Accepted Manuscript

Phosphorus Removal from Aqueous Solution by Nanoscale Zero Valent Iron in

the Presence of Copper Chloride

Osama Eljamal, Ahmed M.E. Khalil, Yuji Sugihara, Nobuhiro Matsunaga

PII: S1385-8947(16)30153-X
DOI: http://dx.doi.org/10.1016/j.cej.2016.02.052
Reference: CEJ 14785

To appear in: Chemical Engineering Journal

Received Date: 18 December 2015

Revised Date: 14 February 2016
Accepted Date: 16 February 2016

Please cite this article as: O. Eljamal, A.M.E. Khalil, Y. Sugihara, N. Matsunaga, Phosphorus Removal from
Aqueous Solution by Nanoscale Zero Valent Iron in the Presence of Copper Chloride, Chemical Engineering
Journal (2016), doi: http://dx.doi.org/10.1016/j.cej.2016.02.052

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Phosphorus Removal from Aqueous Solution by Nanoscale

Zero Valent Iron in the Presence of Copper Chloride

Osama Eljamal *a, Ahmed M. E. Khalil a, b, Yuji Sugihara a and Nobuhiro Matsunaga a
a Department of Earth System Science and Technology, Interdisciplinary Graduate School of

Engineering Sciences, Kyushu University, 6-1 Kasugakoen, Kasuga-shi, Fukuoka, 816-8580,

Japan.b Department of Chemical Engineering, Faculty of Engineering, Cairo University, Giza

12613, Egypt

* Corresponding author. Tel/Fax: +81 92 583 8387,

E-mail address: osama-eljamal@kyudai.jp

Abstract. This study investigates the adsorption of phosphorus by nanoscale zero valent iron

(NZVI) in the presence of copper chloride. The NZVI used for the experiments was

synthesized under optimum conditions using the chemical reduction method. The NZVI was

characterized by transmission electron microscopy, X-ray diffraction,

Brunauer–Emmett–Teller surface characterization and particle size analysis. Batch

experiments were performed under different conditions to study the effect of parameters such

as initial phosphorus concentration, copper chloride load, aerobic, anaerobic, pH and

recovery. The results indicated that the presence of copper chloride effectively enhanced the

adsorption capacity of phosphorus as it produced copper ferrite spinel on NZVI particles’

surface which can adsorb phosphorus and increase its rate of adsorption, and also it

stimulated NZVI corrosion. The adsorption capacity of phosphorus reached 50 mg PO43--P/ g

NZVI in the presence of copper chloride while NZVI without copper chloride reached the

maximum adsorption capacity of 28 mg PO43--P/ g NZVI. Phosphorus recovery batch

1
experiments results showed that the maximum phosphorus recovery achieved at pH 12 was

60 %. But the recovery of phosphorus increased by increasing the molarity of the alkaline

medium (NaOH) solution used for recovery. A complete recovery of phosphorus was gained

using 1 M NaOH solution.

Keywords: Phosphorus removal; Nanoscale zero valent iron; Phosphate recovery; Adsorption;

Bimetallic iron.

1. Introduction

Discharges of wastewater, agricultural areas runoff and landfill leachate into the water bodies

are the most common pollution source of chemical compounds and constitutes the main risk

for reduced water quality [1-3]. One of these pollutants is phosphorus (P), which can be

found in water with forms of orthophosphates, polyphosphates, and organic phosphates [4, 5].

High level of phosphorus concentration in water bodies is known to cause eutrophication [6].

Eutrophication results in the depletion of oxygen that leads to fish death and effects on

aquatic environment. On the other hand, phosphorus is an essential nutrient for all forms of

life and cannot be replaced by other species. Phosphorus is mostly obtained from mined rock

phosphate and existing rock phosphate reserves could be exhausted in next 50 – 100 years [7,

8].

In order to reduce the negative effects of overloading the ecosystems with phosphorus and

recover it for reuse as fertilizers [5], it is necessary to investigate various techniques and

materials that could contribute to the removal of phosphorus.

Nanotechnology offers the potential of an efficient removal of pollutants from water.

Recently, nanoparticles used for removal of chemical substances include metals, nutrients,

organics and inorganics [9]. Amongst this promising class of remediation agents, nanoscale

2
zero valent iron has received the most attention and has been shown to effectively degrade a

wide spectrum of water pollutants, such as halogenated hydrocarbons, nitroaromatic

compounds, azo dyes, perchlorate, nitrate, hexavalent chromium and various heavy metal

ions [10-14]. NZVI particles have extremely small size, high surface area to volume ratio,

surface modifiability, and excellent magnetic properties. Several studies reported that NZVI

particles are very effective for the transformation and detoxification of a wide variety of

common environmental pollutants [11, 15, 16]. Modified NZVI particles, such as catalyzed

and supported nanoparticles, have been synthesized to further enhance the speed and

efficiency of remediation.

Regarding recent reports about phosphorus adsorption, Tu and You [17] reported that

nano-bimetal ferrites could remove phosphorus from water. The results indicated that the

maximum phosphorus adsorption capacity was 13.5 mg/g at initial pH 2.64. Another study

[18] reported that using NZVI as adsorbent could efficiently increase the maximum

phosphorus adsorption capacity to 24.38 mg/g at initial pH 4.0.

