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Environmental Science and Pollution Research (2020) 27:45108–45120

https://doi.org/10.1007/s11356-020-10397-9

RESEARCH ARTICLE

Ammonia recovery from air stripping process applied to landfill


leachate treatment
Heloísa Alves Pereira dos Santos 1 & Armando Borges de Castilhos Júnior 1 & Willian Cézar Nadaleti 2 &
Vitor Alves Lourenço 2

Received: 30 March 2020 / Accepted: 3 August 2020 / Published online: 10 August 2020
# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
The leachate is a type of effluent from landfills containing high concentrations of ammonia, even after normal treatment
procedures are applied. Due to its characteristic, the leachate can adversely impact the environment and public health.
Leachate treatment seeks to remove a series of compounds with adverse characteristics present in this type of effluent.
Ammonia nitrogen is the main problem, easily observed in concentrations near 2000 mg/L. The effluents with high concentra-
tions of ammonia nitrogen can stimulate the growth of algae, reduce the dissolved oxygen in rivers, and cause toxicity on the
aquatic biota, even in low concentrations. Many research for treatment methods aiming to remove this compound, specifically,
have been increasingly deeper, mainly by physical-chemical processes. This study aimed to test the process of air stripping in a
closed system and pilot scale, applied on leachate treatment of landfills, to remove the high concentrations of ammonia nitrogen
and its recovery by the chemical absorption of ammonia on phosphoric acid, resulting in a product with potential application as
agricultural fertilizer, the ammonia phosphate. The leachate flows used were 9, 18, 20, and 40 L/h, and the air flows were 1800
and 3600 L/h. Calcium carbonate (standard grade), commercial hydrated lime (CHL), and sodium hydroxide (standard grade)
were used for pH adjustments. To the ammonia recovery, three flasks were used with 2.5 L of a phosphoric acid solution of 0.12
and 0.24 mol/L. The air stripping tower removed an average of 98% of ammoniacal nitrogen, with an operating time of 4 to
9 days. The volume of air consumed to remove 1 g of ammoniacal nitrogen varied from 9, 91, and 21.6 m3. The ammonia
recovery was about 92% using a phosphoric acid solution, producing the ammonia phosphate.

Keywords Landfill leachate . Ammonia . Air stripping . Nitrogen . Nitrogen recovery

Abbreviations LARESO Solid Waste Research Laboratory


AS Analytical standard LIMA Integrated Environment Laboratory
BOD5 Biological oxygen demand N Nitrogen
Ca(OH)2 Calcium hydroxide NaOH Sodium hydroxide
CHL Commercial hydrated lime NH3 Free ammonia
COD Chemical oxygen demand NH4+ Ammonium ion
NH3-N Ammonia nitrogen
Responsible Editor: Philippe Garrigues NTU Nephelometric turbidity unit
QAIR Airflow
* Willian Cézar Nadaleti QLIX Leachate flow
williancezarnadaletti@gmail.com R Removal
SS Sedimentable solids
1
Department of Sanitary and Environmental Engineering, Federal
SWL Scheduled waste landfill
University of Santa Catarina - UFSC/CTC/ENS, T System operating time
Florianópolis, SC 88010-970, Brazil TFS Total fixed solids
2
Engineering Center, Laboratory of Energy and Environmental TS Total solids
Engineering – LEAE, Post-Graduation Program in Environmental TVS Total volatile solids
Sciences, Federal University of Pelotas – UFPel, CU Color unit
Pelotas, RS 96085-000, Brazil
Environ Sci Pollut Res (2020) 27:45108–45120 45109

