EFFECT OF CU-PUROLITE A400 RESIN ON ADSORPTION OF NITRATE

AND NITRITE IN WASTEWATER TREATMENT

(Kesan Resin Purolite A400-Cu Terhadap Penjerapan Nitrat dan Nitrit dalam Rawatan Air
Sisa)
Fatimah Batubara1, Chairani Selviani1, Muhammad Turmuzi1, Edy Herianto Majlan*, 2,3
1Chemical Engineering Department, Faculty of Engineering, Universitas Sumatera Utara, Medan, 20155, Sumatera Utara,
Indonesia
2Fuel Cell Institute, Universiti Kebangsaan Malaysia, Bangi 43600, Selangor D.E, Malaysia
3Energy Engineering Department, Faculty of Industrial Engineering, Institut Teknologi Yogyakarta, D.I Yogyakarta, 55171,
Indonesia

*Corresponding author: edyhm71@gmail.com

Abstract
The concentration of nitrate and nitrite exceeding the water standard quality causes the potential endanger of human health,
blue-baby syndrome and the growth of aquatic plants (eutrophication). Purolite A400 anion exchange resin impregnated by
Cu (Purolite-Cu) is used to remove nitrate and nitrite in wastewater. The highest saturation capacity was obtained in Purolite
and Purolite-Cu respectively 0.789818 mg/g and 0.68837 mg/g-nitrate and 0.064383 mg/g and 0.054851 mg/g-nitrite.
Measurement using energy dispersion spectrometry (EDS) proves that the increase in adsorption is due to the impregnation of
Cu with the addition of a positive surface charge on the resin by Cu metal. The adsorption capacity of nitrate and nitrite
decreases as the concentration of sulphate, phosphate and chloride increases. Data obtained from fixed-bed column using
Thomas equation model. The breakthrough curve shows the value of Ct/C0 ratio in Purolite and Purolite-Cu. The largest Ct/C0
values were obtained at Purolite and Purolite-Cu respectively 0.5491 & 0.5203-nitrate and 0.4748 & 0.0319-nitrite.

Keyword: Nitrite Adsorption, Nitrate Adsorption, Resin Purolite A400, Wastewater Treatments, Cu Impregnation

Abstrak
Kepekatan nitrat dan nitrit yang melebihi kualiti standard air akan berpotensi membahayakan kesihatan manusia, sindrom biru-
bayi dan pertumbuhan tumbuhan akuatik (eutrophication). Purolite A400 resin pertukaran anion yang impregnasi Cu (Purolite-
Cu) digunakan untuk mengurangkan kandungan nitrat dan nitrit dalam air sisa. Kapasiti ketepuan tertinggi diperolehi pada
Purolite dan Purolite-Cu masing-masing 0.789818 mg / g; 0.68837 mg / g-nitrat dan 0.064383 mg / g; 0.054851 mg / g-nitrit.
Pengukuran dengan menggunakan spektrometri penyebaran tenaga (EDS) membuktikan bahawa peningkatan penjerapan
adalah disebabkan oleh impregnasi Cu dengan penambahan caj permukaan positif pada resin oleh logam Cu. Kapasiti
penjerapan nitrat dan nitrit menurun apabila kepekatan sulfat, fosfat dan klorida bertambah. Data diperolehi daripada kolom
lapisan penjerap tetap menggunakan model persamaan Thomas. Lengkung bulus menunjukkan nilai nisbah Ct / C0 dalam
Purolite dan Purolite-Cu. Nilai Ct / C0 terbesar diperoleh pada Purolite dan Purolite-Cu masing-masing 0.5491 & 0.5203-
nitrat dan 0.4748 & 0.0319-nitrit.

Kata kunci: Penjerapan Nitrit, Penjerapan Nitrat, Resin Purolit A400, Rawatan Air Sisa, Impregnasi Cu

Introduction

Nitrogen is an essential element for all living things that can be oxidized to nitrate and nitrite. The content of
nitrates and nitrites in water bodies greatly affects water quality. Nitrates are stable and water-soluble ions and
have a low tendency of adsorption or co-precipitation [1]. Nitrate concentrations that exceed the quality standard
in water are caused by the use of nitrate-containing fertilizers, human and animal wastes that are not pre-treated
[2]. The consequences of nitrate contamination include: potential human health hazards, methemoglobinemia in
infants called blue-baby syndrome and crop growth (eutrophication) [3]. Therefore, the nitrate and nitrite removal
process is done first so that the pollutant load produced can meet the minimum concentration standard that has
been determined.

Methods of processing nitrate and nitrites include: physics methods such as; reverse osmosis [4], ion exchange
[5], a reduction catalyst [6], electro-dialysis [7], and the process of activated carbon [8], chemical methods such
as; chemical denitrification [9], biological methods such as; nitrification-denitrification is thermophilic [10], ion
exchange membrane bioreactor [11] and microbial denitrification [12]. Selection of adsorption method is one of
the most suitable for the operation of a simple, cost effective, easy to implement, a great efficiency in the uptake
of ions and no secondary pollutants [13]. While the adsorption through the ion exchange mechanism is an efficient
method for the removal of some oxy-anions because the adsorbents can be regenerated and reused [14]. The
adsorbent which has been applied by the research institute, and earlier as natural resins, zeolites modified by the
addition of H2SO4 [15], the amine group quarter-modified chitosan beads [14], and the alloy Zr (IV) with sugar
beet pulp [16]. Synthetic resin used in the allowance for nitrate and nitrite is an anion exchange resin strong base
that has the adsorption capacity of large, such as ion-exchange resin Dowex 21K XLT modified ferrous metals
[17], Purolite A100 [18], Purolite A520E [19]-[20], A-250 IXR [21], Purolite A300 [20], Indion NSSR [22].

