854 0.52 0.49 0.48
-1
Iodine No. (mg g ) ASTM-D-4607 1156 1532 1497
2 -1
Surface Area (m g ) ASTM-(BET-N2) 1159 1541 1508
pH ASTM-D-3838 10.2 6.9 7.0
Ash (%) ASTM-D-2866 2.8 0.80 0.90
Ball Pan Hardness (%) ASTM-D-3802 98.3 98.5 98.3

3.2.2 SEM analysis

It is clearly observed that the smooth surface of untreated GAC was converted to rough surface with increased open
pores. This may result in easy access of perchlorate throughout the GAC reactive centers. The increase porosity
after treatment also reflected in the increased surface area of treated GAC.

Fig. 1. SEM images of virgin and treated GAC a) GAC and b) GAC-PH

3.2.3 XRD analysis

XRD patterns of virgin and treated GAC are shown in Fig. 2. The diffraction peaks around 2 = 25° and 2 = 44°
are observed for all the samples. The 2 at 25° and 44° peaks correspond to the (002) and (100) diffraction planes of
graphite structure respectively. In the XRD spectra of virgin and treated GAC, no obvious change was observed in
the case of (100) plane, but the peak around 2 = 25° slightly increased for the treated GAC. From the Fig. 2, it is
evident that the d(002) value decreased for GAC-PH compared to GAC-AA and virgin GAC. The crystallite size as
calculated using the Scherrer equation, (stacking size or crystallite size, Lc= K/βcos  (where K is the apparatus
constant and equal to 1,  is the wavelength of Cu Kα 0.15418nm,  is the Bragg’s angle and β is the half value
width) was found to be decreased on acid modification. The smaller microcrystalline and the formation of
interlamellar pores can increase surface reactivity and adsorption performance of treated GAC.

8
 Fig 2: XRD pattern of virgin and treated GAC

3.2.4 FTIR analysis

Fourier transformation infrared spectra of virgin and treated GAC are shown in Fig. 3. The broad absorption band
observed at 3433 cm-1 is attributed to the hydroxyl stretching vibration. The band at 1618 cm-1 observed in the case
of GAC corresponds to the C=C and C=O stretching vibrations. For acid modified GAC, the band at 1618 cm-1
became feeble. The extra bands observed in GAC disappears in the case of acid treated GAC, may be due to the
removal of impurities from the surface of GAC.

Fig 3: FTIR spectra of virgin and treated GAC.

3.2.5 Raman analysis

Raman spectra of carbon materials show two broad bands, called D (disordered) and G (graphitic) bands at 1360 cm -
1
and 1580 cm-1 respectively. The G band is obtained from the stretching vibrations of sp2 carbon atoms in the
carbon ring or long carbon chain in graphite, which is used to find the degree of symmetry and order of the graphite
structure. The D band is obtained due to the disordered arrangement and low symmetry of graphite lattice structure
which gives the disorderness or defects in the crystalline nature of the carbon materials. The intensity ratio of D
band to that of G band (ID/IG) and the average crystallite size La are used as parameters for graphitization. The

9
average particle size La can be calculated from the relation La = 4.35*IG / ID (Seliem et al., 2011). The Raman
spectra of the virgin and treated GAC are shown in Fig. 4. The two peaks around 1367 cm-1 and 1585cm-1 for virgin
and treated GAC are corresponding to the D band and G band that indicating the comparable amorphous carbon
structure and graphite like structure of all the samples. The La value of GAC, GAC-AA and GAC-PH are 4.22, 4.09
and 3.65 nm respectively. The above results indicate that, the acid treatment is beneficial for the formation of a more
ordered structure which may further lead to an increase in the number of unsaturated carbon atoms on the surface of
GAC-PH and GAC-AA and can increase the adsorption of perchlorate due to the active sample surface.

Fig 4: Raman spectrum of virgin and treated GAC.

