Environmental Engineering and Management Journal May/June 2007, Vol.6, No.

3, 175-187
http://omicron.ch.tuiasi.ro/EEMJ/

“Gh. Asachi” Technical University of Iasi, Romania

______________________________________________________________________________________________

REMOVAL OF PERSISTENT ORGANIC POLLUTANTS FROM TEXTILE

WASTEWATER BY MEMBRANE PROCESSES
Corina-Petronela Mustereţ*, Carmen Teodosiu
“Gheorghe Asachi” Technical University of Iasi, Faculty of Chemical Engineering, Department of Environmental Engineering
and Management, 71 Mangeron Blvd., 700050 Iasi, Romania

Abstract

The textile industry is a large water consumer. Stringent regulations of wastewater characteristics require the use of membrane
processes for the removal of persistent organic pollutants (POPs) from textile wastewater prior to discharge or recycling of these
effluents.
This paper presents an overview of research related to the removal of persistent organic pollutants from textile industry by
membrane processes, discussing also the correlations with actual pre-treatment and removal rates.
Aspects such as the wastewater matrix, membrane configurations, materials and modules, operational parameters and problems
are presented with a clear focus on removal of POPs from textile wastewater. The particular issues related to the application of
ultrafiltration, nanofiltration and reverse osmosis as advanced treatment stages are considered in correlation with the textile
wastewater characteristics and removal efficiencies requirements. Combination of physico-chemical and biological treatment with
membrane processes represents an efficient solution for the removal of POPs from textile wastewater.

Keywords: membrane processes, persistent organic pollutants, wastewater recycling, textile industry

1. Introduction consumption of the scarce fresh water resources

At the down of the new millennium water is
becoming a strategic resource in the context of
sustainable development. Water continues to be a
major factor for the survival of humans and
development of human activities that needs our
concern and protection. The water scarcity, together
with the unbalanced equilibrium between supply and
demand in relation to human consumption,
agriculture or industrial use is among the major
problems to reach the Millennium Development
Goals (MDGs).
In many cases, industrial and municipal
wastewaters are discharged without proper treatment
into surface water bodies. As a result, rivers with low
water flows and groundwaters are dangerously
polluted exceeding the values of parameters from
water quality standards. Consequently, officials and
decision makers at all levels are increasing their
efforts not only to control industrial and municipal
wastewater discharges, but also to enhance
wastewater recycling and reuse in order to reduce the
(Zaidi, 2002).
Starting with 1960, the industry attempted to
minimize its negative impacts through pollution
prevention and end-of pipe treatment in a framework
mainly driven by legislative inputs (Teodosiu, 2005).
Sustainable development requires a framework for
integrating environmental policies and development
strategies in a global context (Gavrilescu and Chisti,
2005).
Parallel with the increase of severity and
frequency of droughts experienced in the early 1990s
and in summer 2003, sustainable use of water
resources gains more and more importance in Europe.
In the water policy framework, this issue has been
incorporated into the Water Framework Directive
(WFD), 2000/60/EC (EC Directive, 2000). Through
the WFD, and more recently by means of the
Integrated Management of Water Resources (IWRM),
the EU established an environmental policy which
aims to achieve a good status of surface water and
groundwater in terms of quality and quantity
(Hochstrat et al., 2006).

