Reactions and Separations

Minimize Biofouling of
RO Membranes
Anne Arza Chemical and physical disinfection of feedwater to
Jane Kucera
NALCO Water a reverse osmosis (RO) membrane helps to prevent
fouling and maintain efficient operation.

T
he bane of existence for users of reverse
osmosis (RO) membrane systems (Figure 1) is con-
trolling membrane fouling from microorganisms.
Autopsies of 150 membranes found that all of the mem-
branes had some degree of membrane biofouling (Figure 2)
(1). Forty-nine had microbial colony densities greater than
105 CFU/cm2, which was the direct cause of the membranes’
performance decline. Biofouling was a contributing factor to
the performance decline of the other 101 systems.
Biofouling is the irreversible adhesion on a membrane of
microorganisms and the extracellular polymers (ECPs, i.e.,
biofilm) that they produce. The process of adhesion involves
three steps (2):
1. bacterial adhesion, which can become irreversible in
just hours, even without nutrients present
2. micro-colony formation
3. biofilm maturation and the formation of ECP,
which protects the bacteria from biocides, flow shear, and
predators.
Properties of membranes that favor adhesion and biofilm
formation include:
• surface roughness (Figure 3) — the rougher the surface,
the more adhesion
• surface charge — the more neutral the charge, the more
adhesion of bacteria (which are negatively charged)
• hydrophobicity — the more hydrophobic the mem-
brane, the more adhesion.
Biofilm adhesion is also promoted by dissolved nutri-
ents in the laminar boundary layer next to the membrane,
which is called the concentration polarization layer (3).
Because no convection occurs at the membrane surface, dis-
solved and suspended solids, including nutrients, build up
(Figure 4).
Once a biofilm forms, it protects the underlying bacteria
from disinfecting chemicals and flow shear forces that could
disrupt the film.
Aerobic bacteria in seawater, brackish water, and waste-
water systems, and anaerobic bacteria (e.g., iron- and sulfate-

u Figure 1. This is a typical Separate Source High-Pressure Switch

reverse osmosis (RO) schematic. Flush Supply Pressure Relief
High-Pressure
Biocides or other biofouling Conductivity
ORP Pressure Pressure Low-Pressure Switch RO
preventive measures are Temperature Switch Flow
System
added to the feedwater during Pressure Pressure
pretreatment. Conductivity Product
From
Pretreatment
This article is based on the paper
“Alternative Disinfection for Cartridge High-Pressure
Feed Pump High- Flush Drain
Reverse Osmosis Systems,” Filter
Differential-
presented at the International to Drain
Pressure Pressure Flow
Water Conference, Nov. 2014, Switch
in San Antonio, TX. Drain Reject

60  www.aiche.org/cep  September 2016  CEP Copyright © 2016 American Institute of Chemical Engineers (AIChE)
u Figure 2. This membrane
is covered with a black
biofoulant.
reducing bacteria) in
wells, can all cause
membrane biofoul-
ing. Reverse osmosis
membranes used in
recycle/reuse processes
are exposed to an
even broader range of
microbes, including aerobic, anoxic, and anaerobic species.
The presence of biofouling can be indicated by (4):
• higher differential pressure, which can be evident
within a few days of inoculation
• lower membrane flux, which may or may not occur
prior to the change in differential pressure
• higher operating pressure required to maintain the
product flowrate
• localized scaling in areas of low flow velocity caused
by uneven growth of colonies, which can happen before any
appreciable increase in differential pressure, particularly in
spiral-wound membranes.
Techniques to address biofouling
The objectives of biofouling treatment methods are to
kill the microbes; remove microbes and dead microbial
bodies (which can become food for new growth); prevent
adhesion, propagation, and biofilm maturation; and remove
nutrients that foster microbial growth. Techniques to accom-
plish these objectives include:
• membrane surface modification
• modification of the bacterium and/or organic nutrient
source
• disinfection, removal, or sterilization of the microbes.
