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Journal of Environmental Management 154 (2015) 1e7

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Journal of Environmental Management


journal homepage: www.elsevier.com/locate/jenvman

Removal of ammonium-nitrogen from groundwater using a fully


passive permeable reactive barrier with oxygen-releasing compound
and clinoptilolite
Guoxin Huang a, b, Fei Liu a, *, Yingzhao Yang c, Wei Deng d, Shengpin Li a,
Yuanying Huang e, Xiangke Kong f
a

Beijing Key Laboratory of Water Resources & Environmental Engineering, China University of Geosciences (Beijing), Beijing 100083, China
China Meat Research Center, Beijing Academy of Food Sciences, Beijing 100068, China
Hydro-Engineering Team of Sichuan Metallurgical Geology & Exploration Bureau, Chengdu 611730, China
d
College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, China
e
National Research Center for Geoanalysis, Beijing 100037, China
f
Institute of Hydrogeology and Environmental Geology, CAGS, Shijiazhuang 050061, China
b
c

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 14 November 2014
Received in revised form
6 February 2015
Accepted 10 February 2015
Available online

A novel fully passive permeable reactive barrier (PRB) with oxygen-releasing compound (ORC) and clinoptilolite was proposed for the removal of ammonium-nitrogen from groundwater. The PRB involves a
combination of oxygen release, biological nitrication, ion exchange, and bioregeneration. A pilot-scale
performance comparison experiment was carried out employing three parallel columns to assess the
proposed PRB. The results showed that the PRB achieved nearly complete NH4  N depletion (>99%).
NH4  N of 5.23e10.88 mg/L was removed, and NO2   N of <1.93 mg/L and NO3   N of 2.03
e19.67 mg/L were generated. Ion exchange and biological nitrication both contributed to NH4  N
removal, and the latter played a dominant role under the condition of sufcient oxygen. Biological
nitrication favored a delay in sorption saturation and a release of exchange sites. The ORC could sufciently, efciently supply oxygen for approximately 120 pore volumes. The clinoptilolite ensured a
robust NH4  N removal in case of temporary insufcient biological activities. No external alkalinity
sources had to be supplied and no inhibition of aerobic metabolism occurred. The ceramicite had a
negligible effect on the biomass growth. Based on the research ndings, a full-scale continuous wall PRB
was installed in Shenyang, China in 2012.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Ammonium-nitrogen
Groundwater
In situ remediation
Permeable reactive barrier
Oxygen-releasing compound
Clinoptilolite

1. Introduction
Ammonium-nitrogen contamination of groundwater has
become an environmental and public health issue in developing
and developed countries. In Shenyang, China, NH4  N of up to
10 mg/L in an approximately 40 m deep aquifer beside Hun River
has been observed by our research group. Further, in America,
Australia, England, and Korea, high NH4  N has been recorded in
numerous groundwater contamination plumes (Park et al., 2002;
Manning and Hutcheon, 2004; Patterson et al., 2004; Miller and
Smith, 2009). It is most likely that NH4  N forms harmful disinfection by-products, chlorine-related tastes and odors during

* Corresponding author. 29 Xueyuan Road, Haidian District, Beijing 10083, China.


E-mail address: 21584612@qq.com (F. Liu).
http://dx.doi.org/10.1016/j.jenvman.2015.02.012
0301-4797/ 2015 Elsevier Ltd. All rights reserved.

Downloaded from http://www.elearnica.ir

drinking water treatment, and causes nitrifying bacterial regrowth


in drinking water distribution systems (Zhang et al., 2014).
In situ permeable reactive barrier (PRB) is regarded as one of the
most promising alternatives to conventional ex situ technologies
(e.g., pump-and-treat) for groundwater remediation, and is
receiving increased attention in the literature (Della Rocca et al.,
, 2010;
2007; Thiruvenkatachari et al., 2008; Moraci and Calabro
Hashim et al., 2011; Perego et al., 2013; Erto et al., 2014).
Recently, several lab- and full-scale PRBs have been reported for
remediating groundwater contaminated with NH4  N, involving
aerobic biological nitrication and/or physicochemical sorption
(Park et al., 2002; Patterson et al., 2004; van Nooten et al., 2010,
2011). For single biological nitrication (Lahav and Green, 2000;
Yusof et al., 2010; Mousavi et al., 2012), two semipassive PRBs
were packed with polymer mats for delivering oxygen gas to induce

