Accepted Manuscript Title: Effect of nanoparticles on kinetics release and fractionation of phosphorus Author: Marzieh Taghipour Mohsen Jalali PII: DOI: Reference:
S0304-3894(14)00790-0 http://dx.doi.org/doi:10.1016/j.jhazmat.2014.09.045 HAZMAT 16293
To appear in:
Journal of Hazardous Materials
Received date: Revised date: Accepted date:
1-7-2014 14-9-2014 15-9-2014
Please cite this article as: M. Taghipour, M. Jalali, Effect of nanoparticles on kinetics release and fractionation of phosphorus, Journal of Hazardous Materials (2014), http://dx.doi.org/10.1016/j.jhazmat.2014.09.045 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Effect of nanoparticles on kinetics release and fractionation of phosphorus Marzieh Taghipour and Mohsen Jalali
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Department of Soil Science, College of Agriculture, Bu-Ali Sina University, Hamedan, Iran
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Highlights
Pseudo second- order model described well P release.
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We examined the effect of nanoparticles on release and fractionation of P in soils.
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PHREEQC could simulate the P release very well in all studied treated soils. After P release, the percentage of organic matter and sulphide–P fraction increased.
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This result reflected that the NPs caused immobilization of P in soils.
Abstract
In this study, we examined the effect of nanoparticles (Al2O3 and TiO2) on kinetics release, fractionation and speciation of phosphorus (P) in some calcareous soils of western Iran. The maximum (average of five soils) (40.3 mg kg−1) and the minimum (10.5 mg kg−1) P were released by control soils and soils plus 3% TiO2, respectively. Pseudo second- order model described well P release. In order to predict and model the effects of NPs on P release, surface
Corresponding author: E-mail address: [email protected], Tel: +988134502726
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complexation model in PHREEQC program was used. The model could simulate the P release very well in all soils. After P release, the percentage of organic matter and sulphide–P fraction increased markedly following NPs addition, while carbonated-P fraction remained the most
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dominant fraction in all soils. In the initial stage of P release the solution samples in all soils and treatments were saturated with respect to strengite, and undersaturated with respect to other
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phosphate minerals. At the end of P release, all solutions were saturated with respect to
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hydroxyapatite and strengite and undersaturated with respect to other phosphate minerals. These results reflected that the NPs caused immobilization of P in soils and reduced the bioavailable P,
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thus, reducing their environment risk.
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Keywords: Phosphorus, Nanoparticles, Fractionation, Release, Speciation, PHREEQC
1. Introduction
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Although phosphate (P) is an essential element for plant growth in soils, excess P release may
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lead to eutrophication and hence deteriorate the water quality [1, 2]. Phosphorus is discharged to
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aquatic environments by several ways such as discharging from wastewater treatment plants, agricultural activities, and weathering rocks. To date, however, most of the previous studies have focused on enhanced P removal in wastewater treatment plants [3-4]. Because it is the only engineering source that can be significantly reduced. Soil is another important P source. Many soils in Iran have received large amounts of P fertilizers and consequently contain high level of available P [5]. The presence of P in groundwater in western Iran was reported by Jalali [6]. Water and soil pollution by P is in rise, and therefore, there is an increasing demand for the removal of P from water and soil. The adsorption of P onto material significantly affects their mobility in natural environments. Some natural materials have been applied to remediate P in soils and aqueous solutions.
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Successful results have been achived using aluminum oxide [7], iron oxide [8-10], fly ash [11], silicates [12-14], and gas concrete [15]. With the rapid development of nanotechnology, nanoparticles (NPs) have been applied in wastewater and soil remediation due to their small
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sizes, large surface areas, and special chemical reactivity. NPs have a large surface-to-volume ratio compared to other bulk materials therefore, enhanced adsorption properties are achieved by
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their use [16]. Metal oxide nanoparticles, such as titanium dioxide (TiO2), aluminum oxide
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(Al2O3) have received increasing interests due to their widespread industrial, medical and military applications [17-18]. Despite the widespread use of NPs in various fields, there is
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limited information about P immobilization by these nanoparticles [16-22], especially in soil. Thus, the objectives of the present study were to determine the effects of NPs (TiO2 and Al2O3)
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on P release rate, fractionation and speciation in some calcareous soils. Moreover, an adsorption
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2.1. Soils and nanoparticles
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2. Materials and methods
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model with PHREEQC program was used to simulate the experimental results.
