Science of the Total Environment 851 (2022) 158180

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Wastewater irrigation: An opportunity for improving soil phosphorus

availability; PHREEQC modeling and adsorption studies
⁎
Hiva Davand a, Ebrahim Sepehr a, , Hamid Reza Momtaz a, Fatemeh Ahmadi a,b,c
a
Department of Soil Science, Faculty of Agriculture, Urmia University, Urmia, Iran
b
Soil Science and Plant Nutrition, UWA School of Agriculture and Environment, The University of Western Australia, 6009, Australia
c
Tasmanian Institute of Agriculture, University of Tasmania, Hobart, Tasmania 7001, Australia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Irrigation of agricultural soils by wastewa-

ter decreased the P adsorption.
• Zn, and Pb phases are undersaturated in
agricultural soils irrigated by wastewater.
• The lower P buffering capacity was found
in wastewater-irrigated soils.

A R T I C L E I N F O A B S T R A C T

Editor: Frederic Coulon Wastewater, an alternative supply of water and nutrients, is being allocated as a priority for human population sustain-
ability in arid and semi-arid regions. This work proposes phosphorus (P), a vital growth-limiting nutrient, adsorption
Keywords: behavior in wastewater irrigated agricultural soils in comparison to non-irrigated soils using laboratory batch experi-
Isotherm ments. The adsorption mechanism was assessed using different adsorption isotherm models. Saturation indices were
Geochemical modeling
modeled, using the hydro-geochemical transport code PHREEQC and MINTEQ geochemical software. Phosphorus
Phosphorus buffering capacity
Visual MINTEQ
buffering parameters were also calculated based on the standard equations. The equilibrium data were well fitted
with the Freundlich isotherm model. The physical adsorption mechanism was found based on the calculated isotherm
parameters. The maximum adsorption capacity was two times more in non-wastewater irrigated soils than irrigated.
Results highlighted the effectiveness of wastewater irrigation in P availability in soil. Based on the PHREEQC modeling
data, precipitation of Pb and Zn mineral phases was probable in soils by wastewater influence. Meanwhile, the precip-
itation of stable calcium phases, that affect the P sorption and/or co-precipitation, in non-wastewater irrigated soils
was highlighted in the PHREEQC calculations. The standard buffer capacity (SBC) was 43 and 64 L kg−1 in wastewater
irrigated soils and non-irrigated soils, respectively. Findings of the present study demonstrate the importance of waste-
water reuse opportunities for agricultural application, especially soil P availability, and are helpful to minimize the en-
vironmental impacts of wastewater and solid waste.

⁎ Corresponding author.
E-mail address: e.sepehr@urmia.ac.ir (E. Sepehr).

