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Desalination 349 (2014) 7379

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Desalination
journal homepage: www.elsevier.com/locate/desal

Fouling of reverse osmosis membrane for municipal wastewater


reclamation: Autopsy results from a full-scale plant
Fang Tang a, Hong-Ying Hu a,b,, Li-Juan Sun a, Qian-Yuan Wu b, Yan-Mei Jiang a,
Yun-Tao Guan b, Jing-Jing Huang c
a
b
c

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 fouled RO membrane in a full-scale plant for wastewater reclamation was autopsied.


Organic matter (occupied 75% of the deposit) was the major problem for RO membrane.
Hydrophobic acids and hydrophilic neutrals were the largest fractions in deposit.
Hydrophilic neutrals on RO membrane were produced by microbes instead of depositing.
Inorganic scaling of the RO membrane was mainly caused by element Fe, Ca and Si.

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

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F. Tang et al. / Desalination 349 (2014) 7379

attachment and growth) [2,12,13]. Fouling of organic and inorganic


components and microorganisms can occur simultaneously, and these
components may interact in terms of fouling mechanism [14].
Autopsies of fouled RO membranes have improved our understanding of various aspects of membrane fouling. However, most of the previous research on membrane autopsies was mainly focused on the
seawater or brackish water desalination processes. Recently, in MWR
eld, RO membrane is playing a more and more important role and
should be paid more attention due to the complex dissolved organic
matter (DOM), which is produced during biological wastewater treatment and results in high potential of organic fouling and bio-fouling
on RO membrane [12]. Additionally, autopsies of fouled RO membranes
from full-scale membrane applications have rarely been performed due
to their high cost and lengthy duration. Hence, knowledge on the fundamentals of membrane fouling remains incomplete, including dominant
types of fouling and possible fouling mechanisms in the practical applications of membrane processes for MWR [12].
Moreover, autopsies of fouled RO membranes need to be conducted
to elucidate fouling characteristics and behavior associated with feed
water characteristics. Comparison of the components in feed water and
the substances in the deposit on the membrane can help to gure out
which kind of contaminants will deposit on membrane easily and
become the main pollutant on RO membrane surface. Hence, proper pretreatment technologies for RO process could be adopted to remove the
specic components in feed water to decrease the fouling. Chon et al.
(2012) reported that the major foulants of the RO membranes were
hydrophilic fractions of DOM mainly comprised of polysaccharide-like
and protein-like functional groups [15]. However, no comprehensive
study has yet been performed on the changes of DOM fractions depositing on the RO membrane from the secondary efuent.
The main objective of this study was to evaluate the organic and inorganic components in the deposit on the RO membrane surface in
order to provide valuable insight into the fouling characteristics of RO
membranes in an MWR plant. The contents of the main components
(e.g., organic and inorganic constituents) of the deposit were analyzed
and associated with the feed water characteristics to gure out the
major contaminants, which should be removed by pretreatment seriously to minimize the membrane fouling. Resin fractionation was applied to identify logical indexes to evaluate the water quality of RO
inuent and the organic components in the deposit in order to optimize
the pretreatment for RO membrane processes.
2. Materials and methods
2.1. RO membrane process for municipal wastewater reclamation
The RO membrane process for municipal wastewater reclamation
located in Zibo, Shandong Province, China, has a treatment capacity of
4800 m3/day and has been operated for more than 2 years under continuous operating condition. The process ow diagram of the RO membrane process is shown in Fig. 1. In this process, UF membrane was used
as the pretreatment to minimize the fouling of the RO membrane. UF
permeate was pumped into a 2-stage RO system, while RO permeate
was after-treated by decarbonator to remove carbon dioxide or carbonates in RO permeate in order to make the RO permeate more stable for
distribution. The treated RO permeate was distributed to industrial
companies for reuse due to its high water quality.
The characteristics of UF and RO membrane were shown in Table 1.
The RO membrane worked well for 2 months of continuous operation
without chemical cleaning before it was autopsied. The standardized
desalination rate changed little and stabilized at 99.299.6%, while the
standardized permeate ux of RO membrane decreased by 48.5% before
autopsied compared with the initial permeate ux. The acid and alkaline chemical cleaning was conducted for about every 2 months with
10 g/L citric acid solution with pH value of about 2 and NaOH solution
at pH 11.512.0, respectively.