However, most of studies focused on removal of heavy metals by NZVI and very few of the

reports investigated on removal of phosphorus by NZVI [18], and to the best of the authors’

knowledge, there is no literature on phosphorus removal by NZVI in the presence of copper

chloride.

The objective of this work is to investigate the effect of adding copper chloride to NZVI in

order to enhance removal of phosphorus/phosphate from water without intoxicating it. Batch

experiments were conducted for different phosphorus concentrations by adding different

amounts of copper chloride to NZVI to investigate the optimal ratio of copper chloride to

NZVI. Besides, pH effect on adsorption and the recovery of phosphorus were further

investigated.

3
2. Materials and methods

2.1. Materials

Sodium borohydride (NaBH4, 98.0%, Sigma-Aldrich Inc., USA), ferric chloride hexahydrate

(FeCl3.6H2O, 99.0%, Junsei Chemical Co., Japan), potassium dihydrogenphosphate (KH2PO4

99.5%, Kanto Chemical Co., Japan), sodium hydroxide (NaOH, 97%, Wako Co., Japan)

hydrochloric acid (HCl, 35–37%, Wako Co., Japan), and anhydrous copper chloride (CuCl2,

99.9%, Aldrich Inc., USA) were used as received.

2.2. Synthesis of NZVI

NZVI was synthesized as depicted from the following chemical reaction (Eq. 1) [19]

2 FeCl3 + 6 NaBH4 + 18 H2O → 2 Fe0 + 21 H2 + 6 B(OH)3 + 6 NaCl (1)

Solution 1 was prepared by dissolving 5 g of Sodium borohydride in 120 ml of deoxygenated

deionized water (DIW). Solution 2 was prepared by dissolving 5 g of ferric chloride

hexahydrate in 120 ml of DIW in separate flask. Then solution 1 was added to solution 2 using

a roller pump at a rate of 1 L/h with vigorous stirring at 250 rpm under nitrogen atmosphere at

constant temperature 25 ± 0.5 oC using water bath. The synthesis was conducted in 500 mL

four-neck glass flask and left 20 minutes for aging to complete the reaction. The synthesized

iron particles have been filtered by vacuum filter, washed with DIW three times and

immediately used in batch experiments.

2.3. Characterization of NZVI

The physical properties of the synthesized NZVI were thoroughly investigated through our

research. Brunauer–Emmett–Teller (BET) surface area was determined using N2 adsorption at

77 K on a specific surface area analyser (Micromeritics 3Flex, USA). The morphology and

nano image of the synthesized NZVI were obtained on a transmission electron microscope

4
(TEM, JEM-ARM 200F, JEOL Co., Japan). NZVI. Particle size analyser (SALD-2300,

Shimadzu Co., japan) measured the size of particles in ethanol after sonication for 30 minutes.

X-ray diffraction (XRD) was conducted to investigate crystallinity and detect NZVI

composition. The samples were introduced on stainless steel sample holders and analysed

using Cu Kα radiation (λ= 1.5418 Ao) on TTR Rigaku diffractometer operating at 40 kV and 40

mA at scanning speed of 2o min−1 between 3 o to 90o.

2.4. Batch experiments

Several batch experiments were executed to study adsorption of phosphorus and pursue

kinetics of phosphorus removal on NZVI with or without addition of anhydrous copper

chloride. 250 mg of NZVI were introduced to 300 mL conical flask filled with 250 mL of

phosphorus solution (50 mg


 
/L as initial concentration). The flasks were tightly

capped and mixed on orbital shaker (NS-LR, As One Co., Japan) at 200 rpm and 25 oC. A set

of batch experiments was conducted under anoxic conditions with or without the addition of

different amounts of copper chloride (10, 12.5, 25 and 100 mg). Anaerobic state was achieved

by deoxygenating the solutions with flowing nitrogen for 20 minutes prior to initiating

experiments. The performance of NZVI was also tested for phosphorus adsorption without

deoxygenating of deionized water (under oxic conditions). 5 ml of solution were periodically

withdrawn to analyse phosphorus content. The optimum amount of copper chloride with

NZVI, which made a compromise between achieving reliable results in phosphorus

adsorption, cost-effectiveness and environmental safe measures, was used with 250 mg NZVI

5
on the removal of 250 mL of phosphorus solution (1, 5, 10 and 50 mg/L) at the same

conditions previously mentioned in absence of air.

To investigate the effect of pH on adsorption of phosphorus by NZVI, Batch experiments

were anaerobically carried out on the removal of phosphorus of 250 mL solution (50 mg

PO43--P/L) at three different pH mediums (acidic pH 2, neutral pH 7 and alkaline pH 12).

These experiments were performed with or without addition of designated copper chloride

amount to investigate its influence on adsorption process in different pH media as well.

Concentrations of both phosphorus and total iron were inspected at certain periods of time on

the withdrawn 5-mL samples.