http://dx.doi.org/10.1016/j.scitotenv.2022.158180
Received 3 August 2022; Received in revised form 16 August 2022; Accepted 17 August 2022
Available online 23 August 2022
0048-9697/© 2022 Published by Elsevier B.V.
H. Davand et al.
1. Introduction
The increasing growing population along with increasing food supply
caused to consumption of existing water resources in agricultural practices,
especially in arid and semi-arid areas (Peng et al., 2018). Meanwhile, the
water crisis, all over the world, is a serious problem that leads to the use of
non-conventional water resources as complementary supplies (Torit and
Phihusut, 2019). Although wastewater resources may include harmful super-
natants, these are harnessed for agricultural practices through the treatment
and re-use (Muhammad et al., 2019). Nowadays, using wastewater is becom-
ing a very important water resource in central and southeast areas discrepan-
cies between supply and demand are very extreme in these areas.
It is reported that the application of wastewater caused significantly im-
prove in physical and chemical soil properties and nutrient contents of soils
(Amann et al., 2018). de Siqueira Castro et al. (2020) reported that the
plant requirement for nitrogen (N) and phosphorus (P) significantly im-
proved due to wastewater addition. One of the most important strategies
in the re-application of wastewater is P concentration and P recovery
(Kasprzyk et al., 2018). It is reported that >70 % of P for plant growth
can supply from wastewater (Chrispim et al., 2019). Increasing soil P con-
tent can be potentially harmful due to eutrophication and water contamina-
tion (Bashar et al., 2018), however, a wide range of P-rich sources such as
municipal sewage and wastewater are used in all over the world, because
the soil-wastewater chemical interaction is different based on the soil
type and soil characteristics (Wu et al., 2019). Peng et al. (2018) reported
that the P adsorption significantly affects by aluminum and iron oxides,
and Rott et al. (2018) emphasized on the role of organic compounds on P
sorption. Meanwhile, there is a legal limit on wastewater application in
most countries that depends on the type of application.
Various types of chemical techniques are involved in soil P remediation,
and the in situ chemical immobilization is based on the formation and/or
precipitation mechanisms for decreasing dissolved contaminants (Wu
et al., 2019). Based on previous researches (de Siqueira Castro et al.,
2020), the hydrated lime (Ca (OH)2) and calcite (CaCO3) effectively ap-
plied for remediation of P contaminated sites (Torit and Phihusut, 2019),
however, the field conditions are different from laboratory conditions
(Bashar et al., 2018). In this case, the chemical models are helpful to simu-
late the transport of solutes on the laboratory scale (Amann et al., 2018).
However, it is necessary to understanding the P retention mechanisms
and formation of P compounds for modeling the P behavior in soils. Previ-
ous research (Torit and Phihusut, 2019) demonstrated some effective soil
properties such as calcite content and mineralogy on P retention in soils.
Despite the recent advances, a few studies are focused on the mineral re-
action in wastewater-irrigated soils in terms of the adsorption behavior and
stability of P available species in the formed minerals. Meanwhile, the geo-
chemical simulation and modeling of P precipitation based on the carbon-
ate phases is so little. Therefore, the main goal of the present research is
to identify an integrated, holistic, modeling-specific approach that allows
identifying P availability and sorption in calcareous soils irrigated by waste-
water.
2. Material and methods
2.1. Site description
The study was performed in the Boukan province (391 24 N; 31 12 W,
altitude 644 m), West Azarbaijan, Iran. The average monthly temperature
and potential evaporation vary from 1.91 to 23.458 °C, and 1975 to 2001
mm, respectively. The studied area has semi-arid climate conditions
(average rainfall 300 mm). The studied area was affected by wastewater
for two years, from Boukan wastewater treatment center, West Azarbaijan,
Iran which mixed 70 % of domestic origin and 30 % industrial. Although
the wastewater treatment system consists of different parts of treatment
techniques, the effluents are discharged to surface water and agricultural
lands which can affect the soils chemical and physical properties signifi-
cantly (Torit and Phihusut, 2019).
2
Science of the Total Environment 851 (2022) 158180
2.2. Soil analyses
Soil sampling (10 samples, 0–30 cm) was performed in the agricultural
area (Fig. 1), irrigated by wastewater for 2 years. Each soil sample was
consisting of five sub-samples, randomly collected using a steel-less auger.
Ten soil samples were also taken in the same area of the studied zone ran-
domly buyout wastewater treated as control. All soil samples were collected
in plastic bags, labeled, air-dried, and passed through a 2-mm mesh sieve.
The main physicochemical properties, including soil pH and electrical con-
ductivity (EC) (in saturation extract), organic carbon (OC), and soil texture
were measured according to the standard methods (Rott et al., 2018). Soil
calcium carbonate equivalent (CCE) and cation exchange capacity (CEC)
were determined as described by Amann et al. (2018). Available soil P con-
centration (Olsen-P) after extraction by NaHCO3 using UV–Vis spectropho-
tometer (model Varian Carry-220). Soil texture was measured by the
hydrometer method (Aissa-Grouz et al., 2018).
2.3. Wastewater analyses
The wastewater effluent was analyzed for chemical properties. The
catch sampling method is the basic wastewater sampling that is based on
a single sample taken at a specific time. Samples were prepared for analysis
by acid digestion, according to the standard method. Different heavy metals
(Al, As, Cd, Cr, Cu, Co, Hg, Mo, Ni, Pb, Se, Sb, and Zn) content was deter-
mined using atomic absorption spectroscopy. The ionic chromatography
method was carried out to determine the phosphate (PO4), nitrite
(N-NO2), and nitrate (N-NO3) content. The pH and EC of wastewater sam-
ples were undertaken based on the standard methods. To determine of
five-day biochemical oxygen demand (BOD5), samples were adjusted to
pH 6.5–7.5 and stored at 48 °C immediately after collection. Analysis was
carried out according to standard methods using unseeded dilution water
(Standard Methods for the Examination of Water and Wastewater). The
Chemical oxygen demand (COD) in all of the samples was determined
using the routine method of potassium permanganate oxidation according
to the method prescribed by Zhang et al. (2020). An acid-base titration
method (Zheng et al., 2019) was used to determine the inorganic carbon
(IC) in the aqueous phase. This titration method determines total inorganic
−
carbon concentration (carbonate (CO2− 3 ), bicarbonate (HCO3 ), and aque-
ous carbon dioxide (CO2 (aq))) using a 0.01 mol/L hydrochloric acid solu-
tion as a titrant. Mineralization efficiency during the experiments was
evaluated by measuring the decay of the total organic carbon (TOC) using
a TOC analyzer (Shimadzu TOC-VCSH) based on combustion catalytic oxi-
dation at 680 °C.
2.4. Geochemical modeling
Dissolution/precipitation reactions were modeled by PHREEQC (3.4.0
version). The saturation index, SI, was calculated based on the ion activity
product and equilibrium constant (Wu et al., 2019), so the saturated
(equilibrium, SI = 0), undersaturated (mineral dissolution, SI < 0), or su-
persaturated (mineral precipitation, SI > 0) can be determined based on
the given mineral or phase. Two main geochemical reactions are applied
for simulation, containing (1) mineral dissolution until reaching saturation,
and (2) the addition of different moles of CaCO3 and Ca (OH) 2 in different
steps using the methodology described in Benavente et al. (2015), in
isothermal conditions, through REACTION keyword to define irreversible
reactions that transfer specified amounts of elements to or from the aqueous
solution during batch-reaction. The single-ion activity coefficients were ob-
tained using the MINTEQ.v4 thermodynamic database. Table 1 shows the
chemical formula and reaction enthalpies of different phases that included
possible precipitating phases (amorphous tricalcium phosphate (ATCP), di-
basic calcium phosphate dihydrate (DCPD), and octacalcium phosphate
(OCP), calcite (CaCO3) and amorphous silica (SiO2 (a))). Wollastonite
(CaSiO3) and calcium oxide (CaO) were assumed to be the kinetically dis-
solving phases.
H. Davand et al. Science of the Total Environment 851 (2022) 158180