The complementary ions such as chloride, sulfate and phosphate present in the influent solution can reduce the
efficiency of nitrate and nitrite removal. The effect of complementary ions on nitrate and nitrite removal depends
on the amount of charge. One charged chloride ion does not significantly affect the removal efficiency, otherwise
sulphate ions with more than one charge greatly affect the significantly reduced removal efficiency. Based on
previous research studies that have analyzed the effects of complementary ions [20], increasing the concentration
of sulphate complementary ions on Purolite A300 resins can cause a decrease in the efficiency of nitrate removal
in the modified and unmodified resin types. According to [17], low concentration of complementary ion phosphate
reduces nitrate adsorption capacity, and for complementary ion chloride does not significantly decrease the nitrate
adsorption capacity as having the same amount of charge as nitrate ions. Reference [23] suggests that the sequence
of anion exchange resin is decreased in sequences of SO > NO > Cl- > HCO .

Increasing the adsorption capacity of the anion exchange resin is done by metal impregnation method to enlarge
the positive charge of the resin surface [24], the impregnated resin causes an increase of attraction between the
positively charged metal ion and the negative nitrate ion and nitrite resulting in increased adsorption power.
Reference [17] shows that iron impregnation of Fe in Dowex 21K XLT resin and maximum nitrate adsorption
capacity at Dowex and Dowex-Fe respectively 27.6 mg N/g and 75.3 mg N/g. However, metal impregnation is
not only done on resins but can be carried out on natural adsorbents, such as Zr (IV) in sugar beet pulp (Hassan et
al, 2010), Fe (III) in limestone [25] and Mn (II) in zeolites [26].

In this study, nitrate and nitrite removal was performed using a purolite A400 resin adsorbent modified with Cu
metal. This study was conducted to determine the nitrate and nitrite adsorption capacity using Purolite A400 and
Purolite A400-Cu in fixed-bed columns. This study was conducted to determine the value of Ct/C0 ratio on the
effect of initial concentration of nitrate + nitrite mixture and the concentration of complementary ions in the
Thomas equation model.

Materials and Methods

Purolite A400 Resin Impregnation
The Purolite A400 resin is obtained from Purolite Pte Ltd, Singapore which is a strong base anion exchange resin,
in faded yellow spherical beads with a particle size of 300-1200 μm and a density of ± 1.08. The resin comprises
a cross-linked polystyrene polymer structure with divinylbenzene and has a quaternary ammonium functional
group of 1. In this resin the chloride ion as a counterion serves to exchange with another anion [27].

The Purolite A400 resin is impregnated with copper metal (Cu). 10 g of Purolite resin was introduced into 1 L of
CuCl2.2H2O solution, stirred for 1 hour at a stirring rate of 120 rpm. The pH was increased to 8.0 by adding a 1
M NaOH solution and stirred for 1 hour at a stirring rate of 30 rpm. The resin is filtered and washed with distilled
water and dried in the oven for 24 hours at ± 45 °C [17].

Influent Solution
Synthetic wastewater is obtained from the crystalline powder of EMSURE NaNO 3 and EMSURE NaNO2
dissolved with distilled water at each concentration of 50 mg/l and 5 mg/l. For the study of the effect of
complementary ions obtained from the crystal powder of EMSURE Na2SO4, EMSURE Na3PO4 and EMSURE
NaCl with determined concentrations of 45 mg/l and 75 mg/l and for the study of the effect of initial concentration
of NaNO3 and NaNO2 mixtures the concentration was 60 mg/l, 90 mg/l, and 150 mg/l.

Nitrate and Nitrite Analysis

The final concentration (Ct) of nitrate was analyzed by the UV Analyzer Secomam RS232 Pastel tool [28] and the
nitrite content was analyzed by Cary 50 Conc UV-Visible Spectrofotometry-Variant at a maximum wavelength of
543 nm [29]-[30].

Fixed-Bed Column Study

Fixed-bed column uses chromatograph column made of Pyrex tube with a diameter of ± 2.0 cm, height ± 20 cm,
height anion resin in a column of 15 cm and an influent rate to the column at 10 ml/min. The influent wastewater
is pumped using a 12V DC peristaltic pump through a column with down-flow flow, I.V. Needle 21 G x 11/2 and
AC-DC Adapter NAD-012 Namichi. The effluent wastewater samples were collected every 10 minutes and the
nitrate and nitrite content were analyzed using UV Analyzer Secomam and UV-Visible Spectrophotometer.