The five soil samples used in this study were collected from the surface (0-30 cm) soil of Hamadan, western Iran. After being air-dried, the soil samples were passed through a 2 mm sieve. Soil properties were measured by routine methods [23] and reported by Jalali and Ahmadi Mohammad Zinli [24]. Selected chemical and physical properties of the studied soils are given in Table 1. The Olsen-P value ranged from 21.4 to 112.0 mg kg−1, while total P varied from 1079.1 to 1911.9 mg kg−1. Nano-structured TiO2, Al2O3 were purchased (purity, 99.5%) from Tecnan (www.tecnan nanomat.es, Spain) and Nabond (www.nabond.com, China). Characteristics of the NPs were previously reported by Mahdavi et al. [25]. In summary, the particle sizes of TiO2 and Al2O3
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were 12 nm and 11 nm, respectively. The specific surface area (BET) was 45.4 m2 g-1 for TiO2 and 105.8 m2 g-1 for Al2O3.
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2.2. Experiment design Different treatments were used to evaluate the effects of NPs on kinetics release and P
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fractionation. Two NPs (Al2O3 and TiO2) were added to the soil at a rate of 1 and 3%. At the
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first, 1.98 and 1.94 g soil was put into a 50 ml centrifuge tube, then mixed with 0.02 (1% NPs) and 0.06 g (3% NPs) Al2O3 and TiO2, respectively. There were five treatments with 2 replicates:
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control soil (Cs), soil plus 1% Al2O3 (Al-1), soil plus 3% Al2O3 (Al-3), soil plus 1% TiO2 (Ti-1) and soil plus 3% TiO2 (Ti-3). The NPs was completely mixed with the soil to obtain
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homogeneity.
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2.3. Kinetics release of P
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Treated and untreated soils (2 g) were extracted with 20-mL of a 10 mM CaCl2 solutions. The suspensions were shaken for 30 min at 200 rpm in shaking machine, then equilibrated for 0.5, 1,
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4, 16, 28, 40, 52, 64, 76 and 88 h at 25°C, centrifuged at 5000 rpm for 10 min. Afterward, the P concentration in the supernatant was determined by molybdate blue spectrometry method [26].
2.4. Kinetic data analysis
Two kinetic models (pseudo-first-order, pseudo-second-order) were used in order to investigate the release of P with time. The pseudo-first-order can be determined by the following equation [27]: log( − ) = −
1 2.303
(1)
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where qt (mg kg-1) is the amount of P released at time t (h), qe (mg kg-1) is cumulative P released at time t and k1 (h−1) is the rate constant of pseudo-first-order model. The pseudo-second-order model can be expressed in the form [28]:
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1 1 = + 2 2
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(2)
where k2 is the rate constant of second-order adsorption in mg kg-1 h.
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The best fit among the kinetic models is assessed by the linear coefficient of determination (r2)
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and non-linear Chi-square (χ2). The Chi-square test measures the difference between the experimental and model data. This test can be expressed as: ,−, ,
2
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χ2 = ∑
(3)
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where qe,exp is measured P released and qe,cal is the fitted P release from a model. If χ2 were small,
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it would indicate that data from the model are similar to experimental data [29].
2.5. Modelling of P release
In order to predict P release in treated soils, we used surface complexation model in PHREEQC program (version 2.17) [30]. The parameters used to run the model were indicated in Table 2.
2.6. P fractionation
Phosphorus fractionation was carried out before and after release of P from control and treated soils. Soils were sequentially extracted based on the modified Tessier method described by Lucho-Constantino et al. [31]. Phosphorus was separated into four fractions by this method. Easily soluble and exchangeable fractions were extracted by 1 N MgCl2 at pH 7 and P bound to
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carbonates was extracted by CH3COOH/CH3COONa at pH 5. Residue from the previous step was extracted with 0.04 M NH2OH. HCl in 25% CH3COOH and represented the fraction bound to Fe and Mn oxides. Phosphorus bound to organic matter and sulphides were extracted with 8.8
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M H2O2 in 0.02 M HNO3, for 5 h at 85oC followed by addition of a solution of 3.2 M CH3COONH4 in 25% HNO3. After each successive extraction, separation was accomplished by
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centrifugation at 5000 rpm for 10 min and then the P concentration in the supernatant was
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determined.
