Removal of the Ammonia Load of Landfill

Leachate by Struvite Precipitation Using

Low-cost Reagents
Alessio Siciliano, Salvatore De Rosa. Università della Calabria
Chiara Ruggiero. EOS Consulting S.r.l.

CONTACT

Name: Alessio Siciliano

E-mail: alessio.siciliano@unical.it

EXECUTIVE SUMMARY

The landfill leachate is characterised by high nitrogen load and, for this reason, its treatment in con-
ventional biological plants is not recommended.

So, an interest in the chemical precipitation of struvite to recover the nitrogen compounds is cur-
rently growing. However, for the treatment of landfill leachates because the low contents of magne-
sium and phosphorus relative to the ammonia concentrations a large amounts of reagents are re-
quired, making the process expensive.

In this paper, we report the results of an experimental investigation conducted on methanogenic

leachates with the aim of defining a process for struvite precipitation that is able to efficiently re-
cover the nitrogen compounds and that is cheap and easily manageable. In particular, we evaluate
the possibility of using the seawater bittern, a by-product of salt manufacturing, and bone meal, a
by-product derived from the thermal treatment of meat waste, as a low-cost sources of magnesium
and phosphorus respectively.

The experiments were conducted on leachate samples collected from a municipal solid waste land-
fill, testing reaction times between 1 and 15 min, pH values between 7 and 11 and stoichiometric
ratios between 1 and 1.5. During each test, which was conducted at room temperature in batch mode
in 0.8L glass flasks, the reaction mixture was stirred at 300rpm for a set time and then left to settle
for 30min.

The results of a first set of tests carried out with the theoretical stoichiometric ratios for struvite
formation showed that the removal of ammonia molar concentration increased in response to in-
creasing pH and reached a plateau about of 76% in a pH range between 10 and 11.

Changing the stoichiometric ratios, the efficiency of ammonia removal growths with the amounts of
Mg+2 and PO4-3-P, reaching a maximum abatement of about 90% with molar doses of PO4-3-
P/NH4+-N=1.3 and Mg+2/NH4+-N=1.3. Moreover, with these dosages, the almost complete recovery
of the PO4-3-P and an abatement of magnesium close to 87% were achieved. Furthermore, the dif-
fractogram of the produced precipitate confirmed the actual formation of struvite powder.

INTRODUCTION

Landfill leachate contains high concentrations of ammonium which poses a serious problem in
wastewater treatment. A variety of treatment technologies have been developed for the removal of
 nitrogen load. The most common and economical method to remove nitrogen from wastewater is
the process of biological nitrification and denitrification. However, high content of ammonia has a
toxic effect on microorganisms (Kim et al., 2007), which may lead to a decrease in the treatment ef-
fectiveness. Autotrophic processes (SHARON-ANAMMOX) are suitable for the treatment of high
concentrated wastewaters, but their control and management are complex and difficult.

Among alternative treatment methods, interest is currently growing in the chemical precipitation of
struvite (MgNH4PO46H2O), a mineral that can be reused as a slow-release fertiliser (Kim et al.,
2007; Renou et al., 2008, Tünay et al., 1997; Türker and Çelen, 2007; Uludag-Demirer et al., 2005).
However, for the treatment of landfill leachates, because of the very low contents of magnesium
and phosphorus relative to the ammonia concentrations, large amounts of the reagents are required,
making the process expensive. To reduce the costs of the process, some research has evaluated the
feasibility of using seawater bittern, a by-product of salt manufacturing, as a low-cost source of
magnesium ions for the treatment of wastewater (Ayoub et al., 2000; Lee et al., 2003). However, no
studies have reported the use of alternative sources of phosphorus, which is much more rare and ex-
pensive, and the consumption of which generally represents the primary cost of the treatment (Di
Iaconi et al., 2010). In the present paper, we evaluate the possibility of using bone meal, a by-
product derived from the thermal treatment of meat waste, as a low-cost source of phosphorus for
struvite precipitation. This compound is not directly usable as fertilizer because it is soluble only in
a strongly acid environment and, being suitable only for limited utilizations, is usually put into land-
fill in Europe (Coutand et al., 2008; Deydier et al., 2005).

In the present work by exploiting the high phosphorus content of the bone meal we made the stru-
vite precipitation process economically sustainable.

The experiments carried out allowed to develop a process that using only low cost sources is effec-
tive and easily manageable and that has the potential to be applied on a large scale.

