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Desalination
journal homepage: www.elsevier.com/locate/desal
Environmental Simulation and Pollution Control State Key Joint Laboratory, School of Environment, Tsinghua University, Beijing 100084, P.R. China
State Environmental Protection Key Laboratory of Microorganism Application and Risk Control (SMARC), Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, P.R. China
China Power Engineering Consulting Group Corporation, Beijing 100120, P.R. China
H I G H L I G H T S
a r t i c l e
i n f o
Article history:
Received 13 April 2014
Received in revised form 11 June 2014
Accepted 15 June 2014
Available online xxxx
Keywords:
Wastewater reclamation
Membrane process
Reverse osmosis
Membrane fouling
Autopsy
DOM fraction
a b s t r a c t
A fouled RO membrane from a full-scale municipal wastewater reclamation plant was autopsied to elucidate
fouling characteristics and behavior associated with feed water quality. Organic pollution (occupied 75% of
the deposit) was the major problem for the RO membrane. The deposit dissolved in NaOH solution was
2.37 g-DOC/m2 and largely comprised of microbial-derived organic matter (OM) and humic-like OM. Hydrophobic acids (HOA) and hydrophilic neutrals (HIN) were the two largest fractions in the deposit among the six fractions of HOA, hydrophobic bases (HOB), hydrophobic neutrals (HON), hydrophilic acids (HIA), hydrophilic bases
(HIB) and HIN. HOA fraction could deposit on the membrane easily and should be monitored as key fractions to
predict the organic fouling of RO membrane. HIN fraction occupied 34.2% of the total DOC in the deposit, but it
was suggested that HIN fraction in the deposit was produced by the microorganisms on the membrane instead
of depositing. The inorganic scaling of the RO membrane was mainly caused by element Fe, Ca and Si. The content
of Fe was the highest (349.18 mg/m2), since Fe deposited on the RO membrane much more easily than other
elements. Ca presented the lowest deposition ratio (0.0017%) due to the effective function of the antiscalant.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Wastewater reclamation and reuse is a viable and attractive
approach to dealing with the global water scarcity and becoming an
emerging issue throughout the world [1]. Reclaimed water has been
accepted as indirect drinking water production and used in many
aspects, such as irrigation, power plant cooling water, industrial process
water and groundwater recharge [2]. Recently, with an increasing demand of high quality reclaimed water, reverse osmosis (RO) membrane
Corresponding author at: Environmental Simulation and Pollution Control State Key
Joint Laboratory, School of Environment, Tsinghua University, Beijing 100084, P.R. China.
Tel.: +86 10 6279 4005; fax: +86 10 6279 7265.
E-mail address: hyhu@tsinghua.edu.cn (H.-Y. Hu).
http://dx.doi.org/10.1016/j.desal.2014.06.018
0011-9164/ 2014 Elsevier B.V. All rights reserved.
has been widely used and represents an important option for municipal
wastewater reclamation (MWR) due to its high removal efciency of
pollutants, stable water quality and easy operation [37].
However, dissolved matters in feed water can adsorb, accumulate, or
precipitate within or on the RO membrane polymer matrix leading to
membrane fouling [8]. RO membrane fouling is still a major concern
and presents at high levels in the application of RO technology, because
it deteriorates the performance of membranes (e.g., causing serious ux
decline and affecting the produced water quality) and increases both
capital and operational costs [911].
The major types of fouling mechanisms on RO membrane are
cake layer formation (particles and colloids), concentration polarization
(dissolved inorganic matters), electrostatic repulsion and/or hydrophobic interactions (dissolved organic matters), and biofouling (microbial
74
Chlorine
Antiscalant
Compressed
Reductant
air
Backwash
Chemical
cleaning
Secondary treatment
effluent (100)
Self-cleaning
filter
UF system
Middle
water tank
UF concentrate
(10)
Water cleaning
Chemical
cleaning Non-oxidizing
biocide
Water distribution
(60)
Clean water Decarbonator
tank
RO system
Cartridge
filter
RO concentrate
(30)
Fig. 1. Flow diagram of the RO membrane process for municipal wastewater reclamation.