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2.7. P speciation
The program visual MINTEQ was chosen in this paper as a chemical speciation model for
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calculating saturation index (SI) and P species [32]. Phosphorus speciation was carried out before and after release of P from soils. As input values soil pH, and the concentrations of SO42-,
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NO3-, P, Al, Fe, K, Na, Mg and Ca were used. The MINTEQ runs were performed at 25oC.
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Oversaturation is indicated if SI>0, whereas the solution is under saturated with respect to the
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solid if SI Fe-Al oxides–P (7.2%) > exchangeable-P (1.4%) (Fig. 6).
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These results were similar to the results observed by Zhang et al. [35; Jalali and Ranjbar [49]; Halajnia et al. [50] and Alvarez-Rogel et al. [51] who found that P was bounded to carbonates,
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fraction for P in soils.
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whereas Motavalli and Miles [52] and Richards et al. [53] reported that Fe-Al bound was largest
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After P release, distribution of P in control soils follows the sequence of: carbonated-P (62.5% to 77.1%) > organic matter and sulphide -P (16.4% to 37.4%) > Fe-Al oxides–P (4.3% to 7.2%) > exchangeable-P (0.2% to 1.3%). With the increase of NPs, the exchangeable, Fe-Al bound and carbonated-P decreased from 1.1% (control) to 0.85% (3% TiO2), 5.4% (control) to 3.5% (3% TiO2) and 67.5% (control) to 56.2% (3% TiO2), respectively, while the organic matter and sulphide-P were increased from 25.9% (control) to 39.4% (3% TiO2). Thus, carbonated- P fraction remained the most dominant fraction in all soils and all treatments and organic matter and sulphide–P fraction increased markedly following NPs addition. This result reflected that the NPs caused immobilization of P in soils and reduced the available P, consequently reducing their environment risk.
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Liu and Zhao [54] studied the effects of iron phosphate NPs on Pb2+ fraction in soils. They found that NP treatments resulted in significant shift in soil-bound Pb2+ fraction from more easily extractable Pb2+ to the least available form (the residual Pb2+). Cui et al. [55] reported that the
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applications of nano hydroxyapatite in a contaminated soil significantly decreased exchangeable fraction of Cu and Cd and transformed them from active to inactive fractions. There are no
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published data on the effect of NPs on P fractionation in soils, thus, these results cannot be
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compared.
The relationships between the released P from soils (Cs, Al-1 and Ti-1) and different P fractions
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in the soils were shown in Figure 7. It seemed that the amounts of P released was significantly correlated with total- P (r = 0.66 to 0.88) and Fe- Al oxide- P (r = 0.31 to 0.33), but was not
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correlated with exchangeable, carbonated and organic matter and sulphide- P fractions.
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Furthermore, in treated soils with 3% of Al2O3 and TiO2, the amount of P released was correlated
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with total- P and Fe- Al oxide- P fractions (data not shown). This means that Fe- Al oxide- P might be easily released from the soils, and it was main contributors to the P-release source in
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the control and treated soils. This was very similar to the previous studies [35; 56].
3.4. Effect of nanoparticle treatment on P speciation in soils In all soils treated with NPs and in control soils, in the initial stage of P release the solution samples were saturated with respect to strengite (Fe(OH)2 H2PO4) (SI= 1.23) and undersaturated with respect to other phosphate minerals. At the end of P release, all solutions were saturated with hydroxyapatite (HA, Ca5(PO4)3OH) (SI= 5.61) and strengite (SI= 2.38). Taghipour and Jalali [57] investigated P species controlling P release by organic acids. They indicated that soil P release was controlled by a combination of octacalcium phosphate, dicalcium phosphate dehydrate, dicalcium phosphate and magnesium phosphate minerals.
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The percentage distribution of P species in control and treated solutions (initial stage and end of P release) from the MINTEQ output is summarized in Table 6. In the initial stage of release of P between 47.9 (Ti-1) to 85.5% (Ti-1), 4.6 (Ti-1) to 26.7% (Ti-3) and 3.4% (Ti-1) to 19.2% (Ti-1)
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of total P in solutions present as H2PO4-, HPO42- and CaHPO4, respectively. At the end of P release, the percentage of HPO42- and CaHPO4 in all soils and all treatments increased, while the
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percentage of H2PO4- decreased. Our results therefore apparently suggest a decrease of
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availability of P after the addition of NPs in the soils.
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4. Conclusion
The present study was conducted to evaluate the effect of NPs on kinetics release and
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fractionation of P in some calcareous soils. The addition of NPs to soil reduced P release with time. Kinetic analyses indicated that the time-dependent P release followed pseudo-second-order
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kinetics. We used surface complexation model to simulate the release of P from treated soils.
