Chemosphere 66 (2007) 22332238

www.elsevier.com/locate/chemosphere

Technical Note

Repeated use of MAP decomposition residues for the removal

of high ammonium concentration from landll leachate
Shilong He a, Yu Zhang a, Min Yang
a

a,*

, Wenli Du b, Hiroyuki Harada

SKLEAC, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
b
Liulitun Sanitary Landll Site, Beijing 100049, China
c
Institute of Environmental Chemistry, SAGA University, Japan
Received 13 February 2006; received in revised form 10 September 2006; accepted 12 September 2006
Available online 13 November 2006

Abstract
The residues of magnesium ammonium phosphate (MAP) decomposed by heating under alkali conditions were repeatedly used as the
sources of phosphate and magnesium for the removal of high ammonium concentration from landll leachate. Up to 96% of ammonium

in MAP powder could be released under the following conditions: NH
4 :OH molar ratio, 1:1; temperature, 90 C; heating time, 2 h.
Fourier transform infrared spectra and X-ray diraction analysis of MAP before and after heating demonstrated that MAP was mainly
+
in
transformed to amorphous magnesium sodium phosphate (MgNaPO4), which makes it possible for the NH
4 to replace Na
MgNaPO4 to form more stable struvite. Successful ammonium removal was achieved by using the MAP decomposition residues as
the sole phosphate and magnesium sources. The ammonium removal decreased gradually following the increase of MAP reuse cycles,
and in the 6th cycle, ammonium removals of 84% and 62% were achieved for synthetic wastewater and landll leachate, respectively.
Analysis of the surfaces of MAP powders acquired at dierent reuse cycles using scanning electron microscopy with energy dispersive
X-ray suggested that the existence of calcium, kalium and aluminum ions in landll leachate might have inhibited the formation of
MAP through competition with ammonium ions for phosphate ions. It is estimated that reuse of MAP for 3 cycles could save about
44% chemical costs.
 2006 Elsevier Ltd. All rights reserved.
Keywords: MAP; Landll leachate; Ammonium removal; MAP reuse

1. Introduction
Sanitary landlls have been widely used for municipal
solid waste disposal in China as well as in other countries
because of their low cost and eectiveness. Beijing, the capital of China, has constructed seventeen landll sites in its
suburbs, and these sites produce a large amount of leachate
(about 8.0 105 to 9.0 105 m3 every year). Landll leachate from these sites generally contains high concentrations
1
of NH
to several
4 N ranging from several hundred mg l
1
thousand mg l with relatively low BOD to COD and

Corresponding author. Tel.: +86 10 62923475; fax: +86 10 62923541.

E-mail address: yangmin@mail.rcees.ac.cn (M. Yang).

0045-6535/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2006.09.016

COD to NH
4 N ratios (Lo, 1996), which poses a major
problem in wastewater treatment.
Conventional nitricationdenitrication biological processes, which have been widely utilized for ammonium
removal from municipal and many industrial wastewaters,
are not appropriate for treating landll leachate because of
the lack of sucient electron donors in leachate and the high
energy requirement for aeration (Grabinska-Loniewska,
1991; Dogen et al., 2001; Li and Zhao, 2001). While new biological techniques like short-cut nitrication/denitrication
and anaerobic ammonium oxidization have demonstrated
potential in solving the above problems, they are still under
study and it is not yet possible to constantly control the nitrication process in the nitrite-formation dominating step
(Jetten et al., 1997; Strous et al., 1997).

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S. He et al. / Chemosphere 66 (2007) 22332238