In order to recover phosphorus from previously-performed batch experiments, the spent

adsorbents from batch experiments that investigated the influence of pH were placed in high

alkaline solutions (pH 12) of 250 mL DIW in conical flasks (300 mL capacity) and left on the

shaker for two hours. Samples (5 mL each) were periodically collected at specific intervals of

time to analyze phosphorus concentrations. In addition, the recovery of phosphorus was

carried out in various sodium hydroxide solutions of different molarities (0.04, 0.1, 0.25, 0.4

and 1 M) to investigate the effect of molarity on the recovery percentage.

To achieve a satisfied quality control, all experiments were tested in triplicates during our

study to check on the reproducibility of work and accuracy of results.

6
2.5. Analysis

Concentrations of phosphorus and iron compounds in solution samples were colorimetrically

obtained by using an UV–Vis spectrophotometer (DR 3900, Hach Co., USA) via USEPA

PhosVer 3 (Ascorbic acid method) at 880 nm and TPTZ (2,4,6-Tri(2-pyridinyl)-1,3,5-triazine)

method at 590 nm, respectively [20].

3. Results and discussion

3.1. Property of NZVI

NZVI showed a high BET surface area per unit mass (61 m2/g), which is greater than other

reported values [21-24]. The synthesis conditions were carefully selected from other researches

[19] to achieve the best reactive pristine NZVI produced from reduction in emulsion. The high

concentration of ferric chloride precursor and influent of sodium borohydride solutions along

with its high flow rate, all these factors contributed to enhancing specific surface area of NZVI.

TEM images of synthesized nano iron illustrated aggregation of particles in a

necklace-structure form as depicted in Figure 1. The size of these particles was estimated

according to various taken images to be about 40 nm in average. This estimated value was

emphasized using particle size analyser in which a close result was obtained about particle size

distribution of NZVI ranging from 15-60 nm, while more than 80% by weight of NZVI

particles have diameters less than 50 nm. The composition of synthesized particles was

inspected by analysing XRD pattern. Figure 2a shows a major peak of intensity at 44.8o 2θ

indicating the presence of zero valent iron in the synthesized nanoscale iron.

3.2. Phosphorus removal

7
Series of batch experiments were carried out to investigate different effects of copper chloride

load values, initial pH value, and dissolved oxygen on phosphorus removal by NZVI.

The performance of phosphorus removal by NZVI with addition of a specific amount of CuCl2

(25 mg, 1:10 of CuCl2/NZVI mass ratio) was compared against phosphorus removal by NZVI.

Figure 3 shows the phosphorus removal profiles for NZVI in different cases (with anaerobic

condition, aerobic condition and addition of copper chloride mass) .The removal efficiency of

the phosphorus by NZVI provided with CuCl2 addition is around two times more than that by

NZVI at the same time of 30 minutes and three times faster in overall (to reach a certain value

at both of them). The kinetics of phosphorus removal under aerobic condition seems to be

faster at the beginning than that under anaerobic condition then they both reaches the same

equilibrium value. Aerobic atmosphere offered more iron corrosion to nanoscale iron surface

which in turn helped in more phosphorus adsorption as ferric (hydr)oxides are good sorbents

for contaminants [18, 25-27].

Generally, the adsorption capacity of NZVI in these experiments was 28 mg


 
/g Fe

which was enhanced at least 1.7 times more than its original value by adding small amount of

copper chloride (25 mg). Thus, a complete removal had occurred by NZVI/CuCl2 within 30

minutes. By reviewing different sorption capacities of iron-based compounds illustrated by

Almeelbi et al. [18], the obtained sorption capacity in this study was the highest among others

as presented in the graph in figure 4 (see Table 1 for further illustration). [28]

3.3. Effect of different copper chloride loads

Different loads of copper chloride (10, 12.5, 25 and 100 mg) were added during phosphorus

removal (50 mg


 
/L) by 250 mg of NZVI from 250 mL solution accounting for

different CuCl2 to NZVI mass ratios (1:25, 1:20, 1:10 and 1:2.5, respectively). Figure 5

describes the difference in performance of NZVI towards the removal of phosphorus via

8
varying copper chloride loads. It was found that adding a load of 5 mg CuCl2 removed

phosphorus within 100 minutes followed by removal in 80 minutes for 12.5 mg CuCl2 load,

and then phosphorus was removed in 30 minutes by adding 25 mg of CuCl2. Finally, when 100

mg CuCl2 was applied, phosphorus was removed by NZVI in 10 minutes. By increasing the

amount of CuCl2, the kinetics of adsorption becomes faster, and adsorption capacity of NZVI

increased by this addition. In case of CuCl2-free NZVI, the adsorption capacity was the lowest

with 22 mg

 
/ g NZVI.