G. Huang et al. / Journal of Environmental Management 154 (2015) 1e7

oxidation of NH4  N into NO3   N=NO2   N (Patterson et al.,


2002). Another semipassive PRB was equipped with diffusive oxygen emitters to provide a nonlimiting molecular oxygen supply
(van Nooten et al., 2008). Even though these PRBs achieved good
nitrication performances, they produced high residual dissolved
oxygen (DO) of 24.0 9.7 mg/L (van Nooten et al., 2008), and
caused higher operation and maintenance costs as well as operational complexity arising from the use of oxygen injection systems
(reservoirs pumps plumbing) and electric power. To overcome
these shortcomings, oxygen-releasing compound (ORC) including
calcium peroxide and magnesium peroxide presents a potential
choice because it can combine with water to form oxygen gas
(Cassidy and Irvine, 1999; Liu et al., 2006; Dong et al., 2009). ORC
mixed well with cement, sand, and other materials has been successfully applied to aerobic biodegradation of some organic contaminants such as BTEX (benzene, toluene, ethylbenzene, and pxylene), MTBE (methyl tert-butyl ether), and COD (chemical oxygen
demand) (Liu et al., 2006; Dong et al., 2009; Yeh et al., 2010).
However, very little is known about ORC for supporting biological
nitrication in PRBs. The corresponding ORC oxygen-releasing capacity, N removal and transformation mechanisms, and inorganic
geochemical characteristics are worthy of further study. For single
ion exchange (Cooney et al., 1999; Dong et al., 2009), zeolite,
including clinoptilolite, mordenite, heulandite, etc. is the most
common ammonium ion exchanger. Zeolite has been well
demonstrated to be effective for treatment of NH4  N and suitable for in situ applications as a PRB material (Booker et al., 1996;
Park et al., 2002; Du et al., 2005; Wen et al., 2006). Even so, questions arise regarding sorption saturation and regeneration. As is
well known, either a periodical material replacement or chemical
regeneration after saturation renders the PRB technology less
passive and less economically favorable (van Nooten et al., 2010).
Chemical regenerants account for more than 50e60% of the total
costs even with regenerant reuse (Njoroge and Mwamachi, 2004).
Until now, a few research studies have focused on in situ biological
regeneration of zeolite by means of injecting external molecular
oxygen into PRBs (van Nooten et al., 2008, 2010, 2011). However,
using ORC to accomplish bioregeneration or delay NH4  N
breakthrough is still lacking.
Here, we report a novel fully passive ORC and clinoptilolite PRB
for removing NH4  N from groundwater. The concept is based on
a combination of oxygen release-biological nitrication-ion
exchange-bioregeneration for the efcient depletion of NH4  N
and the delayed saturation of clinoptilolite. The main function of
ORC in an upgradient zone is to release oxygen. Clinoptilolite in a
downgradient zone is to remove residual NH4  N, ensuring a
robust NH4  N removal. Shifts in exchange equilibria allow the
occurrence of NH4  N desorption when ammonium-poor
groundwater is owing through the saturated clinoptilolite. The
nitrifying bacteria on the reactive media utilize the released oxygen
to oxidize soluble NH4  N in water, increasing the N products and
delaying the NH4  N breakthrough. The objectives of this study
were to: (1) evaluate the NH4  N removal performance of the
proposed PRB; (2) characterize the ORC oxygen-releasing capacity;
(3) explore the clean up mechanisms; (4) investigate the inorganic
geochemistry; (5) determine the feasibility of bioregeneration or
delayed sorption saturation; and (6) identify the effect of ceramicite
on biomass growth.
2. Materials and methods
2.1. Materials and chemicals
River sand (~1 mm) was donated by a quarry in Shenyang, China.
Natural clinoptilolite (1e2 mm, purity 97%, cation exchange