Formation of magnesium ammonium phosphate (MAP),

a crystal with a solubility as low as 0.0023 g per 100 ml H2O,
has been considered to be an eective method for the
removal of ammonium because of its high reaction rate
and low residual ammonium concentration (Li et al.,
1999). The method of MAP precipitation has been extensively studied to treat wastewater with high NH
4 content
(Altinbas et al., 2002; Ozturk et al., 2003), and the NH
4
N concentration could be reduced from 5618 mg l1 to
112 mg l1 within 15 min under a molar ratio of Mg2+:
3
NH
of 1:1:1 for treating landll leachate (Li and
4 :PO4
Zhao, 2001). The main obstacle to widespread application
of the MAP process is the high consumption of phosphate
and magnesium salts, which leads to a high operating cost.
So it is of great importance to reduce the consumption of
fresh phosphate and magnesium during MAP formation.
In our previous study, recycling of phosphate and magnesium was proposed by heating MAP at 300 C to release
ammonia (Yang et al., 2004). Ammonia gas produced during MAP decomposition could be oxidized to nitrogen gas
through selective oxidization, and the MAP residues might
be able to be reused for ammonium removal as the phosphate and magnesium sources. However, the conditions
for MAP decomposition and the eciency of the decomposed MAP for ammonium removal have not yet been
evaluated.
The objective of this study was to clarify the conditions
for MAP decomposition, and to evaluate the possibility of
using the MAP decomposition residues as the sources of
phosphate and magnesium. The eciency of ammonium
removal from landll leachate was compared with that
from synthetic wastewater to investigate the eects of coexisting compositions, and the reduction of chemical costs by
the method was estimated.
2. Materials and methods
2.1. Material
Landll leachate was taken from the Liulitun Sanitary
Landll Site located in the northern suburb of Beijing.
The composition of the landll leachate used in the experiments is shown in Table 1. Synthetic wastewater was prepared by dissolving 3.8207 g ammonium chloride into
500 ml tap water to make a solution containing NH
4 N
of 2000 mg l1.
Magnesium chloride (MgCl2 6H2O), ammonium
chloride (NH4Cl) and di-sodium hydrogen phosphate
(Na2HPO4 12H2O) of analytical grade were purchased
from the Sigma Chemical Company (USA).

2.2. Experiment
The decomposition of MAP was conducted in alkali
solution. Factors aecting MAP decomposition were evaluated by varying the molar ratio of OH:NH
4 within a
range from 0.25 to 1.00, the heating temperature from
60 C to 100 C, and the heating time from 0.5 h to 4.0 h.
NH
4 release eciency was used as the indicator for selecting MAP decomposition conditions. Experiments for MAP
preparation, decomposition, and reuse for ammonium
removal were performed as follows.
(1) MAP precipitate was generated by adding 18.8779 g
MgCl2 6H2O, 3.8207 g NH4Cl and 28.1396 g Na2HPO4 12H2O to 500 ml deionized water (molar ratio
1
of Mg:N:P = 1.3:1:1.1; initial NH
4 N, 2000 mg l ),
and agitated for 2 h at pH 9.0 (Stratful et al., 2001).
(2) The precipitate was collected using a 0.45 lm membrane lter and washed for three times with deionized
water. The ltrate before washing was taken for
2+
quantication of NH
and PO3
4 , Mg
4 .
(3) The collected solids (MAP) on the lter were heated
after NaOH was added at given temperatures.
(4) All of the decomposed MAP residues were added to
500 ml synthetic wastewater containing 2000 mg l1
NH
4 N or landll leachate, and agitated for 2 h at
pH 9.0. Steps 2, 3 and 4 were repeated.
All of the experiments were performed in triplicate.
2.3. Analysis
The collected precipitates and the decomposed MAP
residues were washed with pure water for three times, dried
in an oven at 40 C for 48 h, and then analyzed by X-ray
diraction (XRD, D/max-RB, Rigaku, Japan), Fourier
transform infrared (FTIR) spectroscopy (PE2000, USA),
and scanning electron microscopy with energy dispersive
X-ray analysis (SEM-EDS, S-3000, Hitachi, Japan). The
3
concentrations of NH
4 and PO4 were measured according
Standard Methods (APHA, 1998), and the concentration
of Mg2+ was determined using an atomic absorption spectrophotometer (AA-6300, Shimadzu, Japan).
3. Results and discussion
3.1. Determination of MAP decomposition conditions
The eects of OH:NH
4 ratios on MAP decomposition
were investigated under the following conditions: heating

Table 1
Average composition of leachate
Alk. (as CaCO3)

COD

BOD

NH
4 N

TP

SS

pH

Mg

Ca

Al

Ni

Fe

Cr

11 120

6800

2300

2400

8.16

2520

7.58.1

268

78.5

1750

13.5

0.74

1.82

3.21

The unit for all items except pH is mg l1.