UFSC Federal University of Santa Catarina (Sprovieri et al. 2020). Traditional treatment methods have
C.H.C. Commercial hydrated lime been insufficient to meet the wastewater discharge standard
Symbols established by CONAMA Resolution Number 430/11 (Brazil
% Percentage 2011) whose maximum allowable concentration for total am-
μS Microsiemens monia nitrogen is 20 mg/L.
cm Centimeter Technological alternatives for initial or post-treatment of
g Gram leachate specifically target the removal of ammoniacal nitro-
h Hours gen, such as the physical-chemical process named air extrac-
L Liter tion, which consists of the removal of one or more volatile
min Minute components from the liquid phase, with the passage of forced
mL Milliliter air through the liquid (Metcalf and Eddy 2003). This method
mm Millimeter is based on favoring the non-ionized ammonia volatilization,
W Watt usually obtained by increasing the contact between the leach-
ate and the air and by raising the pH (Gomes et al. 2009).
Ammonia volatilization to the atmosphere is one of the main
Introduction mechanisms of ammonia nitrogen removal. In wastewater,
free ammonia (NH3), which is volatile, is in equilibrium with
Landfill leachate is a by-product generated from the final dis- ammonium ion (NH4+) as presented in Eq. 1:
posal of solid waste, considered an environmental liability
with negative impacts on human health and the environment NH3 ðgÞ þ H2 O↔NHþ −
4 ðaqÞ þ OH ðaqÞ ð1Þ
(Sprovieri et al. 2020). Its composition varies according to the
This chemical equilibrium is directly influenced by the ef-
characteristics of the site, age, and seasonality of the landfill.
fluent pH. The pH of crude leachate generally ranges from 3 to
Generally, this residue presents high concentrations of chlo-
7.5, depending on the degradation phase of the landfill (Costa
rides, biodegradable and refractory organic matter, solids,
et al. 2019). Thus, to favor the volatilization of ammonia
heavy metals, xenobiotic compounds, inorganic salts, micro-
which at pH 9.25 is 50% ionized and 50% free, the pH should
organisms, and ammoniacal nitrogen (Costa et al. 2019;
be increased by adding an alkalinizing chemical species,
Baettker et al. 2020).
correcting the pH to 11 units and temperature of 25 °C.
The leachate generated in Brazilian landfills presents high
Therefore, the percentage of free ammonia will rise to 99%.
concentrations of organic material, a result of the consumption
Based on this property, the process of air stripping (Metcalf
profile of the local population (Costa et al. 2019).
and Eddy 2003) occurs when the free-form ammonia-contain-
Furthermore, according to Monteiro et al. (2002) and
ing liquid effluent comes into contact with a forced air stream,
Tränkler et al. (2005), the country’s tropical climate, with high
transferring it from a liquid phase to a gas phase, called a gas
temperatures and volumes of precipitation, favors the process
phase “Drag Air.”
of waste degradation and the formation of leachate. Low con-
The application of the air stripping process is widespread in
centrations of biodegradable organic matter, and so a higher
several industrial segments (Leite et al. 2009), but regarding
content of recalcitrant organic matter, usually occur only in
the landfill leachate, there are still knowledge gaps to be filled
old landfills (Costa et al. 2019; Baettker et al. 2020). However,
to allow a wide process use. Therefore, the application of air
according to Costa et al. (2019), the country has several land-
stripping in a closed system removing the ammonia, instead of
fills at an advanced age, and it is precisely these landfills
being released into the atmosphere, has a good perspective of
which contain high concentrations of ammoniacal nitrogen
use. It is still usual to adopt open systems, in stuffed towers or
in the leachate.
drag tanks, to remove ammonia from the leachate and then
In addition to toxicity due to the microorganisms responsi-
release it in the gaseous form directly into the atmosphere.
ble for the biological treatment applied to the leachate, high
Furthermore, although there are studies on the use of closed
concentrations of ammoniacal nitrogen in the post-treatment
systems, they are still scarce when compared to open systems.
effluent can stimulate the growth of algae, promoting the de-
In addition to air pollution, depending on the level of contact
pletion of dissolved oxygen and becoming toxic to the aquatic
and the period of exposure, gaseous ammonia can cause re-
biota due to the presence of ammonia (Sprovieri et al. 2020).
spiratory, eye, and throat irritation, and even pulmonary prob-
The presence of nitrogen compounds, mainly in the ammoni-
lems and severe skin irritation (USEPA – UNITED STATES
acal form in Brazilian leachate, has environmental and public
ENVIRONMENTAL PROTECTION AGENCY 1993,
health relevance, as they reach concentrations above 2000 mg/
1995).
L (Gomes et al. 2009; Costa et al. 2019). Its inefficient remov-
The air stripping process can decrease ammonia nitrogen
al results in economic and health problems, requiring adequate
(NH3-N) concentrations by adjusting the pH of wastewater to
treatment before releasing this wastewater into water bodies
45110 Environ Sci Pollut Res (2020) 27:45108–45120