Techniques to modify membrane properties, such as
roughness, charge, or hydrophilicity, include coating the
membrane and using a membrane made of a different
polymer to minimize bacterial adhesion. Antimicrobial
nano­particles, such as silver, titanium dioxide, and carbon
nanotubes, incorporated into membranes can help to limit
adhesion.
Bacterium modification and disinfection reduce the
concentration of viable microorganisms in the feedwater
flowing to a membrane. The three basic methods of bacte-
rium modification and disinfection are physical, thermal, and
chemical.
Physical disinfection techniques include ultraviolet (UV)
radiation, membrane filtration (microfiltration [MF] and
ultrafiltration [UF]), and sand filtration. These techniques
either modify the bacterium itself to hinder reproduction
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
Thin Film Surface
u Figure 3. The rough
surface and hydro­
Polysulfone Backing
phobic properties of this
polyamide RO membrane
favor bacterial adhesion.
(UV) or remove bacteria according to particle size (MF, UF,
and sand filtration). These methods, however, can be capital-
intensive and do little to address biofilm once it has formed.
Other physical approaches are not yet commercialized,
including electrochemical, ultrasonic, and thermosonication
techniques.
During electrochemical treatment, a microbial suspen-
sion passes between two electrodes, which subject the
bacteria to a pulsed electric field. The field disrupts the cell
wall, killing the bacteria (5).
Ultrasound (sonication) is a chemical-free process that
causes cell disruption by inducing cavitation in a solution.
Bubbles form and break, generating turbulence and pressure
differences that can rupture the microorganisms (5).
Sonication can also be combined with high tempera-
tures (48°C) to rupture microorganisms, in a process called
thermo­sonication. This technique is capable of damaging
cells to the point that they are unable to adequately generate
extracellular polymeric substance (EPS) on an RO mem-
brane, forming fewer and less-aggregated colonies than in
untreated water (5).
Thermal processes are generally not applicable to
standard RO membranes, which have a stability limit of
45°C — well below the sterilization temperature required for
No Convection Laminar Boundary Layer
Turbulent Region
Convection
Bulk
Solute
Diffusion
No Convection Laminar Boundary Layer
p Figure 4. Because there is no convection in the concentration
polarization layer on the surface of a membrane, dissolved nutrients and
suspended solids can build up and promote bacterial growth.
CEP  September 2016  www.aiche.org/cep  61
Reactions and Separations

thermal deactivation. High-temperature membranes intended Biocides are classified as oxidizing or non-oxidizing.
for food/beverage and pharmaceutical applications typically Of the oxidizing biocides, chlorine is most commonly used
tolerate temperatures up to 90°C for short periods of time for membrane applications because it is easy to use, widely
(usually during disinfection and cleaning). available, and able to deactivate most pathogenic micro­
Chemical biocides are used to treat feedwater to organisms quickly (3). However, because chlorine tends to
membranes systems as well. The efficacy of a biocide form disinfection byproducts (DBPs), such as trihalometh-
depends on: anes (THMs) and haloacetic acids (HAAs), other biocides
• the type of biocide and its mechanism of attack are increasingly being employed, including chloramine,
• the concentration of the biocide; higher concentrations chlorine dioxide, ozone, bromine, iodine, 1-bromo-3-chloro-
typically provide greater efficacy 5,5-dimethylhydantoin (BCDMH), peroxide/peracetic
• the occurrence of side reactions that generate inert acid, potassium permanganate, copper sulfate, sodium
compounds bisulfite, dichloroisocyanurate (DCC), 2,2-di-bromo-3-­
• the presence of compounds other than microorganisms, nitrioproprionamide (DBNPA), and isothiazolones.
such as organics, that compete for the biocide chemical This article limits the discussion of physical and chemi-
• the pH of the solution cal RO membrane disinfection techniques to those summa-
• the temperature; higher temperatures improve efficacy rized in Table 1.
• the residence time of exposure; longer exposures
increase efficacy Chlorine
• the type of microorganisms present Chlorine is used to disinfect feedwater in pretreatment
• the growth state of the microorganisms systems before it reaches the RO membranes. It works
• the status and maturity of the biofilm. by oxidizing the cellular material of the microorganism.