The adsorption capacity of nitrate and nitrite (mg N) removed from the influent solution passing through the
column is expressed in q, whereas qtotal in the fixed-bed column is the area under the absorbed nitrate concentration
curve Cad (Cad = Co-Ct) (mg/l ) against the effluent time (t, min) and calculated by the following refer to (1) [31];
[19].

t  total t  total
Q Q
q total 
1.000 C
t 0
ad dt
1.000  (C
t 0
0 - C t )dt
= (1)

The maximum adsorption capacity (mg/g) is calculated from the following refer to (2).
q total
q eq 
w (2)
With w is the mass of adsorbent (g) used in the fixed-bed column.

Adsorption Model
The equation (3) model used in the fixed-bed column is the Thomas model as the following [32]:

 C o    kTh q0 m   kTh q0 Veff 

   1    
  C t    Q   Q 
ln (3)

which Veff = Volume of effluent, Veff = Q.t, so equation 3. can be written as follows [19]:

 C o    k Th q 0 m 
   1     k Th C 0 t
ln   C t    Q  (4)

Which kTh = Thomas rate constant (mL / min mg), qo = maximum solute concentration (nitrate) in solid phase
(mg/g), m = mass of adsorbent in column (g), Q = volumetric flow rate (mL/min), C o = inlet nitrate concentration
(mg N/L), Ct = concentration of nitrate outlet at time t (mg N/L) and t = filtration time (min). The kT and qo values
are determined from the slope and intercept in the linear line plot which is ln(C 0/C-1) against time, t.

Result and Discussion

Characteristics of Anion Exchange Resin
The morphology and elemental composition of the Purolite A400 and Purolite A400-Cu resins were analyzed
using SEM (Scanning Electron Microscope)-Jeol 6510-LA and EDS (Energy Dispersion Spectrophotometry)-Jeol
6510-LA each shown in Figure 1 and Figure 2. Surface Purolite A400 resin is fine, while the Purolite A400-Cu
resin is rough because there is deposition of other materials on the surface which are thought to originate from Cu
deposition. Furthermore, the dispersion pattern of elemental composition can be seen that in the Purolite-Cu resin,
the presence of Cu peak that is not present in Purolite content. It is proven that Purolite resin can impregnate Cu
elements as presented in Table 1. The Cu elements contained in Purolite A400 resin are 19.34 %. The content of
several metal elements found in the resin varies. The Fe element contained in Dowex 21K XLT is 1.7 ± 0.5 %
[17].
 (a) (b)
Figure 1. SEM Test Results (a) Purolite A400 Resin and (b) PuroliteA400-Cu Resin (100x magnification).

(a) (b)

Figure 2. Results of EDS Analysis (a) Purolite A400 Resin and (b) PuroliteA400-Cu Resin

The Cl content determined by EDS analysis was 7.98% and 9.67 % for Purolite and Purolite-Cu, respectively.
Kalaruban et al [17] proved that the slight increase of the Cl content on Purolite-Cu is might cause by some Cl
residues from CuCl2.2H2O that does not react, removed by washing using distilled water to make a Purolite-Cu
modification. The chloride ion (Cl-) in the resin is an interchangeable main anion [27]. Metal impregnation on the
resin may increase the surface positive charge at all pH values [17] resulting in negatively charged nitrate
adsorption with the outer surface of the resin by electrostatic forces [33]. Furthermore, Namasivayam and
Sangeetha [34] suggest that Zn impregnation results in a positive zeta potential increase in coir pith as the Zn
positive charge increases.

Table 1. Composition of Purolite and Purolite-Cu Elements

C O Cl Cu Al Si
Adsorbent
(wt %) (wt %) (wt %) (wt %) (wt %) (wt %)
Purolite 86.64 5.38 7.98 - - -
Purolite-Cu 64.30 5.79 9.67 19.34 0.40 0.50

Study of Adsorption Capacity in Fixed-Bed Columns

The adsorption capacity of Purolite A400 resin and Purolite A400-Cu resin to exclude nitrate and nitrite is shown
in Table 2. and Table 3. The adsorption capacity of Purolite and Purolite-Cu on nitrates was 15.769 mg/g and
 13.833 mg/g respectively. The equilibrium capacities are 0.789 mg/g and 0.691 mg/g, respectively. Similarly,
Purolite and Purolite-Cu adsorption capacity against nitrite was 1.287 mg/g and 1.158 mg/g, respectively.
Equilibrium capacities are 0.0643 mg/g and 0.0579 mg/g respectively. The difference in nitrate and nitrate
adsorption capacity using Purolite and Purolite-Cu was 1.962 mg/g and 0.128 mg/g, respectively.

Table 2. Adsorption Capacity of Nitrate Removal Using Purolite and Purolite-Cu

Ct qtotal qeq Ct qtotal qeq

No. Test
(mgL ) -1 (mg N) (mg/g) (mgL ) -1 (mg N) (mg/g)
Nitrate + Nitrite (60 mg/l) 3.3 1.8
1.
Chloride (60 mg/l) 4.2 1.9
Sulphate (60 mg/l) 5.9 15.769354 0.789818 3.2 13.767398 0.68837
Phosphate (60 mg/l) 10.8 3.3

2. Nitrate + Nitrite (75 mg/l) 3.2 5.7

Chloride (45 mg/l) 3.5 5.9
Sulphate (45 mg/l) 3.7 15.480165 0.774008 6.1 13.212035 0.660602
Phosphate (45 mg/l) 9.3 6.3