DESCRIPTION OF THE EXPERIMENTS

The experiments were conducted on leachate samples collected from a municipal solid waste land-
fill, which were characterised in terms of the main chemical parameters according to Standard
1 Methods (APHA, 1998) (Tab1).

Table 1 Leachate properties

Parameter Value Unit
pH 7.8 -
COD 12.0 g/L
Ca+2 0.23 gCa+2/L
NH4+-N 2.60 gNH4+-N/L
Mg+2 0.090 gMg+2/L
PO4-3-P 0.021 gPO4-3-P/L
Fe+2 0.018 gFe+2/L
Cu+2 0.007 gCu+2/L
Conductivity 2.47 mS/cm

The struvite precipitation process was developed using seawater bittern and bone meal as sources of
magnesium and phosphorus respectively. The bittern used was composed by more than 97% mag-
nesium chloride with traces of other seawater elements, and the bone meal had percentages of phos-
phate and calcium of 61.6% and 35.7%, respectively, with only small amounts of sodium and mag-
nesium. The bittern was simply dissolved by mixing 50g into 50 mL of tap water achieving a con-
centration of about 48.5gMg+2/L. The bone meal was mixed with an acid solution to dissolve the
phosphorus content. Specifically, sulphuric acid was used because it prevents the calcium from dis-
solving into the solution; instead, it remains in insoluble form as calcium sulphate. In particular,
38g of bone meal were dissolved in 100mL of 3N sulphuric acid, resulting in a phosphorous con-
centration of about 68gPO4-3-P/L.

The experiments, carried out in duplicate, were done testing reaction times between 1 and 15 min,
pH values between 7 and 11 and molar stoichiometric ratios (Mg+2/NH4+-N=RMN; PO4-3-P/NH4+-
N=RPN) between 1 and 1.5. The pH of the oxidised samples was set using 10N NaOH to produce
the basic conditions needed for struvite precipitation. During each test, which was conducted at
room temperature in batch mode in 0.8L glass flasks, the reaction mixture was stirred at 300rpm for
a set time and then left to settle for 30 min. After the precipitate settled, the NH4+-N, PO4-3-P and
Mg+2 levels of the supernatant were determined.

The precipitate collected from the test carried out with the identified optimal operating conditions
was analyzed by X-ray diffraction.

RESULTS AND DISCUSSION

The first investigations were done to identify the optimal pH level and the minimum reaction time
required for struvite precipitation. Thus, with RMN and RPN ratios equal at 1:1, tests were performed
using pH values between 7 and 11 and reaction times of 1, 5 and 15 min. The results showed that
the removal of ammonia molar concentration increased in response to increasing pH and reached a
plateau in a pH range between 10 and 11 for all reaction times (Fig. 1). The improvement in ammo-
nia abatement observed with pH enhancement is attributable to the effects of pH variation on the
solubility of struvite crystals. In fact, as mentioned in many studies, the solubility of struvite de-
creases in response to increases in pH (Lee et al., 2003; Ohlinger et al., 1998; Uludag-Demirer et
al., 2005).

100

80

60
N (%)

40

1 min
5 min
20
15 min

0
6 7 8 9 10 11 12
pH

Figure 1 Abatement of ammonia molar concentrationN) vs. pH during tests carried out in various reaction
times with RMN and RPN equal to 1

In particular the results described above are in agreement with Ohlingher et al. (1998), who deter-
mined the minimum struvite solubility to occur at a pH of 10.3, and with both Snoeyink and Jen-
kins (1980) and Stumm and Morgan (1996), who reported a pH of 10.7 as optimal for the formation
of struvite crystals.

Furthermore, Lee et al. (2003) observed that the most favourable pH for ammonia removal is be-
tween 9.5 and 10, in contrast with the lower theoretical value of approximately 8.6. In any case, the
results of our tests showed that, although the ammonia removal improved with reaction time for pH
values between 7 and 9, the maximum efficiencies obtained, estimated to be about 76%, were the
same for all reaction times (Fig. 1). These trends indicate that an increase in pH level, produces not
only the decrease in struvite solubility, but also an increase in the reaction rate, allowing the highest
efficiencies to be obtained in a very short time. Based on these results, we determined that a pH
value of 10 and a reaction time of 1 min were the best conditions for the struvite precipitation.
Moreover, the maximum removal of ammonia is much higher than in other studies that used sea-
water and seawater bittern as sources of magnesium and analytical-grade reagents of phosphorus. In
fact, Lee et al. (2003), dosing the compounds of magnesium with a stoichiometric ratio
NH4+:Mg+2:PO4-3 of 1:1:1 after the pH correction to within the range of 9.5 to 10, observed maxi-
mum abatements of ammonia between 39% and 54%. The greater efficiency reached in our tests is
probably attributable to a better feeding sequence of added reagents. In fact, Kim et al. (2007)
demonstrated that the optimal conditions for the struvite precipitation are created by the addition of
sources of magnesium and phosphorus followed by pH adjustment. In contrast, greater ammonia
abatements have been reached in studies in which analytical-grade reagents dosed in the theoretical
stoichiometric amounts were exclusively used (Li and Zhao, 2003; Ozturk et al., 2003). Regardless,
this efficiency increase is approximately only 10%, confirming the effectiveness of the proposed
method with the use of seawater bittern and bone meal as sources of phosphorus and magnesium.