Fig. 1. Location map of the soil sampling area, Boukan province, West Azarbaijan, Iran.

2.5. Adsorption isotherm and modeling
The adsorption experiment was performed based on a standard
method. Briefly, 1 g of soil samples were added to 20 mL of P solutions at
different initial concentrations (0, 10, 20, 30, 40, and 500 mg L−1) for
2 h (25 ± 1 °C) at 1000 rpm and left for 4 h at room temperature for equil-
ibration. The P stock solution was prepared at the first and the P solutions
by different initial concentrations were made. The 0.01 M calcium chloride
(CaCl2) was considered a background solution for the neutralization of
ionic strength. The P concentration in the samples was determined by
using a Spectrophotometer (Varian Carry-220) at a wavelength of
880 nm, after centrifugation (30 min at1000 rpm) and filtration through
No. 42 Whatman filter paper. All experiments were performed in three rep-
lications. The amount of metal ion adsorbed in the soil was calculated by
the following equation (Xia et al., 2020):
Qe ¼ ðC0  C e Þ  V=m
represented as C0 and Ce, respectively. The adsorbate volume and amount
are represented by V and m, respectively.
The adsorption mechanism can be understood by using adsorption iso-
therm models. It is well known that the Langmuir, Freundlich, Temkin, and
Dubinin–Radushkevich (D–R) equations are the most common equilibrium
models. Based on the Langmuir adsorption model, the adsorption can be
specific inhomogeneous sites as a monolayer adsorption process (Qiu
et al., 2019). The Langmuir isotherm equation is defined as (Qiu et al.,
2019):
Qm ¼ ðK L  C e  Sm Þ=ð1 þ K L  C e Þ (2)
where Qm and Ce were described in Eq. (1), and KL is a constant of the
Langmuir eq. (L g−1). The maximum adsorption capacity (mg kg−1) is
shown as Sm. Although the favorability or unfavourability of the adsorption
system can be determined according to the isotherm shape, a dimensionless
(1) constant, RL, is an equilibrium parameter of the Langmuir isotherm that is
expressed as (Qiu et al., 2019):

The mg of ion adsorbed per soil weight (kg) is shown as Qe, and the ini- 1
RL ¼ (3)
tial and equilibrium ion concentration (mg L−1) in the solution are 1 þ K L C0

Table 1
Dissolving and possible precipitating phases are included in the model. K, solubility constant; ΔHr reaction enthalpy.
Compound Formula log K ΔHr (kJ mol−1) Reference

Wollastonite CaSiO3 (s) 12.99 −81.58 PHREEQC software database

Calcium oxide Cao (s) 32.69 −193.91 PHREEQC software database
ATC Ca3(PO4)2 (s) −28.25 −87 PHREEQC software database
DCPD CaHPO4:2H2O (s) −18.99 23 PHREEQC software database
OCP Ca4H(PO4)3 (s) −47.95 −105 PHREEQC software database
Amorphous silica SiO2 (a) 2.71 13.97 PHREEQC software database
Calcite CaCO3 (s) −8.48 −9.61 PHREEQC software database

