Research Article

Assessment of urban river water quality and developing strategies

for phosphate removal from water and wastewaters: Integrated
monitoring and mitigation studies
Harsha Mahadevan1,3 · K. Anoop Krishnan1   · Renjith R. Pillai1,2 · Sandhya Sudhakaran1,3

Received: 18 December 2019 / Accepted: 18 March 2020

© Springer Nature Switzerland AG 2020

Abstract
In this work, the water quality status of the surface water that lies around the Karamana River basin, Trivandrum urban
area, was studied on the basis of the water quality index (WQI) method. The eutrophic condition of the basin is revealed,
and proper mitigation strategy was adopted for the removal of phosphate species using pillared clay materials. Proper
sampling was carried out in the urban rivers, and various physico-chemical parameters for evaluating the quality of
water were analysed. WQI values obtained for these riverine systems are in the range 317.7–3005.1, indicating that the
water is not suitable without treatment for any domestic activities. Also, phosphate ions in the range 1.98–20.52 mg/L
reflect the dominance of phosphate species in surface water. A proper mitigation strategy was adopted for the selective
removal of phosphate ions using adsorption technique by using zirconium-pillared bentonite clay (ZPBC) prepared by
the stirring–ageing technique. The batch adsorption experiment performed on simulated phosphate solution shows
that for 2.0 g/L of ZPBC a maximum phosphate adsorption capacity of 35.71 mg/g was achieved in 30 min at pH 3.0.
The data obtained were used to study models in kinetics and isotherm. The reusability of spent ZPBC for five continu-
ous cycles without major loss in adsorption capacity using 0.025 M ­Na2CO3 extractant was proved from the desorption
study. A single-stage reactor was also designed from the isotherm data and proved to be effective. The applicability of
the adsorbent towards phosphate anions was successfully checked in the laboratory using surface water collected and
found that the complete removal of phosphate was achieved using 6.0, 8.0 and 10.0 g/L of ZPBC.

Keywords  Urban area · Water quality index · Mitigation · Phosphate · Adsorption · Desorption

1 Introduction the aquatic environment inhibits the penetration of light

into the water bodies, creating an anoxic condition and
Urban river water chemistry is a principal component of destroying flora–fauna of the aquatic environment [1–3].
metropolitan areas as it maintains the survival of the urban Thus, using water quality index (WQI) with international
ecosystem through receiving and flushing out mechanism. standard limits we can determine the water chemistry and
But the discharge of municipal sewage and industrial efflu- hence the status of water pollution in these areas [4, 5].
ents beyond the controlling level cause harmful effects WQI method based on different modes of calculations has
on the lives of city dwellers. The presence of pollutants in been widely developed by many authors to assess water

Electronic supplementary material  The online version of this article (https​://doi.org/10.1007/s4245​2-020-2571-0) contains
supplementary material, which is available to authorized users.

*  K. Anoop Krishnan, [email protected]; [email protected] | 1Hydrological Processes Group, National Centre for Earth
Science Studies (NCESS), Akkulam, Trivandrum 695011, India. 2Department of Chemistry, Mar Ivanios College, Nalanchira, Trivandrum,
India. 3University of Kerala, Trivandrum, India.