an alkaline range by increasing the gas-liquid interface and separated from the sludge deposited at the bottom of the cone,
decreasing the partial pressure of nitrogen by explosion aera- being analyzed for total, fixed, volatile, and sedimentary
tion, removing up to 99% of free ammonia from wastewater solids. Besides the solids, the control variables of the tests
(Youcai 2018). In addition to issues related to workers’ health were pH, apparent color, turbidity, electrical conductivity, to-
and safety, the environmental reason is equally present, as tal COD and NH3-N.
ammonia recovery is potentially important for agricultural
use as nitrogen fertilizer. Ferraz (2010) evaluated the chemical Pilot scale tests
absorption of ammonia by sulfuric acid and obtained recovery
efficiencies of up to 80% in washer flasks. Experimental apparatus
Hence, this study aimed to test the main factors that can
improve the application of the air stripping technique to re- The experimental apparatus consisted of a tower constructed
move ammoniacal nitrogen from leachate, evaluating an alter- of 150-mm-diameter PVC pipe pieces, the useful height of
native for ammonia recovery, with gas scrubbing flasks. The 1.95 m, stuffed with raschig rings, manufactured from 5 cm
goal is to try to contribute to the improvement of a treatment long cut conduits, and 25 mm internal diameter. The tower
technology that aims to adapt the treated leachate to current operated counter-current with downward leachate flow and
standards as well as the non-transference of a pollutant to the upward airflow. The crude leachate was placed in an HDPE
atmosphere, minimizing the environmental impact. The treat- reservoir, about 25 L in capacity and drowned centrifugal
ment efficiency on the variables such as color, turbidity, chem- pump, with a power of 80 W (1/9 cycle), and pumped it to
ical oxygen demand (COD), and solids was also evaluated. the top of the tower. The pump capacity was a maximum of
55 L/min.
The bottom of the tower was fitted with a 150 × 100 mm
Methodology sanitary tee, and a hose fitting returned the leachate to the
reservoir.
The pilot-scale tests took place at the Solid Waste Research The lateral end was closed with a 100 mm cap, where a
Laboratory (LARESO), while bench tests and physical- fitting was fitted for the inlet of the 120 W radial air compres-
chemical analyzes were performed at the Integrated sor hose, capable of pumping up to 3 L/s. The upper part of the
Environment Laboratory (LIMA). Both laboratories belong to tower was closed by a 150-mm cap and used to seal the leach-
the analytical structure of the Department of Sanitary and ate inlet and outflow of ammonia gas along with air as well as
Environmental Engineering at the Federal University of Santa the commercial shower for the distribution of the raw leachate.
Catarina (UFSC), Brazil. The raw leachate used in the experi- The void content of the filling material is 78%, the specific
ments was collected in an equalization tank at a landfill located in area of 220 m2/m3, the usable volume of the 32.2-L air strip-
Biguaçu/SC, Brazil and transported in a tanker truck to UFSC, ping tower, and the 22-L leachate reservoir.
where it remained stored in a 5000-L fiberglass reservoir. The proposed system for the recovery of ammonia re-
moved by the air stripping tower consisted of a sequence of
Bench tests 3 washer bottles (FI = washer bottle 1; F2 = washer bottle 2;
F3 = washer bottle 3) adapted from glass containers, closed
In the bench tests, ammonia stripping was not evaluated, as with plastic caps with holes for passing the gas conductive
there was no introduction of air; thus, only alkalizing agents hose from one container to another. All contained a capacity
were evaluated. Alkalization tests evaluated three chemicals to of 3.5 L each and were filled with 2.5 L diluted phosphoric
be used to raise the pH of the raw leachate: calcium hydroxide acid solution (0.12 mol/L). To calculate the dilution of the
(Ca(OH)2) (analytical standard), commercial hydrated lime acidic solution, an initial ammonia concentration in the crude
(CHL) (type CHIII), and sodium hydroxide (NaOH) analyti- leachate equal to 2000 mg/L was considered, which was
cal standard (AS). The performance of the alkalizing products completely removed by the tower and absorbed by the solu-
was evaluated under three aspects: cost (US$/liter), efficiency tion contained in the 3 vials. The experimental pilot and the
in removing color and turbidity parameters, and volume (mL) material used are presented in Fig. 1.
and dry mass (g) of sludge (48 h in a 105 °C greenhouse)
generated after sedimentation for 1 h. For each alkalization Pilot scale tests
assay, 1 L of crude leachate was added to a beaker and kept
under constant stirring promoted by a magnetic stirrer, where To test the treatment by air stripping with pH elevation, and
small portions of the evaluated chemical were added until the the NH3-N recovery efficiency by the gas scrubber system, 7
pH raised to 12 units. After this procedure, the leachate was tests were performed under different operating conditions,
transferred to an Imhoff cone where it remained for sedimen- evaluating the interference of the flow rates and leachate on
tation for 1 h. After this period, the supernatant was then treatment (Table 1):
Environ Sci Pollut Res (2020) 27:45108–45120 45111

a c

I
H J
Fig. 1 General scheme of pilot operation (a), details of the air stripping tower, ammonia-absorbing scrubber flasks (b), and tower filling material (c)

In tests E4, E5, E6, and E7, where the previous alkalization the physicochemical variables presented in Table 2, as well
of the leachate was evaluated, the reagent mass required for as the analytical methods applied.
the alkalization of 1 L of leachate obtained in the bench tests
was considered. This value was then multiplied by the volume Operating cost analysis
required in the pilot-scale 22 L leachate assays, and the re-
agent was mixed and further sedimented for 1 h using only the To assess the costs of treatment by air stripping and the am-
supernatant in the tower. All assays were performed in the monia collection system, under the different operational con-
batch regime, and monitoring was performed by analyzing ditions studied, the analysis considered an effluent which the