3.3 Contact time for adsorption equilibrium

Contact time between adsorbate and adsorbent is of considerable significance in the water treatment by adsorption
(Dogan et al., 2007). The effect of contact time on adsorption was studied using virgin GAC. Fig.5 shows the effect
of contact time on adsorption of perchlorate by activated carbon with respect to adsorbent dose at the given
experimental conditions and Cs (mg L-1) is the equilibrium concentration of perchlorate on the adsorbent. It is
evident that the amount of perchlorate adsorbed on the activated carbon increased with increasing contact time and
reached an equilibrium value beyond which no more perchlorate is further adsorbed from the solution. The
equilibrium time was found to be 60 minutes for the varying adsorbent doses from 1 to 5 g. At this point, the amount
of perchlorate desorbed from the activated carbon is in a state of dynamic equilibrium with the amount of
perchlorate being adsorbed on the activated carbon. The amount of perchlorate adsorbed at the equilibrium time
reflects the maximum adsorption capacity of activated carbon under the operating conditions. The adsorption
process is initially rapid and became slower near the equilibrium. The initial increase in the perchlorate adsorption is
due to the availability of increased number of active surface sites on GAC for adsorption and the increased
concentration gradient of perchlorate in solution and in the adsorbent. During adsorption, the rate of adsorbate
uptake is controlled by the rate of adsorbate transported from the exterior to the interior sites of the adsorbent
(Malakootian et al., 2014). In the later stage the adsorption of perchlorate is slowed down due to decreased vacant
adsorption sites and the repulsion between the perchlorate ions on the solid and solution phase (Kang et al., 2013).
Similar trends were observed by other researchers on the adsorption of perchlorate. Eva Kumar et al., (2010)
investigated adsorption of perchlorate on granular ferric hydroxide as a function of contact time (1min. to 24hrs) at
two different initial perchlorate concentrations ( 5 and 10 mgL-1) and maximum removal of perchlorate was obtained
within first 30 min., with equilibrium in 60 min., while, Yang et al., (2013) obtained equilibrium in 100 min. for the
adsorption of perchlorate by inorganic- pillared bentonites.

10
 Fig. 5. Effect of contact time and adsorbent dose on perchlorate removal:
(Experimental conditions: adsorbent type - virgin GAC, initial perchlorate concentration – 100 mg L-1, temperature -
°
30 C)

3.4 Effect of initial perchlorate concentration on adsorption

The initial concentration of perchlorate in solution can strongly affect the adsorption kinetics. Effect of initial
perchlorate concentration on adsorption was investigated and it was found that as the concentration increased from
10 mgL-1 to 2000 mgL-1, an increase in the adsorption capacity was obtained. Beyond 2000 mgL-1 there was no
significant increase in the adsorption capacity. Fig. 6 illustrates the relationship between adsorption capacity (q e)
versus the initial concentration (Ci) for virgin and treated activated carbon at given experimental conditions. It can
be seen that the amount of perchlorate adsorbed on the three types of GAC (GAC, GAC-AA, and GAC- PH) at
equilibrium (qe) increases with increase in initial concentration of perchlorate. The adsorption capacity of
perchlorate was increased from 0 mg g-1 to 20.1 mg g-1, 0 mg g-1 to 37.5 mg g-1 and 0 mg g-1 to 44.0 mg g-1 for GAC,
GAC-AA, and GAC- PH respectively from 0 to 2000 mgL-1. This is because the increase in perchlorate ion
concentration increases the interaction between perchlorate ions in the aqueous phase and GAC surface. This also
results in higher uptake of perchlorate for the given mass of GAC. In another words, as the initial concentration
increased, the mass transfer driving force between solid and solution phases would become larger, hence resulting in
higher adsorption of perchlorate. The adsorbate concentrations in the solution can also strongly affect the
mechanism controlling the overall kinetic coefficient (Malakootian et al., 2014). Xu et al., (2014) conducted similar
studies for the removal of perchlorate using GAC based iron compounds at varying initial concentrations and
obtained 86% perchlorate removal at an initial concentration of 4 mgL-1. Beyond this concentration no significant
increase was observed in the removal of perchlorate.

11
 Fig. 6. Effect of initial concentration on perchlorate adsorption.
°
(Experimental conditions: Contact time -1 hr, adsorbent dose – 1 g in 100 mL, temperature - 30 C)