Gaseous chlorine and liquid sodium
Table 1. Physical and chemical techniques are used in pretreatment systems hypochlorite are most often used in
to control microorganism growth. Adapted from (6). pretreatment. Although gaseous chlo-
Relative rine is the most economical, it is also
Method Technique Advantages Limitations Cost* the most toxic and requires special
Physical Ultraviolet • Easy installation • No residual effect $$$$ storage and handling precautions.
(UV) • Effective inactivation • Scaling on UV lights Both chlorine gas and sodium
• Oxidizes organic • Large capital hypochlorite immediately hydrolyze
matter investment in water to form hypochlorous acid
Chemical Chlorine • Effective inactivation • Degrades $ (HOCl):
• Relatively low cost membranes
• Forms byproducts Cl2 + H2O ↔ HOCl + HCl
• Residual disinfection
• Toxic gas NaOCl + H2O ↔ HOCl + NaOH
Chloramine • Less destructive to • Relatively low $
membranes efficacy The reaction of chlorine gas and
• Residual disinfection
water yields an acid, which lowers
the pH of the treated water, while the
Chlorine • Slightly less • Must be generated $$
Dioxide destructive to on-site
reaction of sodium hypochlorite and
membranes water yields caustic, which raises the
• Forms chlorite and
chlorate byproducts pH of the treated water.
• Gas can detonate
Hypochlorous acid is unstable and
decomposes to form hypochlorite ions
• May generate some
free chlorine (OCl–):
Ozone • Effective inactivation • Very short half-life $$$
HOCl ↔ H+ + OCl–
• Oxidizes organic • Degrades
matter membranes
The stability of hypochlorous
Non-oxidizers • Good membrane • Relatively low $$$–
compatibility efficacy $$$$
acid is a function of pH (Figure 5),
temperature, and salinity. It is present
• Expensive
in greater amounts at pH from two
* Estimated cost is based on the combined capital and operating costs.
to approximately neutral. Its kill rate

62  www.aiche.org/cep  September 2016  CEP Copyright © 2016 American Institute of Chemical Engineers (AIChE)
doubles for every 10°C increase in temperature, and higher
salinity reduces its effectiveness.
The efficacy of chlorine treatment is a function of pH,
exposure time, and method of application. An exposure time
of 20–30 min at the head of the pretreatment train provides
maximum efficacy (3). Following exposure, a residual of
0.5–1.0 ppm of free chlorine should be maintained through-
out the pretreatment system for complete disinfection (5, 7).
(Reference 8 describes how to determine the optimum chlo-
rine dosage to achieve this level of residual.)
A continuous feed of chlorine has been shown to be
more effective at hindering the development of biofilm
than shock treatment alone (7). Reference 9 reports that
no biofilm was formed on a seawater RO system carrying
0.04–0.05 ppm residual free chlorine. Continuous feed with
shock treatments during warm weather is even more effec-
tive at controlling biogrowth and development (4).
While chlorination is easy to employ and is also rela-
tively inexpensive, it has some limitations:
• It forms carcinogenic species, such as THMs
and HAAs.
• It is ineffective at controlling some pathogens, includ-
ing Cryptosporidium parvum and Mycobacterium avium,
and at deactivating protozoa and endospores.
• It oxidizes organic molecules into smaller organics.
This may help minimize fouling by larger-chain organics,
such as humic acids, but creates smaller particles that are
converted into assimilable organic carbon (AOC), which
increases microbe growth potential.
• It oxidizes the membrane polymer, which degrades the
integrity of the membranes. The chlorine attacks the amide
100%
100%
90%
80% Cl2 OCl–
80%
70%
Total Combined Chlorine
functional group and destroys the hydrogen-bond linkages in
the polymer (10).
Because of the deleterious effects of chlorine on poly­
amide membranes, free chlorine must be removed to prevent
contact with the membranes. Dechlorination is relatively
simple, and typically employs either sodium bisulfite to
chemically remove free chlorine or carbon filtration to cata-
lytically remove chlorine. Chlorine removal typically takes
about 3–5 min.