3.4. Effect of copper chloride addition

The kinetic profiles of phosphorus removal with NZVI/CuCl2 are shown in Figure 6, which

presents the removal of 1-10 mg


 
/ L only in 5 minutes. A complete removal of

phosphorus concentration of higher initial concentration (50 mg


 
/ L) occurred within

half an hour. Copper chloride reaction with NZVI increased iron corrosion on the surface and

provided its surface with copper and copper ferrite particles. These copper compounds increase

electric conductivity of the surface and aid in sorption of phosphorus molecules by ferrites,

ferrous hydr(oxides) and ferric hydr(oxides). Copper chloride itself was not capable of

adsorbing phosphorus. A control test was performed on copper chloride of 25 mg load to

discover that it did not remove any phosphorus (as shown in figure 5). Thus, the key

components of the adsorption process are copper ferrite compounds (    which

appears in the XRD pattern of the spent CuCl2/NZVI (1:10 wt/wt), shown in Figure 2b, at

deflection angle 2θ around 35o and 63 o. Copper ferrite compounds could have been formed

by the same mechanism discussed in details in our previous report [29]. These compounds

have the ability to adsorb phosphorus, and their adsorption capacity for phosphorus can reach

13.5 mg/g at pH 2.64 (45 oC) [17]. They can also speed up the rate of adsorption as shown in

this study. However, the presence of iron oxides (Fe2O3 and Fe3O4) on the shell of NZVI

9
particles with Cuprospinel (CuFe2O4) compounds ended up increasing the rate of adsorption,

which is observed in Figure 3 when applying oxic condition with phosphorus adsorption by

NZVI, a higher rate was obtained. And the probability of Iron oxides existence was higher

under aerobic condition as follows: 2 Fe0 + O2 + 2H2O Ѝ Fe2+ + 2OH- (Eq. 2 [30]). Also as

indicated by the previous reports (Table 1), iron oxide hydroxides were mainly the main

constituents of adsorbents for phosphorus compounds.

3.5. Effect of pH value

The results of batch experiments concerning phosphorus removal under different pH media

using NZVI revealed its dependency on pH. Figure 7 depicts the adsorption of phosphorus

using NZVI under pH 2, pH 7 and pH 9, and the same investigation under the same acidic,

neutral, and alkaline mediums using NZVI with addition of copper chloride. The results show

that the adsorption of phosphorus increases with decreasing pH value. In case of using NZVI

solely, there was no adsorption in alkaline medium, while the adsorption kinetics of

phosphorus increased from that in neutral to acidic medium. The time necessary for removal of

phosphorus was the indicator for kinetics enhancement which decreased from 60 minutes at pH

7 to 20 minutes at pH 2. On contrary, addition of copper chloride enhanced adsorption in

alkaline medium to approximately the same trend as adsorption of phosphorus using NZVI

only in a neutral medium. Also, the added copper chloride improved NZVI adsorption to

phosphorus in neutral medium, and its adsorption profile is close to that of acidic NZVI as

shown in Figure 7. However, addition of copper chloride failed to improve kinetic performance

in acidic medium. It is proved from total iron analysis (illustrated by figure 8) that the

concentration of corroded iron, indicated by total iron, increases by either decreasing the pH

value or adding copper chloride. This result is clearly shown when comparing the profiles of

total iron concentration of phosphorus adsorption using NZVI with and without copper

10
chloride addition in the neutral and acidic media in Figure 8. However, the relative increase and

concentration of total iron released to the solution resulted from copper chloride addition (70

mg/L) is much less than that generated by acidic action (247 mg/L). To sum it up, copper

chloride plays a role close to acidic action in increasing iron corrosion, speeding up electron

transfer rate and providing iron (hydr)oxide layer which aid in phosphorus adsorption.

Moreover, copper compounds formed at the surface of nanoscale iron particles seemed to

catalyse the adsorption of phosphorus.

3.6. Adsorption kinetics

The XRD pattern of spent CuCl2/NZVI (1:10 wt/wt, Figure 2b) shows the presence of iron

phosphide, which indicates that a chemical adsorption could have been occurred. So two

common adsorption reaction models were used to depict such adsorption cases and fit the

data. They were as follows:

Pseudo-first-order rate equation [31]:



                                                              ;ϯͿ                

ǁŝƚŚůŝŶĞĂƌĨŽƌŵ͗

           (4)

and Pseudo-second-order rate equation [32]:


      (5)


ǁŝƚŚůŝŶĞĂƌĨŽƌŵ͗

  
 " (6)
  ! !

11
where  and  are adsorption capacities (mg adsorbate/g adsorbent) at equilibrium and time

t (h), respectively; 1 is pseudo-first-order rate constant (h-1); and 2 is pseudo-second-order

rate constant g/(mg.h). Adsorption capacity at any time t (qt) can be obtained from Eq. (7):

#$ # %
  (7)
&

where Co and Ct are phosphorus concentration in liquid phase at initial and at time t (mg/L),

respectively; m is the mass of adsorbent (g); and V is the volume of phosphorus solution used

in adsorption batch experiments.

Table 2 shows the results of data fitting using the indicated models, and the results suggested

that the adsorption process using both under-investigated adsorbents followed the

pseudo-first-order reaction model with high correlation coefficient (R2). The results agreed

with the previous discussion. Adsorption of P using NZVI in acidic medium had the highest

reaction rate (k1=10.56 h-1, Table 2, Figure 7), but a close rate could be achieved using NZVI

with added CuCl2 (k1=6.24 h-1, Table 2, Figure 7). It is noticed that the kinetic rates were

higher for NZVI/CuCl2 especially in neutral and alkaline mediums.