3. Nitrate + Nitrite (75 mg/l) 1.8 2.7

Chloride (75 mg/l) 3.4 3.8
Sulphate (75 mg/l) 4.4 14.847253 0.742363 4.0 13.283887 0.664194
Phosphate (75 mg/l) 10.2 16.0

4. Nitrate + Nitrite (90 mg/l) 4.1 1.9

Chloride (60 mg/l) 6.6 2.0
Sulphate (60 mg/l) 10.6 14.195652 0.709783 2.2 13.833468 0.691673
Phosphate (60 mg/l) 11.8 3.5

5. Nitrate + Nitrite (150

mg/l) 1.9 3.0
14.149485 0.707474 12.437557 0.621870
Chloride (60 mg/l) 3.3 1.8
Sulphate (60 mg/l) 4.2 1.9
Phosphate (60 mg/l) 5.9 3.2

The nitrate adsorption capacity using Purolite A400 15.796 mg N/g at the volume of adsorption column (bed
volume) BV 9.235 is greater than using Purolite A400-Cu 13.833 mg N/g at the volume of adsorption column
(bed volume) 10.191 BV. Similarly, the nitrite adsorption capacity using Purolite A400 resin on bed column
volume of 20.700 BV 1.2876 mg N/g is greater than using Purolite A400-Cu 1.158 mg N/g resin at bed volume
18.312 BV. The value of bed volume between Purolite and Purolite-Cu does not have significant difference so it
is considered bed volume value is same on Purolite.

According to [17], Nitrate adsorption capacity using Dowex resin on 1200 BV adsorption column volume is 18.6
and 15.1 mg N/g and Dowex-Fe resin on volume of adsorption column (bed volume) 2500 BV is 31.4 and 24.7
mg N/g. According to [35], nitrate removal using agricultural waste (corn cob) resulted in adsorption capacity at
bed volume of 66 BV 0.6 mg N/g and corn cob inserted amine group on a volume of bed column 400 BV 15.3 mg
N/g. Nitrate adsorption capacity using coconut copra adsorbent on bed volume of 100 BV 0.9 mg N/g and coconut
shell inserted amine group on volume of adsorption column (bed volume) 400 BV 18.6 mg N/g. The adsorption
capacity of the Dowex-Fe resin is larger than that of Dowex resin, as well as using the coconut corn cob and
coconut coupling inserted by the amine group. The increased volume of the adsorption column (bed volume) then
the adsorption capacity also almost increased twice.
 Table 3. Adsorption Capacity of Nitrite Removal Using Purolite and Purolite-Cu
Ct qtotal qeq Ct qtotal qeq
No. Test
(mgL-1) (mg N) (mg/g) (mgL-1) (mg N) (mg/g)

1. Nitrate + Nitrite (60 mg/l) 0.0404 0.0062

Chloride (60 mg/l) 0.0432 0.0062
Sulphate (60 mg/l) 0.0487 1.2876594 0.064383 0.4585 1.0970206 0.054851
Phosphate (60 mg/l) 0.0568 0.8648

2. Nitrate + Nitrite (75 mg/l) 0.0416 0.0411

Chloride (45 mg/l) 0.0557 0.0472
Sulphate (45 mg/l) 0.0664 1.2759674 0.063798 0.0490 1.158801 0.05794
Phosphate (45 mg/l) 0.1258 0.0546

3. Nitrate + Nitrite (75 mg/l) 0.0304 0.0064

Chloride (75 mg/l) 0.0306 0.0231
Sulphate (75 mg/l) 0.0360 1.2704009 0.06352 0.0642 1.1422731 0.057114
Phosphate (75 mg/l) 0.0542 0.0969

4. Nitrate + Nitrite (90 mg/l) 0.1503 0.0913

Chloride (60 mg/l) 0.7836 0.3959
Sulphate (60 mg/l) 2.2876 0.9428985 0.047145 0.7232 0.988727 0.049436
Phosphate (60 mg/l) 3.2257 3.2141

5. Nitrate + Nitrite (150 mg/l) 0.0363 0.0519

Chloride (60 mg/l) 2.2354 0.8301055 0.041505 0.6154 0.8987841 0.044939
Sulphate (60 mg/l) 2.8687 1.5816
Phosphate (60 mg/l) 3.2475 3.3957

Breakthrough Curve on Nitrate Removal

The nitrate adsorption breakthrough curve using Purolite and Purolite-Cu resins with influent nitrate
concentrations of 50 mg/l is shown in Figure 3 and Figure 4. It shows that the effect of complementary ion
concentration will influence the value of adsorption capacity (q o) and Thomas (kTh) constant. The Thomas model
uses a linear regression equation where ln (Co/Ct-1) is the ordinate (x-axis) and time (t) as abscissa (x-axis). The
plot of the ln (Co/Ct-1) value of t represents a straight line with the linear equation given by y = a + bx, where a is
the intercept, indicating the value of the adsorption capacity (q o) and b is the slope, indicating the value of
Thomas's constant (kTh ).

The model parameters for the study of fixed-bed columns using equation 4 as in Table 4, where the flow rate Q =
10 ml/min, influent nitrate concentration Co = 50 mg/l, resin height t = 15 cm. From Table 4 it can be seen that in
nitrate removal using Purolite and Purolite-Cu the value of kTh is greater along with the increase of complementary
ion concentration (chloride, sulphate and phosphate) and smaller when the initial concentration of nitrate + nitrite
mixture is increasing. This shows a decrease in mass transfer rate because there is a difference in the concentration
of complementary ions in the resin to the concentrations of influent nitrate [36].