(*The numbers in the diagram indicated the proportion of the amount of water).
75
Table 1
Characteristics of the UF and RO membrane applied in the processa.
Manufacturer
Membrane type
Membrane material
Membrane ux (L/m2h)
Nominal pore size (nm)
Pressure (MPa)
Recovery rate (%)
Salt rejection (%)
UF
RO
GE
Zee Weed 1000D
Polyvinylidene uoride (PVDF)
Hollow ber membrane
31.51
20
90 (9698)
Hydranautics
Proc10
Aromatic polyamide composite
16
0.81.6 (1.11.3)
65 (5669)
97 (99.099.6)
a
Numbers in brackets were actual operating data for the RO system. The hollow tube of UF membrane was in vacuum and the atmospheric pressure
becomes the driving force, so there was no pressure for UF.
n=148
Secondary effluent
35
35
n=103
20
n=13
15
10
104
103
n=144
n=69
5
0.3
0.2
0.1
0.0
Concentration (mg/L)
30
Concentration (mg/L)
25
SS
20
TP
Secondary effluent
n=365
n=323
n=10
100
n=10
n=40 n=42
10-1
2+
103
n=157
2+
102
n=26
SS
n=32
RO influent
2+
TP
n=11
n=31
n=32
n=31
n=30
n=10
101
100
n=10
n=10
n=10
10-1
TDS Ca Mg Fe Mn Si Al SO 4 Cl alkalinity
n=30
n=33
n=42
n=325
101
n=24
15 n=12
10
104
n=371
102
10-2
25
0.3
0.2
0.1
0.0
n=129
Concentration (mg/L)
Concentration (mg/L)
30
RO influent
n=28
10-2
2+
2+
2+
Fig. 2. Water quality of the secondary efuents and the RO inuents in the plant. (n in the gure represents the number of water samples tested for each items).
76
Table 2
The content of organic and inorganic components in the deposit by loss of ignition analysis.a
Dry weight (g/m2)
4.87 0.44
3.66 0.29
75.31 3.38
1.21 0.39
24.69 3.38
Errors indicate standard deviation (SD) of six replicates of the deposit tested.
element Fe and Mn was relatively low, for about 0.051 mg/L (n = 40)
and 0.044 mg/L (n = 42). In the RO inuents, the average concentration of Ca, Mg, Si, Fe and Mn was 266 mg/L (n = 31), 79 mg/L (n =
30), 12 mg/L (n = 10), 0.037 mg/L (n = 10) and 0.044 mg/L (n =
10). SO24 and Cl were the major anion in both of the secondary efuents and RO inuents. The concentrations of inorganic ions in secondary efuents and RO inuents were quite similar, for the UF
membrane has nothing to do with the ion removal.
3.2. Organic and inorganic components of the deposit
3.2.1. Loss on ignition at 550 C
As shown in Table 2, the deposit was dried in 110 C and the dry
weight was 4.87 0.44 g/m2. Data for mass loss on ignition at 550 C
revealed the content of organic component in the deposit to be 3.66
0.29 g/m2, accounting for 75.31 3.38% of the dry weight. Organic
pollution was the major problem for the RO membrane in terms of the
dry weight. The mass left representing the inorganic component was
1.21 0.29 g/m2 and 24.69 3.38% of the dry weight. The result was
similar to the 86.6% loss on ignition at 550 C for the RO membrane at
stage 1 and 70.1% for stage 2 in pilot plant reported by Rafn et al.
(2012) [7]. However, Kim et al. (2008) reported 43.954.7% organic
foulant and 45.356.1% inorganic foulant for three kinds of RO membranes in pilot plant [10]. The proportion of organic and inorganic component in deposit on RO membrane was largely inuenced by the water
quality of feed water and membrane material.