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The amount of P bounded with organic matter and sulphide (stable fraction) were increased
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following NPs addition. Thus, the results indicated that the addition of NPs reduces P release from soil and reduces its environment risk. But it should be noted that although application of these materials can be more efficient than other adsorbents for P removal from soils and aqueous solution, but some problems with Al and Ti toxicity may arise after their application. In order to provide an adequate explanation for the effects of TiO2 and Al2O3 NPs on the release of P, it is inevitable to analyze the release of Al, Ti and their effects on plants, microorganisms and groundwater pollution.
Acknowledgement
The authors express their sincere thanks to the reviewers.
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pH
EC
OM
Clay
dS m-1
Sand
CaCO3
Olsen-P
Total P
mg kg-1
%
cr
Soil no.
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Table 1 Some chemical and physical properties of studied soils [24]
6.7
0.1
2.1
15.2
61.4
3.7
21.4
1079.1
2
7.1
0.2
1.2
19.2
51.4
13.3
71.0
1674.1
3
7.5
0.3
3.1
45.8
24.2
19.6
70.0
1137.5
4
7.3
0.2
1.1
24.8
59.0
8.5
112.0
1911.9
5
7.1
0.2
1.9
23.2
59.7
4.9
94.0
1818.0
Ac ce p
te
d
M
an
us
1
Page 20 of 32
Table 2 Surface parameters of NPs and equilibrium constants used to simulate P desorption
TiO2
Al2O3
45.4a
105.8a
Surface parameters
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Specific surface area (m2 g-1) Site density (sites nm-2)
cr
2.5b 1.7c
Surface complexation reactions
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SurfcOH + H+ = SurfcOH2+
SurfcOH + PO4-3 + 3H+ = SurfcH2PO4 + H2O
M
SurfcOH + PO4-3 + 2H+ = SurfcHPO4- + H2O
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SurfcOH = SurfcO- + H+
[58]
c
[21]
d
[59]
-9.2 g
15.6 e
14.2 e
22.1 e
24.4 e
29.7f
26.5 f
te
[25]
b
-8.7 d
Ac ce p
a
7.9 g
d
SurfcOH + PO4-3 + H+ = SurfcPO4-2 + H2O
3.9 d
e
[19]
f
Obtained from Fitting
g
[60]
Page 21 of 32
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Table 3 Amounts of P released (mg kg−1) (± SD) from soils (Cs=untreated soil, Al-1=1% Al2O3 plus soil, Al-3= 3% Al2O3 plus soil, Ti-1= 1% TiO2 plus soil, Ti-3=3% TiO2 plus soil) Soil no.
Cs
Al-1
Al-3
Ti-1
1
34.9 ± 1.8a
11.8 ±3.5b
10.2 ±4.7b
10.7 ±3.5b
2
40.6 ± 3.5a
18.3 ±4.3b
11.9 ±3.6d
14.5 ±1.8c
3
30.4 ± 2.3a
10.9 ±5.3b
9.6 ± 0.7b
10.1 ±3.9b
4
42.6 ± 3.4a
19.5 ±6.4b
13.0 ±3.1d
16.0 ±0.3c
11.2 ±0.8d
5
53.3 ± 2.9a
22.9 ±3.2b
15.8 ±2.1d
18.5 ±2.7c
12.6 ±2.3e
Ti-3
9.6 ±0.9b
9.0 ±2.4b
an
us
cr
10.2 ±3.9d
Ac ce p
te
d
M
Data followed by the same letter in the row are not significantly different at the P
S0304-3894(14)00790-0 http://dx.doi.org/doi:10.1016/j.jhazmat.2014.09.045 HAZMAT 16293
To appear in:
Journal of Hazardous Materials
Received date: Revised date: Accepted date:
1-7-2014 14-9-2014 15-9-2014
Please cite this article as: M. Taghipour, M. Jalali, Effect of nanoparticles on kinetics release and fractionation of phosphorus, Journal of Hazardous Materials (2014), http://dx.doi.org/10.1016/j.jhazmat.2014.09.045 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Effect of nanoparticles on kinetics release and fractionation of phosphorus Marzieh Taghipour and Mohsen Jalali
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Department of Soil Science, College of Agriculture, Bu-Ali Sina University, Hamedan, Iran
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Highlights
Pseudo second- order model described well P release.
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We examined the effect of nanoparticles on release and fractionation of P in soils.