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quality of rivers all around the world like Hooghly River characterization is reported by our group [23]. In this work,
in India, Yellow River in China, Suquia River in Argentina, adsorption conditions for simulated phosphate solutions
Amazonian rivers in Brazil and Beheshtabad River in Iran such as contact time with various concentrations 15, 25,
[6–10]. Thus, from the outcome of WQI calculations, the 50 and 100 mg/L and with different temperatures 15, 25
public and government can easily understand the health- and 35 °C were optimized to study various kinetic and iso-
iness of the river and also can take suitable measures therm models. The spontaneity of the adsorption process
regarding human intervention and surface water preser- was investigated using thermodynamic studies. Finally,
vation in the area, particularly in a developing country like the adsorbent was effectively applied for the removal of
India, where rivers are considered as sacred. phosphate in riverine samples collected during fieldwork.
The occurrence of excessive nutrients (N and P) in riv-
ers is mainly due to anthropogenic activities which may
lead to eutrophication, causes uncontrolled algal growth, 2 Materials and methods
ineffective environment for fish and depletion of dissolved
oxygen and affects the biodiversity; in overall, it may lead 2.1 Monitoring studies
to the extinction of a variety of species [11, 12]. Phospho-
rus can be brought to minimal concentration than nitro- 2.1.1 Study area and sampling locations
gen, so in order to control eutrophication special emphasis
is given to phosphorus than nitrogen [13, 14]. Phosphorus Trivandrum, the capital city of Kerala, situated between 8°
compounds such as inorganic phosphate, pyrophosphate, 17′ and 8° 54′ N latitude and 76° 41′ and 77° 17′ E longi-
phosphodiesters and organic phosphate esters are con- tude is blessed with three major rivers. This study is mainly
verted to orthophosphate chemically or enzymatically in concentrated on the highly populated urban areas of this
an aqueous environment. So, orthophosphate is the only district, where the entire Karamana River basin lies. Kara-
prominent form that could be utilized by prokaryotic and mana River (67 km), the major river in this basin, has its
eukaryotic organisms [15, 16]. For the treatment of waste- origin from Chemmunji Motta of Western Ghats, recog-
water, various techniques are reported by researchers, nized as one among the world’s eighth hottest spots by
such as adsorption, oxidation, flocculation–coagulation, the UNESCO world heritage due to its rich biodiversity.
membrane filtration and biological treatment [17, 18]. This river is the major surface water source for the Trivan-
Among them, adsorption is an effective technique for the drum water supply scheme. The best-known tributary of
removal of pollutants because of low cost, minimal sludge Karamana River is Killiyar which is also part of the moni-
production, recovery of adsorbent and high efficiency [1, toring study. Another major canal residing in this basin
2, 19]. So we have opted for an adsorption technique for is Parvathy Puthanar (part of Travancore–Shoranur Canal)
the complete removal of phosphate in river water [20]. having a length of 16.5 km stretching from Akkulam–Veli
Bentonite is an easily available 2:1 natural clay mineral (N) to Kovalam (S) of the city. This canal is also taken for
with low cost and non-toxicity and is widely used for nutri- the water quality study as the sewage is dumped into this
ent removal studies because of its high anion exchange canal from various small drains present in the city. About
capacity. It has an octahedral layer that is sandwiched 70% of the sewage from urban areas is conveyed to the
between two tetrahedral layers with a negative charge sewage treatment plant at Muttathara, but the remaining
on its surface which is mainly balanced by N ­ a+ and C
­ a2+, part is dumped into this riverine system that causes severe
which are exchangeable with pillared cations resulting in problems for the flora and fauna of the aquatic system.
the increase in efficiency in phosphate removal [21, 22]. The sampling sites were identified and recorded using a
So by modifying the precursor bentonite, the efficiency of portable GPS (Make: Garmin, Model: Montana 650, USA),
adsorption towards phosphate could be increased. and the locations from which samples have been collected
The systematic monitoring of water quality of an urban are shown in Fig. S1.
river basin followed by mitigation of a specific anion in the
presence of other co-existing ions is not reported in any 2.1.2 Field work details
of the research work related to water chemistry. The aim
of the present study is to explore the eutrophic condition The samples were collected during the post-monsoon
of the surface water in the urban area of Trivandrum using season (November 2018) from two rivers each namely
the water quality index method followed by adsorption Karamana (stations 1, 2 and 3), Killiyar (stations 4, 5 and
of phosphate anions present in the riverine system using 6) and Parvathy Puthanar canal (stations 7, 8 and 9) from
pillared clay. The mitigation study for phosphate removal about 0.6  m below the water surface. The parameters
on these urban rivers was carried out using the adsor- such as water temperature (°C), pH, electrical conductiv-
bent ZPBC. The preparation of the adsorbent ZPBC and its ity (EC), total dissolved solids (TDS) and dissolved oxygen

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(DO) were measured in situ without pretreatment using a pH and temperature. Although aquatic organisms excrete
calibrated transportable water quality equipment (Make: ammonia, the high concentration of ­NH4+-N in the aquatic
Eutech, Model: Aquaread 1000 D, Germany). Before the system occurs due to the discharge of domestic sewage
laboratory analysis of chloride ­(Cl−), sulphate (­SO42−) and industrial effluents [27]. The source of ­SO42− in urban
and bicarbonate (­ HCO3−), phosphate P ­ O43−-P, ammonia surface water might be from sulphate-bearing fertilizers,
+ −
­(NH4 -N) and nitrate (­ NO3 -N) water samples were filtered sulphuric salts in domestic sewage and also by weather-
using 0.45-µm Whatman TM uniflo PVDF sterile disposable ing of soils. Moreover, sulphates form strong acids that
syringe filters and preserved in an airtight 1-L acid-cleaned change the pH of water [28]. The high value of TDS causes
sealed polyethylene bottle (PE). Before the collection of an increase in salinity, changes the ionic composition of
water samples in PE bottles, they were thoroughly rinsed water, eliminates less tolerant aquatic species and thus
with distilled water. All the field samples were preserved overall affects the quality of surface water [29]. Chlorides
in ice bags to maintain ambient conditions until they get ­(Cl−) are usually combined with sodium and to a lesser
analysed. The method adopted for the determination of extent with calcium, magnesium and potassium, making
chemical parameters of the samples is taken from proce- them a stable component in water. The increase in the con-
dures mentioned in American Public Health Association ­ l− causes acidification of streams and affects the
tent of C
[24]. The chemicals required for the determination of reproduction capability of aquatic plants and animals [30].
chemical parameters were purchased from E. Merck, India. Thus, it affects the water quality and given a weightage
The experiments and calculations were completed within 3. For the WQI calculation, the standard values of surface
a week, and the entire analysis was carried out in triplicate. water were taken from various studies [31–33]. The relative
weight (Wi), quality rating (qi) and WQI are computed using
2.1.3 Examination of the quality of water by WQI method the following equations [34]:
The relative weight and quality rating equation:
The physico-chemical parameters such as pH, EC, DO, TDS, w
­Cl−, ­SO42−, ­NO3−-N, ­PO43− -P and ­NH4+-N were used for the Wi = ∑n i (1)
calculation of WQI. Each parameter was given the weight- i=1 wi
age ­(wi) value from 1 to 5 depending upon their impor-
and
tance in the surface water (Table S1).
DO, EC and nutrient parameters such as ­PO43−-P and Ci
­NO3−-N were given weightage 5 (wi = 5). DO is needed
qi = × 100 (2)
Si
for the survival of flora–fauna of the aquatic system. The
decrease in DO value is an indication of polluted water, Sub-index equation:
and there is a high possibility of eutrophication. The SIi = Wi × qi (3)
eutrophic condition of surface water mainly concentrates
on the amount of ­PO43−-P and ­NO3−-N present. These two Water quality index equation:
anions from fertilizers and detergents when discharged n
into surface water cause the growth of aquatic plants and ∑
WQI = SIi (4)
depletion of DO, finally affecting the water quality by caus- i=1
ing eutrophication. EC is an indirect measure of total dis-
solved salts and also confirms the presence of inorganic where n represents the number of parameters, wi is the
pollutants (industrial effluents) present in surface water. weight of each parameter, Ci is the concentration of the
Thus, EC indicates the state of surface water, i.e. whether ith parameter for each sampling site, Si (mg/L) is the stand-
the water system is suitable for the survival of aquatic life ard for surface water, and ­SIi is the sub-index of the ith
[25]. Hence, we assigned these three parameters a weight- parameter.
age 5.
The reason for assigning the weightage 4 for param- 2.2 Mitigation studies
eters pH, ­NH4+-N, TDS and ­SO42− is as follows: the acidity or
alkalinity of water can be understood by the measurement 2.2.1 Materials
of pH. The flow of fertilizers that contain nutrients, mainly
phosphate and nitrate, into the surface water results in The adsorbent, bentonite clay (AR grade) was procured
higher pH and proliferation of algal growth. Conversely, from Sigma-Aldrich, India, and for pillaring process
the physiological functions of aquatic life are affected at Emsure-grade zirconium (IV) oxychloride was purchased
low pH [26]. So pH indicates the state of water. The con- from Merck, India. For the contact time and tempera-
centration of ­NH4+-N in the surface water depends upon ture studies, simulated stock solution of phosphate