*
Author to whom all correspondence should be addressed: email: corina_musteret@ch.tuiasi.ro; tel./fax: +40 232 237 594
 Musteret and Teodosiu /Environmental Engineering and Management Journal 6 (2007), 3, 175-187
Research concerning the selection of
alternative water sources started several decades ago
and up to the present time two promising technologies
have been implemented: the desalination of seawater
and the recycling/reuse of wastewater. Despite the
fact that great progress has been made regarding the
development of desalination processes, the operating
costs are still rather high, due to the large amount of
necessary energy (related to certain removal
efficiencies). Simultaneously, great efforts have been
made in researching the possibilities to improve the
quality of wastewater through adequate treatment
with the purpose of reusing it at the source. In many
countries, wastewater is subject to secondary stages
of treatment before being discharged in water
streams, yet, other methods, especially advanced
treatment are still necessary in order to be able to
reuse it (Kim et al., 2002; Barjoveanu and Teodosiu,
2006). The low reserves of fresh ground or surface
water at the global scale, correlated with the higher
demands of water for economical and social
development are also key factors for the
implementation of recycling and reuse technologies
(Teodosiu, 2001).
The presence of POPs in industrial
wastewaters leads to a series of ecological and
economical negative effects, such as: causing taste
and smell issues in the downstream water supplies,
forming foam and floating materials, water colouring,
inhibiting the natural self-purification processes,
undesired effects upon living organism (Macoveanu
et al., 1997).
POPs are defined as a group of chemical
compounds with different origins but common
characteristics: semivolatility, hydrophobicity,
bioaccumulation, high toxicity, persistence in
environment, ability to migrate in food chains and
high bioaccumulation potential (Jones and de Voogt,
1999; Gavrilescu, 2005; Beţianu and Gavrilescu,
2006). The global extension of POPs pollution
became apparent with their detection in areas such as
the Arctic, where they have never been used or
produced, at levels posing risks to both wildlife and
humans (Holoubek et al., 2000).
The great part of POPs is generated by the
chemical industry, textile industry (Métivier-Pignon
et al., 2003; Bechtold et al. 2004), pulp and paper
industry (Sumathi and Hung, 2004; Pokhrel and
Viraraghavan, 2004), petrochemical industry (Wong
and Hung, 2004), metallurgical industry, mining
industry, wood industry, metal finishing industry
(Tünay et al., 2004), treatment of landfill leachate
(Bodzek et al., 2004).
In the last decade persistent,
bioaccumulative, and toxic compounds (PBTs) and
especially polyaromatic hydrocarbons (PAH) have
become a major issue of research in order to
investigate their ubiquitous environmental
occurrence, biochemical and toxic effects, human
exposure and health risk assessment. Some of these
pollutants such as polychlorinated biphenils, phenols,
benzenes and dichloro-diphenyl-trichloroethane
176
(DDT) have been produced intentionally in a wide
variety of commercial applications because of their
properties as intermediates or pesticides. Other
persistent and very toxic pollutants such as
polychlorinated dibenzo-p-dioxins and dibenzofurans
have been formed as undesirable by-products, e.g.,
during the manufacture of the chemicals mentioned
earlier, waste combustion, the chlorine bleaching of
pulp and paper, some metallurgical processes etc.
POPs classification was achieved in the
following compound classes (Holoubek et al., 2000):
• polycyclic aromatic hydrocarbons (PAH);
• organochlorinated pesticides (OCP);
• hexachlorobenzene (HCB) and other
polychlorinated benzenes (PCBzs);
• polychlorinated biphenyls (PCB);
• polychlorinated dibenzo-p-dioxins and
dibenzofurans (PCDD and PCDF);
• polychlorinated naphthalenes.
Persistent organic pollutants present in
industrial wastewater are highly resistant to the
biological degradation. Their biodegradation is
possible only under special circumstances and in the
presence of some specialized micro-organism, over a
long period of time. Elimination the POPs from
textile wastewater is achieved by advanced treatment
technologies or by a combination of advanced and
conventional treatment technologies.
Since 1985, due to the development of the
membrane industry, the membrane processes have
been applied to eliminate the POPs which undertake
the primary and secondary treatment unalterated.
Over the past few years, a remarkable progress has
been made in the research field regarding the use of
the membrane processes, which are applied for
removal POPs from textile wastewater.
This study presents an overview research
that has been undertaken for the removal of POPs
from textile wastewater by membrane processes.
Issues such as operational parameters, types of
materials and modules, technical problems related to
normal operation and cleaning, correlations between
the wastewater matrix and selection of membranes
are also discussed related to several case studies for
the treatment of industrial textile wastewater.
2. Persistent organic pollutants generated by the
textile industry
Many persistent toxic pollutants in
wastewater may interfere with the treatment plant
performance; pass through unchanged, transformed,
generated, or accumulated in the sludge. Both organic
and inorganic compounds are included in this
category.
The EPA priority pollutants list includes 129
priority pollutants (organic and inorganic) in 65