3.2.2. FTIR analysis
The FTIR spectra of the secondary efuent, the RO inuent and the
deposit collected on the RO membrane were shown in Fig. 3.
There was little difference between the FTIR spectra of the secondary
efuent and the RO inuent, indicating that there was little difference
between compositions of dissolved matters in the secondary efuent
and RO inuent, which was conrmed by the result in Section 3.1.
The bands at 604 cm1 corresponding to S\O bending were characteristic for the sulphate in the secondary efuent and the RO inuent. The
bands at 1140 cm1 and 1440 cm1 correspond to C\O stretching and
300
200
604
150
100
50
0
500
1440 1620
RO influent
1140
Fe
3410
3550
Deposit
2930
1640
1410
3310
1050
1550
1000 1500 2000 2500 3000 3500 4000
Wave length (cm-1)
Fig. 3. FTIR spectra of the secondary efuent, RO inuent and deposit collected on the RO
membrane.
Transmissivity
400
Secondary effluent
250
300
200
Ca
Mn
100
Al
Si
Mg
0
0.01
0.1
1
10
100
1000
Concentration in RO influent (mg/L)
Ca
Mg
Fe
Mn
Si
Al
0.0017
0.00047
26.42
7.07
0.019
0.43
6
HCl
77
0.5
1.0
1.5
2.0
DOC (g/m2)
2.5
3.0
Fig. 5. DOC and SUVA of the three solutions SHCl, SNaOH and SUPW.
420
Excitation (nm)
Secondary effluent
420
RO influent
380
380
340
340
300
300
260
260
220
280 320 360 400 440 480 520
220
280 320 360 400 440 480 520
420
420
380
Excitation (nm)
SHCl
340
400.0
380
340
SNaOH
800.0
1200
1600
300
300
260
260
220
280 320 360 400 440 480 520
Emission (nm)
220
280 320 360 400 440 480 520
Emission (nm)
2000
2400
2800
3000
Fig. 6. Fluorescence EEM spectra of the secondary efuent, the RO inuent, SHCl and SNaOH. (SNaOH was diluted for one time when testing the uorescence characteristics).
78
HIN
HOA
4
3
2
1
0
HOA
15
HOB
HIN
10
HOB
5
0
HIB
HON
HIB
HON
HIA
HIA
(a)
(b)
protein-like OM; Region III (Ex b 250 nm; Em N 380 nm) and Region V (Ex
N 250 nm; Em N 380 nm) belong to fulvic- and humic-like OM,
respectively; and Region IV (Ex N 250 nm; Em b 380 nm) represents
microbial-derived OM [20].
The uorescence EEM spectra of the secondary efuent and the RO
inuent were quite similar, for UF membrane did not change the component of DOM. However, the uorescence EEM spectra of SHCl and
SNaOH were quite different from the secondary efuent and the RO
inuent.
The uorescence chromophore for S HCl was found at Ex =
270 nm/Em = 440 nm, which belonged to Region V representing the
humic-like OM. This result was conrmed by the SUVA data in Section
3.4.1, which is relatively high for SHCl and revealed the high concentration
of humic substances with aromatic structures desorbed in SHCl.
420
Excitation (nm)
380
420
380
200.0
HIN
400.0
(Secondary
effluent)
600.0
800.0
1000
340
340
1200
1400
1600
300
300
260
260
1800
2000
2200
2400
2600
2800
3000
220
280 320 360 400 440 480 520
220
280 320 360 400 440 480 520
420
420
380
Excitation (nm)
HOA
(Secondary effluent)
HOA-SNaOH
340
400.0
380
340
HIN-SNaOH
800.0
1200
1600
300
300
260
260
2000
2400
2800
220
280 320 360 400 440 480 520
3000
220
280 320 360 400 440 480 520
Fig. 8. Fluorescence EEM spectra of HOA and HIN fractions of DOM in secondary efuent and SNaOH.