S. He et al. / Chemosphere 66 (2007) 22332238

2235
1069
1074 996

3300

1441

80

Absorbance

1480

60

40

NH4 -N Release Efficiency (%)

100

20
4000 3500 3000 2500 2000 1500 1000
-1

0
0.25

Wavenumber (cm )
0.5

0.75

1
-

1.25

25

Molar Ratio (OH :NH4 )

Fig. 1. Eect of OH:NH

4 ratio on ammonium release from MAP
powder.

3.2. Surface analysis on MAP decomposition residues

FTIR and XRD analysis before and after heating were
performed to identify the transformation of MAP during
decomposition, and results are shown in Fig. 2a and b,
respectively. As shown in Fig. 2a, the infrared spectrum
of the MAP decomposition residues shows a similar shape
with that of MAP. However, the characteristic ammonium
bands at 1441 cm1 and 1480 cm1 and the characteristic
NH band at 3300 cm1 almost completely disappeared
after heating (Stefov et al., 2004, 2005), further conrming
the eective removal of NH
4 from MAP by heating under
alkali conditions. XRD analysis indicated that the characteristic MAP crystal disappeared after heating, forming
amorphous solids that could be assigned to amorphous

103

time, 4 h; heating temperature, 100 C, and the results are

shown in Fig. 1. The ammonium release eciency increased
with the increase of OH:NH
4 ratio, and reached a level of
>97% at the OH:NH
4 ratio of 1:1, which was used for the
following experiments.
MAP could also be decomposed by direct heating at
300 C (Abdelrazig and Sharp, 1998; Yang et al., 2004).
However, we found that the MAP residues obtained at
such a high temperature resulted in a low ammonium
removal. Zhang et al. (2004) found that MAP powder
can release ammonium to form MgHPO4 at pH 6 5.0
and temperature P40 C, and the resulting decomposition
residues could be eectively used for ammonium removal.
However, this method allowed about 4% of phosphate
and magnesium to be lost each time of MAP decomposition.
The eects of heating temperature and heating time on
ammonium release were further investigated at the xed
OH:NH
4 ratio of 1:1. The conditions permitting an
ammonium release eciency of >96% were determined as
follows: OH:NH
4 ratio, 1:1; temperature, 90 C; heating
time, 2 h.

20
15
10
5
0
20

40

60

80

2 ( )
Fig. 2. FTIR and XRD analyses of MAP before and after heating
decomposition. (a) FTIR of MAP (upper curve) and MAP decomposition
residues (lower curve). (b) XRD of MAP (upper curve) and MAP
decomposition residues (lower curve).

magnesium sodium phosphate (MgNaPO4). Due to the

2+
extensive face sharing of PO3
4 tetrahedra and Mg(H2O)
+
octahedra in MgNaPO4, Na might be less stable than
those of larger univalent cations like NH
4 (Mathew
+
et al., 1982). Therefore NH
can
replace
Na
in
MgNaPO4
4
to form more stable struvite, which makes it possible to
repeatedly use the MAP residues for removing ammonium
from wastewater.
3.3. Reuse of MAP decomposition residues for ammonium
removal
The MAP residues were repeatedly used for ammonium
removal from synthetic wastewater and landll leachate
without further supplementation of Mg2+ and PO3
4 , and
the results are shown in Fig. 3. For the treatment of synthetic wastewater, the ammonium removal eciency
decreased gradually with the increase of reuse cycles, which
was 84% in the 6th cycle. The residual concentrations of
Mg2+ and PO3
varied in a range between 1020 mg l1
4
1
and 210 mg l , respectively, in the reuse cycles. The
losses of Mg2+ and PO3
during former cycles might be
4
mainly responsible for the decrease of ammonium removal
(accounting for 6%).

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S. He et al. / Chemosphere 66 (2007) 22332238

80

80

60

60
40
40
20

20
0

Residual Con (mg l-1)

NH4+-N Removal (%)

100

0
0

2
3
4
5
Recycling Times

Fig. 3. Reuse of MAP decomposition residues for removing ammonium

from synthetic wastewater and landll leachate (d, j, mNH
4 N
removal, residual Mg2+ and residual PO3
in
synthetic
wastewater;
s,
h,
4
2+
nNH
and residual PO3
in landll
4
4 N removal, residual Mg
leachate).