classes to be regulated by categorical discharge
standards. They are selected on the basis of their
 Removal of persistent organic pollutants from textile wastewater by membrane processes
known or suspected carcinogenity, mutagenicity,
teratogenicity, or high acute toxicity (Qasim, 1999).
The persistent organic pollutants are
included in the priority pollutants category. Persistent
organic pollutants are toxic chemicals that adversely
affect human health and the environmental around the
world. Because they can be transported by wind and
water, most POPs generated in one country can affect
people and wildlife far from where they are used and
released. They persist for long periods of time in the
environment and can accumulate and pass from one
species to the next through the food chain. During the
past three decades, analytical data revealed global
contamination of aquatic and terrestrial environments.
In 1999, the European Commission started
the initiative for a new chemical policy under the
guidance of DG Environment. This is well known by
acronym REACH. The REACH chemicals of
concern, e.g., carcinogens, mutagens, chemicals toxic
to reproduction, and persistent biological pollutants
have to follow an authorization regime (Bender and
Eisenbarth, 2007).
Stockholm Convention on Persistent Organic
Pollutants, signed in May 2001, provides a
framework, based on the precautionary principle, for
the elimination of production, use, import, and export
of the initial twelve POPs (Stockholm Convention,
2001). The Stockholm Convention is derived from the
POP Protocol to the Convention on Long Range
Transboundary Air Pollution of the UN ECE (United
Nations Economic Commission for Europe), a
regional predecessor which came into force in
November 2003. The objective of the Stockholm
Convention on Persistent Organic Pollutants is to
protect human health and environment from POPs
(Steinhäuser and Richter, 2006; Stockholm
Convention, 2001).
In Romania, Government Emergency
Ordinance no.195/2005 on the Environmental
Protection with the subsequent modifications and
completions as well as the water and wastewater laws
(Law no. 107/1996- Water Law, amended by Law no.
310/2004 and Law no. 112/2006) refer both the
classes of priority organic pollutants and their
maximum discharge concentrations or specific
parameter limits in water supply (Government
Emergency Ordinance, 2005; Water Law, 2006).
Thus, these legislative documents stipulate
issues such as:
a. prevention of ecological risks and damages
through measures that focus on pollution
prevention and adequate treatment;
b. creation of special lists and regime for
dangerous substances (pesticides, fertilizers,
other chemicals);
c. identification of the risk zones with high
pollution level.
The most important characteristics of POPs
are given below (Bender and Eisenbarth, 2007;
Beţianu and Gavrilescu, 2006):
Persistence: the POPs resistance to degradation by
chemical, photochemical and biochemical reactions in
water solutions, air or soil, ensures their long term
existence and stability during transport over long
distances (POPs are also found in regions where the
generating substances were never used, especially in
Arctic region and five remote mountains lakes in
Europe);
Bioaccumulation: they are not soluble in water but
most of them associate with living tissues, hence their
significant concentration in fatty tissues;
Toxicity: the capacity to cause harm to people and
environment; acute toxicity is more a mark;
Volatility: the POPs are semivolatile; after release
in the environment they undergo several cycles of
evaporation, air transport and condensation.
Textile wastewater contains several types of
pollutants, such as various azo-dyes, dioxins,
pesticides, dispersants, levelling agents; wastewater
quality is variable and depends on the kind of process
that generates the effluent.
Several studies indicate that a small fraction
of new textiles have very high concentration of
polychlorinated dibenzo-p-dioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs). Dioxins
from this source can be transferred to other
compartments via several pathways. The transfer of
polychlorinated dibenzo-p-dioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs) between
several matrices and pathways are presented in figure
1. A large part of polychlorinated dibenzo-p-dioxins
and polychlorinated dibenzofurans from textile
industry are transferred during washing into sewage
sludge, which is often used as an agricultural fertilizer
and can be the source of dioxins in the food chain
(Križanec and Le Marechal, 2006).
Table 1 presents the processes and effects of
some persistent organic pollutants from textile
industry (Teodosiu, 2001; Bechtold et al., 2004;
Bender and Eisenbarth, 2007, Križanec and Le
Marechal, 2006).
3. Overview of membrane processes applied for
textile wastewater advanced treatment
A membrane is an interphase between two
adjacent phases acting as a selective barrier,
regulating the transport of substances between the
two compartments. The main advantages of
membrane technology as compared with other unit
operations in chemical engineering are related to this
unique separation principle, i.e. the transport
selectivity of the membrane. Separation with
membranes does not require additives, and they can
be performed isothermally at low temperatures and-
compared to other thermal separation processes – at
low energy consumption. Also, upscaling and
downscaling of membrane processes as well as their
integration into other separation or reaction processes
are easy (Ulbricht, 2006).
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Textile industry