Table 1 Pilot scale test operating


conditions Tests Alkalization QAIR (L/h) QLIX (L/h) QAIR/QLIX NH3-N recovery

E1 No 3600 18 200 No
E2 No 1800 9 200 No
E3 No 1800 20 90 Yes/0.12 mol/La
E4 Yes/C.H.C. 1800 20 90 Yes/0.12 mol/La
E5 Yes/NaOH AS 1800 20 90 Yes/0.12 mol/La
E6 Yes/C.H.C. 1800 20 90 Yes/0.24 mol/La
E7 Yes/C.H.C. 1800 40 45 Yes/0.24 mol/La
a
Alkalizing agent
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Table 2 Physicochemical variables analyzed and APHA (2005) sedimentation. After this first stage of testing, the use of the
analytical methods used
analytical standard calcium hydroxide reagent was discarded
Variable Analytical method because it was too expensive, which would make its use on a
real scale unfeasible, and because it did not show significantly
pH Potentiometric higher results than CHL, with a cost up to 100 times lower.
Conductivity (μS/cm) Conductivity meter As for the removal of color and turbidity, the high-
Total COD (mg O2/L) Colorimetric/Closed reflux efficiency of alkalinization is clear. It was observed that to
Ammonia nitrogen (mg NH3/L) Colorimetric/Nessler reagent color removal, Ca(OH)2 and CHL had practically the same
Total Kjeldhal nitrogen (mg NH3/L) Kjeldhal distillation performance, close to 80%, while NaOH AS promoted re-
TS, VS, FS (mg/L) Gravimetric moval of only 40%. Regarding the removal of turbidity, there
SS (mL/L) Imhoff cone was no great difference between the three reagents. Again, the
Color (CU) Colorimetric reagent that showed the worst performance was NaOH AS. It
Turbidity (NTU) Nephelometric was also verified the high sludge production promoted by the
addition of alkalizing agents, mainly calcium hydroxide, both
the analytical standard and the CHL. In the general perfor-
mance evaluation of the studied alkalizing reagents, although
final concentration of ammoniacal nitrogen was equal to or
there were small differences between Ca(OH)2 AS and CHL
less than 20 mg/L. In the economic analysis, the following
with regard to color removals and turbidity and sludge gener-
parameters were considered: electricity costs (equipment op-
ation, the cost with reagent is a limiting factor to the use of AS.
eration), with alkalinization of the leachate (for the
The efficiency of air stripping treatment, evaluated on a
alkalinizers studied), cost of the acid solution (in the concen-
pilot scale, varied greatly depending on the presence or ab-
trations used), and the profit earned on the compound formed
sence of the earlier alkalization step and the applied QAIR/
with the collection of ammonia. The calculation of the total
QLIX ratio. The system shutdown moment was conditioned
cost of electricity (CTE) considered the electricity expenses
to NH3-N concentrations below the standard established by
for the operation of the electrical equipment used in the pilot
CONAMA Resolution Number 430/11, which is 20 NH3-N/L.
(centrifugal pump and the compressor). The price of kWh
Figures 2 and 3 give the decay of ammoniacal nitrogen
used in the calculations followed the data from the National
concentration and an increase in pH over the 4 days in which
Electric Energy Agency with reference to the conventional
the tower was operated. The increase in pH naturally favored
tariff and the value without taxes of Class B3 (other classes:
the removal of ammonia, which becomes volatile gas only
industrial, commercial, services and other activities, public
when it is in the non-ionized form (NH3). At pH 9.25, ammo-
power, and public service). The cost attributed to the alkalin-
nia is 50% ionized and 50% non-ionized. The increase in pH
ization considered the alkalinizing reagent consumption for
is commonly observed in experiments with the application of
pH adjustment, in US$/m3 of leachate. The cost of collecting
leachate in air stripping towers and results from the chemical
ammonia is related to the expenses with the reagent to prepare
balance of the carbonate system, which captures the H+ ions
the acidic solution, and the profit if the by-product of this step
released in the removal of ammonia. The efficiency of the
was commercialized.
removal of N-NH3 was 99% and 85% compared to NTK
(Fig. 3):
The operation of the air stripping tower with a QAIR/QLIX
Results and discussion ratio = 90 and without previous alkalinization of the leachate
required 8 days of operation for the concentration of
The raw leachate used in the tests presented high pH values, ammoniacal nitrogen to drop from 744 to 17 mg/L, a value
typical of leachate in methanogenic degradation phase (Lange within standards established by CONAMA Resolution 430/
and Amaral 2009) (Table 3). NH3-N concentrations showed 11. Santos (2011) obtained N-NH3 removal efficiencies great-
greater oscillation, and the maximum obtained for the er than 98% only after an operation time of 4 to 9 days, even
parameter was 1612 mg/L N, considered low. Costa et al. adopting alkalinization of the leachate using standard analyt-
(2019) report that in Brazil, ammoniacal nitrogen values can ical calcium hydroxide, type hydrated lime, and standard an-
reach up to 2185 mg/L in a stabilized leachate. Li et al. (1999) alytical sodium hydroxide. According to the author, the vol-
observed concentrations between 3000 and 6000 mg/L in ume of air consumed varied from 9.9 to 21.6 m3 for each gram
landfill leachate in Hong Kong. of N-NH3 removed in the tower. Figure 4 shows the decay of
During the bench tests evaluating different alkalizing re- N-NH3 and NTK concentrations. It is noticed that the decay of
agents, the best results were obtained using CHL, showing an NTK is associated with the removal of ammonia.
average color removal and turbidity of 76 and 62%, respec- Figure 5 demonstrates the correlation between the conduc-
tively, and generating about 65 g of sludge/L after 1 h of tivity and the ammoniacal nitrogen concentration:
Environ Sci Pollut Res (2020) 27:45108–45120 45113

Table 3 Physical and chemical


characterization of crude leachate Parameter Unit n Minimum Maximum Average
samples
pH – 10 8.13 8.80 8.51
Conductivity mS/cm 9 16.70 17.89 17.44
COD mg/L 7 3200 5832 4316
Color CU 10 2025 3700 2647
Turbidity N.T.U 10 180 363 261
Ammoniacal nitrogen (NH3-N) mg/L 10 744 1612 1158
Total Kjeldahl nitrogen (NTK) mg/L 9 1104 2076 1584
TS (dry mass) mg/L 10 7642 13,180 8901
TVS mg/L 10 495 4260 2495
TFS mg/L 10 4698 8930 6405
SS mL/L 10 0 3 1