3
H. Davand et al. Science of the Total Environment 851 (2022) 158180

Table 2 (K), respectively (Dubinin, 1960). The adsorption free energy (E, kJ mol−1)
Physiochemical properties of agricultural and non-treated soil samples. is expressed as follows (Rott et al., 2018):
pH EC CEC CCE OC Olsen-P Sand Silt Clay
pffiffiffiffiffiffiffiffiffiffi
(dS m−1) (cmolc kg−1) (%) (%) (mg kg−1) (%) E ¼ 1= 2βDR (7)
Wastewater irrigated soils
Minimum 7.2 0.25 7.9 5 1.5 20 12 25 11 The chemisorption mechanism is known by E values between 20 and
Maximum 7.9 0.41 21.3 22 3.3 63 64 62 36 40 kJ mol−1, and physisorption and ion exchange processes are known
Average 7.6 0.34 16.8 12.2 2.3 37 26 49 25
CV (%) 0.02 0.13 0.3 0.2 0.3 0.2 0.4 0.2 0.3
by the adsorption energy in the range of 1–8 kJ mol−1 and 8–16 kJ
mol−1, respectively. The experiments were conducted in three replicates.
Non-irrigated soils
Minimum 7.1 0.21 6.4 9 0.5 18 17 25 10
Maximum 7.8 0.33 14.3 24 2.7 42 64 65 37
2.6. Phosphorus buffering indices
Average 7.6 0.29 10.2 12.9 1.1 26 27 49 24
CV (%) 0.02 0.12 0.2 0.2 0.4 0.4 0.3 0.2 0.2 As a point of productivity and environmental pollutions, P fertilizer
EC: electrical conductivity; CEC: cation exchange capacity; CCE: calcium carbonate management should be considered that is affected by soil P buffering indi-
equivalent; OC: organic carbon. ces (Rott et al., 2018). The importance of buffer capacity in characterizing
phosphate availability to plants has been demonstrated in previous re-
search (Muhammad et al., 2019). Buffer capacity will vary according to
the solution concentration at which the isotherm slope is measured, and
where the parameters were described in the previous equations. The iso-
consequently, various indices have been used to express this parameter
therm is linear (RL = 1), irreversible (RL = 0), favorable (0 < RL < 1),
(Freundlich (1906). Different P buffering indices, including the maximum
and unfavorable (RL > 1) based on the parameter (Qiu et al., 2019).
buffering capacity (MBC), Equilibrium buffer capacity (EBC), standard
The Freundlich isotherm model is an empirical equation focused on the
buffering capacity (SBC), and standard phosphorus requirement (SPR)
physical adsorption on surfaces (homogenous and heterogeneous)
were calculated as follow:
(Freundlich, 1906). The Freundlich equation can be expressed as below
Maximum buffer capacity (MBC): maximum slope of the Langmuir
(Qiu et al., 2019):
uniform surface isotherm calculated from KL × Sm.
Standard buffering capacity (SBC): slope of the tangent to the Langmuir
Qm ¼ K F  CeðnÞ
1
(4) adsorption isotherm at an equilibrium phosphorus concentration of 0.3 μg
phosphorus/mL.
Equilibrium buffering capacity (EBC): slope of the Freundlich isotherm
where the adsorbed ions amount (mg kg−1), and equilibrium concentration
at the natural equilibrium phosphorus concentration extracted by 0.01 M
(mg L−1) were shown by Qm, and Ce respectively. The Freundlich constant,
CaCl2.
KF, represents the adsorption capacity (mg g−1), and n is the adsorption in-
Standard phosphorus requirement (SPR): slope of the tangent to the
tensity constant value (dimensionless).
Langmuir adsorption isotherm at an equilibrium phosphorus concentration
Based on the Temkin adsorption equation, the adsorbent–adsorbate in-
of 0.4 mg L−1.
teractions caused to decrease in the adsorption energy by increasing the
surface coverage, linearly. The Temkin equation is expressed as (Rott
2.7. Statistics
et al., 2018):
The statistical relationships were applied to check the normal distribu-
Qm ¼ A þ K T  LnðC e Þ (5) tion of data at first, so the coefficient of determination (R2) and the root
mean square error (RMSE) were used to evaluate the goodness of fit equilib-
rium data. The statistical equations are as follows (Muhammad et al.,
where Qm and Ce are described previously, A (L g−1), is the intercept and KT
2019):
(J mol−1) is the constant value of the Temkin equation. The physical and
chemical adsorption have occurred at KT at <40 kJ mol−1 and >40 kJ P 
mol−1, respectively (Muhammad et al., 2019). qmod − qexp 2
2
The Dubinin–Radushkevich equation is used to distinguish between the R ¼ P  P  ð8Þ
qmod − qexp 2 þ qexp − qmod 2
physical and chemical adsorption of P ions. The D–R isotherm model is
expressed as (Muhammad et al., 2019):
where qmod and qexp are the constant value from the isotherm equation and