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PHREEQC could simulate the P release very well in all studied treated soils. After P release, the percentage of organic matter and sulphide–P fraction increased.
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This result reflected that the NPs caused immobilization of P in soils.
Abstract
In this study, we examined the effect of nanoparticles (Al2O3 and TiO2) on kinetics release, fractionation and speciation of phosphorus (P) in some calcareous soils of western Iran. The maximum (average of five soils) (40.3 mg kg−1) and the minimum (10.5 mg kg−1) P were released by control soils and soils plus 3% TiO2, respectively. Pseudo second- order model described well P release. In order to predict and model the effects of NPs on P release, surface
Corresponding author: E-mail address: [email protected], Tel: +988134502726
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complexation model in PHREEQC program was used. The model could simulate the P release very well in all soils. After P release, the percentage of organic matter and sulphide–P fraction increased markedly following NPs addition, while carbonated-P fraction remained the most
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dominant fraction in all soils. In the initial stage of P release the solution samples in all soils and treatments were saturated with respect to strengite, and undersaturated with respect to other
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phosphate minerals. At the end of P release, all solutions were saturated with respect to
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hydroxyapatite and strengite and undersaturated with respect to other phosphate minerals. These results reflected that the NPs caused immobilization of P in soils and reduced the bioavailable P,
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thus, reducing their environment risk.
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Keywords: Phosphorus, Nanoparticles, Fractionation, Release, Speciation, PHREEQC
1. Introduction
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Although phosphate (P) is an essential element for plant growth in soils, excess P release may
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lead to eutrophication and hence deteriorate the water quality [1, 2]. Phosphorus is discharged to
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aquatic environments by several ways such as discharging from wastewater treatment plants, agricultural activities, and weathering rocks. To date, however, most of the previous studies have focused on enhanced P removal in wastewater treatment plants [3-4]. Because it is the only engineering source that can be significantly reduced. Soil is another important P source. Many soils in Iran have received large amounts of P fertilizers and consequently contain high level of available P [5]. The presence of P in groundwater in western Iran was reported by Jalali [6]. Water and soil pollution by P is in rise, and therefore, there is an increasing demand for the removal of P from water and soil. The adsorption of P onto material significantly affects their mobility in natural environments. Some natural materials have been applied to remediate P in soils and aqueous solutions.
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Successful results have been achived using aluminum oxide [7], iron oxide [8-10], fly ash [11], silicates [12-14], and gas concrete [15]. With the rapid development of nanotechnology, nanoparticles (NPs) have been applied in wastewater and soil remediation due to their small
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sizes, large surface areas, and special chemical reactivity. NPs have a large surface-to-volume ratio compared to other bulk materials therefore, enhanced adsorption properties are achieved by
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their use [16]. Metal oxide nanoparticles, such as titanium dioxide (TiO2), aluminum oxide
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(Al2O3) have received increasing interests due to their widespread industrial, medical and military applications [17-18]. Despite the widespread use of NPs in various fields, there is
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limited information about P immobilization by these nanoparticles [16-22], especially in soil. Thus, the objectives of the present study were to determine the effects of NPs (TiO2 and Al2O3)
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on P release rate, fractionation and speciation in some calcareous soils. Moreover, an adsorption
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2.1. Soils and nanoparticles
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2. Materials and methods
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model with PHREEQC program was used to simulate the experimental results.
The five soil samples used in this study were collected from the surface (0-30 cm) soil of Hamadan, western Iran. After being air-dried, the soil samples were passed through a 2 mm sieve. Soil properties were measured by routine methods [23] and reported by Jalali and Ahmadi Mohammad Zinli [24]. Selected chemical and physical properties of the studied soils are given in Table 1. The Olsen-P value ranged from 21.4 to 112.0 mg kg−1, while total P varied from 1079.1 to 1911.9 mg kg−1. Nano-structured TiO2, Al2O3 were purchased (purity, 99.5%) from Tecnan (www.tecnan nanomat.es, Spain) and Nabond (www.nabond.com, China). Characteristics of the NPs were previously reported by Mahdavi et al. [25]. In summary, the particle sizes of TiO2 and Al2O3
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were 12 nm and 11 nm, respectively. The specific surface area (BET) was 45.4 m2 g-1 for TiO2 and 105.8 m2 g-1 for Al2O3.