3.5 Effect of pH

The solution pH, superficial charge of the adsorbent, ionization degree of different contaminants and separation of
functional groups influencing the active sites of the sorbent are playing an important role in the adsorption process
(Malakootian et al., 2016). The adsorption of perchlorate from solution by adsorbent is found to be significantly
affected by the pH value, as it influences the surface charge of the adsorbent as well as the degree of ionization of
the perchlorate in solution. The effect of pH on the adsorption of perchlorate by virgin and treated GACs was
studied in the pH range of 1- 9 by keeping all the other parameters constant and the results are shown in Fig. 7. The
results revealed that the removal of perchlorate was strongly dependent on the pH of the solution. The adsorption
capacity of GAC, GAC- AA and GAC-PH increases by decreasing pH of the solution from 9 to 1 The amount of
perchlorate adsorbed on GAC, GAC- AA and GAC-PH increases from 1.8 to 3.7 mg g-1, 4.2 to 9.3 mg g-1 and 7.4 to
9.9 mg g-1 respectively by decreasing pH of solution from 9 to 1 and the maximum removal capacity was observed
at pH 1 for all the three types of samples. Decreasing solution pH increases the number of hydrogen ions and thus
increases the number of positively charged sites and thereby increases the attraction between perchlorate ions and
the adsorbent surface. However, at higher pH, the surface charge on the adsorbent became negative and adsorption
decreases due to the presence of hydroxyl ions which show competition with perchlorate anions for the available
binding sites (Malakootian et al., 2016). Similar behavior for the adsorption process of perchlorate was observed by
Quada et al. (Quada et al., 2016). Xu et al., (2011, 2013) and Baidas et al., (2011) observed acidic pH to be
favorable for the removal of perchlorate to a maximum extent compared to the basic pH.

12
 Fig. 7. Effect of pH on perchlorate adsorption
(Experimental conditions: Adsorbent dose - 1 g in 100mL, ClO4- concentration - 100 mg L-1, contact time - 1 hour,
°
temperature - 30 C)

3.6 Effect of temperature

The effect of temperature on adsorption of perchlorate by GAC, GAC-AA, and GAC-PH is showed in Fig. 8. The
effect of temperature was studied in the range of 303 to 363 K with an initial perchlorate concentration of 100 mg L-
1
, an adsorbent dose of 1g and a contact time of 1 hour. The results revealed that adsorption of perchlorate by virgin
GAC decreases from 1.2 to 0.62 mg g-1 with increase in temperature indicating an exothermic process. This shows
that the adsorption of perchlorate by GAC is by physi-sorption, caused by van der Waals attraction between the
activated carbon surface and perchlorate ions. As the temperature increases, the physical binding between
perchlorate and the active sites of the adsorbent weakens. On the other hand, adsorption of perchlorate by acid
treated GAC viz., GAC-AA and GAC- PH increases from 1.8 to 7.4 mg g-1 and 1.8 to 9.1 mg g-1 respectively with
increase in temperature indicating an endothermic process. The enhancement in the adsorption capacity of acid
treated GACs with temperature may be attributed to the chemical interaction between the active sites on the
adsorbent surface and the perchlorate ions.

Fig. 8. Effect of temperature on perchlorate adsorption.

(Experimental conditions: Adsorbent dose - 1 g in 100mL, ClO4- concentration - 100 mg L-1, contact time - 1 hour)

13
3.7 Effect of co-existing ions

In general, perchlorate contaminated water contains several other common anions like nitrate, chloride and sulphate
which can compete with perchlorate in the adsorption process. The effect of co-existing ions on adsorption was
studied using acetic acid treated GAC. In order to illustrate the effect of interfering anions, adsorption studies were
carried out by varying the initial concentrations of co-existing anions from 0 to 200 mg L-1. Adsorption of
perchlorate was studied in the presence of anions viz., SO42- , Cl- and NO3- at given experimental conditions and
results are shown in Fig. 9. A reduction in the perchlorate removal was observed with the increase of the anion
concentration. This may be due to the competition among the anions for the adsorption sites on the GAC surface,
which is decided by the concentration, charge and size of the anions. The perchlorate removal was adversely
affected by ions in the order NO3-> SO42- >Cl-.
Among these anions, nitrate showed relatively strong effect on the adsorption process. With the concentration of
nitrate being increased from 0 to 200 mg L-1, the removal efficiency of perchlorate was decreased from 9.8 to 6.6 mg
g-1 while the anions of SO42- and Cl- exhibited weak interference in the adsorption process. The removal efficiency
of perchlorate was decreased from 9.8 to 7.7 mg g-1 and 9.8 to 8.1 mg g-1 for sulphate and chloride ions respectively,
when their concentrations were increased to 200 mg L-1. Depending upon the material used for the removal of
perchlorate, the effect of co-existing anions on the removal efficiency varied. Fang et al., (2012) observed a
significant decrease in the removal efficiency for perchlorate using DWCNTs in the presence of sulfate. Chitrakar et
al., (2012) and Bagherifam et al., (2014) found HDPy-montmorillonite to be highly selective for perchlorate in the
presence of co-existing anions like Cl-, NO3-, SO42- and CO32-.