During the alkalinization, there was a small removal of The removal of NH3-N in 7 days of the experiment was
ammoniacal nitrogen due to the agitation promoted to homog- 98%, reaching in this period the final concentration of 18 mg/
enize the mixture. With the increase of the pH, naturally, the L. About 14 m3air/g of NH3-N was removed by the tower.
ammonia started to volatilize and was lost to the atmosphere Comparing to the result obtained in the E2 experiment, where
during this process. The reduction in the concentration of the tower was operated under the same conditions (alkaliniza-
NH3-N in this stage was 15%, going from 1253 to 1087 mg/ tion with Cal. Hydr.), practically the same performance was
L. Figure 6 shows the decay in the concentrations of NTK and obtained. Once again, the correlation between the conductiv-
NH3-N, as well as the effect of the previous alkalinization on ity parameter and the ammoniacal nitrogen concentration is
these two parameters. shown in Fig. 8.
The removal of ammoniacal nitrogen promoted by alkalin- The raw leachate was made alkaline with the addition of
ization results in a decrease in the NTK concentration, since in commercial hydrated lime, with 60 g/L of leachate concentra-
the samples used in this study, NH3-N represents on average tion, which raised the pH from 8.35 to 12. With alkalinization
about 70% of NTK. It was also noted that alkalinization and subsequent sedimentation for 1 h, 81% color and 75%
causes a greater removal of ammoniacal nitrogen in the first turbidity were removed and the volatilized ammonia was
days of the experiment. Figure 7 shows the decay of the am- 13%. This occurs spontaneously due to the elevation of the
moniacal nitrogen concentration and the pH behavior, which pH and the agitation promoted to homogenize the mixture of
initially was 8.67 in raw leachate and 12.08 after alkaliniza- leachate and lime. After sedimentation, the supernatant was
tion. During the experiment, the pH decreases again until recirculated in the air stripping tower for 9 days. The final
reaching 9.3 after 7 days. This decrease in pH was also ob- concentration of N-NH3 reached 10 mg/L, a removal equiva-
served in the E2 experiment using commercial hydrated lime. lent to 99%. Figure 9 demonstrates the decline in N-NH3

Fig. 2 Behavior of pH and N-


NH3 concentration (QAIR =
3600 L/h; QLIX = 18 L/h; t = time
in days, T = 18.5 °C)
45114 Environ Sci Pollut Res (2020) 27:45108–45120

Fig. 3 Behavior of pH and NH3-


N concentration (QAIR =
1800 L h; QLIX = 9 L/h; t = time in
days, T = 18.5 °C)

concentration and pH over the days that the system was oper- system, no significant differences were observed in its perfor-
ated. There was also a 75% removal of NTK. mance when compared to the hydrated lime tests. The latter is
Table 4 shows the performance of the air stripping tower in much more cost-effective, about 10 times cheaper than the
the different proposed treatments. The results obtained from analytical standard reagent. A positive point regarding the
E1 and E2 showed that, even without the previous leachate use of NaOH AS is the lower generation of sludge, about
alkalization step, it was possible to remove up to 99% of 2 g of dry sludge for each liter of leachate, while the addition
ammonia nitrogen in the shortest time (96 h), due to the ap- of commercial hydrated lime yielded about 65 g/L about.
plication of the higher QAIR/QLIX (equal to 200). In terms of The costs for operating the air stripping tower are high. The
air volume required for ammonia removal, the lowest values highest cost is associated with the consumption of electricity.
were also obtained, approximately 10 m3/g of ammonia nitro- The best performance was obtained with operation of the tow-
gen removed. er at a ratio of QAR/QLIX = 200, with an average cost of ap-
At E4, when the system operated under the same condi- proximately 270 R$/m3 of treated leachate, or 51.642 US$/m3
tions as E3, the effects of the previous alkalization were eval- according to the currency converter of the Central Bank of
uated again, and a consumption of 13 m3 air/g of ammonia Brazil in on July 21, 2020. Regarding the costs of the collec-
nitrogen was removed, with 98% of ammonia removed at tion system, the best performance was obtained with the use of
168 h and 55% absorbed in the washing bottles. In E5, which less concentrated acid solution due to the high price of the
aimed to evaluate the performance of another alkalizing agent, reagent used. In general, these two technologies combined
NaOH AS and its effect on air stripping and the recovery proved to be efficient in removing ammoniacal nitrogen and

Fig. 4 Behavior of NH3-N and


NTK concentrations (QAIR =
1.800 L/h; QLIX = 20 L/h; with
0.12 mol/L H3PO4 solution
withdrawal, T = 18.5 °C)
Environ Sci Pollut Res (2020) 27:45108–45120 45115