capacity 130e150 mg/100 g, BrunauereEmmetteTeller area


670 m2/g) was obtained from Faku, China and found to contain SiO2
(67.09 wt%), Al2O3 (12.44 wt%), CaO (8.81 wt%), MgO (1.22 wt%),
K2O (1.20 wt%), and Fe2O3 (0.78 wt%). ORC beads (2e3 cm) were
obtained from China University of Geosciences (Beijing), China,
which consisted of CaO2 (20 wt%, purity 50%, main impurity
Ca(OH)2), Ca-bentonite (10 wt%), portland cement (25 wt%), river
sand (15 wt%), and tap water (30 wt%) (trial production). Ceramicite
(1e2 mm) was purchased from Ma'anshan Huaqi Environmental
Protection Sci-Tech Development Co., Ltd., China. Shenyang tap
water spiked with ammonium chloride was used as synthetic
groundwater with initial NH4  N of 5.0e11.0 mg/L. Unless
otherwise indicated, all chemicals used were analytical reagent
grade as received.
2.2. Column experiment setup and operation
A pilot-scale performance comparison experiment was carried
out employing three parallel Plexiglas columns (PRBs 1e3, 20 cm
i.d., 180 cm high) (Fig. 1 and Table 1). PRB 1 was packed with clinoptilolite (150 cm high) to control for the effects of oxygen release,
ion exchange, and biological nitrication. PRB 2 was packed with
ORC (30 cm high) and clinoptilolite (120 cm high) to simulate the
proposed PRB. PRB 3 was packed with ORC (30 cm high), ceramicite
(30 cm high), and clinoptilolite (90 cm high) to identify the effect of
ceramicite as supporting material on the biological growth. 8 intermediate sampling ports were positioned along the height of
each PRB, at 20 (port 1), 40 (port 2), 60 (port 3), 80 (port 4), 100
(port 5), 120 (port 6), 140 (port 7), and 160 cm (port 8) from the inlet
end. River sand (30 cm high) in the sand zones near the inlets was
to simulate a natural aquifer and ensure ow distribution. River
sand was mixed well with ORC beads in the ORC zones in an effort
to buffer the rise in pH. U-bend polyvinyl chloride tubing was utilized to control water table and carry efuent away for disposal.
It is important to note that the PRBs were not inoculated and
their packing media were not replaced during operation. Each PRB
was continuously fed with synthetic groundwater in a downow
mode using a multiport peristaltic pump set (BT 100-1F drive, DG-4
pump head, Baoding Longer Precision Pump Co., Ltd., China) at a
ow rate of 15 mL/min (Darcy velocity 0.7 m/d). PRBs 1, 2, and 3
were operated for 183, 282, and 234 pore volumes (PVs) (corresponding to 147, 188, and 188 days) in the dark at 13e28  C,
respectively. Water samples were collected from the inlets, outlets,
and intermediate sampling ports, and stored at 4  C until analysis.
2.3. Analytical methods, instruments and data processing
NH4  N was determined using a ow injection analyzer
(Lachat, Model QC 8000, USA), employing spectrophotometry with
salicylic acid. NO3   N and NO2   N were measured using an ion
chromatograph (Dionex, Model ICS-2100, USA). The lower detection limits for NH4  N, NO3   N, and NO2   N were 0.01, 0.10,
and 0.03 mg/L, respectively. DO and water temperature were
measured using a portable DO meter (Hach, Model HQ30d, USA).
pH was monitored using a digital pH meter (Hach, Model MP-6,
USA). Total hardness (TH) was determined using EDTA (ethylenediaminetetraacetic acid) titration method (APHA, 2005). Total
alkalinity (TA) was measured using an alkalinity test kit (Hach,
Model AL-DT, USA), employing 0.16 N H2SO4 with a digital titrator
(Model 16900). In each analysis, at least one in ve samples was
duplicated and the deviation between the two samples was always
less than 5%. Total nitrogen (TN) (mg/L) was dened as the sum of
NH4  N (mg/L), NO2   N (mg/L), and NO3   N (mg/L). The
number of PVs was expressed as the ratio of accumulated water
volume (L) over time to pore volume of reactive media (L). Data are

G. Huang et al. / Journal of Environmental Management 154 (2015) 1e7

Fig. 1. (a) Schematic and (b) photograph of the continuous ow experimental setup showing permeable reactive barriers (PRBs) 1, 2, and 3 as well as packing structures, ow
direction, U-bend tubing, and sampling ports.

Table 1
Congurations of the three permeable reactive barriers (PRBs) used for study.
Column

PRB 1
PRB 2
PRB 3

Sand zone

ORC zone

Clinoptilolite zone

Ceramicite zone

Average porosity (%)

Sand (kg)

Height (cm)

ORC (kg)

Sand (kg)

Height (cm)

Clinoptilolite (kg)

Height (cm)

Ceramicite (kg)

Height (cm)

12.0
12.0
12.0

30
30
30

0
6.8
6.8

0
5.5
5.5

0
30
30

42.8
33.5
32.8

150
120
90

0
0
6.0

0
0
30

presented as means of triplicate measurements.