Chloramine
Chloramine is an oxidizing biocide that includes
three species known collectively as combined chlorine:
mono­chloramine (NH2Cl), dichloramine (NHCl2), and
tri­chloramine or nitrogen trichloride (NCl3). Although
dichloramine and trichloramine are stronger biocides than
monochloramine, they are very unstable. Monochloramine
is stable and not as prone to imparting a chlorinous taste and
odor to water. The concentration of the combined chlorine
species is a function of pH (Figure 6).
Chlorine and ammonia gas are combined to create
chlora­mine in a process called chloramination:
HOCl + NH3 ↔ NH2Cl + H2O
2HOCl + NH3 ↔ NHCl2 + 2H2O
3HOCl + NH3 ↔ NCl3 + 3H2O
The chloramination reactions are strongly dependent
on pH, relative concentration of the reactants, and tempera-
ture. At 25°C, the reaction time to form monochloramine
is minimized at a pH of 8.4 (11). One mole of hypo­chlorous
acid reacts with 1 mole of ammo-
nia to form 1 mole of mono­
chloramine. On a weight basis,
NH2Cl
this corresponds to a chlorine-
to-nitrogen ratio of about 5:1.
Higher ratios slow the reaction,
and lower ratios yield more

60%
60% dichloramine and trichloramine
Saturation

(11). The reaction rate increases

50%
with temperature.
40% 40% Because the reaction to
produce monochloramine is a
30% HOCl
reversible reaction, chlorine and
20% 20% NHCl2 ammonia gas will always be in
equilibrium with monochlora-
10% NCl3
mine. The chlorine present can
0%
1 2 3 4 5 6 7 8 9 10
degrade RO membranes, and the
3 5 6 7 8
pH pH ammonia gas can reversibly swell
the membranes, allowing more
p Figure 5. Chlorine treatment should be conducted p Figure 6. Chloramine disinfection needs to
at a pH between 2 and approximately 7.5, where HOCl operate at pH greater than 7 to avoid the creation of salt to pass into the permeate.
predominates (4). dichloramine. Monochloramine has only

Copyright © 2016 American Institute of Chemical Engineers (AIChE) CEP  September 2016  www.aiche.org/cep  63
Reactions and Separations
0.4% of the biocidal capability as hypochlorous acid (12),
and it has slower kinetics (13). Slower kinetics allow residual
monochloramine to remain in distribution systems longer
than chlorine residuals, making monochloramine more
desirable for municipal water distribution systems. However,
because of the slower kinetics, it might take days or weeks to
accomplish an acceptable level of disinfection; that may be
suitable for water distribution systems, but not for RO feed-
water disinfection, which needs to be virtually immediate.
Determining the concentration of monochloramine
needed to treat water requires breakpoint chlorination
(Figure 7). The maximum concentration of monochloramine
occurs when all of the ammonia has reacted with the added
chlorine; this point is called the monochloramine hump. Any
chlorine added after this point produces other chloramine
species, and this continues until the breakpoint, after which
any chlorine added yields only free chlorine, is reached.
The advantage of chloramination over chlorination is
chloramine’s diminished capability to form hazardous dis­
infection byproducts. But chloramination has limitations:
• When the total organic carbon (TOC) concentration
exceeds about 3 ppm, organic chloramines form, which have
little or no disinfectant capabilities (14).
• The reaction rate is very slow.
• Chloramines are not as effective on pathogenic micro-
organisms as chlorine.
• Ammonia added to generate chloramine also provides
nutrients for nitrifying bacteria, which may cause nitrate
concentrations in water treated with chloramination to rise.
Because chlorine and monochloramine are in
equilibrium, water treated with chloramine needs to be
treated prior to RO. Although most membrane manu-
facturers allow for a chloramine exposure of about
300,000 ppm-hr until salt passage doubles, this exposure is
calculated based on pure chloramine (without the accom­
panying free chlorine and free ammonia gas).