PCP,
Chloranil dyestuff,
Other sources?

Uncontaminated Contaminated Domestics

textiles textiles dust

Dry cleaning Wastewater Skin surface,

residues Hair

Sevage Shower water

sludge

Food
PCP – Polychlorinated chain
phenols

Fig. 1. Transfer of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans

Table 1. Processes and effects of some persistent organic pollutants from textile industry

Persistent organic pollutants Effects Processes

Aromatic amines Carcinogenic effect Textile industry, dyeing
Dioxazine Carcinogenic effect Textile industry, dyeing
Antraquinone Carcinogenic effect Textile industry, dyeing
Pentachlorophenol Carcinogenic effect Processing of cotton
Chloranil Carcinogenic effect Textile industry, dyeing
Phthalocyanine Carcinogenic effect Textile industry, dyeing
Harmful effects on neuraxis, liver and kidney;
Phenolic compounds Textile industry, dyeing
carcinogenic effect

Membrane processes have three clear
advantages over conventional techniques (Judd, 2003
a):
• Separation is achieved without requiring a phase
change, and is therefore more energetically
efficient than distillation;
• Little or no accumulation takes place in the
process which therefore operates continuously
under steady-state condition without necessitating
regeneration cycles, unlike adsorptive separation
processes;
• Little or no chemical addition is required, unlike
conventional clarification which generally relies
on the addition of chemical coagulants and
flocculants.
Membrane processes although initially used
for water treatment purposes (sea water desalination
and surface water treatment), have nowadays many
applications in industrial wastewater treatment,
especially for recycling/reuse and for the reduction of
waste volume and toxicity by
separation/concentration.
The modular design, ease of adaptation to
existent facilities and the simple maintenance are all
advantages of membrane systems. The main
disadvantages are: membrane fouling/scaling and
frequent backwashings (that induce higher
operational costs) and investment costs. Since
membrane productivity (and consequently the
feasibility of expanding the process to large scale
applications) depends on the wastewater
characteristics, operating conditions and resulted
permeate fluxes and removal efficiencies, a thorough
selection, evaluation and optimization of the
membrane system applied for a certain wastewater
matrix is always required (Barjoveanu and Teodosiu,
2006; Teodosiu, 2002). The mass transfer through
membranes is driven by a difference of potential on
the two sides of the membrane. According to the type
of potential, membrane processes may be classified
as: chemical potential or concentration difference,
pressure driven processes and electric driven
membrane processes (Barjoveanu and Teodosiu,
2006). Table 2 gives a classification of the membrane
processes according to the driving force, as well as
the separated phases (Cheryan, 1998).