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(1000 mg/L) was prepared using ­KH2PO4 purchased from is the volume of phosphate solution in mL, and m is the
Merck, India. For the spectrometric determination of phos- mass of the adsorbent in grams.
phate, E. Merck chemicals were used (ascorbic acid, ammo- The reusability of the adsorbent (ZPBC) was investi-
nium heptamolybdate tetrahydrate, potassium antimony gated by conducting desorption studies. The phosphate-
(III) oxide tartrate hemihydrates).The desorption studies loaded ZPBC was centrifuged and washed thoroughly with
were carried out using NaOH, N ­ a2CO3, HCl and ­NaHCO3 Milli-Q water to remove any unabsorbed phosphate ions.
supplied from Merck, India. All chemicals used were AR The desorption experiments were carried out using NaOH,
grade, and the reagents were prepared using Milli-Q water. ­Na2CO3, HCl and ­NaHCO3 as desorption agents. Among
them, ­Na2CO3 was found to be more effective and was
2.2.2 Procedure adopted for ZPBC—zirconium‑pillared selected for further studies. The regenerated clay was used
bentonite clay for adsorption, and the sorption experiment was contin-
ued for five cycles.
The successful synthesis of ZPBC and the detailed proce- The effect of the adsorbent dosage (2.0, 4.0 6.0, 8.0 and
dure carried out using the stirring–ageing technique are 10.0 g/L) was carried out for the phosphate removal stud-
reported in our previous work [23]. A brief description ies. The filtered riverine samples collected during the field
of the procedure adopted for pillared clay preparation is work were used for the dosage experiment. The entire
as follows: about 4 mL/min of 0.2 zirconium oxychloride test was conducted in duplicate, and the mean values are
(500 mL) is added dropwise to an RB flask containing the reported.
stirring solution of sodium bentonite (12 g) kept at room
temperature. The process is continued for 10 min, and
after that 40 mL of the remaining zirconium solution was 3 Results and discussion
added to the stirring mixture as described above and kept
for ageing for another 10 min. The same slot addition of 3.1 Monitoring studies
aliquot and ageing is continued until 6 h and 25 min is
reached. Finally, the mixture is stirred vigorously for 2 h 3.1.1 Hydrochemical characteristics
followed by 4-h ageing. After checking the pH, the solu-
tion was centrifuged and the residue part is washed with Physico-chemical parameters reflect the surface water
deionized water to free from chloride. The material is then quality, and the result obtained during analysis is shown in
dried at 80 °C, milled, labelled as ZPBC and kept in the bot- Table 1. The surface water temperature varied from 29.1 to
tle for further studies. The pillaring of Zr onto precursor 31.4 °C during the sampling period. The acidity and basic-
clay is confirmed from various spectroscopic techniques ity of the water are well understood by pH studies. In the
that were reported in our work mentioned above. present study, it can be seen that pH values varied from
7.01 to 8.71 from stations 1 to 9. A wide variation for DO
values was obtained for all the stations during in situ meas-
2.2.3 Batch adsorption experiments
urements. The lower DO was obtained for stations 7, 8 and
9 with values ranging from 3.01 to 3.32 mg/L. The DO con-
The effect of contact time (10, 20, 30, 40 and 50 min), ini-
centration obtained for the canal is very much lower, i.e.
tial phosphate concentrations (15, 25, 50 and 100 mg/L)
below the standard limit (5 mg/L) of WHO (2011) for drink-
and temperatures (15, 25 and 35 °C) for the adsorption of
ing purposes and also below the standard limit of surface
phosphate were studied by taking 2.0 g/L of ZPBC in Erlen-
water (6 mg/L). Sewage channel is joining this canal at dif-
meyer flasks optimized at pH 3.0 using 0.1 M NaOH and
ferent points leading to nutrient load, weed growth and a
0.1 M HCl. Then, treated solutions with varying different
decrease in DO. Stations 7, 8 and 9 reported a high value
concentrations of phosphate were analysed using ultra-
of EC compared to all other stations and are found to be
violet–visible NIR spectrophotometer (Make: Shimadzu,
above the surface water standard limit (400 µS/cm). The
Model: UV-3600 plus, Germany) measured at a wavelength
high value of EC in the canal indicates a high degree of
of 880 nm by ammonium molybdate method [24]. The
pollution due to the dumping of sewage waste. TDS values
amount of phosphate adsorbed was calculated by using
for Karamana River and Killiyar were within the permissible
the following equation:
limit (500 mg/L) of WHO (2011), but in the case of Parvathy
[( )]
C 0 − CA V Puthanar, values are very high (1782.01 to 1987.30 mg/L).
q= (5) The values are higher than the surface water standard
m
(1200 mg/L). The TDS level in Parvathy Puthanar is high
where C0 is the initial phosphate concentration and CA is due to septic and domestic sewage waste present in the
the concentration of phosphate at equilibrium in mg/L, V water. The bicarbonate levels from stations 1–6 were