10
I II III
8
Chloramination Free Chlorination
Monochloramine
6 Hump
Residual
Cl2:N, 5:1
4 2NaClO2 + H2O2 + H2SO4 → 2ClO2 + NaSO4 + O2 + 2H2O
2
Breakpoint
Cl2:N, 9:1
0
0 2 4 6 8 10 12 14
Assume ammonia is present
Chlorine Dose
p Figure 7. Chloramination occurs at low chlorine doses (region I). After
the monochloramine hump has been reached, less-desirable species form
(region II). After the breakpoint has been reached, only free chlorine is
generated (region III). Adapted from (14).
64  www.aiche.org/cep  September 2016  CEP
Sodium thiosulfate, UV radiation, and ascorbic acid are
used to remove chloramine, but carbon filtration and sodium
bisulfite are the most common methods. During carbon
filtration, fresh carbon can remove chloramines in as little as
10 min, but as long as 30 min may be required for a used bed.
Chlorine dioxide
Chlorine dioxide is an oxidizing biocide that has grown
in popularity for disinfection, color reduction, and taste
and odor control in the last two or three decades (11, 15). It
minimizes the production of THM byproducts by oxidizing
THM precursors, but it uses and/or forms chlorite and chlo-
rate byproducts. The U.S. Environmental Protection Agency
(EPA) has established a maximum contaminant level goal
(MCLG) of 0.8 ppm for chlorite. Since 75% of the chlorine
dioxide that is added to water forms chlorite, the maximum
allowable chlorine dioxide concentration is 1.3 ppm, unless
a chlorate removal process is employed (11). There is no
MCLG for chlorate, although evidence suggests that it is a
potential health hazard (16).
Chlorine dioxide is highly volatile and is not stable in
concentrated solutions. The gas also detonates upon com-
pression. Thus, chlorine dioxide must be generated on-site.
The conventional method for generating chlorine dioxide
involves mixing sodium chlorite with chlorine gas or hypo-
chlorous acid:
2NaClO2 + Cl2 → 2ClO2 + 2NaCl
2NaClO2 + HOCl + HCl → 2ClO2 + H2O + 2NaCl
Because the chlorine gas or hypochlorite might not react
completely, some free chlorine could remain in the system
and damage the RO membrane. For this reason, major
membrane manufacturers do not recommend using chlorine
dioxide. Although membranes may be compatible with pure
chlorine dioxide, chlorine dioxide generated on-site from
chlorine and sodium chlorate is often contaminated with free
chlorine that can damage membranes.
Thus, other chemistries were developed to generate
chlorine dioxide to minimize or eliminate the presence of
free chlorine:
5NaClO2 + 4HCl → 4ClO2 + 5NaCl + 2H2O
RO membrane compatibility with pure chlorine diox-
16 ide depends on dosage, exposure time, and pH. Studies of
the effects of chlorine dioxide on RO membranes report
increases in salt passage through the membrane at almost
any pH; however, higher pH amplifies damage (17, 18).
Despite membrane compatibility issues, chlorine dioxide
is an effective biocide. Studies have shown that less than
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
0.1 ppm of chlorine dioxide can successfully deactivate
common water pathogens (e.g., Salmonella paratyphi B,
Eberthella Typhosa, and Shigells Dysenterias) in 5 min (19).
Furthermore, chlorine dioxide is as effective, and in some
cases more effective, than chlorine on Escherichia coli,
Salmonella typhosa, and Salmonella paratyphi (20).
Chlorine dioxide works best on relatively clean surface
waters where the concentrations of oxidant-demanding spe-
cies such as iron, manganese, and organics are low (11). It
should be located after clarification and filtration to lower
the oxidant demand.
Chlorine dioxide does not produce THMs or HAAs,
and it can be a more effective disinfectant than chlorine. Its
usefulness is limited because:
• It can damage RO membranes.
• The method uses and/or forms chlorite and chlorate.
• It is highly volatile and explosive.
• It is difficult to dose when oxidant-demanding species
are present.