3.7. Recovery of phosphorus

Phosphorus was recovered by desorption process at high pH (12) from the spent NZVI and

NZVI/CuCl2 resulted from batch experiments investigating pH effect. The spent solids that

resulted from examining the influence of acidic medium pH 2 and alkaline medium pH 10 are
12
denoted as SpH 2 and SpH 10, respectively. Their kinetic profiles are shown in figure 9 in

which the maximum recovery percentage achieved by spent particles was around 60 % (30 out

of 50 mg

 
/L) from NZVI/CuCl2. The original equilibrium adsorption time was

roughly 60 min while the recovery (desorption) time was about the same value. The recovery

of phosphorus in case of spent NZVI/CuCl2 was in general slightly higher than that of spent

NZVI, pointing out to a higher desorption equilibrium values and kinetics. It is noticeable

that the recovery of phosphorus was low (about 41.5 %, 8.3 released out of 20 mg P/L

originally adsorbed) from spent NZVI/CuCl2 resulted from batch experiment operated at pH

10. It could be the formation of copper hydroxide compounds on the surface of NZVI

prevented desorption of a part of phosphorus in the recovery process.

The recovery of phosphorus from spent NZVI or NZVI/CuCl2 can reach 100% at higher basic

medium (1 M NaOH). When operating on the recovery of phosphorus from spent NZVI or

NZVI/CuCl2 (resulted from batch experiments with neutral medium at initial P concentration

50 mg/L) using sodium hydroxide solutions of different molarities (0.04, 0.1, 0.25, 0.4 and 1

M), the results appeared in Figure (10) showed the effect of molarity of NaOH on the

recovery percentage. The recovery of both spent irons were relatively close to each other, so

the results were plotted together with mean values. It is obvious that the more alkaline the

solution was, a better recovery was gained.

Conclusions

The present study targeted improving the kinetics and adsorption capacity of nanoscale zero

valent iron for phosphorus/ phosphorus. The synthesized NZVI was suitable in size (40 nm)

and specific surface area (61 m2/g) to give a representative adsorption capacity of 28 mg


 
/ g NZVI in neutral conditions, similar to previous reports worked with the same

issue. The adsorption capacity increased by copper chloride action via addition up to 50 mg

13


 
/ g NZVI and a complete removal was shortened to half of its original time (60 min).

Increasing copper chloride load led to enhancing kinetics of removal, but it is important to

select a load which provides satisfactory results without endangering environment or wasting

money. A ratio of 1:10 of CuCl2/NZVI was previously selected in most of batch experiments

especially on 50 mg

 
/L to clearly show kinetic profiles. These processes, such as

increased corrosion rate, the formation of iron hydroxides that aided in phosphorus

adsorption and production of copper ferrite compounds that catalysed the adsorption intake,

played an important role in providing higher adsorption capacities and kinetics for

phosphorus removal via NZVI with copper chloride load. Investigating pH effect on

phosphorus adsorption showed its influence on the adsorption process as the amount of

adsorbed phosphorus incubated using NZVI increased along with decreasing pH value. The

best performance carried out using acidic NZVI was closely resembled by adsorption using

NZVI/CuCl2 in a neutral medium. Also, addition of CuCl2 increased adsorption capacity of

NZVI for phosphorus from zero to 20 mg


 
/L in alkaline medium. In addition, the

amount of recovered phosphorus was slightly higher when released from spent NZVI/CuCl2

than that of ordinary NZVI. There was a direct relation between the degree of alkalinity of the

basic solution used in phosphorus recovery and the amount of phosphorus recovered. A

complete recovery was achieved in an alkaline solution of 1 M sodium hydroxide solution.

Conflict of Interest

There are no conflict of interests to declare.

Acknowledgements

14
This work was financially supported by Kyushu University, Japan.

References

[1] R.G. Stahl, The genetic toxicology of organic compounds in natural waters and
wastewaters, Ecotoxicology and environmental Safety 22 (1991) 94-125.

[2] M. Vega, C. Fernandez, T. Blazquez, J. Tarazona, A. Castano, Biological and chemical

tools in the toxicological risk assessment of Jarama River, Madrid, Spain, Environmental
pollution 93 (1996) 135-139.

[3] K. Mandel, A. Drenkova-Tuhtan, F. Hutter, C. Gellermann, H. Steinmetz, G. Sextl,

Layered double hydroxide ion exchangers on superparamagnetic microparticles for recovery
of phosphate from waste water, Journal of Materials Chemistry A 1 (2013) 1840-1848.

[4] N.Y. Mezenner, A. Bensmaili, Kinetics and thermodynamic study of phosphate adsorption
on iron hydroxide-eggshell waste, Chemical Engineering Journal 147 (2009) 87-96.

[5] O. Eljamal, J. Okawauchi, K. Hiramatsu, Product Rich in Phosphorus Produced from

Phosphorus-Contaminated Water, Advanced Materials Research, Trans Tech Publ, 2014, pp.
261-265.

[6] C.J. Penn, J.G. Warren, Investigating phosphorus sorption onto kaolinite using isothermal
titration calorimetry, Soil Science Society of America Journal 73 (2009) 560-568.