Fig. 9. Effect of co-existing ions on adsorption of perchlorate by GAC – PH

(Experimental conditions: Adsorbent dose - 1 g in 100mL, ClO4- concentration - 100 mg L-1, contact time - 1 hour,
temperature - 30◦C)

3.8 Adsorption isotherm

Analysis of the experimental adsorption data by fitting them to different isotherm models is an important step to find
the suitable model that can be used for design purpose (Hameed et al., 2007). Several models have been published in
literature to describe the experimental data of adsorption isotherms. In this work, Langmiur and Freundlich isotherm
were used to describe the relationship between the amount of perchlorate adsorbed and its equilibrium
concentration.

14
(i). Langmuir isotherm

Langmuir isotherm is based on the following assumptions: i) adsorption cannot proceed beyond monolayer coverage
ii) all surface sites are equivalent and can accommodate only one adsorbate molecule and iii) the ability of a
molecule to adsorb at a given site is independent of the occupation of neighboring sites.

Langmuir isotherm is expressed as,

Ce 1 Ce
= + …………… (3)
qe Q0 b Q0

Where Ce (mg L-1) is the concentration of perchlorate in solution at equilibrium, q e (mg g-1) is the adsorption
capacity at equilibrium, Q0 (mg g-1) gives the maximum adsorption capacity at complete coverage and b (L mg-1) is
the Langmuir constant reflecting the energy of adsorption. Linear plots of Ce/qe versus Ce for GAC, GAC-AA and
GAC-PH are shown in Fig. 10. The theoretical monolayer saturation capacity Qo and Langmuir constants for virgin
and treated GACs were evaluated from the slope and intercept of the linear plot and are summarized in Table 3. An
R2 value > 0.99 indicated that the adsorption data of perchlorate onto virgin and treated GAC were best fitted to the
Langmuir isotherm model. Hence it can be concluded that perchlorate was adsorbed mainly in the form of
monolayer coverage on the surface of the adsorbent. The Q0 value obtained from the Langmuir isotherm plots also
indicated that the maximum perchlorate adsorption capacity of GAC-PH (42.3 mg g-1) is higher than that of GAC-
AA (35.3 mg g-1) and virgin GAC (25 mg g-1).

Fig. 10. Langmuir plots for adsorption of perchlorate by virgin and treated GACs.

15
 Table 3-Langmuir constants for treated and virgin activated carbon
Type Conc (C0) Langmuir constants Correlation
(mg L-1) Q0 b (L mg-1) K=Q0.b RL coefficient
-1
(mg g ) (L g-1) ( R2)
50 0.869
100 25.00 0.003 0.078 0.769
GAC 200 0.625 0.994
500 0.400
1000 0.250
2000 0.143

50
0.599
100 35.3 0.0134 0.473
GAC-AA 200 0.427
500 0.272 0.992
1000 0.130
2000 0.069
0.036

50 0.408
100 0.256
GAC- PH 200 42.3 0.029 0.147
1.227
500 0.065 0.996
1000 0.033
2000 0.017
The essential characteristics of the Langmuir isotherm can be expressed in terms of a dimensionless constant called
equilibrium parameter RL, which is defined by:
1
RL = …………….. (4)
1+bC0

Where b is the Langmuir's adsorption constant and C0 is the initial perchlorate concentration (mg L-1). The
adsorption is irreversible if RL= 0, favorable if 0 <RL< 1, linear if RL= 1, or unfavorable if RL> 1. RL values indicated
in Table 3 confirm that the adsorption of perchlorate on the GAC, GAC-AA and GAC-PH are favorable at room
temperature. The Langmuir equilibrium constant K= Q 0.b was also calculated and given in Table 3.

(ii). Freundlich isotherm

The Freundlich isotherm model assumes that the adsorption takes place on heterogeneous surfaces which have
different adsorption energies. The most important multisite or multilayer adsorption isotherm for heterogeneous
surfaces is the Freundlich isotherm which is characterized by the heterogeneity factor 1/n, and is represented by the
equation:
1⁄
n
q e = k f Ce ……………. (5)

or the linearized form of the equation:

1
log qe = log k f + log Ce ………………. (6)
n

Where, Ce (mg L-1) is the equilibrium concentration of the adsorbate in solution, q e(mg g-1) is the adsorption
capacity at equilibrium. kf and n are Freundlich constants with n giving an indication of how favorable the

16
adsorption phenomenon and kf represents the quantity of perchlorate adsorbed onto activated carbon for a unit
equilibrium concentration.