Fig. 5 Relation between the


conductivity and the NH3-N (E1)
concentration

recovering ammonia. However, a simplified financial analysis removal and ammonia recovery system. First, with
showed that the operational cost of these two combined pro- alkalization and subsequent sedimentation for 1 h, 81% color
cesses can make the application of the system on a full-scale and 75% turbidity were removed and volatilized ammonia
unfeasible. was 13%. This occurs spontaneously due to increased pH
The main objective of E6 was to evaluate the performance and agitation promoted for homogenization of the leachate
of the ammonia absorption system using a more concentrated and lime mixture. After sedimentation, the supernatant was
acidic solution. Regarding the chemical absorption of ammo- recirculated in the air stripping tower for 216 h. The final
nia, the increase of H+ ions promoted by the lower dilution of concentration of NH3-N reached 10 mg/L, a 99% equivalent
the acid solution made the ammonia recovery reach 90% ef- removal. In all trials, it was noted that NTK removal is asso-
ficiency. Analyzing the performance of vial 1 in relation to the ciated with ammonia removal, as reported by Souto (2009) in
total ammonia recovered by the system shows that over 70% his experiments in which no significant change in organic
of the recovered ammonia is retained in the first vial. nitrogen was observed during the application of the air strip-
Therefore, an alternative to facilitate the operation of the ab- ping process. Ammonia mass removed by air stripping was
sorption system would be to size the first vial with a larger 20.69 g and air consumption 388.8 m3, which is equivalent to
volume of solution, or more concentrated solution than the a ratio of 18.9 m3 air/g NH3-N removed.
other vials, designed only to absorb the excess ammonia. Ferraz (2010) obtained similar results, 21 m3 air/g of am-
Experiment E7 evaluated the influence of leachate flow on monia nitrogen removed for experiments where commercially
drag tower performance in terms of ammonia nitrogen hydrated lime alkalinized leachate, also type CHIII, and 29 m3

Fig. 6 Behavior of NH3-N and


NTK concentrations (QAIR =
1800 L/h; QLIX = 20 L/h;
alkalization with Cal. Hydr.
Com., with 0.12 mol/L H3PO4
solution withdrawal, T = 18.5 °C)
45116 Environ Sci Pollut Res (2020) 27:45108–45120

Fig. 7 Behavior of NH3-N


concentration and pH (QAIR =
1800 L/h; QLIX = 20 L/h;
alkalization with Cal. Hydr.
Com., with collection in
3.5 mol/L H3PO4 solution)

air/g of ammonia nitrogen removed for experiments with non- 92%, performance similar to that obtained in the previous
alkaline leachate. COD removal was 36%, the highest among experiment.
all treatments proposed in previous trials. This may be related The experiments carried out in this study showed that, in
to the system operating time in this experiment, which was general, the air stripping technique applied to leachate treatment
also longer than the others, exposing the leachate to aeration is efficient from the point of view of ammonia nitrogen remov-
longer. An effluent that has ammoniacal nitrogen in concen- al, where removals above 98% were obtained. Comparing these
trations above 500 mg/L, COD values above 2000 mg/L, and results with other studies already developed in this area is a
high alkalinity is considered difficult to treat by biological difficult task, as each proposed treatment presents particularities
process, mainly due to the high toxicity of nitrogen. For this that are often unclear or not mentioned in the source. Another
reason, there is a need to remove ammonia before a biological aspect that makes it difficult to compare results with other stud-
process, so that microorganisms that degrade organic matter ies is the size of the experimental apparatus. In most cases,
do not have their metabolism affected by the toxic effect of studies have been carried out on benchtops with a leachate
ammonia (Clement and Merlin 1995). Regarding ammonia volume of less than 10 L (Cheung et al. 1997; Marttinen et al.
absorption, there was no influence of the QAIR/QLIX ratio on 2002; Huang and Shang 2006; Yokoyama et al. 2009), and
the ammonia recovery by the flasks. Regarding the mass of sometimes studies have been carried out not on towers but on
ammonia removed by air stripping, the system recovered aerated drag tanks provided by mechanical stirrers.

Fig. 8 Relationship between


conductivity and NH3-N (E4)
concentration. T = 18.5 °C
Environ Sci Pollut Res (2020) 27:45108–45120 45117

Fig. 9 Behavior of N-NH 3


concentration and pH (QAIR =
1800 L/h; QLIX = 40 L/h;
alkalization with Cal. Hydr.
Com., With collection in
3.5 mol/L H3PO4 solution, T =
18.5 °C)