3. Results and discussion
3.1. Overall performances of PRBs 1, 2, and 3
Nearly complete NH4  N depletion (percent removal >99%)
was achieved in PRBs 1, 2, and 3 (Fig. 2), demonstrating their ideal
removal capacities. Nevertheless, different spatial and temporal
trends in NH4  N distribution were observed: for PRB 1, at the
inlet NH4  N of 5.29e10.80 mg/L, low NH4  N (0.11 mg/L)
was constantly found at ports 3, 6 and the outlet during operation
over the 183 PVs (Fig. 2a); for PRB 2, at the inlet NH4  N of
5.29e10.90 mg/L, NH4  N uctuated between 0.01 and 7.67 mg/L
at port 3, and afterward was maintained at a low, stable level of
0.10 mg/L at port 6 and the outlet during operation over the 282
PVs (Fig. 2b); for PRB 3, at the inlet NH4  N of 5.10e10.70 mg/L,
NH4  N gradually decreased to a value below 0.10 mg/L between
the inlet and port 6, and was maintained invariably constant at the
outlet during operation over the 234 PVs (Fig. 2c). The differences
in NH4  N distribution among the three PRBs were probably
attributed to different nitrogen removal and transformation
mechanisms.
3.2. ORC oxygen-releasing capacity and DO distribution
The DO content at ports 3 of PRBs 2 (5.50e22.00 mg/L) and 3
(8.47e22.00 mg/L) was much higher than the level at port 3 of PRB
1 (2.00 mg/L) (Fig. 3) and gas bubbles, presumably of oxygen,

31
25
31

were seen in the samples from ports 3 of PRBs 2 and 3 when


sampling during the rst half of operation (before PV 120 for PRB 2;
before PV 100 for PRB 3). These suggested that the ORC beads had a
capacity to provide oxygen (Eq. (1)). The spatial and temporal
trends in DO distribution for PRBs 2 and 3 were similar to each
other. The DO content was the highest at ports 3, and was followed
by the inlets, outlets, and other intermediate ports during the rst
half of operation due to the facts that ports 3 were downgradient
and most close to the ORC zones (Fig. 3b and c). However, like PRB 1,
the DO concentration at the intermediate ports and the outlets was
lower than that at the inlets during the second half of operation
(after PV 120 for PRB 2; after PV 100 for PRB 3), demonstrating the
exhaustion of the ORC beads (Fig. 3b and c). It is therefore
concluded that the ORC medium could sufciently, efciently
supply oxygen for approximately 120 PVs for PRB 2 and 100 PVs for
PRB 3.

CaO2 H2 O / 0:5O2 CaOH2

(1)

3.3. N removal and transformation


For PRB 1, NH4  N of 5.25e10.77 mg/L was reduced, and
NO2   N of <1.19 mg/L and NO3   N of <2.13 mg/L were formed
during the 183 PVs (Fig. 4a). Besides, the sum of NO2   N and
NO3   N formed was much lower than NH4  N reduced, and TN
removed was a little lower than NH4  N removed (Fig. 4a). These
results indicated that only a proportion of NH4  N removed
(<26%) was biologically transformed to NO2   N and NO3   N

G. Huang et al. / Journal of Environmental Management 154 (2015) 1e7

Fig. 2. Changes in spatial and temporal distribution of NH4  N and its percent
removal in permeable reactive barriers (PRBs) (a) 1, (b) 2, and (c) 3 at a ow rate of
15 mL/min in a long-term study. Distances of the sampling ports from inlet are given in
the legend, together with their names.

(Eqs. (2)e(4)) due to the deciency of oxygen (Fig. 3a). Taking into
account the usually very poor DO (<3 mg/L) in real groundwater
(Yeh et al., 2010), biological nitrication will be further weaken in
PRB 1. By combining the results of Figs. 2a and 4a, it is evident that
abiotic ion exchange by the clinoptilolite had a good ability to
remove the remaining NH4  N (>74%) (Eq. (5)) in the absence of
oxygen gas.
Ammonia oxidizing bacteria

NH
H2 O
! NO
2 2H
4 1:5O2

(2)
Nitrite oxidizing bacteria

NO
! NO
2 0:5O2
3
Nitrifying bacteria

NH
H2 O
! NO
3 2H
4 2O2

(3)

(4)

Fig. 3. Changes in spatial and temporal distribution of dissolved oxygen (DO) in


permeable reactive barriers (PRBs) (a) 1, (b) 2, and (c) 3 at a ow rate of 15 mL/min in a
long-term study. Vertical dashed lines represent the times when the oxygen-releasing
compound beads are exhausted. Distances of the sampling ports from inlet are given in
the legend, together with their names.