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).

2.2. Preparation for samples


2.2.1. Water sampling
Three different kinds of water samples, secondary efuent, UF permeate and RO permeate, were collected weekly from the plant to investigate the removal of organic and inorganic contaminants. All of the
water samples were taken back to laboratory and ltered immediately
by glass ber lters (0.45 m) to eliminate suspend solids, and stored
at 4 C to minimize the changes of constituents in the water.
2.2.2. Fouled RO membrane and collection of foulant samples
The fouled RO membrane module was collected from the rst stage
of RO modules and stored at 4 C to minimize the changes of constituents on RO membrane surface. Foulant samples were collected with a
small exible ruler on RO membrane of specic area size.
2.2.3. Extraction of RO membrane fouling
Three different kinds of solutions (1 M HCl, 1 M NaOH and ultrapure
water) were used to desorb the deposit on the fouled RO membranes. A
piece of fouled RO (effective surface area: 100 cm2) membranes was
consecutively soaked in 1 L each of 1 M HCl, 1 M NaOH and UPW for 2
h with moderate stirring. The pH of the three different kinds of solutions
desorbed RO membranes foulants was adjusted to 7.0 0.2 using NaOH
and HCl and then the three solutions were ltered immediately by glass
ber lters (0.45 m). The three solution samples were referred as SHCl,
SNaOH and SUPW.
2.3. Analytical methods
Inductively coupled plasma mass spectrometry (IRIS Intrepid II XSP,
Thermo Fisher, USA) was used to detect the concentration of inorganic
elements. The functional groups or components of the water samples
and the deposit samples were characterized by Fourier transform infrared (FTIR) spectrometer (Thermo Nicolet NEXUS, USA). The water samples and the deposit samples were pretreated by lyophilizer (EYELA
FDU-1100, Japan) and then analyzed by FTIR. UVvision spectrophotometric analyses of the samples were carried out with a UV-2401PC
UV-VIS recording spectrophotometer (SHIMADZU Corporation, Japan).
The dissolved organic carbon (DOC) concentration of the samples was
measured with a TOC-5000A analyzer (SHIMADZU Corporation,
Japan). Fluorescence spectroscopy analysis was used in this paper to
characterize the type of dissolved organic matters (DOM) and the excitation emission matrix (EEM) uorescence spectra was recorded on a
uorescence spectrophotometer (F-7000, Hitachi, Japan).

F. Tang et al. / Desalination 349 (2014) 7379

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.

2.4. Resin fractionation of DOM


Resin fractionation is based on the original protocol and a modied
one introduced by Zhang et al. (2009) [1618]. DOM in a water sample
was divided into six Resin-fractions: hydrophobic acids (HOA), hydrophobic bases (HOB), hydrophobic neutrals (HON), hydrophilic acids
(HIA), hydrophilic bases (HIB), and hydrophilic neutrals (HIN).

3. Results and discussion


3.1. Water quality of the secondary efuents and the RO inuents
The water quality of the secondary efuents and the RO inuents in
the plant was shown in Fig. 2. The water quality of the RO inuents
changed little compared to the secondary efuents in terms of chemical
oxygen demand (COD), biochemical oxygen demand (BOD5), DOC,
40

ammoniacal nitrogen (NH3N) and total phosphorus (TP), but except


suspended substance (SS). The average SS values were 13.7 mg/L and
4.2 mg/L for the secondary efuents and the RO inuents, respectively.
The removal of SS by UF membrane was 69.3%. The average DOC concentrations for the secondary efuents and the RO inuents were
10.43 2.66 mg/L and 10.57 2.75 mg/L, respectively. It is indicated
that UF membrane worked as pretreatment for RO membrane had little
effects on DOM and mainly remove particles and colloids in the secondary efuents.
Silt density index (SDI) was used to describe the capacity of RO inuent after pretreatment to foul RO membranes. The SDI values of the RO
inuents ranged 0.63.84 (n = 622), which could meet the SDI limitation (b 5) for the RO membrane.
TDS in the secondary efuents and RO inuents was 2737 mg/L (n =
270) and 2727 mg/L (n = 32). The average concentration of Ca, Mg and Si
in the secondary efuents was 265 mg/L (n = 325), 80 mg/L (n = 323)
and 10 mg/L (n = 10), respectively, while the average concentration of
40