[7] D. Cordell, J.-O. Drangert, S. White, The story of phosphorus: global food security and
food for thought, Global environmental change 19 (2009) 292-305.

[8] O. Eljamal, J. Okawauchi, K. Hiramatsu, M. Harada, Phosphorus sorption from aqueous

solution using natural materials, Environmental earth sciences 68 (2013) 859-863.

[9] D.K. Tiwari, J. Behari, P. Sen, Application of Nanoparticles in Waste Water Treatment 1,
(2008).

[10] S.R. Kanel, B. Manning, L. Charlet, H. Choi, Removal of arsenic (III) from groundwater
by nanoscale zero-valent iron, Environmental science & technology 39 (2005) 1291-1298.

[11] X.-q. Li, W.-x. Zhang, Iron nanoparticles: the core-shell structure and unique properties
for Ni (II) sequestration, Langmuir 22 (2006) 4638-4642.

15
[12] G.V. Lowry, K.M. Johnson, Congener-specific dechlorination of dissolved PCBs by
microscale and nanoscale zerovalent iron in a water/methanol solution, Environmental
Science & Technology 38 (2004) 5208-5216.

[13] Y.-H. Tee, E. Grulke, D. Bhattacharyya, Role of Ni/Fe nanoparticle composition on the
degradation of trichloroethylene from water, Industrial & engineering chemistry research 44
(2005) 7062-7070.

[14] W. Yan, A.A. Herzing, C.J. Kiely, W.-x. Zhang, Nanoscale zero-valent iron (nZVI):
aspects of the core-shell structure and reactions with inorganic species in water, Journal of
contaminant hydrology 118 (2010) 96-104.

[15] B. Karn, T. Kuiken, M. Otto, Nanotechnology and in situ remediation: a review of the
benefits and potential risks, Environmental health perspectives (2009) 1823-1831.

[16] P.G. Tratnyek, R.L. Johnson, Nanotechnologies for environmental cleanup, Nano Today
1 (2006) 44-48.

[17] Y.-J. Tu, C.-F. You, Phosphorus adsorption onto green synthesized nano-bimetal ferrites:
equilibrium, kinetic and thermodynamic investigation, Chemical Engineering Journal 251
(2014) 285-292.

[18] T. Almeelbi, A. Bezbaruah, Aqueous phosphate removal using nanoscale zero-valent iron,
Journal of Nanoparticle Research 14 (2012) 1-14.

[19] Y.-H. Hwang, D.-G. Kim, H.-S. Shin, Effects of synthesis conditions on the
characteristics and reactivity of nano scale zero valent iron, Applied Catalysis B:
Environmental 105 (2011) 144-150.

[20] A. Eaton, M. Franson, Association APH, Association AWW, Federation WE. 2005,
Standard methods for the examination of water & wastewater (2005).

[21] Y.-P. Sun, X.-q. Li, J. Cao, W.-x. Zhang, H.P. Wang, Characterization of zero-valent iron
nanoparticles, Advances in colloid and interface science 120 (2006) 47-56.

[22] R. Yuvakkumar, V. Elango, V. Rajendran, N. Kannan, Preparation and characterization of

zero valent iron nanoparticles, Dig. J. Nanomater. Biostruct 6 (2011) 1771-1776.

[23] Y. Zhang, Y. Li, J. Li, L. Hu, X. Zheng, Enhanced removal of nitrate by a novel
composite: nanoscale zero valent iron supported on pillared clay, Chemical Engineering
Journal 171 (2011) 526-531.

16
[24] Y. Liu, S.A. Majetich, R.D. Tilton, D.S. Sholl, G.V. Lowry, TCE dechlorination rates,
pathways, and efficiency of nanoscale iron particles with different properties, Environmental
Science & Technology 39 (2005) 1338-1345.

[25] R. Chitrakar, S. Tezuka, A. Sonoda, K. Sakane, K. Ooi, T. Hirotsu, Phosphate adsorption

on synthetic goethite and akaganeite, Journal of Colloid and Interface Science 298 (2006)
602-608.

[26] L. Zeng, X. Li, J. Liu, Adsorptive removal of phosphate from aqueous solutions using
iron oxide tailings, Water Research 38 (2004) 1318-1326.

[27] L.-g. Yan, Y.-y. Xu, H.-q. Yu, X.-d. Xin, Q. Wei, B. Du, Adsorption of phosphate from
aqueous solution by hydroxy-aluminum, hydroxy-iron and hydroxy-iron–aluminum pillared
bentonites, Journal of hazardous materials 179 (2010) 244-250.

[28] J. Xiong, Z. He, Q. Mahmood, D. Liu, X. Yang, E. Islam, Phosphate removal from
solution using steel slag through magnetic separation, Journal of Hazardous Materials 152
(2008) 211-215.

[29] A.M. Khalil, O. Eljamal, S. Jribi, N. Matsunaga, Promoting nitrate reduction kinetics by
nanoscale zero valent iron in water via copper salt addition, Chemical Engineering Journal
287 (2016) 367-380.

[30] G.C. Yang, H.-L. Lee, Chemical reduction of nitrate by nanosized iron: kinetics and
pathways, Water research 39 (2005) 884-894.