Ozone
Ozone (O3) is an allotropic form of oxygen and a
strong oxidizing biocide used to disinfect feedwater in RO
pre­treatment systems before the water contacts the RO
membranes. It is a colorless gas at room temperature and
condenses to a blue liquid, but it is extremely unstable.
It oxidizes the cellular material of microorganisms either
directly or through decomposition that forms other radical
species that react with organic matter. Ozone is a 50% stron-
ger oxidizer than chlorine and acts more than 3,000 times
faster. It is effective at deactivating bacteria, viruses, pro-
tozoa, and endospores. However, under certain conditions,
ozone can create bromates or bromine compounds that have
been found to be carcinogenic.
Ozone and the radicals it decomposes into weaken the
biofilm matrix, which allows for removal of the biomass by
shear forces. The free radicals can also form peroxide, which
penetrates the cell walls of microorganisms and disrupts
cell physiology.
Ozone decomposes rapidly in water to form hydroxyl
free radicals (•OH) that are effective at destroying micro­
organisms, or directly reacts with the organics present in
the feed:
O3 + OH– → •O2– + •HO2–
O3 + Organic → Organicox
The materials of construction for the generation equip-
ment and the distribution equipment should be selected
carefully, because ozone is extremely corrosive and will
attack almost all metals except Type 316 stainless steel, gold,
and platinum. Most plastics (with the exception of fluoro­
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
polymers) are not suitable for systems that handle ozone.
The overall efficiency of ozone is difficult to predict
because the presence of natural organic materials, water
characteristics, temperature, and pH all affect efficiency.
Ozone dosage is based on two factors: the amount of ozone
needed to stoichiometrically consume the contaminants
present; and the amount of ozone needed for disinfection,
in mg/L, which is based on concentration over time. Both
factors require correct injection and mixing time, and in
addition, ozone must physically come into contact with the
contaminants. Filtration is almost always required to remove
particulates. Any excess ozone will create off-gas, which
must be destroyed.
In nature, ozone is generated mainly by electricity and
radiation. Ozone can be commercially generated by electri-
cal discharge (corona discharge), electrolysis of acid, UV
radiation, radiochemical methods, and other (less common)
chemical methods. Electrical discharge generation is by far
the most common, safe, and economical approach.
To electrically generate ozone, extremely dry air or
pure oxygen is exposed to a uniform high-voltage electric
discharge. The gas generated is transferred to the water
via eduction, injection, or diffusion, or in a packed tower.
Because ozone degrades quickly, it must interact in a near-
plug-flow reactor. Generating ozone is approximately four
times more expensive than generating chlorine.
Because it is highly oxidizing, ozone must be removed
before it reaches the RO membrane. Adsorption, catalysis,
chemical, UV, time decay, or thermal methods can be used
for ozone removal. Catalytic removal of ozone employs
metal oxides and elevated temperatures (85°F–160°F), and
thermal destruction requires elevated temperatures; neither
metal oxides or high temperatures are compatible with most
membranes. The most practical methods for ozone removal
in RO applications are carbon adsorption and UV radia-
tion. During UV removal, a 254-nm light adds energy to
the ozone, converting it into water and oxygen. Carbon and
UV destruction should be located close to the membrane to
allow the ozone to remain in the system as long as possible
to maximize the sanitation benefits.
Ozone is very effective at preventing biofouling, but its
usefulness is limited because:
• Low doses of ozone may not effectively deactivate
some viruses, spores, and cysts.
• The correct dosage is often hard to predict because of
changing water characteristics, and monitoring dosages can
be difficult.
• It must be generated on-site, which reduces shipping
and handling hazards but requires technology for production,
contact, and destruction.
• In most cases, filtration is required.
• Under specific conditions, ozone can create bro-
CEP  September 2016  www.aiche.org/cep  65
Reactions and Separations
mates or bromine compounds that have been found to be
carcinogenic.
• It is more expensive than other forms of fouling control.