 equilibrium capacity from experimental data, respectively. n represents the
Qm ¼ qDR exp −βDR  ε2DR ð6Þ
several concentration series.
The RMSE is expressed as (Rott et al., 2018):
where Qm (mmol g−1) is described previously, the D-R empirical constant
values are qDR (mmol g−1) and βDR (mol2 J−2). The εDR parameter is referred
to as the Polanyi potential and can be calculated as RT ln (1 + (1/Ce)), where qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
R and T are the gas constant (8.314 J mol−1 K−1) and absolute temperature RMSE ¼ ∑ni¼1 ðPi − Oi Þ2 =n ð9Þ

Table 3
Characterization of treated wastewater (average) and comparison of effluent by standard limits.
pH EC BOD5 COD TOC IC PO4 Cd Cu Co Ni Pb Zn
−1 −1 −1
(dS m ) (mg L ) (μg L )

Treated wastewater 7.82 6.04 20 40 33.8 135 7.5 1.20 8.52 0.027 12.12 45.31 325
Standard limita 6.5–8.5 6.0–7.0 30 60 40 15 0.006 100 1000 1000 2000 1000 2000
WHO standard (mg L−1) 6.0–8.5 6.5–7.5 31 50 40 20 – 0.01 0.2 0.1 0.2 5.0 2.0
a
Standard published by the Iranian Department of Environment (DOE) for discharge to agricultural soils (mg L−1).

4
H. Davand et al. Science of the Total Environment 851 (2022) 158180

25
The predicted and measured values, number of initial concentrations (A)
were shown by Pi and Oi and n, respectively. 20
CaO
The better goodness of fit can demonstrate by lower RMSE and higher Ca(SO4).2H2O
15
R2 values (Rott et al., 2018). Optimization of different adsorption parame-

Saturation index
CaSiO3
ters was performed using Solver 2015. 10 Ca4H(PO4)3
CaHPO4.2H2O
5
Ca3(PO4)2
3. Results and discussion
CaCO3
0
SiO2
3.1. Soil and wastewater analyses -5

The main physicochemical properties of agricultural and nonagricul- -10

tural soils are summarized in Table 2. Although the soils were neutral in -15
pH, and nan-saline (EC < 2 dS m−1) in nature, they varied widely in CEC 4 5 6 7 8 9 10

ranging from 10.2 to 16.8 cmolc kg−1 (Table 2). The soil CCE was >5 %
pH
which showed their calcareous nature. Consequently, they were classified
as non-saline and non-sodic (ESP < 15 %), calcareous (CCE > 5 %) soils
6
(B)
4
(Table 2) (Theregowda et al., 2019). The soil texture was all classified as
loam. Soil OC was significantly higher (average 2.3 %) in agricultural 2

Saturation index
soils irrigated by wastewater than in non-treated soils (average 1.1 %). 0
Higher Olsen-P concentration in agricultural soils (average 37 mg kg−1) -2 Zn(OH)2 (am)
may be due to the application of wastewater. According to Torit and Pb(OH)2
-4 ZnOH)2
Phihusut (2019), the microbial activity acting on mineralization regulates Zn(OH)2 (beta)
-6
the levels of P available in soils treated by wastewater. Meanwhile, Wu
et al. (2019) reported an increase in soil OC and P available concentration, -8

following the application of treated wastewater for two years. -10

Table 3 shows the main chemical and biological properties of 4 5 6 7 8 9 10

treated wastewater. Comparing the results by the Iranian Department of

pH
Environment (DOE) and WHO standard limits (Table 3) showed that 25

although the biological parameters such as TOC, COD, and BOD5 were all 20
(C)
less than standard limits, higher values of inorganic carbon (IC), P, and 15
SiO2
N-NO− 3 concentrations were found in the wastewater samples (Table 3). 10 CaCO3
Saturation index