[31] S. Lagergren, About the theory of so-called adsorption of soluble substances, (1898).

[32] Y.-S. Ho, G. McKay, The kinetics of sorption of divalent metal ions onto sphagnum
moss peat, Water Research 34 (2000) 735-742.

17
 

200 nm 50 nm 20 nm

Figure 1: TEM images of NZVI at resolutions of 200, 50 nm and 20 nm, respectively.

18
;ĂͿ
1200
&ĞϬ

900
Intensity

600

300 Ϭ
&Ğ

0
0 10 20 30 40 50 60 70 80 90
2ϴ (degrees)

;ďͿ

ϯϱϬ
Ϭ
ϯϬϬ &Ğ

ϮϱϬ
/ŶƚĞŶƐŝƚLJ;W^Ϳ

ϮϬϬ

ϭϱϬ FeP

CuFe2 O4.Fe3O4
Ϭ
ϭϬϬ CuFe2O4.Fe3O4 &Ğ
FeP
FeP
ϱϬ FeP FeP

Ϭ
Ϭ ϮϬ ϰϬ ϲϬ ϴϬ ϭϬϬ ϭϮϬ
Ϯ੓;ĚĞŐƌĞĞƐͿ

Figure 2: X-ray diffraction (XRD) patterns of (a) NZVI with prominent peaks for Fe0 and (b) spent
NZVI/CuCl2.

19
 
50
NZVI (Anoxic)
NZVI (Oxic)
40 1:10 CuCl'/NZVI
PO43--P (mg/L)

30

20

10

0
0 50 100 150 200
Time (min)


Figure 3: Effect of copper chloride addition and oxic conditions on phosphorus adsorption by NZVI.

20
 ϭϬϬй ϯϬ
ϵϬй
Ϯϱ
ϴϬй
ϳϬй
ϮϬ
ϲϬй
WĞƌĐĞŶƚĂŐĞ

,ŽƵƌƐ
ϱϬй ϭϱ
ϰϬй
ϭϬ
ϯϬй
ϮϬй
ϱ
ϭϬй
Ϭй Ϭ
ϭ Ϯ ϯ ϰ ϱ ϲ ϳ ϴ
ZĞƉŽƌƚEƵŵďĞƌ

WŚŽƐƉŚĂƚĞƌĞŵŽǀĂůй ZĞŵŽǀĂůƚŝŵĞ͕Ś

Figure 4: Adsorption of phosphorus by iron-based materials based on several reports (refer to Table 1 for
further illustrations).

21
 50
1:2.5
1:10
40 1:20
1:25
25 mg CuCl'
PO43--P (mg/L)

250 mg NZVI
30

20

10

0
0 50 100 150 200
Time (min) 

&ŝŐƵƌĞϱ͗ĨĨĞĐƚŽĨĚŝĨĨĞƌĞŶƚĐŽƉƉĞƌĐŚůŽƌŝĚĞůŽĂĚƐ;ƌĂƚŝŽƐĂƌĞŽĨƵůϮ ͬEs/ŵĂƐƐĞƐͿ͘

  

22
 50
50
10
5
10
40 1

PO43--P (mg/L)
8
6
PO43--P (mg/L)

4
2
30 0
0 20 40 60
Time (min)

20

10

0
0 10 20 30 40 50 60
Time (min) 

&ŝŐƵƌĞϲ͗ƉŚŽƐƉŚŽƌƵƐƌĞŵŽǀĂůŽĨĚŝĨĨĞƌĞŶƚŝŶŝƚŝĂůĐŽŶĐĞŶƚƌĂƚŝŽŶƐ;ŵŐͬ>ͿďLJƵůϮͬEs/;ϭ͗ϭϬǁƚͬǁƚͿĂŶĚEs/;/ŶƐĞƌƚĞĚĐŚĂƌƚͿ

23
 50
pH 2 (NZVI)
pH 2 (NZVI/CuCl')
pH 7 (NZVI)
40 pH 7 (NZVI/CuCl')
pH 10 (NZVI)
pH 10 (NZVI/CuCl')
PO43--P (mg/L)

30

20

10

0
0 10 20 30 40 50 60
Time (min)

&ŝŐƵƌĞϳ͗ĨĨĞĐƚŽĨƉ,ŽŶƉŚŽƐƉŚŽƌƵƐĂĚƐŽƌƉƚŝŽŶ;ƌĞĂĐƚŝŽŶĐŽŶĚŝƚŝŽŶƐ͗ϱϬŵŐͬ> (   (/LƐŽůƵƚŝŽŶƚƌĞĂƚĞĚƵƐŝŶŐϮϱϬŵŐ
Es/͖ĂŶĚƵƐŝŶŐϭ͗ϭϬŵĂƐƐƌĂƚŝŽŽĨƵůϮͬEs/ŝŶĐĂƐĞŽĨĂĚĚŝƚŝŽŶͿ͘

24


&ŝŐƵƌĞϴ͗dŽƚĂůŝƌŽŶĐŽŶĐĞŶƚƌĂƚŝŽŶǀĞƌƐƵƐƚŝŵĞŽĨďĂƚĐŚĞdžƉĞƌŝŵĞŶƚƐƚŚĂƚƐƚƵĚŝĞĚƉ,ĞĨĨĞĐƚ͘

25
 50 SpH 2 (NZVI)
SpH 2 (NZVI/CuCl')
SpH 10 (NZVI)
Recovery of PO43--P (mg/L)

40 SpH 10 (NZVI/CuCl')

30

20

10

0
0 20 40 60 80 100 120
Time (min)

Figure 9: Recovery of phosphorus from spent iron in alkaline medium of pH 12.