Figure 2 Abatement of ammonia molar concentration (N) vs. RPN during tests carried out with various values of
RMN and an initial pH=10

To identify the optimal amounts of chemicals under these reaction conditions, further investigations
were done using RMN and RPN values between 1.1 and 1.5. The results show that the increase in the
efficiency of ammonia removal correlated with the amounts of Mg+2 and PO4-3-P. In particular, for
every RMN ratio tested, the ammonia removal increased in response to the amount of phosphorous,
reaching a maximum increase in efficiency of about 10% at RPN ratios of 1.3 in terms of the reduc-
tions observed with the least amounts of added phosphorous (Fig. 2). A similar behaviour was ob-
tained in response to increasing amounts of magnesium, which highlights the negligible increase in
ammonia removal at RMN values higher than 1.3. Together, these results indicate that a maximum
efficiency of ammonia removal near 90% was achieved with RMN and RPN values equal to 1.3; thus,
these values can be considered optimal for the treatment process.

Figure 3 Abatement of phosphorus molar concentration (P) vs. RMN during tests carried out with various values
of RPN and an initial pH=10

Figure 4 Abatement of magnesium molar concentration (M) vs. RPN during tests carried out with various values
of RMN and an initial pH=10

The improvement in the performance of the treatment determined by the higher availability of mag-
nesium and phosphorus in terms of the ammonia molar concentration has also been demonstrated
in other studies, the results of which are consistent with those previously described (Di Iaconi et al.,
2010; Türker and Çelen, 2007; Uludag-Demirer et al., 2005).

The need for greater availability of magnesium and phosphorus than the theoretical stoichiometric
assay is attributable to the possible formation of magnesium complexes and insoluble compounds of
phosphorus that can reduce the struvite formation. This was confirmed by the recovered amounts of
phosphorus and magnesium observed at the end of the treatment. In fact, the almost complete re-
covery of the PO4-3-P achieved with the ratios indicated above (Fig. 3), higher by approximately 9%
than the ammonia removal, is representative of the precipitation of some other compounds. In fact,
after the treatment, the Ca+2 concentration was reduced to 6% of its initial value, suggesting the
formation of calcium phosphate. Instead, the generally lower recovered amounts of magnesium
(Fig. 4) are indicative of the formation of complexes that are able to limit the precipitation of Mg+2.
However, the high removal rate for magnesium, close to 87% using the identified reagent amounts
(Fig. 4), indicates the formation of struvite powder. This is confirmed by X-ray diffractogram of the
precipitated produced which shows positions and intensity of the peaks match with those of real
pure struvite (Fig. 5).

Figure 5 XRD diffractogram of precipitate collected at the end of treatment (pH=10, R MN=1.3, RPN=1.3) (a) com-
pared to struvite standard (b)

CONCLUSIONS

The experiments for this study identify a process that is able to recover the nitrogen load of meth-
anogenic leachate in an easily manageable way. In particular using bittern and bone meal as low-
cost magnesium and phosphorus sources, respectively, it was possible to recover up to 90% of the
ammonia nitrogen as struvite powder. The proposed treatment, in addition to be effective for leach-
ate treatment, has fewer drawbacks on the environment. In fact the use of by-products of magnesi-
um and phosphorus to promote the struvite precipitation considerably reduces the consumption of
chemical reagents, in particular, using compounds such as the bone meal, considered as wastes with
problems of storage and disposal and with a cost that probably will not increase in the near feature.
This avoids the utilization of natural resources of phosphorus which are limited and whose price
instead will probably increase. Moreover, the high recovery levels of phosphorus obtainable with
the defined precipitation conditions results into a residual concentration of about 32mgPO4-3-P /L,
removable in a traditional specific biological process. Thus, on the basis of these considerations,
this method has the potential to be applied on a large scale as pre-treatment of landfill leachate.

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