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

COD BOD5 DOC NH3-N

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

COD BOD5 DOC NH3-N

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+

TDS Ca Mg Fe Mn Si Al SO4 Cl alkalinity

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

F. Tang et al. / Desalination 349 (2014) 7379

Table 2
The content of organic and inorganic components in the deposit by loss of ignition analysis.a
Dry weight (g/m2)

Organic content (g/m2)

Organic content (% of DW)

Inorganic content (g/m2)

Inorganic content (% of DW)

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

C\H bending, respectively. The band at 1620 cm1 corresponding to


C_C stretching was characteristic for aromatic ring modes, alkenes. The
bands at 3410 and 3550 cm1 corresponding to O\H stretching were
characteristic for bonded and non-bonded hydroxyl groups and water.
The major bands of the deposit according to the FTIR spectra were at
1050, 1410, 1550, 1640, 2930 and 3310 cm1. Compared to the FTIR
spectra of the secondary efuent and the RO inuent, the FTIR spectra
of the deposit samples showed no band at 604 cm1 indicating that sulphate did not deposit on the membrane. The bands at 1050 cm1 and
1410 cm1 correspond to C\O stretching and C\H bending, respectively, which was similar with the bands of the secondary efuent and
RO inuent. The bands at 1550 cm1 and 1640 cm1 corresponding
C_C stretching were characteristic for aromatic ring modes, alkenes.
The number and intensity of the bands at 15001690 cm1 for the deposit were larger than that for the secondary efuent and RO inuent,
indicating that organic matters with aromatic ring or unsaturated carbon bonds could deposit on the RO membrane easily than other kinds
of organic matters during the membrane running. The bands at 2930
correspond to C\H stretching and the band at 3310 cm1 was characteristic for water [19].

3.3. Specic inorganic element of the deposit


The concentrations of elements in RO inuent and the contents of elements in deposit on RO membrane were shown in Fig. 4. The deposition ratio, which of the elements was shown in Table 3, is dened as
the percentage of the amount of the specic inorganic element deposited on the membrane in the total amount of the inorganic element in RO
inuent for 60 days in this paper.
The inorganic component of the deposit mainly comprised of element Fe, Ca, Mn, Si and Al. Fe content in deposit was 349.18 mg/m2,
while the concentration of Fe in the RO inuent was low, in the ranges
of 0.030.06 mg/L. Fe concentration in RO inuent is relatively low compared with other elements, while Fe content in deposit is the highest.
The deposition ratio of Fe was 26.4%, which is much higher than other
elements. Fe deposited on the RO membrane much more easily than
other elements.

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.

Content in deposit (mg/m2)

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)

Fig. 4. Concentration of elements in RO inuent and content of elements in deposit on RO


membrane.

F. Tang et al. / Desalination 349 (2014) 7379


Table 3
Deposition ratio of elements in the deposit on the membrane.
Element

Ca

Mg

Fe

Mn

Si

Al

Deposition ratio (%)

0.0017

0.00047

26.42

7.07

0.019

0.43

SUVA (L/mg cm-1)

6
HCl

77

Si in the deposit presented in a relatively high content level, which


was 76.46 mg/m2. The deposition ratio of Si was 0.019%. However, Si
was quite difcult to be removed by physical or chemical cleaning for
the plant.
The nature of inorganic component in deposit of RO membranes
depends essentially on inorganic feed water composition, the
chemicals used in pretreatment and on chemical equilibria of
sparingly soluble salts in brine [11]. However, there was no specic
pretreatment in terms of Fe or Si removal. Hence, wastewater
upstream with high Fe or Si concentration should be controlled seriously or be transferred to other treatment plants to decrease the
concentration in RO inuent in case of Fe or Si pollution on RO
membrane surface.

3.4. Dissolvable organic component of the deposit


NaOH
2
UPW
0
0.0

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.