The Freundlich plots of log qe versus log Ce for GAC, GAC-AA and GAC-PH are shown in Fig. 11. The correlation
coefficients and the values of the KF and 1/n calculated from intercept and slope of the Freundlich plots are given in
Table 4. The value of 1/n ranging between 0 and 1 is a gauge of adsorption intensity or surface heterogeneity,
becoming more heterogeneous as its value approaches to zero (Hameed et al., 2007). A value of 1/n below 1 and a
correlation coefficient less than 0.9 indicates that Freundlich isotherm is not followed for this process.

Fig.11.Freundlich plots for adsorption of perchlorate by virgin and treated GACs

Table 4 - Freundlich constants

Type Freundlich constants Correlation coefficient
1-1/n 1/n -1 ( R2)
kf ( mg L g ) 1/n

GAC 0.366 0.577 0.933

GAC-AA 4.118 0.291 0.984

GAC- PH 7.473 0.246 0.988

From the adsorption isotherm studies, it can be concluded that the adsorption of perchlorate on virgin and treated
GAC follows Langmuir model better than Freundlich model.

3.9 Adsorption kinetics

A kinetic study of adsorption process is important to describe the controlling mechanism, which is the fundamental
factor of mass transfer, and perchlorate adsorption rate. To investigate the adsorption mechanism of perchlorate by
virgin and treated GAC, the Lagergren pseudo-first-order and pseudo-second-order models have been employed (Ho
and McKay., 1999). Adsorption kinetics was conducted with a perchlorate solution having an initial concentration of
100 mg L-1. It was observed that the adsorption of perchlorate by virgin and treated GACs were very fast in the first
30 min. The adsorption rate then slowed down, and the reaction approached almost equilibrium within 60 min.
(i). The Lagergren pseudo- first order kinetic model:

17
Lagergren proposed a pseudo-first-order kinetic model which was successfully applied to describe the kinetics of
many adsorption systems. The Lagergren-first-order rate equation is represented as:
k1 t
log(qe − q) = log qe − ………….. (7)
2.303

Where qe and q are the amount of perchlorate adsorbed (mg g-1) at equilibrium and at time t (min) respectively, and
k1 (min-1) is the Lagergren rate constant of pseudo-first-order adsorption. Values of qe and k1 for virgin and treated
GACs were calculated from the slope and intercept of log (q e-q) versus time plot respectively and are given in Table
5. It was found that the calculated qe values do not agree with the experimental qe values. Also, the lower correlation
coefficients obtained suggest that the adsorption of perchlorate on virgin and treated activated carbon do not follow
the pseudo-first-order kinetics.

(ii). The pseudo-second-order kinetic model:

The adsorption kinetics may also be described by a pseudo-second-order kinetic model. The linearized integral form
of the model is represented as
t 1 t
= + …………… (8)
q k2 q2
e qe

Where k2 (g mg-1min-1) is the equilibrium rate constant of pseudo-second-order adsorption. Compared with the
pseudo-first-order model, the pseudo-second-order model fitted the experimental data better. The pseudo-second
order model was based on the following assumptions: (i) the adsorption followed the Langmuir isotherm, and (ii) the
rate-limiting process should be chemical adsorption (iii) the rate of occupation of adsorption sites is proportional to
the square of number of unoccupied sites. The pseudo-second-order plots of GAC, GAC-AA and GAC-PH are
shown in Fig. 12. From the slopes and intercepts of the linear plots obtained by plotting t/q versus t, the values of the
pseudo-second order rate constants; qe and k2 were calculated and are given in Table 5. For both virgin and treated
GACs, the results showed very good compliance with the pseudo-second-order equation. Regression (R2) values
close to unity and the adequate fitting of the plots confirmed that the adsorption of perchlorate by virgin and treated
GACs followed pseudo- second order kinetics.