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2.2. Experiment design Different treatments were used to evaluate the effects of NPs on kinetics release and P
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fractionation. Two NPs (Al2O3 and TiO2) were added to the soil at a rate of 1 and 3%. At the
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first, 1.98 and 1.94 g soil was put into a 50 ml centrifuge tube, then mixed with 0.02 (1% NPs) and 0.06 g (3% NPs) Al2O3 and TiO2, respectively. There were five treatments with 2 replicates:
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control soil (Cs), soil plus 1% Al2O3 (Al-1), soil plus 3% Al2O3 (Al-3), soil plus 1% TiO2 (Ti-1) and soil plus 3% TiO2 (Ti-3). The NPs was completely mixed with the soil to obtain
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homogeneity.
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2.3. Kinetics release of P
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Treated and untreated soils (2 g) were extracted with 20-mL of a 10 mM CaCl2 solutions. The suspensions were shaken for 30 min at 200 rpm in shaking machine, then equilibrated for 0.5, 1,
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4, 16, 28, 40, 52, 64, 76 and 88 h at 25°C, centrifuged at 5000 rpm for 10 min. Afterward, the P concentration in the supernatant was determined by molybdate blue spectrometry method [26].
2.4. Kinetic data analysis
Two kinetic models (pseudo-first-order, pseudo-second-order) were used in order to investigate the release of P with time. The pseudo-first-order can be determined by the following equation [27]: log( − ) = −
1 2.303
(1)
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where qt (mg kg-1) is the amount of P released at time t (h), qe (mg kg-1) is cumulative P released at time t and k1 (h−1) is the rate constant of pseudo-first-order model. The pseudo-second-order model can be expressed in the form [28]:
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1 1 = + 2 2
cr
(2)
where k2 is the rate constant of second-order adsorption in mg kg-1 h.
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The best fit among the kinetic models is assessed by the linear coefficient of determination (r2)
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and non-linear Chi-square (χ2). The Chi-square test measures the difference between the experimental and model data. This test can be expressed as: ,−, ,
2
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χ2 = ∑
(3)
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where qe,exp is measured P released and qe,cal is the fitted P release from a model. If χ2 were small,
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it would indicate that data from the model are similar to experimental data [29].
2.5. Modelling of P release
In order to predict P release in treated soils, we used surface complexation model in PHREEQC program (version 2.17) [30]. The parameters used to run the model were indicated in Table 2.
2.6. P fractionation
Phosphorus fractionation was carried out before and after release of P from control and treated soils. Soils were sequentially extracted based on the modified Tessier method described by Lucho-Constantino et al. [31]. Phosphorus was separated into four fractions by this method. Easily soluble and exchangeable fractions were extracted by 1 N MgCl2 at pH 7 and P bound to
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carbonates was extracted by CH3COOH/CH3COONa at pH 5. Residue from the previous step was extracted with 0.04 M NH2OH. HCl in 25% CH3COOH and represented the fraction bound to Fe and Mn oxides. Phosphorus bound to organic matter and sulphides were extracted with 8.8
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M H2O2 in 0.02 M HNO3, for 5 h at 85oC followed by addition of a solution of 3.2 M CH3COONH4 in 25% HNO3. After each successive extraction, separation was accomplished by
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centrifugation at 5000 rpm for 10 min and then the P concentration in the supernatant was
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determined.
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2.7. P speciation
The program visual MINTEQ was chosen in this paper as a chemical speciation model for
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calculating saturation index (SI) and P species [32]. Phosphorus speciation was carried out before and after release of P from soils. As input values soil pH, and the concentrations of SO42-,
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NO3-, P, Al, Fe, K, Na, Mg and Ca were used. The MINTEQ runs were performed at 25oC.
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Oversaturation is indicated if SI>0, whereas the solution is under saturated with respect to the
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solid if SI Fe-Al oxides–P (7.2%) > exchangeable-P (1.4%) (Fig. 6).
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These results were similar to the results observed by Zhang et al. [35; Jalali and Ranjbar [49]; Halajnia et al. [50] and Alvarez-Rogel et al. [51] who found that P was bounded to carbonates,
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fraction for P in soils.