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within the permissible limit of 120 mg/L of (WHO 2011)

NH4+- N (mg/L)
for drinking purposes but slightly high values for other
stations. The concentrations of ­Cl− and ­SO42− varied from
43.21 to 128.32 mg/L and 45.04 to 143.61 mg/L, respec-

10.92
5.32
3.42
9.72
8.03
3.61
4.03
5.21
1.80
2.01
2.56
tively, indicating that the values are within the standard
limit (250 mg/L). The major nutrients such as ammonia
PO43—P (mg/L)

­(NH4+-N), phosphate ­(PO43−-P) and nitrate ­(NO3−-N) also

affect the quality of water, and their limit beyond per-
missible limits causes serious health problems in rivers.

20.52
17.34
15.02

8.13
7.35
3.68
3.84
5.92
1.98
2.56
2.27

Among the nutrient parameters, mainly phosphate is eas-

ily absorbed by plants, causing increased productivity of
NO3—N (mg/L)

phytoplanktons resulting in eutrophication, and finally

the entire area becomes deserted [35]. ­PO43−-P values
23.15 for all the stations ranged from 1.98 to 20.52 mg/L with
12.08
18.24
17.91
10.07
12.01

6.26
5.91
6.62
6.01
8.82

the maximum in stations 7, 8 and 9. In general, all the

stations ­PO43−-P values were found to be exceeding the
SO42− (mg/L)

permissible limit (> 0.1 mg/L) prescribed by WHO (2011)

and surface standard limit set by researchers. Moreo-
143.61
137.12
129.23

86.78
40.02
68.45
71.05
89.23
45.04
51.01
46.32

ver, it is reported that for phosphate values greater than

1.0 mg/L, there is a high risk of eutrophication. The values
for ­NO3−-N and N ­ H4+-N varied from 5.91 to 23.15 mg/L and
Cl− (mg/L)

128.32
116.38
107.21

85.30
28.76
76.23
82.53
43.21
57.06
61.56
95.26

1.80 to 10.92 mg/L, respectively, having high values for

Parvathy Puthanar. N ­ O3−-N values for stations 1–5 were
within 10 mg/L as per surface water standards, whereas
HCO3− (mg/L)

­NH4+-N was higher for all stations with values above the
permissible limit (0.5 mg/L). Higher ammonia creates an
349.82
146.25
289.96
266.89

55.99
83.12
87.56
54.31
79.12
56.32
49.12

oxygen demand in these stations and also releases nitrous

oxide gas produced as a result of the denitrification pro-
cess. The trend obtained from the nutrient analysis is as
DO (mg/L)

follows: ­PO43−-P > NH4+-N > NO3−-N. The level of nutrients,

especially phosphate present in the riverine systems, is
1.22
3.01
4.46
3.21
3.32
4.01
4.92
6.01
6.32
5.23
4.12

high due to the dumping of sewage wastes, both solid and

liquid from small drainage channels or from people resid-
TDS (mg/L)
Table 1  Results of physico-chemical parameters of Karamana River basin

1987.30
1873.01
1782.01

783.72
884.76
145.20
154.60
220.12
58.08
53.01
73.37

ing banks of rivers. The phosphate level is tremendously

high in Parvathy Puthanar, indicating the disappearance
of the canal in the nearby future due to eutrophication. So
proper treatment strategies must be introduced for saving
EC (µS/cm)

1086.89
884.65
221.21
275.01
88.01
87.31
89.21
220.23

the rivers and canal from nutrient pollution, particularly

2483.0
2341.2
2156.7

from phosphate.
7.63
0.58
8.71
8.32
7.52
8.01
7.35
7.45
7.01
7.12
7.23

3.1.2 Interpretation of WQI
pH
Temperature (°C)

The WQI value obtained from the calculations for nine sta-
tions is presented in Table 2. The results showed that WQI
values are varying for different sampling sites. WQI values
calculated for the Karamana River and Killiyar are in the
29.66
0.62
31.4
30.1
29.6
30.0
29.1
29.2
29.5
29.2
29.2

range 317.7–370.71 and 581.62–910.96, respectively. For

Parvathy Puthanar, WQI values > 2200. The surface water
Standard deviation

standard was considered for the calculation of the water

quality index method. In other studies, WQI is calculated
on the basis of the drinking water standard. So the com-
Stations

parison of our results with them is not possible. In some

Mean

places of urban areas, people use water directly for bathing

9
8
5
6
7
1
2
3
4

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Table 2  WQI values obtained Stations 1 2 3 4 5 6 7 8 9

