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Technical Note
a,*
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
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).
2234
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
2235
1069
1074 996
3300
1441
80
Absorbance
1480
60
40
100
20
4000 3500 3000 2500 2000 1500 1000
-1
0
0.25
Wavenumber (cm )
0.5
0.75
1
-
1.25
25
103
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).
2236
80
60
60
40
40
20
20
0
100
0
0
2
3
4
5
Recycling Times
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
3-
Cost of NaOH
Average cost
3
2
1
0
Recycle Times
Fig. 5. Chemical costs for treating landll leachate in dierent reuse
cycles.
2237
Acknowledgements
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