However, the eciency for the treatment of landll

leachate was much lower than that for synthetic wastewa-

ter, especially from the 2nd cycle, although the raw wastewater even contains a relatively high concentration of
Mg2+ and some PO3
4 , as shown in Table 1. It is possible
that accumulation of some leachate components of MAP
might inhibit the formation of MAP in later cycles.
Another possible reason is the reduced free Mg2+ concentration due to the formation of Mg2+ complex. The surface
composition of the MAP residues obtained in dierent
reuse cycles was analyzed by SEM-EDS, and the results
are shown in Fig. 4. With the increase of reuse cycle, the
peaks of Mg, P, O, and Na (the major elements of MAP
decomposition residues) decreased, whereas the peaks for
calcium, kalium and aluminum appeared and increased,
suggesting that one or more newly-appeared metal ions
might be responsible for the decreasing ammonium removal
eciency. Although the Ca2+ concentration was quite low
in comparison with other ions, as shown in Table 1, its
eects on MAP formation could not be neglected (Kristell
et al., 2005). The K ion, on the other hand, might compete
with NH
4 to form struvite analogs (MgKPO4) (Mathew

Fig. 4. SEM-EDS analysis of MAP residues in dierent reuse cycles.

S. He et al. / Chemosphere 66 (2007) 22332238

5
2+

Chemical Cost ( T-1)

3-

Costs of Mg and PO4

Cost of NaOH
Average cost

3
2
1
0

Recycle Times
Fig. 5. Chemical costs for treating landll leachate in dierent reuse
cycles.

2237

during ammoRepeated losses of Mg2+ and PO3

4
nium removal might be mainly responsible for the
decrease of ammonium removal.
(3) The MAP decomposition residues could also be
reused for the removal of ammonium from landll
leachate as the sole phosphate and magnesium
sources, and the ammonium removal was 62% in the
6th cycle. The accumulation of some leachate components, such as Ca, K, and Al, on MAP might be
responsible for the lower ammonium removal eciency.
(4) Through the estimation of chemical costs, a reuse
cycle of 3 should be reasonable for the treatment of
landll leachate and about 44% chemical costs could
be saved.

Acknowledgements
et al., 1982), since its concentration in leachate was very
high in this case. Since Al3+ is able to form Al2(PO4)3 precipitates, its eects on the formation of MAP should not be
neglected, either. However, further research is required to
clarify the main inhibiting factors.

This work was supported by the State High Tech

Research and Development Project of China for younger
researchers (2004AA649280) and the National Nature Sciences Foundation of China (50525824).

3.4. Estimation of chemical costs

References
The chemical costs for treating one ton of landll leachate (ammonia concentration 2400 mg l1) are estimated,
and shown in Fig. 5. The prices of MgCl2 6H2O, Na2HPO4
and NaOH are assumed to be $56 ton1, $200 ton1 and
$288 ton1 (2006 market price), respectively.
Fig. 5 indicates that the total chemical costs would be
$4.5 ton1 if the MAP residues are not reused. The reuse
of MAP residues could save the costs of MgCl2 6H2O
and Na2HPO4 addition signicantly. However, the need
for adding NaOH counteracts the reduction of costs. The
total chemical costs decreases with the increase of reuse
cycles, and about 44% chemical costs could be saved by
reuse the MAP residues for 3 cycles. However, perceptible
reduction of chemical costs could not be expected when the
MAP residues are further reused. So a reuse cycle of 3
should be reasonable for the treatment of landll leachate.
4. Conclusions
The possibility of using MAP decomposition residues
for the removal of ammonium from landll leachate as
the phosphate and magnesium sources were investigated,
and the following conclusions could be obtained.
(1) The conditions permitting >96% ammonium release
eciency were determined as: OH:NH
4 ratio, 1:1;
temperature, 90 C; heating time, 2 h.
(2) The MAP decomposition residues could be reused for
the removal of ammonium from synthetic wastewater
as the sole phosphate and magnesium sources, and
the ammonium removal was 84% in the 6th cycle.

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