From the studies found in the literature, two of them were leachates. According to the study, the best results were obtain-
widely used in order to make comparisons, Souto (2009) and ed with a temperature of 60 °C, and they were independent of
Ferraz (2010), because they were studies where air stripping the pH value for 7 h of operation with the ammonia nitrogen
towers with similar dimensions and operating conditions were removal was greater than 95%. Smaoui et al. (2018) studied
used. Regarding the recovery of ammonia associated with the the possibility of pretreatment, using coagulation-flocculation,
air stripping process, the number of scientific works is even Fenton oxidation, or air stripping processes, to improve anaer-
reduced. obic conditions in terms of biogas production during the treat-
Ferraz (2010) using ammonia absorption in sulfuric acid ment of landfill leachate. Under optimized conditions, the au-
solution reports 67 to 97% efficiencies in ammonia absorp- thors obtained removals of 85% ammonia and 26% COD. Air
tion. Comparing with the results obtained in this study, it is stripping was demonstrated as providing a better biogas yield
clear that the use of phosphoric acid can also be a viable than other pretreatments and the better methane yield.
alternative. Ferraz et al. (2013) studied the treatment of old To Hanira et al. (2017a, b), the effect of the height of the
leachate from landfills in an aerated tower on a pilot scale for filling and the types of filling material was more significant
the total removal of ammoniacal nitrogen. The removed am- than the liquid air ratio and the dose of alkalizing agent for
monia was recovered with a solution of 0.4 mol L−1 of H2SO4 removing NH3-N in their studies. According to the results
and deionized water. According to the authors, the solution obtained, an increase in the packing height of the removal
was able to neutralize 80% of the ammonia in 12 L of leachate. reactor results in greater ammonia removal efficiency due to
The effectiveness of neutralizing ammonia with deionized the increased contact time between air and liquid. Regarding
water was 75%. Leite et al. (2018) approached in his studies the type of filling, the authors cite that light, easily produced,
a pickling process, without the addition of alkaline chemical and high surface area of packing materials gave the best
species and without airflow for the removal of ammonia gas, performance for ammonia removal. Bravin Junior et al.
to reduce the concentration of ammoniacal nitrogen in the (2016) investigated the application of corrugated conduct in
landfill leachate, obtaining a removal efficiency of 99– air stripping of ammoniacal nitrogen. The authors observed
99.5% ammoniacal nitrogen and 29.23–69.20% COD. that the higher the airflow and the lower the liquid flow, the
Liu et al. (2015) used a combined treatment process of air more efficient was the removal of NH3-N by reducing the
stripping, Fenton, sequencing batch reactor, and coagulation to resistance to mass transfer. With a ratio of 4000 between the
remove the pollutants in landfill leachate. The experiment flows, they obtained 70.9% removal with a loss of pressure of
showed that the removal rate of COD, 5-day BOD, and ammo- 5 mmca, lower than that seen in conventional towers with the
nia nitrogen were 92.8%, 87.8%, and 98.0%, respectively. same dimensions. The authors emphasize that this difference
Hanira et al. (2017a, b) used a lab-scale ammonia stripping is due to the absence of filling in the corrugated ducts, reduc-
reactor was used to treat raw and diluted scheduled waste land- ing the power required for air insufflation. Thus, considering
fill leachate. The experiment successfully removed 76% for raw the absence of filling and adoption of corrugated ducts, it can
leachate and 80% for diluted leachate of NH3-N, respectively. be inferred that the duct cavities allow flow with high turbu-
Campos et al. (2013) studied the process of the air stripping lence and renewal of the contact surfaces, reducing the resis-
technology for the removal of ammonia from landfill tance to mass transfer.
45118

Table 4 Air stripping tower performance in the different treatments proposed

Parameter Unit E1 E2 E3 E4 E5 E6 E7

Initial–Final R Initial–Final R Initial–Final R Initial–Final R Initial–Final R Initial–Final R Initial–Final R


(T = 96 h) (%) (T = 96 h) (%) (T = 192 h) (%) (T = 168 h) (%) (T = 192 h) (%) (T = 168 h) (%) (T = 216 h) (%)

pH – 8.45–9.13 – 8.49–9.13 – 8.8–9.21 – 12.05–9.25 – 12.1–10.11 – 12.08–9.3 – 12–9.05 –


Conductivity mS/cm 17.5–14.9 15 17.2–14.3 17 16.7–12.9 23 15.9–12.8 19 > limit NR 15.6–13.3 15 15.9–13.2 17
COD mg/L 5832.7–2616 55 4980–3081 38 3200–2109 34 3990–2854 28 3769–2794 26 3610–2757 24 3420–2185 36
Color U.C 2025–1319 35 2980–2292 23 2790–2321 17 530–421 21 1190–762 36 410–345 16 386–312 19
Turbidity N.T.U 180–113 37 310–227 27 250–177 29 65–52 20 155–106 32 55–43 22 54–32 41
NH3-N mg/L 1563–16 99 809–17 98 744–17 98 1087–15 99 1103–20 98 995–18 98 950–10 99
NTK mg/L 2010–319 84 1230–321 74 1104–287 74 1405–339 76 1300–287 78 1308–355 73 1228–302 75
TS mg/L 13,150–12,980 1 7764–7629 2 7716–7682 <1 2565–2445 5 3345–3228 3 3790–3660 3 3610–3530 2
VTS mg/L 4220–4090 3 537–439 18 495–457 8 955–835 13 1405–1368 3 1000–980 2 930–870 6
FTS mg/L 8930–8890 <1 7227–7190 <1 7221–7225 0 1610–1609 <1 1940–1860 4 2790–2680 4 2680–2660 <1
SS mL/L 0–NR – 0–NR – 0–NR – NR–NR – NR–NR – NR–NR – NR–NR –

T = system operating time (h); R = removal (%)


In these tests, the system for ammonia recovery was not coupled, as it could hinder the drag airflow at the tower exit. In test E3, the gas scrubber system was coupled and for a QAIR/QLIX ratio of 90, it took
2 times longer operation time of the air stripping tower for the same ammonia removal efficiency. In this case, in terms of the volume of air required for removal, it was also necessary to double tests 1 and 2,
about 21 m3 air/g of ammonia nitrogen removed. However, 62% of the removed ammonia was recovered from the washer flasks
Environ Sci Pollut Res (2020) 27:45108–45120
Environ Sci Pollut Res (2020) 27:45108–45120 45119