Ultraviolet radiation
Ultraviolet radiation is electromagnetic radia-
tion in the 100–400-nm wavelength range. It is broken
into four sub­categories: UV-A (400–315 nm), UV-B
(315–280 nm), UV-C (280–200 nm), and vacuum UV
(VUV) (200–100 nm). Primary disinfection by UV occurs
in the 200–300-nm wavelength range (11). VUV is not used
for disinfection because it rapidly dissipates and degrades
organics into an easily consumable food source for bio­
logical species (5).
UV disinfection is a physical method. The process
transfers electromagnetic energy to an organism’s genetic
material (DNA, RNA), destroying its ability to reproduce,
or UV directly inactivates the organism by creating photons
that are adsorbed by the proteins and nucleotides in the cell.
For cell disruption to occur, the organism’s DNA must
adsorb energy at the correct wavelength and light must be
available with sufficient energy. The optimal wavelength for
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presented at the 62nd Annual International Water Conference,
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2. Subramani, A., and E. M. V. Hoek, “Biofilm Formation, Cleaning,
Reformation of Polyamide Composite Membranes,” Desalination,
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66  www.aiche.org/cep  September 2016  CEP
cell disruption is 250–270 nm, and low-pressure lamps emit
at a wavelength of 254 nm. Under certain circumstances,
cells may repair themselves faster than they are being
degraded; increasing the exposure time and the amount of
radiation reduces the reversal potential and increases the
effectiveness of UV.
UV radiation is effective at killing protozoa, but is less
effective on bacteria, viruses, and endospores. Its perfor-
mance is improved when it is used in conjunction with
hypochlorite, peroxide, or other chemical methods. Factors
that affect efficacy include wavelength, dosage, exposure
time, and the manner of distribution of light in the water. UV
treatment is adversely impacted by high levels of turbidity,
total suspended solids, iron, and humic acids (5). A preven-
tive maintenance program is required to prevent fouling of
the UV system.
UV light is typically generated by placing a voltage
across a gas mixture contained in lamp tubes. The gas is
temporarily excited by the voltage and emits photons as
it returns to a lower energy state. The wavelength of the
emitted light depends on the specific gas mixture. Although
mercury vapor lamps are commonly employed, other types
11. Black & Veatch Corp., “White’s Handbook of Chlorination
and Alternative Disinfectants,” 5th Ed., John Wiley and Sons,
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Water Works Association, 58 (11), pp. 1475–1482 (Nov. 1966).
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Notrosomanas europaea by Propidium Monoazide Quantitative PCR
and Live/Dead BacLight Methods,” Applied and Environmental
Microbiology, 75 (17), pp. 5555–5562 (Sept. 2009).
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processes/disinfection/chemical/disinfectants-chloramines.htm
(accessed May 22, 2014).
15. Snowden-Swan, L., et al., “Disinfection Technologies for Potable
Water and Wastewater Treatment: Alternative to Chlorine Gas,”
http://citeseerx.ist.psu.edu/viewdoc/download?doi=10.1.1.398.9072
&rep=rep1&type=pdf (July 1998).
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Studies of Sodium Chlorate (CAS No. 775-09-09) in F344/N Rates
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Copyright © 2016 American Institute of Chemical Engineers (AIChE)
of lamps, such as metal halide, pulsed UV, excimer, and light
emitting diode (LED) lamps, may also be used.
UV disinfection costs more than chlorine dis­infection,
but can be competitive in some cases when the cost of
removing chlorine from the feed stream is considered.
Operational expenses include the costs for power consump-
tion, cleaning chemicals and supplies, equipment repairs,
and replacement of lamps and sleeves.
UV treatment has no residual effects on the system and
therefore requires no removal step. The UV irradiation sys-
tem should be placed as close as possible to the membrane
to minimize the time between when the water is irradiated
and when it reaches the RO membrane.
UV systems are effective at destroying specific bio­
logical species in bulk water and are relatively easy to install
and maintain. UV disinfection creates no harmful byprod-
ucts that could negatively impact membranes, its efficacy is
not affected by pH, and it requires no chemical handling.
The limitations of UV disinfection include:
• As a standalone treatment, it does not kill some species.
• Performance can suffer in light-scattering waters.