Table 4. Parameter of Thomas Equation on Nitrate Removal

kT q0 kT q0
Test
Purolite Purolite-Cu
Nitrate + Nitrite (60 mg/l) 0.044 3.199 0.024 3.578
Chloride + Sulphate + Phosphate (45 mg/l) 0.036 3.238 0.004 2.087
Chloride + Sulphate + Phosphate (75 mg/l) 0.060 3.915 0.063 3.735
Nitrate + Nitrite (90 mg/l) 0.042 2.769 0.020 3.527
Nitrate + Nitrite (150 mg/l) 0.098 4.132 0.062 3.389
Each figure shows that nitrate removal using Purolite with an initial concentration of nitrate + nitrite mixture of
60 mg/l has a smaller Ct/Co ratio of 0.5357 compared with concentrations of 90 mg/l and 150 mg/l of 0.5491 mg/l
and 0.5433 mg/l. While at Purolite-Cu Ct/Co ratio slightly smaller was obtained at the initial concentration of
nitrate + nitrite mixture of 90 mg/l 0.5203 compared with a concentration of 60 mg/l 0.5239. But at the initial
concentration of nitrate + nitrite mixture of 150 mg/l the value of Ct/Co ratio obtained was greater 0.5641. For the
effect of the concentration of chloride, sulphate and phosphate supplementation using Purolite the Ct/Co ratio
is smaller at 45 mg/l 0.5291 than the concentration of 75 mg/l 0.5355. Meanwhile, when using Purolite-Cu
chloride, sulphate and phosphate concentration 45 mg/l also has a significantly lower Ct/Co ratio of 0.5064
than concentration 75 mg/l 0.5555. The value of Ct/Co ratio affects the final concentration (Ct) and the filtration
time when the resin surface absorbs nitrate ions in the column

Figures 3 and 4 show that the Ct/Co ratio of Purolite-Cu is smaller than that of Purolite without impregnation. This
is because the time to reach saturation is longer because the active side of Purolite-Cu is larger so that more adsorb
the nitrate ion. According to [17], when there are complementary ions in the influent solution, the time to reach
saturation is faster using Purolite than Purolite-Cu because the number of active sides on the Purolite resin surface
is less than Purolite-Cu. The resin becomes saturated faster when the concentration of chloride ions is added to a
solution containing nitrate ions and the saturation level is estimated to have been achieved when the ratio value
of effluent concentration to influent concentration (Ct/Co) of the column is greater [20].
The characteristic of the breakthrough curve increased more sharply in Purolite and Purolite-Cu. The faster the
saturation is achieved, the higher the Ct/Co ratio. This occurs because the residence time in the column does not
take much time to reach the adsorption equilibrium and the effluent nitrate solution leaves the column before the
equilibrium is reached because the contact time between nitrate ions with Purolite is short so that the allowance
efficiency decreases in saturation time [36].

Breakthrough Curve on the Nitrite Allowance

Nitrite adsorption breakthrough curves using Purolite and Purolite-Cu resins with influent nitrite concentrations
of 5 mg/l are shown in Figure 5 and Figure 6. The model parameters for the fixed-bed column study use Equation
4 as in Table 5, where flow rate Q = 10 ml/min, influent nitrite concentration Co = 5 mg/l, resin height t = 15 cm.
From Table 3 it can be seen that at nitrite removal using Purolite-Cu the value of kTh is greater along with the
increase of complementary ion concentration (chloride, sulphate and phosphate) and smaller when the initial
concentration of nitrate + nitrite mixture is increasing. This shows a decrease in mass transfer rate because there
is a difference in the concentration of complementary ions in the resin to the concentrations of influent nitrate
[36].

Table 5. Parameter of Thomas Equation on Nitrite Removal

kT q0 kT q0
Test
Purolite Purolite-Cu
Nitrate + Nitrite (60 mg/l) 0.012 4.948 0.197 9.254
Chloride + Sulphate + Phosphate (45 mg/l) 0.035 5.195 0.009 4.866
Chloride + Sulphate + Phosphate (75 mg/l) 0.019 5.384 0.092 7.384
Nitrate + Nitrite (90 mg/l) 0.137 4.614 0.143 5.505
Nitrate + Nitrite (150 mg/l) 0.171 5.332 0.171 5.914
 0.6

0.5

0.4
Nitrate + Nitrite (60 mg/l)
Nitrate + Nitrite (90 mg/l)
Nitrate + Nitrite (150 mg/l)
Ct/Co 0.3 Nitrate + Nitrite (60 mg/l)-Cu
Nitrate + Nitrite (90 mg/l)-Cu
Nitrate + Nitrite (150 mg/l)-Cu
0.2

0.1

0
0 10 20 30 40
Time (minute)

Figure 3. Breakthrough Curve on Nitrate Removal by Effect of Initial Concentration of Nitrate and Nitrite
Blends Using Purolite and Purolite-Cu.