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whereas Motavalli and Miles [52] and Richards et al. [53] reported that Fe-Al bound was largest
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After P release, distribution of P in control soils follows the sequence of: carbonated-P (62.5% to 77.1%) > organic matter and sulphide -P (16.4% to 37.4%) > Fe-Al oxides–P (4.3% to 7.2%) > exchangeable-P (0.2% to 1.3%). With the increase of NPs, the exchangeable, Fe-Al bound and carbonated-P decreased from 1.1% (control) to 0.85% (3% TiO2), 5.4% (control) to 3.5% (3% TiO2) and 67.5% (control) to 56.2% (3% TiO2), respectively, while the organic matter and sulphide-P were increased from 25.9% (control) to 39.4% (3% TiO2). Thus, carbonated- P fraction remained the most dominant fraction in all soils and all treatments and organic matter and sulphide–P fraction increased markedly following NPs addition. This result reflected that the NPs caused immobilization of P in soils and reduced the available P, consequently reducing their environment risk.
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Liu and Zhao [54] studied the effects of iron phosphate NPs on Pb2+ fraction in soils. They found that NP treatments resulted in significant shift in soil-bound Pb2+ fraction from more easily extractable Pb2+ to the least available form (the residual Pb2+). Cui et al. [55] reported that the
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applications of nano hydroxyapatite in a contaminated soil significantly decreased exchangeable fraction of Cu and Cd and transformed them from active to inactive fractions. There are no
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published data on the effect of NPs on P fractionation in soils, thus, these results cannot be
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compared.
The relationships between the released P from soils (Cs, Al-1 and Ti-1) and different P fractions
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in the soils were shown in Figure 7. It seemed that the amounts of P released was significantly correlated with total- P (r = 0.66 to 0.88) and Fe- Al oxide- P (r = 0.31 to 0.33), but was not
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correlated with exchangeable, carbonated and organic matter and sulphide- P fractions.
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Furthermore, in treated soils with 3% of Al2O3 and TiO2, the amount of P released was correlated
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with total- P and Fe- Al oxide- P fractions (data not shown). This means that Fe- Al oxide- P might be easily released from the soils, and it was main contributors to the P-release source in
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the control and treated soils. This was very similar to the previous studies [35; 56].
3.4. Effect of nanoparticle treatment on P speciation in soils In all soils treated with NPs and in control soils, in the initial stage of P release the solution samples were saturated with respect to strengite (Fe(OH)2 H2PO4) (SI= 1.23) and undersaturated with respect to other phosphate minerals. At the end of P release, all solutions were saturated with hydroxyapatite (HA, Ca5(PO4)3OH) (SI= 5.61) and strengite (SI= 2.38). Taghipour and Jalali [57] investigated P species controlling P release by organic acids. They indicated that soil P release was controlled by a combination of octacalcium phosphate, dicalcium phosphate dehydrate, dicalcium phosphate and magnesium phosphate minerals.
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The percentage distribution of P species in control and treated solutions (initial stage and end of P release) from the MINTEQ output is summarized in Table 6. In the initial stage of release of P between 47.9 (Ti-1) to 85.5% (Ti-1), 4.6 (Ti-1) to 26.7% (Ti-3) and 3.4% (Ti-1) to 19.2% (Ti-1)
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of total P in solutions present as H2PO4-, HPO42- and CaHPO4, respectively. At the end of P release, the percentage of HPO42- and CaHPO4 in all soils and all treatments increased, while the
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percentage of H2PO4- decreased. Our results therefore apparently suggest a decrease of
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availability of P after the addition of NPs in the soils.
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4. Conclusion
The present study was conducted to evaluate the effect of NPs on kinetics release and
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fractionation of P in some calcareous soils. The addition of NPs to soil reduced P release with time. Kinetic analyses indicated that the time-dependent P release followed pseudo-second-order
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kinetics. We used surface complexation model to simulate the release of P from treated soils.
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The amount of P bounded with organic matter and sulphide (stable fraction) were increased
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following NPs addition. Thus, the results indicated that the addition of NPs reduces P release from soil and reduces its environment risk. But it should be noted that although application of these materials can be more efficient than other adsorbents for P removal from soils and aqueous solution, but some problems with Al and Ti toxicity may arise after their application. In order to provide an adequate explanation for the effects of TiO2 and Al2O3 NPs on the release of P, it is inevitable to analyze the release of Al, Ti and their effects on plants, microorganisms and groundwater pollution.
Acknowledgement
The authors express their sincere thanks to the reviewers.
Reference
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cr
phosphorus due to long-term corn production. Can. J. Soil Sci. 75 (1995) 311–318.
us
[54] R. Liu, D. Zhao, Reducing leachability and bioaccessibility of lead in soils using a new class of stabilized iron phosphate nanoparticles. Water Res. 41 (2007) 2491–2502.
an
[55] H. Cui, J. Zhou, Q. Zhao, Y. Si, J. Mao, G. Fang, J. Liang, Fractions of Cu, Cd, and enzyme activities in a contaminated soil as affected by applications of micro- and nanohydroxyapatite. J.
