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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
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
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
31
25
31
(1)
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)
Z M NH
4 / Z NH4 M
(5)
Fig. 5. Scanning electronic microscope images of the clinoptilolite: (a) a biolmuncoated original surface; (b) a biolm-coated surface.
Z NH
4 2O2
Nitrifying bacteria
Z H H NO
3 H2 O
(6)
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.