0.6

0.5

0.4

Ct/Co 0.3

0.2

Chloride + Sulphate + Phosphate (45 mg/l)

Chloride + Sulphate + Phosphate (75 mg/l)
0.1 Chloride + Sulphate + Phosphate (45 mg/l)-Cu
Chloride + Sulphate + Phosphate (75 mg/l)-Cu

0
0 10 20 30 40
Time (Minute)

Figure 4. Breakthrough Curve on Nitrate Removal by Effect of Compound Ion Concentration of Chloride,
Sulphate and Phosphate Using Purolite and Purolite-Cu.
 0.6

0.5
Nitrate + Nitrite (60 mg/l)
Nitrate + Nitrite (90 mg/l)
0.4
Nitrate + Nitrite (150 mg/l)
Nitrate + Nitrite (60 mg/l)-Cu
Nitrate + Nitrite (90 mg/l)-Cu
Ct/Co 0.3
Nitrate + Nitrite (150 mg/l)-Cu

0.2

0.1

0
0 10 20 30 40
Time (minute)

Figure 5. Breakthrough Curve on Nitrite Removal by Effect of Initial Concentration of Nitric and Nitrite Blends
Using Purolite and Purolite-Cu.
0.6

0.5

0.4

Ct/Co 0.3

0.2

Chloride + Sulphate + Phosphate (45 mg/l)

0.1 Chloride + Sulphate + Phosphate (75 mg/l)
Chloride + Sulphate + Phosphate (45 mg/l)-Cu
Chloride + Sulphate + Phosphate (75 mg/l)-Cu
0
0 10 20 30 40
Time (minute)

Figure 6. Breakthrough Curve on Nitrite Removal by Effect of Compound Ion Concentration of Chloride,
Sulphate and Phosphate Using Purolite and Purolite-Cu.

Each figure shows that nitrite removal using Purolite with an initial concentration of nitrate + nitrite mixture of
60 mg/l has a greater Ct/Co ratio of 0.4748 compared with concentrations of 90 mg/l and 150 mg/l of 0.2487 and
0.1649. While at Purolite-Cu the Ct/Co ratio value at the initial concentration of nitrate + nitrite mixture 60 mg/l
was significantly smaller to 0.0319. At the initial concentration of nitrate + nitrite mixture of 90 mg/l the value of
Ct/Co ratio decreased to 0.1959. But at the initial concentration of nitrate + nitrite mixture 150 mg/l the value of
Ct/Co ratio only slightly decreased 0.1410. For the effect of the concentration of chloride, sulphate and phosphate
ions using Purolite a smaller Ct/Co ratio value was obtained at a concentration of 45 mg/l 0.4185 compared with
a concentration of 75 mg/l 0.4542. However, when using Purolite-Cu the concentration of chloride, sulphate and
phosphate 45 mg/l has a larger Ct/Co ratio of 0.4808. But at the concentration of chloride, sulphate and phosphate
75 mg/l the value of Ct/Co ratio still shows a small number of 0.2229. The Ct/Co ratio value influences the final
concentration (Ct) and the filtration time when the resin surface absorbs nitrite ions in the column.
Figures 5 and 6 show that the Ct/Co ratio using Purolite-Cu is significantly smaller and the time to reaches
saturation is longer since the active side of Purolite-Cu resin has more pores so that the adsorbed nitrite ion is
greater than Purolite. However, for the influence of the concentration of chloride, sulphate and phosphate 45 mg/l,
the Ct/Co ratio using Purolite is smaller than Purolite-Cu. This is inconsistent with existing theory because of the
role of kT and qo values in the Ct/Co ratio. If the value of kT and qo using Purolite-Cu is relatively smaller then
Ct/Co ratio value will be greater than Purolite.

Breakthrough curve rose sharply due to the influence of the initial concentration of the mixture of nitrate + nitrite
60 mg/l and the effect of complementary ion concentration chloride, sulphate and phosphate 75 mg/l. According
to [23], a breakthrough curve increased enormously because it deals with complementary ion in the influent nitrite
solution and the rate of mass transfer. Breakthrough point was achieved in a higher influent concentration and
increasing concentration of influent adsorbate made the breakpoint time is diminished as the resin active site
binding adsorbate saturated faster [32].

According to [36], the value of the external mass transfer coefficient has a significant influence on the
breakthrough curve. If the value of the external mass transfer coefficient is greater, the C t/Co ratio value is not
close to 1 (close to some constant value, value <1 and asymptotically constant after a certain time). While the
value of the external mass transfer coefficient is smaller, the value of Ct/Co ratio asymptotically becomes more
constant close to 1.

Conclusion
The adsorption capacity is increased by modifying the adsorbent with metal impregnation process that aimed at
enlarging the surface positive charge. The copper element content (Cu) was obtained from Purolite A400 resin of
19.34 % and the adsorption capacity at nitrate and nitrate removal using Purolite A400 and Purolite A400-Cu resin
were 15.769 mg/g-nitrate & 13.833 mg/g-nitrate and 1.287 mg/g-nitrite & 1.158 mg/g-nitrite respectively.

The ratio of Ct/C0 to nitrate and nitrate removal using Purolite A400-Cu resin is smaller and the saturation time is
achieved longer because the active side of Purolite-Cu is larger, thus more adsorbing nitrate and nitrite ions. The
value of Ct/C0 in nitrate and nitrite removal obtained is 0.5064 with concentration of chloride, sulphate and
phosphate 45 mg/l while with the initial concentration of nitrate + nitrite 60 mg/l mixture ratio of Ct/C0 is 0.0319.