Z M NH
4 / Z NH4 M

(5)

where Z represents the zeolite, and M represents the


exchangeable cations.
For PRB 2, NH4  N of 5.23e10.88 mg/L was lost, and NO2   N
of <1.93 mg/L and NO3   N of 2.03e19.67 mg/L were generated
during the 221 PVs (Fig. 4b). Clearly, NH4  N reduced was mainly
converted to NO3   N, and to a minor extent to NO2   N, suggesting that biological nitrication played a dominant role in
NH4  N removal. Sometimes (e.g., PVs 9, 99, and 194), similar to
PRB 1, the sum of NO2   N and NO3   N formed was less than
NH4  N reduced and simultaneously TN removed was lower than
NH4  N removed (Fig. 4b). Consequently, it can be deduced that
the rest of the NH4  N reduced was removed by ion exchange,

G. Huang et al. / Journal of Environmental Management 154 (2015) 1e7

Fig. 5. Scanning electronic microscope images of the clinoptilolite: (a) a biolmuncoated original surface; (b) a biolm-coated surface.

Z NH
4 2O2

Fig. 4. Temporal changes in N concentrations for permeable reactive barriers (PRBs)


(a) 1, (b) 2, and (c) 3 at a ow rate of 15 mL/min in a long-term study. Total nitrogen
(TN) is the sum of NO3   N, NO2   N, and NH4  N.

which was consistent with the literature assessing a combined


biological nitrication-ion exchange approach in a sand tank
experiment (Li et al., 2014). Apparently, biotic nitrication and
abiotic ion exchange both contributed to NH4  N removal. The
clinoptilolite used ensured a robust NH4  N removal via ion exchange in case of temporary insufcient biological activities (e.g.,
during the start-up (<18 PVs) or the ORC exhaustion phase (>120
PVs)), as evidenced by data on NH4  N percent removal, DO and
NH4  N concentrations, and NO2   N and NO3   N formations
(Figs. 2e4). In addition, the clinoptilolite served as a solid carrier for
the nitrifying bacterial growth, as shown by comparing the variation in the clinoptilolite's surface (Fig. 5a and b).
It is interesting to note that NO2   N NO3   N generated
exceeded NH4  N removed and negative TN removal was found
at some points in time (such as PVs 18, 68, 78, and 120) (Fig. 4b),
suggesting that the partial NH4  N adsorbed onto the clinoptilolite was released as a result of shifts in exchange equilibria and
concomitantly biologically oxidized by the nitrifying bacteria. The
simultaneous desorption and nitrication could be expressed by
the following simplied reaction (Eq. (6)). Apparently, biological
nitrication was favorable for a delay in sorption saturation and a
release of exchange sites, which threw a new light on sustainable
use of sorption materials for in situ groundwater remediation.

Nitrifying bacteria

Z H H NO
3 H2 O

(6)

where Z represents the zeolite.


For PRB 3, NH4  N of 5.07e10.66 mg/L was eliminated, and
NO2   N of <2.77 mg/L and NO3   N of 2.42e27.56 mg/L were
produced during the 183 PVs (Fig. 4b). Likewise, PRB 3 also relied on
biological nitrication and abiotic sorption to deplete NH4  N,
and a nitrier-mediated release of exchange sites also occurred.
3.4. Inorganic geochemistry
Like PRB 1, the signicant increase in pH was noted in PRBs 2
and 3 in the early period of operation, as demonstrated by the inlet
and outlet values (Fig. 6). In a previous study, a similar phenomenon was also found in a PRB packed with clinoptilolite: the pH
increased from 6.8 to 7.9 (Park et al., 2002). Hydration of clinoptilolite was mainly responsible for the pH increase. As was apparent
from Fig. 6b and c, there were close, positive correlations between
the changes in pH and alkalinity in PRBs 2 and 3. H can be
generated when NH4  N is biologically converted into NO3   N
and/or NO2   N (Eqs. (2) and (4)) by nitriers in an aerobic
environment, resulting in the drops in pH and alkalinity. In
contrast, Ca(OH)2 can be produced when CaO2 releases oxygen gas
(Eq. (1)), leading to the rises in pH and alkalinity. The river sand in
the ORC zones can act as a pH buffer, and control the drastical pH
and alkalinity changes (Xie et al., 2010). Undoubtedly, considering
the hydration of clinoptilolite, the generation of H and Ca(OH)2,
and the pH buffering of river sand, their net result was the increases
in pH and alkalinity in PRBs 2 and 3. This suggested that the alkalinity production by both the hydration of clinoptilolite and the
decomposition of CaO2 exceeded the alkalinity consumption by the
nitrication of NH4  N. Therefore, no external alkalinity sources