for post-monsoon season from
rivers and canal WQI values 317.70 326.84 370.71 581.62 613.91 910.96 2217.87 2558.82 3005.12

and domestic purposes. Even if we take the drinking water of phosphate adsorbed increases and reaches equilibrium
standard limit of WHO, WQI values obtained will be very within 30 min. The maximum qe values obtained are 6.97,
higher indicating unsuitability in drinking purposes. Most 11.30, 19.22 and 19.32 mg/g for various concentrations
of the areas’ river water is used after pretreatment. How- 15, 25, 50 and 100 mg/L within 30 min. As contact time
ever, the concentration of ions, especially nutrient anions, proceeds further, there is no appreciable change in phos-
in all the stations obtained is very high when compared phate adsorption from the solution by the adsorbent due
to the surface water standard limit and also the drinking to the unavailability of the bare clay surface for the uptake
water standard limit. The high phosphate level indicates a of phosphate molecules. The fast adsorption rate is very
great threat to the current aquatic environment, and this crucial and important for the practical application of the
will definitely affect the existence of the future riverine sys- adsorbent [36]. The influence of temperature on the inter-
tems. So a proper mitigation method should be adopted action between ZPBC and phosphate was studied using
at the earliest for the preservation of the aquatic system. three different temperatures 15, 25 and 35 °C under the
optimized condition (Fig. 1b). It can be seen that as the
3.2 Mitigation studies temperature rises the amount of phosphate adsorption
reached 34.83 mg/g at 35 °C. A possible explanation for
3.2.1 Effect of contact time and temperature the increase in the amount of adsorption at higher tem-
peratures can be due to the increase in active sites on the
A maximum of 92.4% phosphate removal was achieved adsorbent surface for adsorption and also rise in the tem-
at pH 3.0 for 15 mg/L phosphate solution concentration perature increases the mobility rate of phosphate species
using an adsorbent (ZPBC) dose of 2.0 g/L. Further increas- onto the surface of the adsorbent. Hence, it is assumed
ing the pH, adsorption decreases appreciably. At pH 3.0, that adsorption is an endothermic one [37].
the surface of the pillared clay becomes more positive that
­ 2PO4− from phosphate solution resulting
tends to attract H 3.2.2 Adsorption kinetics, isotherm and thermodynamic
in effective adsorption. Figure 1a represents the contact studies
time required for various concentrations 15, 25, 50 and
100  mg/L to reach equilibrium using the above-opti- To predict the adsorption chemistry of ZPBC with
mized condition. As contact time proceeds, the amount phosphate (physisorption or chemisorption), the

35 35
(a) (b)
30 30
pH: 3.0 100 mg/L
Adsorbent dose: 2.0 g/L 50 mg/L
Temperature: 30 0C
25 25 mg/L 25
15 mg/L
qe (mg/g)

20 20
qe (mg/g)

15 0C
25 0C
15 15 35 0C

10 10

pH: 3.0
5 5 Adsorbent dose: 2.0 g /L
Equilibrium time: 30 min

0 0
0 20 40 60 0 50 100 150 200
Time (min) C 0 (mg/L)

Fig. 1  Effect of a contact time and b temperature on phosphate adsorption onto ZPBC

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experimental data obtained from contact time for vari- t 1 t

= + (7)
ous initial concentrations 15, 25, 50 and 100 mg/L were qt k2 q2e qe
used for the calculation of using two prominent models:
pseudo-first-order and pseudo-second-order [38, 39], where k1 (1/min) and k2 (g/mg/min) are the pseudo-first-
and the equation is as follows: order and pseudo-second-order rate constants for an
Lagergren pseudo-first-order equation: amount of phosphate adsorbed at equilibrium qe and qt
in mg/g at time t (min), respectively. The values for k1 and
k t qe were calculated from the slope and intercept by plot-
log qe − qt = log qe − 1 (6)
( )
2.303 ting log (qe − qt) against t (Fig. 2a), whereas k2 and qe were
Mckay and Ho pseudo-second-order equation: calculated from the slope and intercept of the plot t/qt
against t (Fig. 2b). Table 3 clearly shows the pseudo-sec-
ond-order with higher R2 value (0.998, 0.985, 0.984, 0.992)
indicating chemisorption as the rate-limiting step in the

6
1.5 (a) (b) pH: 3.0
pH: 3.0
Adsorbent dose: 2.0 g /L Adsorbent dose: 2.0 g/L
1.2 Temperature: 30 0C 5 Temperature: 30 0C
Equilibrium time: 30 min Equilibrium time: 30 min
100 mg /L
0.9 50 mg/L 4 100 mg/L

t/qt (min/mg/g)
log (qe-qt )

25 mg/L 50 mg/L
15 mg/L 25 mg/L
0.6
3 15 mg/L

0.3
2
0
1
-0.3

-0.6 0
0 5 10 15 20 25 0 10 20 30 40
Time (min) Time (min)

Fig. 2  a Pseudo-first-order, b pseudo-second-order kinetic plots for the adsorption of phosphate onto ZPBC

Table 3  Kinetic and isotherm parameters for the adsorption of phosphate onto ZPBC
Kinetic models Parameters Initial concentration (mg/L)
15 25 50 100