26
 100
90
Recovery of PO43--P % 80
70
60
50
40
30
20
10
0
0.04 0.1 0.25 0.4 1
Molarity of NaOH solution (gmol/L)

Figure 10: Recovery of phosphorus from spent NZVI or NZVI/CuCl2 in alkaline medium of NaOH at different
molarities (both spent irons extracted from batch experiments on neutral phosphorus solution of initial

concentration ϱϬŵŐͬ> (   (/L).

27
dĂďůĞϭ͘ĚƐŽƌƉƚŝŽŶŽĨƉŚŽƐƉŚĂƚĞďLJŝƌŽŶͲďĂƐĞĚŵĂƚĞƌŝĂůƐďĂƐĞĚŽŶƐĞǀĞƌĂůƌĞƉŽƌƚƐ͘

 ZĞƉŽƌƚ /ƌŽŶͲďĂƐĞĚŵĂƚĞƌŝĂů dƌĞĂƚĞĚǁĂƚĞƌ WŚŽƐƉŚĂƚĞ ĚƐŽƌƉƚŝŽŶ ZĞĨĞƌĞŶĐĞ

 ŶƵŵďĞƌ ŵĂƚĞƌŝĂů ĐĂƉĂĐŝƚLJ͕

 WŵŐͬŐ

 ϭ ŬĂŐĂŶĞŝƚĞ ^ĞĂǁĂƚĞƌ EĂ,ϮWKϰ ϰ ΀Ϯϱ΁

Ϯ ^LJŶƚŚĞƚŝĐ'ŽĞƚŚŝƚĞ ^ĞĂǁĂƚĞƌ EĂ,ϮWKϰ ϳ͘ϵ ΀Ϯϱ΁


ϯ /ƌŽŶŽdžŝĚĞƚĂŝůŝŶŐ ĞŝŽŶŝnjĞĚǁĂƚĞƌ <,ϮWKϰ ϲ ΀Ϯϲ΁

ϰ /ƌŽŶŚLJĚƌŽdžŝĚĞʹ ŝƐƚŝůůĞĚǁĂƚĞƌ <,ϮWKϰ ΀ϰ΁
ϵ
 ĞŐŐƐŚĞůůǁĂƐƚĞ

ϱ ^ƚĞĞůƐůĂŐ ŝƐƚŝůůĞĚǁĂƚĞƌ <,ϮWKϰ ϱ͘ϯ ΀Ϯϴ΁


ϲ ,LJĚƌŽdžLJͲŝƌŽŶ ĞŝŽŶŝnjĞĚǁĂƚĞƌ <,ϮWKϰ ϰ͘ϴϰ ΀ϭϰ΁

ϳ Es/ ĞŝŽŶŝnjĞĚǁĂƚĞƌ <,ϮWKϰ Ϯϰ͘ϯϴ ΀ϭϴ΁

 ϴ Es/ͬƵůϮ ĞŝŽŶŝnjĞĚǁĂƚĞƌ <,ϮWKϰ ϱϬ /ŶƚŚŝƐƉƌĞƐĞŶƚƌĞƐĞĂƌĐŚ


dĂďůĞϮ͘<ŝŶĞƚŝĐǀĂůƵĞƐĨŽƌƉƐĞƵĚŽĨŝƌƐƚĂŶĚƐĞĐŽŶĚŽƌĚĞƌŵŽĚĞůƐ

Pseudo first order Pseudo second order

Co Ce Removal qe
pH/Materials k1 k2
(mg/l) (mg/l) (%) (mg/l) R2 R2
-1
(h ) (g/mg.h)
pH 2 (NZVI) 50 0.3 99.4 49.7 10.56 0.89 0.0378 0.73
pH 7 (NZVI) 50 28 44 22 2.94 0.99 0.282 0.99
pH 10 (NZVI) 50 50 0 0 0 0 0 0
pH 2 (NZVI/CuCl2) 50 0.23 99.54 49.77 2.34 0.94 0.00168 0.08
pH 7 (NZVI/CuCl2) 50 0 100 50 6.24 0.99 0.468 0.99
pH 10 (NZVI/CuCl2) 50 26.8 46.4 23.2 1.74 0.98 0.156 0.99




 
Highlights
• Phosphorus removal efficiency by NZVI increased with copper chloride addition.
• Removal efficiency was two times higher than that by NZVI only and three times
faster.
• The obtained adsorption capacity in this study was the highest among previous
studies.
• Copper chloride addition greatly enhanced phosphorus adsorption in alkaline medium.
• A complete recovery of phosphorus was achieved using 1 molar solution of NaOH.

30
Graphical Abstract

NZVI

NZVI/CuCl2

31