M
Soils Sediments 13 (2013) 742–752.
[56] L.M. Ma, M. Zhang, Y.H. Teng, Characteristics of phosphorous release from soil in
d
periodic alternately waterlogged and drained environments at WLFZ of the three gorges
te
reservoir. Environ. Sci. 29 (2008) 1035- 1039.
Ac ce p
[57] M. Taghipour, M. Jalali, Effect of low-molecular-weight organic acids on kinetics release and fractionation of phosphorus in some calcareous soils of western Iran. Environ. Monit. Assess. 185 (2013) 5471-82.
[58] A. Torrents, Ph.D. Thesis, Department of Geography and Environmental Engineering, The Johns Hopkins University, Baltimore, MD, 1992. [59] A.T. Stone, A. Torrents, J. Smolen, D. Vasudenvan, J. Hadley, Adsorption of organic compounds possessing ligand donor groups at the oxide/water interface. Environ. Sci. Technol. 27 (1993) 895-909. [60] J.P. Morel, N. Marmier, C. Hurel, N. Morel-Desrosiers, Effect of temperature on the acid– base properties of the alumina surface: Microcalorimetry and acid–base titration experiments. J. Colloid Interface Sci. 298 (2006) 773-779.
Page 19 of 32
pH
EC
OM
Clay
dS m-1
Sand
CaCO3
Olsen-P
Total P
mg kg-1
%
cr
Soil no.
ip t
Table 1 Some chemical and physical properties of studied soils [24]
6.7
0.1
2.1
15.2
61.4
3.7
21.4
1079.1
2
7.1
0.2
1.2
19.2
51.4
13.3
71.0
1674.1
3
7.5
0.3
3.1
45.8
24.2
19.6
70.0
1137.5
4
7.3
0.2
1.1
24.8
59.0
8.5
112.0
1911.9
5
7.1
0.2
1.9
23.2
59.7
4.9
94.0
1818.0
Ac ce p
te
d
M
an
us
1
Page 20 of 32
Table 2 Surface parameters of NPs and equilibrium constants used to simulate P desorption
TiO2
Al2O3
45.4a
105.8a
Surface parameters
ip t
Specific surface area (m2 g-1) Site density (sites nm-2)
cr
2.5b 1.7c
Surface complexation reactions
us
SurfcOH + H+ = SurfcOH2+
SurfcOH + PO4-3 + 3H+ = SurfcH2PO4 + H2O
M
SurfcOH + PO4-3 + 2H+ = SurfcHPO4- + H2O
an
SurfcOH = SurfcO- + H+
[58]
c
[21]
d
[59]
-9.2 g
15.6 e
14.2 e
22.1 e
24.4 e
29.7f
26.5 f
te
[25]
b
-8.7 d
Ac ce p
a
7.9 g
d
SurfcOH + PO4-3 + H+ = SurfcPO4-2 + H2O
3.9 d
e
[19]
f
Obtained from Fitting
g
[60]
Page 21 of 32
ip t
Table 3 Amounts of P released (mg kg−1) (± SD) from soils (Cs=untreated soil, Al-1=1% Al2O3 plus soil, Al-3= 3% Al2O3 plus soil, Ti-1= 1% TiO2 plus soil, Ti-3=3% TiO2 plus soil) Soil no.
Cs
Al-1
Al-3
Ti-1
1
34.9 ± 1.8a
11.8 ±3.5b
10.2 ±4.7b
10.7 ±3.5b
2
40.6 ± 3.5a
18.3 ±4.3b
11.9 ±3.6d
14.5 ±1.8c
3
30.4 ± 2.3a
10.9 ±5.3b
9.6 ± 0.7b
10.1 ±3.9b
4
42.6 ± 3.4a
19.5 ±6.4b
13.0 ±3.1d
16.0 ±0.3c
11.2 ±0.8d
5
53.3 ± 2.9a
22.9 ±3.2b
15.8 ±2.1d
18.5 ±2.7c
12.6 ±2.3e
Ti-3
9.6 ±0.9b
9.0 ±2.4b
an
us
cr
10.2 ±3.9d
Ac ce p
te
d
M
Data followed by the same letter in the row are not significantly different at the P