The DOC of HIN fraction was 8.87 mg/L and occupied 34.2% of
the total DOC in SNaOH, while in secondary efuent DOC of HIN fraction was 1.43 mg/L and occupied only 14.5% of 9.84 mg/L total DOC.
It was inferred that HIN fraction was relatively easily deposited on
the RO membrane among the six fractions or HIN fraction could be
produced by the biolm on the membrane. Zhao et al. (2010) reported that HIN fraction resulted in the highest ux decline compared to HIA, HIB and HOA, indicating that HIN fraction tends to
deposit on the RO membrane [23]. Further study should be conducted to gure out the right explanation.
HON fraction was only 2.10 mg/L and occupied 8.1% of the total DOC
in SNaOH. Though HON fraction was the largest fraction in secondary
efuent, it did not deposit on the RO membrane.
The uorescence EEM spectra of HOA and HIN fractions of DOM
in secondary efuent and SNaOH were shown in Fig. 8, respectively.
Fluorescence chromophore of HOA fraction in secondary efuent was
in Region II, III, IV and V, while in SNaOH the uorescence chromophore of
HOA fraction was mainly in Region IV representing microbial-derived
OM.
Fluorescence chromophore of HIN fraction in secondary efuent was
in Region I, II and IV, while in SNaOH the uorescence chromophore of
HIN fraction was only in Region V.
The composition of HOA and HIN fractions had been changed signicantly. This phenomenon may be explained by the biofouling on the RO
membrane. Microorganisms in the biolm on the membrane assimilated
the organic carbon in feed water and produced microbial-derived OM
and humic-like OM with aromatic structures, which belonged to HOA
and HIN fractions and could deposit on the membrane easily to become
part of the composition of the biolm.
For HOA fraction, the organic matter in Region IV might be produced
by microorganisms on the membrane or might be the matter depositing
on the membrane from feed water.
However, HIN fraction was produced by the microorganisms instead of depositing according to the completely different region of
uorescence chromophore. Combined with the high deposition
level of HIN fraction reported by Zhao et al. (2010), HIN might
work as assimilated organic carbon (AOC) absorbed and transformed by microorganisms on the RO membrane.
4. Conclusions
In this study, a fouled RO membrane for municipal wastewater reclamation was autopsied and the deposit on the membrane was analyzed
in terms of the organic and inorganic components, which were compared with those in the secondary efuent and RO inuent. The following conclusions were made:
(1) Organic pollution was the major problem for the RO membrane, since organic component in the deposit accounted
for 75.31 3.38% of the dry weight. The deposit dissolved
in alkaline solution was 2.37 0.32 g-DOC/m2 and largely
comprised of microbial-derived OM and humic-like OM
with unsaturated carbon bonds or aromatic ring.
(2) RO membrane was polluted by element Fe, Ca and Si. Fe deposited on the RO membrane much more easily than other
elements in terms of the deposition ratios, while Si presented
in a relatively high content level in the deposit and was difcult to remove by physical or chemical cleaning. Ca presented in a high concentration (266 mg/L) in the RO inuent and
a high content (157.78 mg/m2) in the deposit, but the deposition ratio was the lowest (0.0017%) because of the effective
function of the antiscalant (PWT Titan ASD 200).
79
(3) HOA and HIN fractions were the two largest fractions in the deposit on the RO membrane among the six fractions of HOA, HOB, HON,
HIA, HIB and HIN. HOA fraction might be produced by microorganisms on the membrane or might be the HOA fraction in RO feed
water depositing on the membrane, while HIN fraction was
produced by the microorganisms on the membrane instead of
depositing.
Acknowledgements
This study was funded by National High-Tech R&D Program of China
(863 Program) (No. SS2013AA061805). The research is supported by
the Collaborative Innovation Center for Regional Environmental Quality.
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