The effluent was much higher in Pb, Zn, Cu, and Ni compared to other 5 CaO

heavy metals (Table 3). The wastewater used contain low quantities of CaSiO3
0
CaHPO4.2H2O
heavy metals generally and thus the pollution of wastewater sample by -5 Ca3 (PO4)2
heavy metals is negligible and does not affect its application. Higher P con- Ca4H(PO4)3
-10
centration (7.5 mg L−1) was found in the wastewater sample than standard
-15
limits (Table 3).
-20

-25
3.2. Geochemical modeling 4 5 6 7 8 9 10

The P bioavailability and chemical behavior in the soil can influence by pH

several factors, mainly precipitation and dissolution (Carrillo et al., 2020).
4
The saturation index is an important factor that is relevant to the P precip- (D)
itation capability in soil based on the solution chemical composition 2
Saturation index

(Pramanik et al., 2020). Phosphorus saturation indices in agricultural soil 0

irrigated by wastewater and non-irrigated soils are shown in Fig. 2. Differ- -2 Zn(OH)2 (am)
ent soil properties result in different P reaction pathways which affect a spe- Zn(OH)2
-4
cific ion retention characteristic (Pap et al., 2020). Zn(OH)2 (am)
-6
Based on the results, most of the solid phases are undersaturated in soils Pb(OH)2

irrigated by wastewater except Ca4H (PO4)3, however, all Ca-solid phases -8

are supersaturated in non-treated soils (Fig. 2). Co-precipitation is probable -10

for Zn and Pb phases that are supersaturated, especially in non-treated soils. 4 5 6 7 8 9 10

Calcium oxyhydroxides are more stable thermodynamically than amor- pH

phous compounds, but short-term kinetics showed the metastable existence
of hydrated, poorly crystalline calcium oxyhydroxides in treated mixtures. Fig. 2. Variation of the saturation index of calcium and heavy metals phases by pH
Based on the Gay-Lussac-Ostwald or Ostwald step rule, the nucleation of in (A, B) non-treated soil and (C, D) agricultural soil irrigated by wastewater using
a more soluble phase (metastable phase) is kinetically favored over less sol- PHREEQC software.
uble analogs (such as calcite) because of the lower interfacial energy be-
tween minerals and water (Peng et al., 2018).

3.3. Adsorption isotherms
Fitting the adsorption data to the different isotherm models is critical
step to assess the adsorption mechanism and describe how solutes interact
with adsorbents (Li et al., 2021). The P adsorption isotherms of wastewater
irrigated, and non-irrigated agricultural soils are shown in Fig. 3.
Non-wastewater irrigated soils had more P adsorption capacity than agri-
cultural soils treated by wastewater (Fig. 3 and Table 4). This indicates
that the P may be more mobile and available in agricultural soils irrigated
by wastewater than in non-treated soils. To better understand of P adsorp-
tion mechanism, the most common isotherm models were fitted to the ad-
sorption data (Table 4). According to the statistical analysis, The Freundlich

5
H. Davand et al. Science of the Total Environment 851 (2022) 158180

250
(A)

200

P-Sorbed (mg kg-1)

150

100 Treated soil

Control

50

0
0 2 4 6 8 10 12 14 16

Equilibrium concentrations (mg L-1)

250 250
(B) (C)

200 200
P-Sorbed (mg kg-1)
P-Sorbed (mg kg-1)

150 150

100 Langmuir 100

Freundlich Langmuir
Temkin Freundlich
Temkin
50 50

0 0
0 2 4 6 8 10 0 2 4 6 8 10 12 14
Equilibrium concentrations (mg L-1) Equilibrium concentrations (mg L-1)

Fig. 3. (A) Phosphorus adsorption in agricultural soil irrigated by wastewater and non-treated soil. (B) Different isotherm models fitted to the experimental data in (B) non-
treated soil, and (C) agricultural soil treated by wastewater.

equation was described that data well (Table 4) in wastewater irrigated and intensity can be assessed by n parameter based on the Freundlich equation
non-treated agricultural soil samples that is based on the reversible P ad- which was 1.35 and 1.50 in agricultural and non-treated soils, respectively.
sorption during the sorption process (Kok et al., 2018). The adsorption Meanwhile, KF values were 34 and 56 L kg−1 in agricultural and non-

Table 4
Calculated isotherm equation parameters for adsorption of phosphorus by agricultural and non-treated soil samples.
Freundlich Langmuir Temkin Dubinin–Radushkevich

KF n R 2
RMSE Qm KL R 2
RMSE A KT R 2
RMSE qDR βDR E R2 RMSE
−1 −1 −1 −1 −1 −1 2 −2 −1
(L mg ) (mg kg ) (Lmg ) (L g ) (J mol ) (mmol g ) (mol J ) (kJ mol )