G. Huang et al. / Journal of Environmental Management 154 (2015) 1e7

thereafter decreased with time increasing, leading to the outlet


hardness being higher than the inlet value during the second half of
operation (Fig. 6b and c).
3.5. Implications of pilot-scale performances to full-scale
application
PRB 1 signicantly depended on ion exchange using the clinoptilolite to eliminate NH4  N under the condition of insufcient oxygen (Figs. 3a and 4a). Nevertheless, the clinoptilolite will
eventually become saturated in the presence of NH4 and other
competing cations (Na, K, Ca2, etc.), making ion exchange undependable for groundwater treatment. Also, periodical chemical
regeneration or even a medium replacement will render this PRB
less economically favorable.
On a basis of observed NH4  N at port 4 of PRB 3 (Fig. 2c), the
ceramicite as a biolm carrier had a negligible effect on the biomass
growth. There were a slight difference in NH4  N removal performance (Fig. 2b and c) and a similar change in N transformation
between PRBs 2 and 3 (Fig. 4b and c). Furthermore, ceramicite is
approximately 10 times higher than clinoptilolite. For these reasons, the ceramicite is not recommend as a reactive medium for
future eld applications.
The pH of 7.32e8.21 and the maximum hardness of 400 mg
CaCO3/L in the outlets from PRBs 2 and 3 (Fig. 6b and c) were
lower than their respective limitation values (pH 6.5e8.5 and
hardness 450 mg CaCO3/L for drinking use) of quality standard for
groundwater of China (SBTS, 1993). Hence, there were minor
negative effects of pH and hardness on groundwater
hydrochemistry.
From the above analysis, ORC and clinoptilolite were chosen as
the reactive media for the full-scale groundwater plume remediation at a site beside Hun River in Shenyang, China. Following design,
a continuous wall PRB, consisting of an upgradient ORC zone (5
oxygen source wells, 400 mm i.d., 40 m deep) and a downgradient
clinoptilolite zone (15 m long, 0.6e1 m wide, 40 m deep) was
installed across the plume to remove NH4  N via ion exchange
and nitrication in July 2012. The changes in hydrogeological parameters, mineral precipitaiton, and microorganism identication
are being investigated.
Fig. 6. Temporal changes in total alkalinity (TA), total hardness (TH), and pH for
permeable reactive barriers (PRBs) (a) 1, (b) 2, and (c) 3 at a ow rate of 15 mL/min in a
long-term study.

had to be supplied for the nitrifying bacterial growth.


On the other hand, in combination with the changes in
NH4  N, NO2   N, NO3   N, and pH (Figs. 4 and 6), the pH
(7.32e7.94 for PRB 2; 7.32e8.21 for PRB 3) did not appear to be
detrimental to the enzymatic activity of the nitrifying bacteria.
Researchers have reported that a pH value helping for microbial
growth should be kept in the range of 6.5e8.5 (Liu et al., 2006;
Yusof et al., 2010; Mousavi et al., 2012). Kong et al. (2014) found
the high pH (>8.5) in the efuent of an aerobic reaction column
packed with zeolite during the rst 15 days. To ensure a robust pH
control system in future applications, the combination of K2HPO4
and KH2PO4 can be used as the basic components of the ORC beads
(Yeh et al., 2010).
There was a decrease in hardness in the outlet of PRB 1 (Fig. 6a),
suggesting that the clinoptilolite was able to sorb the hardness
(Dong et al., 2009). Similarly, a diminished hardness was also
observed in the outlets of PRBs 2 and 3 during the rst half of
operation (Fig. 6b and c), indicating that the clinoptilolite was also
able to sorb the hardness caused by CaO2, Ca(OH)2, and Cabentonite from the ORC material. However, the sorption capacity