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 Removal of persistent organic pollutants from textile wastewater by membrane processes

Table 2. Membrane processes

Process Driving Force Retentate Permeate

Osmosis
Dialysis
Microfiltration (MF)
Ultrafiltration (UF)
Nanofiltration (NF)
Reverse osmosis (RO)
Electrodialysis
Pervaporation
Chemical potential Solutes, water
Concentration difference Large molecules, water
Pressure Suspended particles, water
Pressure Large molecules, water
Pressure Small molecules, divalent
salts, dissociated acids,
water
Pressure All solutes, water
Voltage, current Non-ionic solutes, water
Pressure Non-volatile molecules,
water
Water
Small molecules, water
Dissolved solutes, water
Small molecules, water
Monovalent ions,
undissociated acids, water
Water
Ionized solutes, water
Volatile small molecules,
water

3.1. Membranes materials of ceramic materials, sintering (ceramic

Membrane structure is very important for the
membrane characteristics, but also for the separation
process, because it determines the operational
parameters and the performance of the filtration
process. According to their structure, membranes can
be classified according to the representation in Fig. 2
(adapted from Cheryan, 1998 and Baker, 2004):
Membranes may also be classified according to the
material composition, which is either organic
(polymeric) or inorganic (ceramic or metallic), or on
the basis of their physical structure, i.e. of their
morphology. The membrane morphology is
dependent on the exact nature of the material and/or
the way in which it is processed (Luque et al., 2005;
Nunes and Peinemann, 2006).
The range of available membrane materials
employed in wastewater treatment is very broad, and
they vary rather more widely in chemical composition
than in bulk morphology. Membranes can be
produced by stretching, sub-atomic particle
bombardment combined with etching and, in the case
nanofiltration membranes have only recently
arrived in the marketplace).
By far the most significant of the
polymeric membranes applied to the water industry
are those produced by phase inversion, a fabrication
process which produces an anisotropic material
which may then be used as a substrate for a film
composite membrane.
An overview of the state-of-the-art
polymeric materials, used for the manufacturing of
commercial membranes, is given in table 3
(Ulbricht, 2006).
Total worldwide consumption of membranes, based
on membrane surface area, is approximately as
follows (Wagner, 2001):
- composite RO membranes: 85%;
- composite NF membranes: 3-5%;
- polysulfone UF and MF membranes: 5-7%;
- other membranes (polyacrylonitrile, ceramic
materials and cellulose system): 3-5%.

Isotropic membranes
Isotropic microporous Nonporous dense Electrically charged
membrane membrane membrane

Anisotropic membranes
Loeb-Sourirajan Thin-film composite Supported liquid
anisotropic membrane anisotropic membrane membrane

Liquid-filled
pores

Polymer matrix

Fig. 2. Membrane classification and associated structures

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Table 3. Polymeric materials and related membrane processes