• Filtration is required to remove sediment and other
particles that can shade microorganisms from the light.
• If the wavelength is not carefully controlled, it
can break down large organics into a food source for
microorganisms.
• There is no residual kill effect, so placement of the unit
in close proximity to the membrane system is critical.
• UV units are prone to scaling and fouling, particularly
in high-hardness waters.
• The equipment can be expensive.
Additional techniques
Non-oxidizing biocides. Non-oxidizing biocides that
are compatible with membranes include 2,2-di-bromo-
3-nitrioproprionamide (DBNPA) and isothiazolones.
Typically these chemicals are only suitable for use on clean
membranes, as they lack the ability to handle high concen-
trations of microorganisms.
When using non-oxidizing biocides, it is important to
consider the end use of the water being treated as well as
any local regulatory restrictions. For example, when used
for potable water applications, DBNPA should only be used
offline.
Also consider whether there are any other compounds
in the water that could reduce the effectiveness of non-
oxidizing biocides. For example, DBNPA is deactivated by
bisulfite and other reducing agents.
Other chemical techniques. Adding a caustic to increase
the pH of the water creates a negative charge that repulses
organics. However, this method may incur additional cost to
return the pH back to neutral.
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
Bromine, iodine, and 1-bromo-3-chloro-5,5-­
dimethylhydantoin (BCDMH) are oxidizers that behave
similarly to chlorine, but are weaker and create residuals that
are difficult to remove. These options are significantly more
expensive than hypochlorite. BCDMH, however, is a solid,
which may be advantageous in some operations where a
liquid biocide is not required.
Other oxidizing compounds, such as potassium perman-
ganate (KMnO4), hydrogen peroxide, and hydrogen per-
oxide used in conjunction with peracetic acid, can be used
similarly to chlorine, but they are less effective, pose safety
and handling hazards, or are more expensive. Hydrogen
peroxide and peracetic acid are effective at reaching stagnant
areas in pretreatment systems.
Sodium bisulfite or sodium metabisulfite (noncatalyzed)
can be used as a shock treatment on a periodic basis, par-
ticularly for destroying aerobic bacteria. This is a relatively
low-cost option, but impacts permeate quality if used online.
Biochemical methods. Biochemical methods such as
enzymes, bacteriophages, and signaling molecules can be
used to alter how a biofilm forms or to inhibit biofilm forma-
tion. These methods are expensive and may only be effective
or stable under specific conditions, but are biodegradable
and maintain low toxicity in the system.
Operational methods. For systems that have a medium
to low risk of fouling, preventive cleaning may replace or
supplement biocide addition. This approach requires a clean-
ing system and unit downtime. The chemical cost is moder-
ate, but execution is labor intensive. Chemicals may degrade
membranes with repeated cleanings.
Concluding thoughts
The best way to determine which technique or chemical
will be the most effective on a biological species is to con-
duct pilot tests. Sometimes a single technique is not the best
solution. Often, a combination of techniques — for example,
ultrafiltration paired with an oxidizing biocide, ozone and
UV, or an oxidizing and non-oxidizing biocide — may be
more effective than a single technique. CEP
ANNE ARZA is a senior engineer in the engineering process and develop-
ment group at NALCO Water (Email: alarza@nalco.com). She has more
than 24 years of experience in chemical engineering and chemical and
mechanical water treatment, and has held technical positions with
Culligan, BetzDearborn, and Thomson Scientific. She has a BS in chemi-
cal engineering from the Univ. of Illinois, Urbana.
JANE KUCERA is a global senior technical consultant at NALCO Water
(Email: jkucera@nalco.com), where she is responsible for the design
and technical review of global water treatment projects. She has
34 years of experience with membrane processes, and holds a BA in
chemistry from Linfield College and an MS in chemical engineering from
the Univ. of California, Los Angles (UCLA), where she began her work
with reverse osmosis (RO) membranes. She is the author of Reverse
Osmosis: Design, Processes, and Applications for Engineers and the
editor of Desalination: Water from Water.
CEP  September 2016  www.aiche.org/cep  67