4. Conclusions
Based on the research ndings the main conclusions were as
follows:
(1) PRBs 1, 2, and 3 all had ideal NH4  N removal capacities
(percent removal >99%). PRB 1 signicantly depended on ion
exchange to eliminate NH4  N due to a lack of oxygen.
PRBs 2 and 3 dominantly relied on biological nitrication to
remove NH4  N under the condition of sufcient oxygen.
(2) The ORC medium could sufciently, efciently supply oxygen
for approximately 120 and 100 PVs for PRBs 2 and 3,
respectively.
(3) Biological nitrication was favorable for a delay in sorption
saturation and a release of exchange sites, and the clinoptilolite ensured a robust NH4  N removal in case of temporary insufcient biological activities and served as a solid
carrier for the nitrifying bacterial growth.
(4) No external alkalinity sources had to be supplied for the nitrifying bacterial growth in PRBs 2 and 3, and the pH
(7.32e7.94 for PRB 2; 7.32e8.21 for PRB 3) did not appear to
be detrimental to the enzymatic activity of the nitrifying
bacteria.

G. Huang et al. / Journal of Environmental Management 154 (2015) 1e7

(5) The ceramicite had a negligible effect on the biomass growth.


It is not recommend as a reactive medium for future eld
applications.
Acknowledgments
This study is nancially supported jointly by NSFC (41172226),
National Program of Control and Treatment of Water Pollution
(2009ZX07424-002-002), China Postdoctoral Science Foundation
(2013M541111)
and
Beijing
Excellent
Talents
Program
(2012D001055000001).
References
APHA, 2005. Standard Methods for the Examination of Water and Wastewater,
twenty-rst ed. American Public Health Association, Washington, DC.
Booker, N.A., Cooney, E.L., Priestley, A.J., 1996. Ammonia removal from sewage using
natural Australian zeolite. Water Sci. Technol. 34, 17e24.
Cassidy, D.P., Irvine, R.L., 1999. Use of calcium peroxide to provide oxygen for
contaminant biodegradation in a saturated soil. J. Hazard. Mater. B69, 25e39.
Cooney, E.L., Booker, N.A., Shallcross, D.C., Stevens, G.W., 1999. Ammonia removal
from wastewaters using natural australian zeolite. I. characterization of the
zeolite. Sep. Sci. Technol. 34, 2307e2327.
Della Rocca, C., Belgiorno, V., Meri, S., 2007. Overview of in-situ applicable nitrate
removal processes. Desalination 204, 46e62.
Dong, J., Zhao, Y., Zhang, W., Hong, M., 2009. Laboratory study on sequenced
permeable reactive barrier remediation for landll leachate-contaminated
groundwater. J. Hazard. Mater. 161, 224e230.
Du, Q., Liu, S., Cao, Z., Wang, Y., 2005. Ammonia removal from aqueous solution
using natural Chinese clinoptilolite. Sep. Purif. Technol. 44, 229e234.
Erto, A., Bortone, I., Di Nardo, A., Di Natale, M., Musmarra, D., 2014. Permeable
adsorptive barrier (PAB) for the remediation of groundwater simultaneously
contaminated by some chlorinated organic compounds. J. Environ. Manag. 140,
111e119.
Hashim, M.A., Mukhopadhyay, S., Sahu, J.N., Sengupta, B., 2011. Remediation technologies for heavy metal contaminated groundwater. J. Environ. Manag. 92,
2355e2388.
Kong, X., Bi, E., Liu, F., Huang, G., Ma, J., 2014. Laboratory column study for evaluating a multimedia permeable reactive barrier for the remediation of ammonium contaminated groundwater. Environ. Technol. 22, 1e8.
Lahav, O., Green, M., 2000. Bioregenerated ion-exchange process: the effect of the
biolm on the ion-exchange capacity and kinetics. Water SA 26, 51e57.
Li, S., Huang, G., Kong, X., Yang, Y., Liu, F., Hou, G., Chen, H., 2014. Ammonium
removal from groundwater using a zeolite permeable reactive barrier: a pilotscale demonstration. Water Sci. Technol. 70, 1540e1547.
Liu, S.-J., Jiang, B., Huang, G.-Q., Li, X.-G., 2006. Laboratory column study for
remediation of MTBE-contaminated groundwater using a biological two-layer
permeable barrier. Water Res. 40, 3401e3408.
Manning, D.A.C., Hutcheon, I.E., 2004. Distribution and mineralogical controls on
ammonium in deep groundwaters. Appl. Geochem 19, 1495e1503.