Pseudo-first-order k1 (1/min) 0.147 0.117 0.119 0.117

qe (mg/g) 4.73 9.57 12.88 15.35
R2 0.852 0.983 0.933 0.890
Pseudo-second-order k2 (g/mg/min) 0.329 0.063 0.062 0.055
qe (mg/g) 6.89 10.75 15.87 20.00
R2 0.998 0.985 0.984 0.992
Isotherm models Parameters Temperatures
15 °C 25 °C 35 °C
0
Langmuir Q (mg/g) 27.03 30.30 35.71
b (L/mg) 0.09 0.15 0.17
R2 0.997 0.996 0.992
Freundlich KF (mg/g) 4.56 7.16 11.25
n (L/mg) 2.49 3.04 3.92
R2 0.929 0.980 0.984

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phosphate adsorption process [40]. The rate constant k2, versus Ce (Fig. 3a). The value for KF and n is obtained from
for the adsorption of phosphate, was found to decrease the log qe versus log Ce (Fig. 3b). The favorability of the
for various initial phosphate concentrations (15 mg/L to adsorption is represented by the equilibrium parameter
100 mg/L). By obtaining pseudo-second-order kinetics, it RL [47]:
is confirmed that sorption onto ZPBC proceeds by elec-
1
trostatic interaction between adsorbent and adsorbate. RL = (10)
1 + bC0
Similar results are obtained for phosphate removal using
other adsorbents [41, 42]. where b is the Langmuir constant and C0 is the initial con-
The adsorption capacity of the adsorbent is mathemati- centration of phosphate solution. The favorability of the
cally calculated by using two common models, Langmuir adsorption process is represented in the order 0 < RL < 1.
[43] and Freundlich [44], with the help of isotherm data Table  3 shows the higher regression coefficient
for various temperatures 15, 25 and 35 °C. Langmuir iso- (R 2 > 0.97) for Langmuir isotherm indicating the suit-
therm occurs on the homogenous adsorbent surface indi- ability of the model in explaining the adsorption of
cating monolayer adsorption, but for Freundlich isotherm phosphate onto pillared clay. As temperature rises (15
adsorption occurs on heterogeneous surfaces and more to 35 °C), Q0 value (27.03 to 35.71 mg/g) also increases
possibly adsorption is a multilayered one [45, 46]. The confirming the endothermic nature. The increase in b
equations of these two models are given in Eqs. 8 and 9: value (0.09 to 0.17) with the rise in temperature conveys
Langmuir equation: the strength and affinity of the clay surface towards
Ce C phosphate species as reported elsewhere [48]. The val-
1
= + e (8) ues of RL were found to be between 0 and 1 for the vari-
qe bQ0 Q0
ous initial concentrations of phosphate (15–100 mg/L)
Freundlich equation: confirming the favorability of the adsorption of phos-
phate species onto adsorbent [49]. A comparative study
1 on phosphate adsorption using ZPBC and other modi-
log qe = log KF + log Ce (9)
n fied bentonite clay minerals is presented in Table 4 and
where qe (mg/g) represents the amount of phosphate found that ZPBC prepared by the novel method is a bet-
adsorbed on the solid zirconium-pillared adsorbent and ter adsorbent than reported.
Ce (mg/L) is the concentration of phosphate solution at The spontaneity and feasibility of the adsorption
equilibrium. Q0 (mg/g) is the monolayer adsorption capac- process were studied using thermodynamic parameters
ity, and b (L/mg) is the energy of adsorption. KF is the Fre- (free energy ∆G 0; enthalpy ∆H 0; entropy ∆S 0) at opti-
undlich constant, and n represents the intensity of adsorp- mized conditions pH 3.0, temperatures 15, 25 and 35 °C,
tion. The value of b and Q0 is obtained from the plot Ce/qe adsorbent dose 2.0 g/L and various initial phosphate

5 1.8
(a) (b)
1.5
4
pH: 3.0
Adsorbent dose: 2.0 g /L
Equilibrium time: 30 min 1.2
Ce/qe (g/L)

3
log qe

0.9
2
0.6
15 0C pH: 3.0
15 0C 25 0C Adsorbent dose: 2.0 g /L
1 25 0C 35 0C Equilibrium time: 30 min
35 0C 0.3

0 0
0 20 40 60 80 100 120 -1 -0.5 0 0.5 1 1.5 2 2.5
Ce (mg/L) log Ce

Fig. 3  a Langmuir, b Freundlich isotherm plots for the adsorption of phosphate onto ZPBC

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Table 4  Comparison of Adsorbent Q0 (mg/g) pH Temp (°C) Adsorbent Time (min) Conc: (mg/L) References
adsorption capacity using dose (g/L)
various modified bentonite
adsorbents for the removal of Zenith/Fe 11.15 7.0 25 0.4 120 0.05–5 [55]
phosphate studies
Al-Bent 12.70 3.0 – 4.0 360 25–60 [56]
Fe-Bent 11.20 3.0 – 4.0 360 25–60 [56]
Al-ABn 12.87 5.0 25 2.0 360 2–60 [48]
Al-ABn-AB 11.11 5.0 25 2.0 720 2–60 [48]
NT-25La 14.00 6.0 25 0.75 60 0.5–80 [57]
Bephos™ 26.5 7.0 25 0.4 30 0.05–20 [58]
ZrNaBT 7.25 7.0 25 1.0 1440 2–35 [59]
ZPBC 30.30 3.0 25 2.0 30 15–100 Present work
ZPBC 35.71 3.0 35 2.0 30 15–100 Present work