Acknowledgement
This work was supported by University of Sumatera Utara under the talented program. We thank to Integrated
Laboratory in Semarang, Indonesia for the resin test analysis result of the research.

References
1. Rajeswari, M., Rajakumar, S. & Ayyasamy, P. M. (2015). Evaluation of Nitrate Removal in Aquatic
System: A General View. International Journal of Emerging Research in Management & Technology,
9359 (12): 186 – 194.
2. Hanafi, H. A. & Azeema, S. M. A. (2016). Removal of Nitrate and Nitrite Anions from Wastewater
Using Activated Carbon Derived from Rice Straw. Journal of Environmental & Analytical Toxicology,
6 (1): 1 – 6.
3. Chatterjee, S., Lee, D. S., Lee, M. W. & Woo, S. H. (2008). Nitrate Removal from Aqueous Solutions
by Cross-Linked Chitosan Beads Conditioned with Sodium Bisulfate. Journal of Hazardous Material,
166, 508 – 513.
4. Madaeni, S. S. & Koocheki, S. (2010). Influence of Di-hydrogen Phospate Ion on Performance of
Polyamide Reverse Osmosis Membrane for Nitrate and Nitrite Removal. Journal Porous Material, 17,
163 – 168.
5. Hekmatzadeh, A. A., Karimi-Jashani, A., Talebbeydokhti, N. & Klove, B. (2012). Modeling of Nitrate
Removal for Ion Exchange Resin in Batch and Fixed-Bed Experiments. Desalination, 284, 22 – 31.
6. Guy, K. A., Xu, H., Yang, J. C., Werth, C. J. & Shapley, J. R. (2009). Catalytic Nitrate and Nitrite
Reduction with Pd - Cu/PVP Colloids in Water: Composition, Structure, and Reactivity Correlations.
Journal Phys Chem, 113, 8177 – 8185.
7. Bel, E. S., Hmida, H., Ouejhani, A., Lalleve, G., Fauvarque, J. F. & Dachraoui, M. (2013). A Novel
Anionic Electrodialysis Membrane Can Be Used to Remove Nitrate and Nitrite from Wastewater.
Desalination and Water Treatment 23:1 – 3, 13 –19.
8. Khan, M. A., Ahn, Y. T., Kumar, M., Lee, W., Min, B., Kim, G., Cho, D. W., Park, W. B. & Jeon, B. H.
(2011). Adsorption Studies for the Removal of Nitrate Using Modified Lignite Granular Activated
 Carbon. Separation Science and Technology, 46, 2575 – 2584.
9. Sabzali, A., Gholami, M., Yazandbakhsh, A. R., Khodadadi, A., Musavi, B & Mirzaee, R. (2006).
Chemical Denitrification of Nitrate from Groundwater via Sulfamic Acid and Zinc Metal. Journal
Environmental Health Science Engineering, 3 (3): 141 – 146.
10. Lopez-Vazquez, C. M., Kubare, M., Saroj, D. P., Chikamba, C., Schwarz, J., Daims, H. & Brdjanovic,
D. (2013). Thermophilic Biological Nitrogen Removal in Industrial Wastewater Treatment. Appl
Microbiol Biotechnol. 98 (2): 945 – 5.
11. Matos, C. T., Velizarov, S., Crespo, J. G & Reis, M. A. M. (2006). Simultaneous Removal of Perchlorate
and Nitrate from Drinking Water Using the Ion Exchange Membrane Bioreactor Concept. Water
Research. 40 (2): 231 – 240.
12. Zhang, Y. & Angelidaki, I. (2012). Bioelectrode-Based Approach for Enhancing Nitrate and Nitrite
Removal and Electricity Generation from Eutrophic Lakes. Water Research, 46 (19): 6445 – 6453.
13. Hannachi, C., Guesmi, F., Fatma, K., Missaoui & Hamrouni, B. (2014). Application of Adsorption
Models for Fluoride, Nitrate and Sulfate Ion Removal by AMX Membrane. International Journal of
Technology, 5 (1): 60 – 69.
14. Sowmya, A & Meenakshi, S. (2013). An Efficient and Regenerable Quartenary Amine Modified
Chitosan Beads for The Removal of Nitrate and Phosphate Anions. Journal of Environmental Chemical
Engineering, 1 (4): 906 – 915.
15. Shaikh, I. I & Chendake, Y. J. (2016). Removal of Ammonium Nitrate from Aquaculture by Sorption
Using Zeolite.” International Journal of Scientific Research in Chemistry, 1 (1): 42 – 48.
16. Hassan, M. L., Kassem, N. F & El-Kader, H. A. A. (2010). Novel Zr (IV)/Sugar Beet Pulp Composite
for Removal of Sulfate and Nitrate Anion. Journal of Applied Polymer Science, 117 (4): 2205 – 2212.
17. Kalaruban, M., Loganathan, P., Shim, W. G., Kandasamy, J., Naidu, G., Tien, V. N. & Vigneswaran, S.
(2016). Removing Nitrate from Water Using Iron-Modified Dowex 21K XLT Ion Exchange Resin:
Batch and Fluidised-Bed Adsorption Studies. Separation and Purification Technology, 158, 62 – 70.