Fig. 12. Pseudo second-order model plots of all the three types of GACs

18
 Table 5- Comparison of first order and second order adsorption rate constants and calculated and
experimental qevalues

Type First order kinetics Second order kinetics

qe(exp)
(mg g-1) k1(min-1) qe(cal) R2 k2 qe (cal) R2
(mg g-1) (g mg-1min-1) (mg g-1)

GAC 3.51 0.055 2.24 0.985 0.020 4.12 0.995

GAC- AA 9.00 0.070 4.17 0.818 0.044 9.23 0.997

GAC- PH 9.80 0.093 5.16 0.887 0.030 10.42 0.997

The values of activation energy, Ea (kJ/mol) and sticking probability, S* (JK mol-1) have been calculated from the
experimental data. The calculation is made using modified Arrhenius type equation related to surface coverage (Ө)
as follows (Saroj et al., 2014)
𝐶𝑒
𝜃 = (1 − ) ……………….. (9)
𝐶0

−𝐸𝑎
𝑆 ∗ = (1 − 𝜃)𝑒 𝑅𝑇 ……………………… (10)

The sticking probability, S*, is a function of the adsorbent / adsorbate system under consideration and it indicates
the potential of an adsorbate to remain on the adsorbent (AlShamaileh 2007; Fecher et al., 1990). It depends on the
temperature of the system and must satisfy the condition 0< S*<1. The values of Ea and S* were calculated from
slope and intercept of the plot of log (1- Ө) ≡ log (Ce/C0) verses 1/T respectively (given in Fig. 13) and are shown in
Table 6. The negative value of Ea for virgin GAC indicates the exothermic nature of the adsorption while the
positive values for acid treated GACs indicate the endothermic nature of the adsorption (Amin 2009). A value of S*
<<1, it indicates that the probability of perchlorate to stick on to the surface of treated GACs is very high.

19
 Fig. 13. Sticking probability plot for perchlorate adsorption by virgin and treated GACs

Table 6- Activation energy and sticking probability values

Type Activation energy (Ea), Sticking probability (S*),
kJ mol-1 JKmol-1
GAC -0.9600 1.3000
GAC-AA 8.7800 0.0250
GAC-PH 24.4300 0.0004

3.10 Thermodynamic treatment of the adsorption process

The physical or chemical nature of adsorption of perchlorate on the treated GACs was predicted by estimating the
thermodynamic parameters. The changes in thermodynamic parameters such as free energy (ΔGo), enthalpy (ΔHo)
and entropy (ΔSo) were evaluated from the following equations.
Cs
Kc = …………… (11)
Ce

∆G0 = −RTlnK c ……………. (12)

∆S0 ∆H0
log10 K c = − [van’t Hoff equation] ……………(13)
2.303R 2.303RT

Where Ce (mgL-1) is the equilibrium concentration of perchlorate in solution, Cs (mgL-1) is the equilibrium
concentration of perchlorate on the adsorbent and Kc is the equilibrium constant. R is the universal gas constant and
T is the temperature in Kelvin. ∆S0 and ∆H0 are the change in entropy and enthalpy of adsorption, respectively. The
Gibb’s free energy (∆G0) was calculated from the equation (4) and the values of ∆S0 and ∆H0 were evaluated from
the slope and intercept of van’t Hoff plots respectively.

Using van’t Hoff equation, the thermodynamic parameters for the adsorption process (Table 7) were calculated by
plotting log Kc verses 1/T and is given in Fig. 14(a) and 14(b). While studying the effect of temperature on the
adsorption of perchlorate by virgin GAC, we found that the adsorption capacity decreased with increase in
temperature from 303 to 363K. As the adsorption of perchlorate by virgin GAC is physi-sorption in nature, only acid
treated GAC data were subjected to further thermodynamic treatment.

From van’t Hoff plots (Fig 14a and 14b), the enthalpy of adsorption (∆H0) values for GAC-PH and GAC-AA were
obtained as 54.47 and 53.44 kJ mol-1 respectively. The positive values of ∆H0 confirmed the endothermic nature of
the adsorption process in the studied temperature range of 303 to 363K and the adsorption process was likely due to
the electrostatic interactions of perchlorate ions on acid treated GAC as discussed already. The endothermic nature
of adsorption process confirms the chemisorption of perchlorate onto acid treated GACs.

The adsorption process resulted in an increase in entropy of the system. Usually adsorption of gases on solid is
accompanied by a decrease in entropy as the molecules from the disordered gaseous state find an ordered
arrangement on the surface of the solid. In case of adsorption from solutions, it is expected that the perchlorate ions
on the GAC surface get arranged more chaotically compared to the situation in the aqueous solution. There is an
enhanced randomness at the solid/solution interface during the adsorption of perchlorate on treated GACs. In spite
of being endothermic in nature, the spontaneity of the adsorption process was ensured by a decrease in the Gibb’s

20
free energy of the system. The ∆G0 values showed a gradual decrease in the temperature range from 323 to 363K for
acid treated GACs

