Supporting Information

Removal of Emerging Wastewater Organic Contaminants

by Polyelectrolyte Multilayer Nanofiltration Membranes
with Tailored Selectivity

Yunkun Wang,1 Ines Zucker,2,3 Chanhee Boo,4* and Menachem Elimelech5*

1
Shandong Key Laboratory of Water Pollution Control and Resource Reuse,
School of Environmental Science and Engineering, Shandong University,
Qingdao 266237, China
2
Porter School of Environmental Studies, Faculty of Exact Sciences, Tel
Aviv University, Tel Aviv 69978, Israel
3
School of Mechanical Engineering, Faculty of Engineering, Tel Aviv
University, Tel Aviv 69978, Israel
4
Water Cycle Research Center, National Agenda Research Division, Korea
Institute of Science and Technology (KIST), Seoul, 02792, Republic of
Korea
5
Department of Chemical and Environmental Engineering, Yale University,
New Haven, Connecticut 06520-8286

(*Email: chanhee.boo@kist.re.kr; menachem.elimelech@yale.edu)

Number of Pages: 9
Number of Figures: 3
Number of Tables: 2

S-1
Estimation of NF Membrane Pore Size. The average pore size of the PEM membranes was
determined based on a pore transport model that incorporates steric (size) exclusion and hindered
convection and diffusion from the rejection data of reference inert organic solutes. Neutrally
charged and highly water-soluble organic molecule — dextrose (Sigma-Aldrich, St. Louis, MO)
— was used as the organic tracer. Prior to NF experiments, the membrane was pre-compacted
under 10.3 bar (150 psi) hydraulic pressure with DI water as the feed for 4 h. After compaction,
dextrose was injected to the feed to obtain a concentration of 40 mg/L (as total organic carbon,
TOC) and subsequent experiments were conducted at 4.1, 6.2, 8.3, and 10.3 bar with a crossflow
velocity of 21.4 cm/s and a feed temperature of 25.0  0.5 °C. The permeate flux was recorded
after the system was run for 1 h at each pressure. Permeate and feed samples were taken for TOC
analysis (TOC V-CSH, Shimadzu Corp., Japan) to determine the rejection of dextrose. Details on
the pore size estimation based on the pore transport model using the measured rejection of the
organic tracer are provided in the Supporting Information (Table S1) and our previous study. 1

The real rejection of the reference organic solutes, Rr, can be determined using the following
equation derived from the pore transport model: 2

K c
Rr  1  (S1)
1  exp(  Pe) 1  K c 

where Kc is the hydrodynamic hindrance coefficient and Pe is the pore membrane Peclet number.
Details on the calculation of Kc and Pe are given elsewhere.2, 3 The distribution coefficient or
partition coefficient of a solute,  , between a solution and a membrane pore links the
thermodynamic description of solute transport thorough the membrane to the pore geometrical
factor when only steric interactions (i.e., size exclusion) are considered:
2
c'  r 
  (1   ) 2  1  s  (S2)
c  rp
 

where c ' is the average solute concentration within the pore, c is the concentration just outside

the pore, and  is the ratio of the solute radius, rs , to the pore radius, rp .

The real rejection in eq S1 relates the solute permeate concentration to the membrane surface
concentration on the feed side, which is different from the bulk feed concentration due to

S-2
concentration polarization. We applied film theory to correlate the observed rejection (Ro, data
obtained from the reference organic solute rejection) and the real rejection by accounting for
concentration polarization:2

1  Rr 1  Ro J v
ln  ln  (S3)
Rr Ro kf

where kf is the mass transfer coefficient and Jv is the permeate water flux.

The following optimization process was performed to estimate the membrane pore size from
the retention data of reference organic solutes. First, the real retention of the reference organic
solutes was determined from observed retention using eq S3. The model parameters in eq S1,
K c and Pe that are uniquely related to Rr, were determined by fitting the real retention date to

the model (eq S1) using an optimization procedure (Solver, Microsoft Excel). The parameters
K c and Pe are solely dependent on the variable  (ratio of solute radius to membrane pore

radius, rs / rp ) and thus used to obtain  for each organic solute and the membrane. With the

determined value of  and the given solute radius, rs , the membrane average pore radius was

calculated for each reference organic solute retention data.

S-3
Table S1. Properties of dextrose (organic tracer) and pore radius of PEM NF membranes
estimated from organic tracer experiments.

MW Solute Radius Pore

Membrane Organic Tracer Landa () Radius
(g/mol) (rs, nm) (nm)

2-Layer 0.399 0.813

4-Layer 0.613 0.528

Dextrose 180 0.324
6-Layer 0.687 0.472

NF270 0.720 0.407

S-4
 Table S2. Physicochemical properties of emerging organic contaminants.

Molecular Dissociation
Organic Chemical
Compounds Weight Constant
Contaminants Structure
(g/mol) (pKa)

Perfluorooctanoic acid
414 -0.1-2.84, 5
(PFOA)
Perfluoroalkyl
Substances
(PFASs)
Perfluorooctanesulfonic
538 -3.36
acid (PFOS)

Amoxicillin
Trihydrate 419 2.7-9.67
Pharmaceuticals
and (AMT)
Personal
Care
Products
(PPCPs) Tetracycline
Hydrochloride 480 3.3-9.78
(THE)

S-5
 A

Water Permeability (L m-2h-1bar-1)

350 100

Water Contact Angle (

80
300
60
250
40
40

20 20

0 0
PSf Support NF270

B
0
PSf Support
Zeta Potential (mV)

-5 NF270

-10
-15
-20
-25
-30
3 4 5 6 7 8 9
pH
Figure S1. (A) Water permeability and water contact angle of PSf substrate and commercial
NF270 membrane. Water permeability was measured at applied hydraulic pressure of 6.9 bar
(100 psi) after 4 h compaction using DI water as feed at adjusted pH of 7.0  0.1, crossflow
velocity of 21.4 cm/s, and temperature of 25  0.5 °C. For water contact angle measurement, a
5-μL water droplet was placed on the membrane surface and the contact angle was monitored
for 1 min. Error bars represent standard deviations of two contact angles from three different
membrane samples. (B) Zeta potential of PSf substrate and commercial NF270 membrane.
Measurements were performed with a solution containing 1 mM KCl and 0.1 mM KHCO 3.
Background solution pH was adjusted to from 3 to 9 using KOH or HCl. The error bars represent
standard deviation and were calculated from eight measurements.

S-6
 100 Carbon Sulfur
Oxygen Nitrogen

Area Fraction (%)

80

20

10

0
PSf 2-bilayers 4-bilayers 6-bilayers

Figure S2. XPS analysis of the surface of PSf substrate and PEM NF membranes. Fraction of
carbon, oxygen, sulfur, and nitrogen relative to the sum of elements present at the membrane
surface.

S-7
 4-bilayers
100 Na2SO4

Rejection (%)
80
60 Sequential
Measurement
40 NaCl
20
0 CaCl2

0 10 20 10 0
Concentration (mM)
Figure S3. Salt rejections of 4-bilayer membrane sequentially evaluated at 2, 10, 20, 10,
and 2 mM sodium chloride, calcium chloride, and sodium sulfate concentrations using an
identical membrane coupon. Other experimental conditions were as follows: hydraulic
pressure of 6.9 bar (100 psi), feed solution pH of 7.0  0.1, crossflow velocity of 21.4 cm/s,
and temperature of 25.0  0.5 °C.

S-8
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