18. Bulgariu, L., Ceica, A., Lazar, L., Cretescu, I & Balasanian, I. (2010). Equilibrium and Kinetics Study
of Nitrate Removal from Water by Purolite A100 Resin. Revista de Chimie, 61 (11): 1136 – 1141.
19. Nur, T., Shim, W. G., Loganathan, P., Vigneswaran S. & Kandasamy, J. (2014). Nitrate Removal Using
Purolite A520E Ion Exchange Resin: Batch and Fixed-Bed Column Adsorption Modelling.
International Journal of Environmental Science and Technology, 12 (4): 1311 – 1320.
20. Primo, O., Rivero, M. J., Urtiaga, A. M. & Ortiz, I. (2009). Nitrate Removal from Electro-Oxidized
Landfill Leachate by Ion Exchange. Journal of Hazardous Materials, 164 (1): 389 – 393.
21. Li, W. B., Song, Y. B., Xu, H. K., Chen, L. Y., Dai, W. D & Dong, M. (2015). Ion-Exchange Method in
the Collection of Nitrate from Freshwater Ecosystem for Nitrogen and Oxygen Isotope Analysis: A
Review. Environmental Science Pollution Research, 22 (13): 9575 – 9588.
22. Farajpourlar, M., Rao, S. R. M. & Rao, V. V. B. (2013). Studies on Fixed and Fluidized Bed Ion
Exchange Column to Treat Wastewater. IOSR Journal of Environmental Science, Toxicology and Food
Technology, 6 (1): 1 – 6.
23. Li, H & Yang, C. (2015). Nitrite Removal Using Ion Exchange Resin: Batch vs. Fixed Bed Performance.
Separation Science and Technology, 50 (11): 1721 – 1730.
24. Loganathan, P., Vigneswaran, S. & Kandasamy, J. (2013). Enhanced Removal of Nitrate from Water
Using Surface Modification of Adsorbents - A Review. Journal of Environmental Management, 131,
363 – 374.
25. Swarna, A. (2014). Removal of Arsenic Using Iron Coated Limestone. Western Kentucky University,
Top Scholar. Master Theses & Specialist Projects. Paper 1342.
26. Zou, W., Han, R., Chen, Z., Jinghua, Z. & Shi, J. (2006). Kinetic Study of Adsorption of Cu (II) and Pb
(II) from Aqueous Solutions Using Manganese Oxide Coated Zeolite in Batch Mode. Colloids and
Surfaces A: Physicochemistry Engineering Aspects, 279 (1, 2 & 3): 238 – 246.
27. Purolite (2017, September 7). Technical Data. ISO 9002. [Online] Available: www.purolite.com..
28. Faiku, F & Haziri, A. (2016). Assesment of The Water Quality of Lumbardhi River, Prizren (Kosovo).
Bulgarian Chemical Communications, 48 (4): 646 – 658.
29. Zhang, J., Yang, C., Chen, C & Yang, X. (2013). Determination of Nitrite and Glucose in Water and
Human Urine with Light-Up Chromogenic Response Based on The Expeditious Oxidation of 3,3’, 5,5’-
tetramethylbenzidine by Peroxynitrous Acid. Analyst, 138 (8): 2398 – 2404.
30. Roohparvar, R., Shamspur, T. & Mostafavi, A. (2016). Application of Modified Silica Coated Magnetite
Nanoparticles to Separation-Preconcentration and Determination of Nitrite. Chemical & Metallurgical
Engineering Journal, European Science Publishing Ltd, 4, 101 – 103.
31. Xu, X., Gao, B., Yue, Q., Li, Q. & Wang, Y. (2013). Nitrate Adsorption by Multiple Biomaterial Based
Resins: Application of Pilot-Scale and Lab-Scale Products. Chemical Engineering Journal, 234, 397 –
405.
32. Chowdhury, Z. Z., Zain, S. M., Rashid, A. K., Rafique, R. F. & Khalid, K. (2013). Breakthrough Curve
Analysis for Column Dynamics Sorption of Mn (II) Ions from Wastewater by Using Mangostana
garcinia Peel-Based Granular-Activated Carbon. Journal of Chemistry.
33. Loganathan, P., Vigneswaran, S., Kandasamy, J. & Bolan, N. S. (2013). Removal and Recovery of
Phosphate from Water Using Sorption. Critical Reviews in Environmental Science and Technology, 4
(8): 847 – 907.
34. Namasivayam, C. & Sangeetha, D. (2005). Kinetic Studies of Adsorption of Thiocyanate onto ZnCl2
Activated Carbon from Coir Pith, an Agricultural Solid Waste. Chemosphere, 60 (11): 1616 – 1623.
35. Kalaruban, M., Loganathan, P., Shim, W. G., Kandasamy, J., Ngo, H. H. & Vigneswaran, S. (2016).
Enhanced Removal of Nitrate from Water Using Amine-Grafted Agricultural Wastes. Science of the
Total Environment, 565, 503 – 510.
36. Babu B, V. & Gupta, S. (2005). Modeling and Simulation for Dynamics of Packed Bed Adsorption.
Proceedings of International Symposium & 57th Annual Session of IIChE in association with AIChE
(CHEMCON-2004), Mumbai.