Conclusions Baettker E, Kozak C, Knapik HG, Aisse MM (2020) Applicability of


conventional and non-conventional parameters for municipal land-
fill leachate characterization. Chemosphere 126414:126414. https://
Regarding the performance evaluation of the three alkalizing doi.org/10.1016/j.chemosphere.2020.126414
reagents tested, it is highlighted: BRAZIL, MINISTÉRIO DO MEIO AMBIENTE, CONSELHO
NACIONAL DO MEIO AMBIENTE – CONAMA (2011)
Resolução n° 430 de maio de 2011. Dispõe sobre as condições e
1. CHL, in addition to raising the leachate pH, promoted
padrões de lançamento de efluentes; complementa e altera a
significant removal of color and turbidity, on average 76 Resolução no 357, de 17 de março de 2005, do Conselho
and 62%. CHL also has the lowest cost among the re- Nacional do Meio Ambiente-CONAMA. D.O.U
agents evaluated and is an easily purchased product. Campos JC, Moura D, Costa AP, Yokoyama L, Araujo FVDF,
Cammarota MC, Cardillo L (2013) Evaluation of pH, alkalinity
However, the use of 60 g/L leachate promoted the forma-
and temperature during air stripping process for ammonia removal
tion of approximately 65 g of dry sludge, which would from landfill leachate. Journal of Environmental Science and Health
represent an additional work in the operation of the leach- Part A 48(9):1105–1113. https://doi.org/10.1080/10934529.2013.
ate treatment plant using this technique. It is recommend- 774658
Cheung KC, Chu LM, Wong MH (1997) Ammonia stripping as a pre-
ed for future studies to investigate the applicability of the
treatment for landfill leachate. Water Air Soil Pollut 94:209–221.
sludge generated in the previous alkalinization process at https://doi.org/10.1007/BF02407103
the landfill itself as a covering material. Clement B, Merlin G (1995) The contribution of ammonia and alkalinity
2. The air stripping process removed on average 98% of am- to landfill leachate toxicity to duckweed. The Science of the Total
monia nitrogen, with an operating time of 4 to 9 days and Environmental 17:71–79. https://doi.org/10.1016/0048-9697(95)
04563-G
using 9 to 21 m3 of air for every 1 g of NH3-N removed. Costa AM, Alfaia RG d SM, Campos JC (2019) Landfill leachate treat-
However, the system showed little potential for COD re- ment in Brazil—an overview. J Environ Manag 232:110–116.
moval, with a maximum removal efficiency of 36%. https://doi.org/10.1016/j.jenvman.2018.11.006
3. With regard to the ammonia absorption system, efficiencies Ferraz FM (2010) Recuperação da amônia liberada no processo de “air
stripping” aplicado ao tratamento de lixiviado de aterros sanitários.
were obtained which ranged from 55 to 92%, which is re- Dissertation, Escola de Engenharia de São Carlos da Universidade
lated mainly to the airflow in which the tower was operated de São Paulo
and the concentration of acid absorption solution. The best Ferraz FM, Povinelli J, Vieira EM (2013) Ammonia removal from land-
performance of this system was obtained with QAIR/QLIX fill leachate by air stripping and absorption. Environ Technol
34(15):2317–2326. https://doi.org/10.1080/09593330.2013.767283
ratio = 45 and acid solution concentration of 0.24 mol/L. Gomes LP et al (2009) Estudos de caracterização e tratabilidade de
4. The costs for operating the air stripping tower are high, lixiviados de aterros sanitários para as condições brasileiras.
with the highest cost being associated with electricity con- ABES. Projeto PROSAB, Rio de Janeiro
sumption. The best performance was achieved with the Hanira NML, Hasfalina CM, Rashid M, Luqman CA, Abdullah AM
(2017a) Effect of dilution and operating parameters on ammonia
operation in a QAR/QLIX = 200 ratio tower, with an aver- removal from scheduled waste landfill leachate in a lab-scale am-
age cost of approximately 51.642 US$/m3 of treated monia stripping reactor. In IOP Conference Series: Materials
leachate. And in relation to the costs of the absorption Science and Engineering 206(1):012076
system, the acid solution has a very high cost, being nec- Hanira NML, Hasfalina CM, Rashid M, Luqman CA, Abdullah AM
(2017b) Effect of dilution and operating parameters on ammonia
essary the study of less expensive alternatives. However, removal from scheduled waste landfill leachate in a lab-scale am-
there is the possibility of the sale of the fertilizer solution monia stripping reactor. In IOP Conference Series: Materials
generated from the chemical absorption of ammonia. Science and Engineering 206:1–10
Moreover, in terms of electricity costs, landfills are in- Huang JC, Shang C (2006) Air stripping. Advanced physicochemical
treatment. Handbook of Environmental Engineering. Human Press
creasingly implementing CDM projects aimed at selling Junior ASB, Delduque T P, Valéria K, Prates C, Fazolo A (2016)
carbon credits, where methane gas generated in landfills is Aplicação de conduto corrugado em air stripping de nitrogênio
burned or reused as energy. As a result, electricity costs amoniacal. Congresso Técnico Científico da Engenharia e da
would not be really a problem. In addition, proceeds from Agronomia CONTECC’2016, Foz do Iguaçu-PR
Lange LC, Amaral MCS (2009) Geração e Características do Lixiviado.
the sale of credits can also be reapplied to improve efflu- In: Gomes, L. P. (Coord). Estudos de caracterização e tratabilidade
ent treatment technologies. de lixiviados de aterros sanitários para as condições brasileiras. Rio
de Janeiro: ABES. Projeto PROSAB
Leite VD, Fernandes F, Jucá JFT, Gomes LP, Lopes WS, Sousa JT, Silva
FMF, Caetano MO (2009) Estudo do Processo de Stripping de
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