concentrations 15, 25, 50 and 100 mg/L. The relation- the spontaneity of the adsorption process [18]. The value
ship between these parameters is represented by the obtained for ∆G0 (< − 20 kJ/mol) indicates the importance
following equations: of electrostatic interaction followed by surface complexa-
tion on phosphate adsorption onto pillared clay [50]. The
ΔG0 = −RT ln K0 (11) positive value for ∆H0 (38.24 kJ/mol) gives an idea that
adsorption occurs by the endothermic process, and also
ΔS0 ΔH 0 the positive value for ∆S0 (133.52 J/mol/K) indicates that
ln K0 = − (12)
R RT there is an increase in randomness and also the affinity of
phosphate ions towards the adsorbent surface. A similar
∆G0 is the Gibb’s free energy in kJ/mol, R is the univer-
observation was obtained for modified bentonite for the
sal gas constant (R = 8.314 J/mol/K) and T is the absolute
removal of the anionic pollutant from the aqueous phase
temperature in Kelvin. The equilibrium constant k0 is calcu-
[51, 52].
lated from the plot of lnqe/Ce versus qe and extrapolating
to zero at three different temperatures. The value of ∆H0
3.3 Application of the adsorbent into the riverine
(kJ/mol) and ∆S0 (J/mol/K) was calculated from the slope
system
and intercept of the plot (lnk0 vs. 1/T) (Fig. 4a).The results
obtained are shown in Table S2. The value obtained for
The efficiency of the adsorbent (ZPBC) for the removal of
∆G0 (− 0.909, − 2.428, − 3.328 kJ/mol) is negative indicating
phosphate was confirmed by the real sample analysis of

1.4 140
(a) (b) 10.0 g /L
8.0 g /L
1.2 pH : 3.0 120 6.0 g /L
Adsorbent dose: 2.0 g /L 4.0 g /L
Equilibrium time: 30 min 2.0 g /L
1 100
Removal (%)

0.8
ln K 0

80

0.6 60

0.4 40

0.2 20

0 0
0.0031 0.0032 0.0033 0.0034 0.0035 1 2 3 4 5 6 7 8 9
1/T (1/K) Sampling stations

Fig.4  a Plot of ln K0 versus 1/T for the adsorption of phosphate onto ZPBC, b effect of adsorbent dosage for the removal of phosphate spe-
cies from Trivandrum urban area water samples by ZPBC [experimental conditions: contact time 30 min, temperature 30 °C]

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riverine samples collected from nine stations. The com- of other ions depends on the type of interaction formed
position of water samples is depicted in Table  1. The by the competing ions on the surface of the adsorbent.
optimized conditions such as contact time (30 min), tem- Phosphate ions are tetrahedral and form both inner and
perature (30 °C) and initial concentration (15 mg/L) were outer complexes with the adsorbent, and also zirconium-
confirmed from the batch adsorption experiments. The pH pillared clays have a high affinity towards phosphate
of the solution was not adjusted (the same pH reported species. Sulphate ions form inner sphere complex only
during fieldwork). The phosphate solution was spiked to a small extent with the adsorbent, and as a result a
13.02, 12.44, 12.73, 11.32, 11.16 and 9.08 mg/L, respec- slight decrease in concentration of S­ O 42− ions from
tively, for the water samples from stations 1 to 6, and the the adsorbent-treated water sample occurred. Also,
collected water samples as such were used for the remain- the availability of different forms of phosphate species
ing stations. The effects of adsorbent dose (2.0, 4.0, 6.0, ­( H 2PO 4− and H
­ PO 42−) in the adsorbent-treated water
8.0 and 10.0 g/L) were studied and are shown in Fig. 4b. also makes the adsorbent more selective towards phos-
It is evident from the figure that as the dosage amount phate than sulphate ions. There are also other cationic
increases the percentage removal of phosphate increases species in the water, such as C ­ a2+ and M
­ g2+, which can
and almost complete removal of phosphate was obtained also influence phosphate adsorption. The binding of
by using different dosages for different samples. Almost these ions can enhance phosphate adsorption by mak-
99.9% phosphate removal was obtained for stations 1 ing the surface of the adsorbent more electropositive
to 3, 4 to 6 and 7 to 9 using 6.0, 8.0 and 10.0 g/L of the or by forming intermediate ternary complexes [20].
adsorbent. Other ions like ­Cl− and ­NO3−-N form outersphere com-
plexes (weaker interactions) with the adsorbent, and as
3.4 WQI calculation after ZPBC treatment a result the concentration of ­Cl− and ­NO3−-N present in
surface water slightly decreases, water quality increases
The adsorbent-treated surface water samples were taken and WQI decreases. The decrease in concentration of
for the analysis of various physico-chemical parameters ammonium ions in adsorbent-treated riverine samples
mentioned in WQI calculation, and the result obtained is may be due to the conversion of ammonium to nitrate
shown in Table S3. The values obtained by WQI calcula- or by exchange with the interlayer cations of the adsor-
tion for the ZPBC-treated surface water samples are as bent. A very small change in the concentration of DO
follows: 42.79 (station 1), 50.51 (station 2), 52.16 (station occurred during the experiment, but it is not responsi-
3), 72.14 (station 4), 75.58 (station 5), 98.74 (station 6), ble for bringing down the WQI values. The values of pH
200.65 (station 7), 204.3 (station 8) and 256.65 (station also slightly decreased during adsorbent treatment onto
9). The values obtained are very lower when compared surface water samples. The pH values after ZPBC treat-
to WQI calculated for adsorbent untreated riverine sam- ment were within the surface standard limit of 6.5–9.2.
ple (Table 2). This indicates that after treating with the The values for TDS were slightly decreased due to the
adsorbent, a tremendous change in the quality of water adsorption of the anions and cations onto the adsorbent.
has occurred. It was also found from Table S3, the anionic Even though the values of EC and TDS for the adsorbent-
species that has been removed almost 99.9% from the treated water decreased, they are not within the surface
adsorbent-treated surface water sample was phosphate. water standard limit. This proves that ZPBC is a very good
Before adsorbent treatment, the concentration of phos- selective adsorbent for the removal of phosphate spe-
phate ions present in stations 1 to 9 was 1.98, 2.56, 2.27, cies from wastewaters. By using the adsorbent, the con-
3.68, 3.84, 5.92, 15.02, 17.34 and 20.54 mg/L. But after centration of phosphate anions can be brought below
treating with ZPBC, for stations 1 to 3; 0.005 mg/L, sta- 0.1 g/L (surface water standard); thereby, the eutrophic
tions 4 to 6; 0.006, 0.007, 0.007 mg/L, and for stations 7 condition of the riverine system can be minimized to an
to 9; 0.007 mg/L of phosphate ions are only remaining in extent. But some of the cations and anions present in
the water sample. This highlights the efficiency of ZPBC the adsorbent-treated surface water samples are still
in removing phosphate ions from the surface water. above surface water standard limit. The decrease in WQI
This resulted in the tremendous decrease in WQI values. value after treatment with the pillared clay was mainly
Another factor that promoted the decrease in WQI to a due to phosphate removal. For the domestic use of the
small extent is as follows: It is clear from Table S3 that the riverine water, the concentration of these anions and
concentration of ­SO42−, ­NO3−-N and ­NH4+-N also varied. cations has to be reduced. Thus, it is proved that our low-
The slight decrease in the concentration of these anions cost and eco-friendly adsorbent ZPBC is very efficient
follows the order: ­SO42− > Cl− > NO3−-N. The selectivity of for the selective adsorption of phosphate, and in future,
an adsorbent towards a particular ions in the presence the investigated materials can be applied in the field in