Wastewater-irrigated soils
Minimum 24 1.02 0.96 0.01 290 0.07 0.96 0.01 0.42 7 0.94 0.03 0.006 2.02 × 10−5 1.57 0.93 0.07
Maximum 49 1.58 0.99 0.03 451 0.17 0.98 0.04 45 92 0.95 0.06 0.010 7.15 × 10−4 2.64 0.95 0.08
Average 34 1.35 0.98 0.02 368 0.12 0.97 0.03 26 59 0.94 0.05 0.008 3.67 × 10−4 2.10 0.94 0.07
CV (%) 0.20 0.20 – – 0.20 0.30 – – 0.31 0.11 – – 0.001 1.01 × 10−4 0.05 – –

Non-irrigated soils
Minimum 44 1.20 0.95 0.01 380 0.11 0.95 0.03 38 65 0.94 0.04 0.002 1.71 × 10−5 3.16 0.94 0.07
Maximum 66 1.66 0.97 0.01 520 0.25 0.98 0.05 66 97 0.97 0.05 0.009 2.03 × 10−5 4.32 0.95 0.09
Average 56 1.50 0.96 0.01 450 0.17 0.97 0.04 59 75 0.96 0.04 0.005 1.87 × 10−5 3.74 0.94 0.08
CV (%) 0.10 0.11 – – 0.21 0.30 – – 0.21 0.22 – – 0.001 1.01 × 10−5 0.09 – –

KF is the Freundlich equation constant; n is the empirical constant of the Freundlich equation; Qm is maximum adsorption capacity; KL is the Langmuir equation constant; A is the
empirical constant; KT is the constant value of the Temkin equation; qDR and βDR are the empirical Dubinin-Radushkevich equation constants, and E is the adsorption free energy.

6
H. Davand et al. Science of the Total Environment 851 (2022) 158180

agricultural soils, which decreased 18.5 % in agricultural soils irrigated by Table 6

wastewater. The same results were found by Li et al. (2020). Correlation coefficients of buffering capacity indices and some soil properties.
According to the Langmuir isotherm parameters, the Qm and KL param- Soil properties Langmuir Freundlich Temkin
eters were equal to 368 and 450 mg kg−1 and 0.12 and 0.17 L mg−1 in ag- KL MBC SBC EBC KT
ricultural wastewater irrigated soils and non-treated soil, respectively
Clay (%) 0.932⁎⁎ 0.914⁎⁎ 0.859⁎⁎ 0.813⁎ 0.771⁎
(Table 4). The maximum P adsorption capacity was significantly higher in
CCE (%) 0.785⁎ 0.706⁎ 0.695⁎ 0.750⁎ 0.781⁎
non-treated than agricultural soils, which indicated more P mobility and CEC (cmolc kg−1) 0.713⁎ 0.719⁎ 0.732⁎ 0.608ns 0.516ns
availability in agricultural soils irrigated by wastewater. The ease of adsorp- OC (%) 0.046ns 0.064ns 0.071ns 0.086ns 0.002ns
tion processes can be predicted by higher KL values (Muisa et al., 2020). ** and * significant at 0.01 and 0.05 probability level
Manikam et al. (2019) reported that blockage of P adsorption sites by ns: not significant at 0.01 probability level.
organic matter caused to decrease in the P adsorption capacity in soils
irrigated by wastewater. Nepfumbada (2021) reported that the maximum
P adsorption was 4 times lower in soils treated with wastewater than It is reported that the determination of buffering indices based on the
in non-treated soils. Muhammad et al. (2019) found that wastewater multivariate regression models is more effective than absorption isotherms
application caused P to be stored by lower energy bonds and its usability (Bashar et al., 2018). So, in the present study, the statistical relationship be-
to increase. tween P buffering capacity indices and physiochemical properties was in-
The statistical parameters (low R2 and high RMSE) showed that the vestigated. According to the results, a significant relationship was found
Temkin isotherm model could not fit to the equilibrium data well between clay content and soil buffering indices (Table 5). The significant
(Table 4). The chemical or physical adsorption mechanisms can be evalu- statistical relationships were not found for other soil physiochemical prop-
ated by using the D-R equation. Based on the results (E < 8 kJ mol−1), erties, so were not included in the model (Table 6).
the physical adsorption mechanism is the main mechanism for P adsorption
both in wastewater irrigated and non-irrigated soils (Table 4). The individ- 3.5. Principal component analyses
uality of the adsorbate and the adsorbent are preserved in the physical ad-
sorption mechanism (Chrispim et al., 2019). The pollution of wastewater irrigated soils with different heavy
metals (HMs) was assessed based on the principal component analyses by
pollution load index (PLI) precisely (Fig. 4). Meanwhile, PCA analyses
3.4. Phosphorus buffering parameters is useful to identify how the variables were interconnected with each
other (Wang et al., 2020). Two significant PCs (Dim 1 and Dim 2) were
It is well known that the P phyto-availability is dependence on soil P detected with total variance of 71.5 % (Fig. 4), which the PC1
buffering capacity (Jiang et al., 2019). Phosphorus fertilizer recommen- (Dim 1) contained 55.8 % of total variables with positive loading on the dif-
dation is usually determined based on the P concentration in soil solu- ferent heavy metals and 15.7 % of the total variability was explained by
tion, that is affected by soil properties (de Siqueira Castro et al., PC2 (Dim 2) (Fig. 4A).
2020). Phosphorus buffering parameters are summarized in Table 5 Biplot graphs represents both the observations and the variables with a
which are calculated from sorption isotherms. Kasprzyk et al. (2018) specific direction along with the specific PC axis (Amann et al., 2018).
reported that prediction of soil buffering parameters using sorption iso- Based on the results (Fig. 4B), the wastewater irrigated, and non-irrigated
therms is easier than desorption, about P availability for plants. Accord- soils contain different regions of the plots with well-defend patterns. The
ing to the results (Table 5), maximum buffering capacity (MBC) varied clustering of irrigation water showed in ellipse indicated the significant im-
from 44.2 L kg−1 to 65 L kg−1 in agricultural soils irrigated by wastewa- pact of treated wastewater irrigation on the heavy metals enriched and pol-
ter and non-irrigated soils, respectively. The average MBC, SBC, and luted soil. The negative side of the PCA showed the lowest content of heavy
EBC were decreased by 32, 32, and 33 %, respectively in treated soils metals which is belongs to the non-irrigated soils.
by wastewater (Table 5).
4. Conclusion