Fig.14 (a).Van’t Hoff plot for perchlorate adsorption by GAC- PH Fig. 14 (b).Van’t Hoff plot for perchlorate
adsorption by GAC-AA

Table 7-Thermodynamic parameters for perchlorate adsorption

∆G0 ∆H0 ∆S0

Type Temp (K)
(kJ mol-1) (kJ mol-1) (JK-1mol-1)
323 -1.31
GAC-AA 343 -3.09 54.5 167.9
363 -6.67
323 -0.56
GAC- PH 343 -2.34 53.4 164.7
363 -6.87

4. Conclusions
Granular activated carbon has been widely used in water treatment. Even though activated carbon could remove
perchlorate, its efficiency is low. GAC on modification using surfactants have shown high adsorption capacities for
perchlorate from various literatures, cannot be used for the treatment of drinking water. A cost effective method with
high adsorption capacity was developed for the removal of perchlorate from drinking water by acid modification of
granular activated carbon. The present study showed that the large positive charge obtained by a simple acid
treatment on GAC drastically enhanced the perchlorate adsorption. After the acid modification process, the graphite
crystallite size of GAC decreases and the decrease is more for GAC-PH than GAC-AA.The equilibrium time was
found to be 60 minutes and remains the same for varying adsorbent dose and adsorbate concentration. The
maximum removal efficiency was observed at pH 1 due to the increased H+ concentration on GAC surface.
Therefore acid pH is more favorable for the removal of perchlorate from water. Temperature has reverse effects on
virgin and treated GACs. The adsorption of perchlorate by GAC decreases with increase in temperature where as for
acid treated GACs, the adsorption increases. This is because of the fact that perchlorate adsorption in virgin GAC
takes place through physisorption while in the case of acid modified GAC perchlorate adsorption is through
chemisorption. Maximum adsorption capacities were observed as 20.1, 37.5 and 44.0 mg g-1 for GAC, GAC-AA
and GAC-PH respectively at 303K. Perchlorate contaminated water contains several other common anions like
nitrate, chloride and sulphate which can compete with perchlorate in the adsorption process. The co-existing anions
like nitrate, chloride and sulphate exhibited negative effect on the removal of perchlorate and the reduction in

21
 perchlorate adsorption was maximum for nitrate ions compared to sulphate and chloride. Langmiur and Freundlich
isotherm were used to describe the relationship between the amount of perchlorate adsorbed and its equilibrium
concentration. It was found that the equilibrium data was better described by Langmuir isotherm model. The results
revealed that monolayer adsorption isotherms were sufficient to describe the equilibrium adsorption of perchlorate
from aqueous solutions. Further, the adsorption kinetics of perchlorate on GAC, GAC-AA and GAC-PH showed
that the uptake process was rapid and the process obeyed the pseudo second order model. The positive ∆H0 values
indicated the endothermic nature of the adsorption process whereas, the positive ∆S 0 values showed the enhanced
randomness at the solid/solution interface during the adsorption. The negative values of ∆G 0 indicated the feasibility
and the spontaneous nature of adsorption of perchlorate on treated GAC surface.

5. Acknowledgement

The authors acknowledge Director and Deputy Director (Propellants, Polymers, Chemicals and Materials Entity),
Vikram Sarabhai Space Centre for the support.

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Figure Captions

Fig. 1. SEM images of virgin and treated GAC a) GAC and b) GAC-PH
Fig. 2. XRD pattern of virgin and treated GAC
Fig. 3. FTIR spectra of virgin and treated GAC.
Fig. 4. Raman spectrum of virgin and treated GAC.
Fig. 5. Effect of contact time and adsorbent dose on perchlorate removal: (Experimental conditions: adsorbent type -
°
virgin GAC, initial perchlorate concentration – 100 mg L-1, temperature - 30 C)
Fig. 6. Effect of initial concentration on perchlorate adsorption. (Experimental conditions: Contact time -1 hr, adsorbent
°
dose – 1 g in 100 mL, temperature - 30 C)
Fig. 7. ffect of pH on perchlorate adsorption (Experimental conditions: Adsorbent dose - 1 g in 100mL, ClO4-
°
concentration - 100 mg L-1, contact time - 1 hour, temperature - 30 C)
Fig. 8. Effect of temperature on perchlorate adsorption. (Experimental conditions: Adsorbent dose - 1 g in 100mL,
ClO4- concentration - 100 mg L-1, contact time - 1 hour)
Fig. 9. Effect of co-existing ions on adsorption of perchlorate by GAC – PH (Experimental conditions: Adsorbent dose
- 1 g in 100mL, ClO4- concentration - 100 mg L-1, contact time - 1 hour, temperature - 30◦C)
Fig. 10. Langmuir plots for adsorption of perchlorate by virgin and treated GACs.
Fig. 11.Freundlich plots for adsorption of perchlorate by virgin and treated GACs
Fig. 12. Pseudo second-order model plots of all the three types of GACs
Fig. 13. Sticking probability plot for perchlorate adsorption by virgin and treated GACs
Fig.14 (a).Van’t Hoff plot for perchlorate adsorption by GAC- PH
Fig. 14 (b).Van’t Hoff plot for perchlorate adsorption by GAC-AA