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order to construct permeable reactive barriers (PRBs) for W (C − Ce )(1 + 0.15Ce )

phosphate removal in real conditions. = 0 . (16)
V 4.545Ce

From Eq. (16), the mass of ZPBC required to achieve

3.5 Design of single‑stage batch reactor 93.46, 84.32, 72.96 and 62.16% removal by treating the
definite volume of phosphate ion-containing effluent
The mathematically modelled equations from kinetic and having an initial concentration C0 (15, 25, 50, 75, 100 mL)
isotherm studies can be used for optimizing the stages in can be calculated. The theoretical and experimental mass
the single-stage batch reactor [38, 53]. In this study, the of ZPBC versus different volumes of effluent for different
single-stage batch reactor is designed by using Langmuir percentages of removal of phosphate is depicted in Fig. 5a.
isotherm data of phosphate ions. The main purpose of the Also, the experimental and theoretical mass of adsorbent
design is to reduce the phosphate solution from an initial versus different initial concentrations and different vol-
concentration Co to Ct (mg/L) in a phosphate solution con- umes for the adsorption of phosphate ions from aqueous
taining V (L) of water. At the same time when W (g) of ZPBC solutions is shown in Fig. 5b. Similar works for the devel-
is added, there is a change in phosphate ion solution from opment of a single-stage reactor are reported by other
q0 to qt. The mass balance equation for the removal of the researchers [54].
phosphate ions from the aqueous phase to that loaded on
the surface of the adsorbent is given by 3.6 Desorption studies and cost estimation
of the adsorbent
(C0 − Ct )V = (qt − q0 )W. (13)
At equilibrium conditions, q0 = 0, Ct = Ce, qt = qe, Ct = Ce, The desorption capacity of the adsorbent determines its
Eq. (13) becomes economic value for the mitigation of phosphate species
from real water samples. The concentrations of N ­ a2CO3
W C − Ce were varied from 0.005 to 0.1 M and found that by using
= 0 . (14)
V qe 0.025 M ­Na2CO3 maximum phosphate was desorbed from
Q0 bCe
ZPBC within 3 h. The adsorption–desorption experiment
From (8), qe = 1+bCe
 . Substituting it in Eq. 14, we obtain was carried out for five cycles using 0.025  M ­Na2CO3,
(C − Ce )(1 + bCe ) and the results are shown in Fig. S2. After five cycles, the
W
= 0 . (15) adsorption capacity of pillared clay declined from 92.6 to
V Q0 bCe
77.5% and recovery of phosphate decreased from 90.6 to
Substituting Langmuir constants Q0 = 30.30 and b = 0.15 75.3%. The loss of the adsorbent during the five sorption
(298 K) from Table 4, then Eq. (15) becomes cycles is found to be minimum, showing the capability of
the pillared clay in batch reactor systems.

50 1.4
(a) (b)
Experimental Calculated 1.2
Mass of adsorbent (g)

40 Experimental Calculated
Mass of adsorbent (g)

1 125 mL
100 mL
30 75 mL
93.46 % 0.8
84.32 % 50 mL
72.96 %
20 62.16 % 0.6

0.4
10
0.2

0 0
0 2 4 6 8 10 12 0 50 100 150 200
Volume of effluent (L) C0 (mg/L)

Fig. 5  a Mass of adsorbent ZPBC against different volumes for different percentage removal of phosphate ions and b mass of adsorbent
ZPBC against different initial concentrations and different volumes for removal of phosphate ions from aqueous solutions

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