Miller, D.N., Smith, R.L., 2009. Microbial characterization of nitrication in a


shallow, nitrogen contaminated aquifer, Cape Cod, Massachusetts and detection
of a novel cluster associated with nitrifying Betaproteobacteria. J. Contam.
Hydrol. 103, 182e193.
Mousavi, S., Ibrahim, S., Aroua, M.K., 2012. Sequential nitrication and denitrication in a novel palm shell granular activated carbon twin-chamber upow bioelectrochemical reactor for treating ammonium-rich wastewater. Bioresour.
Technol. 125, 256e266.
, P.S., 2010. Heavy metals removal and hydraulic performance in
Moraci, N., Calabro
zero-valent iron/pumice permeable reactive barrier. J. Environ. Manag. 91,
2336e2341.
Njoroge, B.N.K., Mwamachi, S.G., 2004. Ammonia removal from an aqueous solution
by the use of a natural zeolite. J. Environ. Eng. Sci. 3, 147e154.
Park, J.-B., Lee, S.-H., Lee, J.-W., Lee, C.-Y., 2002. Lab scale experiments for permeable
reactive barriers against contaminated groundwater with ammonium and
heavy metals using clinoptilolite (01-29B). J. Hazard. Mater. B95, 65e79.
Patterson, B.M., Grassi, M.E., Davis, G.B., Robertson, B.S., Mckinley, A.J., 2002. Use of
polymer mats in series for sequential reactive barrier remediation of
ammonium-contaminated groundwater: laboratory column evaluation. Environ. Sci. Technol. 36, 3439e3445.
Patterson, B.M., Grassi, M.E., Robertson, B.S., Davis, G.B., Smith, A.J., Mckinley, A.J.,
2004. Use of polymer mats in series for sequential reactive barrier remediation
of ammonium-contaminated groundwater: eld evaluation. Environ. Sci.
Technol. 38, 6846e6854.
Perego, C., Bagatin, R., Tagliabue, M., Vignola, R., 2013. Zeolites and related mesoporous materials for multi-talented environmental solutions. Microporous
Mesoporous Mater. 166, 37e49.
SBTS (State Bureau of Technical Supervision), 1993. Quality Standard for Ground
Water (GB/T 14848-93). Beijing.
Thiruvenkatachari, R., Vigneswaran, S., Naidu, R., 2008. Permeable reactive barrier
for groundwater remediation. J. Ind. Eng. Chem. 14, 145e156.
van Nooten, T., Diels, L., Bastiaens, L., 2011. A laboratory-scale mixed multibarrier for
removal of ammonium from landll leachate contamination. Int. J. Environ. Eng.
3, 240e252.
van Nooten, T., Diels, L., Bastiaens, L., 2008. Design of a multifunctional permeable
reactive barrier for the treatment of landll leachate contamination, laboratory
column evaluation. Environ. Sci. Technol. 42, 8890e8895.
van Nooten, T., Diels, L., Bastiaens, L., 2010. Microbially mediated clinoptilolite
regeneration in a multifunctional permeable reactive barrier used to remove
ammonium from landll leachate contamination: laboratory column evaluation. Environ. Sci. Technol. 44, 3486e3492.
Wen, D., Ho, Y.-S., Tang, X., 2006. Comparative sorption kinetic studies of ammonium onto zeolite. J. Hazard. Mater. B133, 252e256.
Xie, L., Liu, F., Liu, Y., 2010. Improving property of ller in oxygen-releasing
permeable reactive barrier. Environ. Sci. Technol. 33, 44e48 (in Chinese).
Yeh, C.-H., Lin, C.-W., Wu, C.-H., 2010. A permeable reactive barrier for the bioremediation of BTEX- contaminated groundwater: microbial community distribution and removal efciencies. J. Hazard. Mater. 178, 74e80.
Yusof, N., Hassan, M.A., Phang, L.Y., Tabatabaei, M., Othman, M.R., Mori, M.,
Wakisaka, M., Sakai, K., Shirai, Y., 2010. Nitrication of ammonium-rich sanitary
landll leachate. Waste Manag. 30, 100e109.
Zhang, S., Wang, Y., He, W., Wu, M., Xing, M., Yang, J., Gao, N., Pan, M., 2014. Impacts
of temperature and nitrifying community on nitrication kinetics in a movingbed biolm reactor treating polluted raw water. Chem. Eng. J. 236, 242e250.