26
Fig. 1

Fig. 2

27
Fig.3.

Fig. 4.

28
Fig.5.

Fig.6

29
Fig.7

Fig.8

30
Fig. 9

Fig.10

31
Fig.11

Fig.12

32
 Fig.13

Fig.14 (a). Fig. 14 (b).

33
Table Captions

Table 1-Effect of acid treatment on the adsorption of perchlorate

Sample Adsorption capacity (mg g-1)
GAC 3.5
GAC+ HCl 9.7
GAC+ H2SO4 9.1
GAC+ HNO3 7.7
GAC+ H3PO4 9.8
GAC+ Oxalic acid 5.1
GAC+ Citric acid 1.4
GAC+ Formic acid 9.1
GAC+ Acetic acid 9.2
GAC+ Tartaric acid 6.0

Table 2-Physical properties of granular activated carbon (GAC)

Parameters Test Method Test Result Parameters Test Method
Moisture (%) ASTM-D-2867 3.0 0.23 0.29
-3
Apparent Density (g cm ) ASTM-D-2854 0.52 0.49 0.48
-1
Iodine No. (mg g ) ASTM-D-4607 1156 1532 1497
2 -1
Surface Area (m g ) ASTM-(BET-N2) 1159 1541 1508
pH ASTM-D-3838 10.2 6.9 7.0
Ash (%) ASTM-D-2866 2.8 0.80 0.90
Ball Pan Hardness (%) ASTM-D-3802 98.3 98.5 98.3

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 Table 3-Langmuir constants for treated and virgin activated carbon
Type Conc (C0) Langmuir constants Correlation
(mg L-1) Q0 b (L mg-1) K=Q0.b RL coefficient
-1
(mg g ) (L g-1) ( R2)
50 0.869
100 25.00 0.003 0.078 0.769
GAC 200 0.625 0.994
500 0.400
1000 0.250
2000 0.143

50
0.599
100 35.3 0.0134 0.473
GAC-AA 200 0.427
500 0.272 0.992
1000 0.130
2000 0.069
0.036

50 0.408
100 0.256
GAC- PH 200 42.3 0.029 1.227 0.147
500 0.065 0.996
1000 0.033
2000 0.017

Table 4 - Freundlich constants

Type Freundlich constants Correlation coefficient
1-1/n 1/n -1 ( R2)
kf ( mg L g ) 1/n

GAC 0.366 0.577 0.933

GAC-AA 4.118 0.291 0.984

GAC- PH 7.473 0.246 0.988

Table 5- Comparison of first order and second order adsorption rate constants and calculated and
experimental qevalues

35
 Type First order kinetics Second order kinetics
qe(exp)
(mg g-1) k1(min-1) qe(cal) R2 k2 qe (cal) R2
(mg g-1) (g mg-1min-1) (mg g-1)

GAC 3.51 0.055 2.24 0.985 0.020 4.12 0.995

GAC- AA 9.00 0.070 4.17 0.818 0.044 9.23 0.997

GAC- PH 9.80 0.093 5.16 0.887 0.030 10.42 0.997

Table 6- Activation energy and sticking probability values

Type Activation energy (Ea), Sticking probability (S*),
kJ mol-1 JKmol-1
GAC -0.9600 1.3000
GAC-AA 8.7800 0.0250
GAC-PH 24.4300 0.0004

Table 7-Thermodynamic parameters for perchlorate adsorption

∆G0 ∆H0 ∆S0

Type Temp (K)
(kJ mol-1) (kJ mol-1) (JK-1mol-1)
323 -1.31
GAC-AA 343 -3.09 54.5 167.9
363 -6.67
323 -0.56
GAC- PH 343 -2.34 53.4 164.7
363 -6.87

36