Ca was the second largest inorganic component in the deposit and


the content was 157.78 mg/m2, while the average concentration of Ca
in the RO inuent was the highest (266 mg/L). However, the deposition
ratio of Ca was 0.0017%, which was the lowest among the six specic elements. This phenomenon could be explained by the effective function
of the antiscalant (PWT Titan ASD 200) used in this plant. The injection
of the antiscalant also worked on element Mg; it was why the status of
Mg was quite similar with that of Ca.

420

Excitation (nm)

Secondary effluent

3.4.2. Fluorescence EEM spectrum


Fluorescence EEM spectra of the secondary efuent, the RO inuent,
SHCl and SNaOH were shown in Fig. 6. The EEMs were divided into 5 regions
(Region I to Region V) based on the characteristics of each type of OM.
Region-I and Region-II (Ex b 250 nm; Em b 380 nm) represent aromatic

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)

3.4.1. DOC and SUVA


DOC and SUVA of the three solutions SHCl, SNaOH and SUPW were
shown in Fig. 5. SUPW has relatively low DOC (0.21 0.01 g/m2) and
low SUVA (0.46 0.02 L/mg cm1) compared to SHCl and SNaOH.
DOC of SNaOH was 2.37 0.32 g/m2, much higher than the 0.41
0.02 g/m2 DOC of SHCl. Most organic matter could be dissolved easily
by alkaline solution and that is why alkaline cleaning is more effective
than acid cleaning in most RO plant for MWR.
However, SUVA of SHCl was 6.10 0.48 L/mg cm1, much higher
than the 3.22 0.22 L/mg cm1 of SNaOH. It was inferred that the deposit dissolved in acid solution mainly comprised of the organic compounds
with aromatic structures.

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

F. Tang et al. / Desalination 349 (2014) 7379

HIN

HOA
4
3
2
1
0

HOA
15
HOB

HIN

10

HOB

5
0

HIB

HON

HIB

HON

For SNaOH, there were two different uorescence chromophore found


at Ex = 280 nm/Em = 360 nm and Ex = 320 nm/Em = 390 nm,
which belonged to Region IV and Region V, respectively, indicating the
large amount of microbial-derived OM and humic-like OM in the deposit
on the RO membrane. Since these kinds of microbial-derived OM and
humic-like OM could adsorb on the membrane surface easily and increase
fouling, their removal from secondary efuent can provide a substantial
increase in the life of membranes [21].

HIA

HIA

(a)

(b)

Fig. 7. DOC concentration (mg/L) of resin-fractions of DOM in secondary efuent and


SNaOH. The six Resin-fractions are hydrophobic acids (HOA), hydrophobic bases (HOB), hydrophobic neutrals (HON), hydrophilic acids (HIA), hydrophilic bases (HIB), and hydrophilic neutrals (HIN).

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)

3.4.3. Resin fractionation analysis of DOM


Because of the largest amount of organic matter dissolved in SNaOH
among the three solutions, SNaOH was analyzed deeply instead of SHCl
and SUPW. DOC of resin-fractions of DOM in secondary efuent and
SNaOH were quite different as shown in Fig. 7.
In the secondary efuent, the hydrophobic and hydrophilic fractions
occupied 67.7% and 32.3%, respectively. HON fraction was the largest
one among the six fractions of HOA, HOB, HON, HIA, HIB and HIN. The
DOC of HON fraction was 3.01 mg/L and occupied 30.6% of the total
DOC. The second largest fraction was HOA and the DOC of HOA fraction
was 2.85 mg/L.
In SNaOH, the hydrophobic fractions occupied 59.0% of the total DOC,
which was also a little higher than the 41.0% of hydrophilic fractions.
HOA and HIN fraction became the two largest fractions among the six
fractions. Gray et al. (2007) summarized and reported that HIN fraction
and HOA fraction (mainly comprised of humic acid) were the main
foulant on the UF and NF membrane [22]. This phenomenon was similar
to the result in this paper.
The DOC of HOA fraction was 12.28 mg/L and occupied 47.3% of the
total DOC in SNaOH. HOA fraction was dominated by humic substances,
which could deposit on the membrane and should be monitored
as key fractions to forecast and control the organic fouling of RO
membrane.

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.

F. Tang et al. / Desalination 349 (2014) 7379

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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