In summary, the irrigation of agricultural soils by wastewater caused

to improving P availability and reduce the P adsorption. Significantly
Table 5 lower P adsorption capacity was found in soils irrigated with wastewa-
Phosphorous buffering parameters in agricultural and non-treated soil samples.
ter. It is possible that high precipitation of calcium oxyhydroxides in
MBC SBC EBC SPR non-treated soils caused to decrease in P mobility, and then potential
(L kg−1) (mg kg−1) bioavailability. Based on the PHREEQC calculations, Zn, and Pb phases
are undersaturated in agricultural soils irrigated by wastewater. Phos-
Wastewater irrigated soils
Minimum 35.4 27.5 25.5 −25.9 phorus release from the labile pool into the soil solution was easier in
Maximum 55 56 52.4 8.2 the wastewater irrigated agricultural soils than non-irrigated soils due
Average 44.2 43 42.6 −3.3 to the lower buffering capacity. The clustering of irrigation water indi-
CV (%) 0.11 0.14 0.10 0.30 cated the significant impact of treated wastewater irrigation on the
Non-irrigated soils heavy metals enriched and polluted soil.
Minimum 45.2 52 53 −19.1
Maximum 80.2 70.3 73.4 14.7 Funding
Average 65 64 64 6.8
CV (%) 0.16 0.23 0.12 0.20
This research was supported by the Urmia University Research Council,
Regression equations R2 West Azarbaijan, Iran.
MBC =19.25 (clay %) – 360.53 0.95⁎⁎
SBC =12.56 (clay %) – 165.92 0.98⁎⁎ CRediT authorship contribution statement
EBC =18.92 (clay %) – 384.03 0.87⁎⁎

MBC: maximum buffering capacity; SBC: standard buffer capacity; EBC: equilibrium H. Davand: methodology, and validation; E. Sepehr and H. Momtaz con-
buffer capacity; SPR: standard phosphorus requirement. ceptualization, methodology, and review; F. Ahmadi: Writing – review &
⁎⁎ Significant at 0.01 probability level. editing, and Visualization.

7
H. Davand et al. Science of the Total Environment 851 (2022) 158180

Fig. 4. Principal Component Analysis (PCA) of enrichment factor (EF) and Pollution load index (PLI) [(A) PCA of the variables showing their major contribution, (B) PCA-
Biplot analysis representing the clustering of textile dyeing wastewater towards major contribution].

Data availability Acknowledgments

Data will be made available on request. The authors are thankful to the Office of Vice Chancellor for Research
and Technology, Urmia University, Iran.
Declaration of competing interest
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