Morphology
Barrier Membrane
Polymer
Barrier type Cross-section thickness process
(µm)
Nonporous Anisotropic ~0,1 GS, RO
Cellulose acetates Mesoporous Anisotropic ~0,1 UF
Macroporous Isotropic 50-300 MF
Cellulose nitrate Macroporous Isotropic 100-500 MF
Cellulose, regenerated Mesoporous Anisotropic ~0,1 UF, D
Perfluorosulfonic acid polymer Nonporous Isotropic 50-500 ED
Polyacrylonitrile Mesoporous Anisotropic ~0,1 UF
Polyetherimides Mesoporous Anisotropic ~0,1 UF
Polyethersulfones Mesoporous Anisotropic ~0,1 UF
Macroporous Isotropic 50-300 MF
Polyethylene terephthalate Macroporous Isotropic track-etched 6-35 MF
Polyphenilene oxide Nonporous Anisotropic ~0,1 GS
Poly(styrene-co-divinylbenzene), Nonporous Isotropic 100-500 ED
sulfonated or aminated
Polytetrafluoroethylene Macroporous Isotropic 50-500 MF
Nonporous ~0,1 GS
Polyamide, aliphatic Macroporous Isotropic 100-500 MF
Polyamide, aromatic Mesoporous Anisotropic ~0,1 UF
Polyamide, aromatic, in situ Nonporous Anisotropic/composite ~0,05 RO, NF
synthesized
Polycarbonates, aromatic Nonporous Anisotropic ~0,1 GS
Macroporous Isotropic track-etched 6-35 MF
Polyether, aliphatic crosslinked, in Nonporous Anisotropic/composite ~0,05 RO, NF
situ synthesized
Polyethylene Macroporous Isotropic 50-500 MF
Polyimides Nonporous Anisotropic ~0,1 GS, NF
Polypropylene Macroporous Isotropic ~0,1<1-10 MF
Polysiloxanes Nonporous Anisotropic/composite ~0,1 GS, PV, NF
Polysulfones Nonporous Anisotropic ~0,1 GS
Polyvinyl alcohol, crosslinked Nonporous Anisotropic <1-10 PV
Polyvinylidenefluoride Mesoporous Anisotropic ~0,1 UF
Macroporous Isotropic 50-300 MF
Symbols: GS – gas separation; RO – reverse osmosis; UF – ultrafiltration, MF – microfiltration; D – dialysis; ED – electrodialysis; NF –
nanofiltration; PV – pervaporation.

The selection of an adequate membrane for
wastewater treatment and reuse is difficult, and some
general information about the process environment
must be available to make a proper selection. The first
step is to determine the preferred process or
combination of processes (RO, NF, UF or MF) and
investigate the membrane materials available. Based
on the process environment the best suited
membrane materials can then be selected. Table 4
gives a classification of the chemical resistance of
several membrane materials (Wagner, 2001).
Tables 3 and 4 may be helpful in membrane
selection.

Table 4. Chemical resistance of several membrane materials

Composite CA PSO PVDF PAN SiO2 Cellulose

3 < pH < 8 √ √ √ √ √ √ √
pH<3 or pH >8 √ × √ √ √ √ √
Temp > 35˚ C √ × √ √ √ √ √
Humic acid (√) √ × × (√) × √
Proteins √ (√) √ (√) (√) √ √
Polysaccharides (√) × √ × (√) √ ×
Textile waste √ × √ (√) √ × ×
Aliphatic hydrocarbon × × × (√) √ √ √
Aromatic hydrocarbon × × × √ × √ (√)
Oxidizers × (√) √ √ (√) √ (√)
Ketones, Esters × × × √ × √ (√)
Alcohol √ × √ √ √ √ √
Symbols: √ - means high resistance; (√) – means either that the information is based on theory or that practical results have proved to be dubious;
× - means low resistance.

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 Removal of persistent organic pollutants from textile wastewater by membrane processes
3.2. Applications of membrane filtration in removal of
POPs from wastewater treatment
As commercial membranes are available
over a wide range of pore sizes, membrane filtration
technologies can effectively remove various POPs
from textile wastewater (Ciardelli et al., 2000; Bes-
Pia et al., 2002; Fersi et al., 2005).
Generally, especially microfiltration is
effective in removing suspended solids and colloids,
while ultrafiltration apart from these pollutants may
remove a variety of organic materials, including
POPs. Nanofiltration and reverse osmosis are
effective in removing dissolved inorganic and organic
compounds.
Reported applications of membrane
processes include the separation of organic dyestuffs
from textile processing effluents. For economical
reasons, such applications are still limited to the cases
where contaminants and/or water can be recovered
for recycling or reuse. Table 5 lists some applications
reported in the literature for textile wastewater
treatment (Ciardelli et al., 2000; Zhou and Smith,
2002; Fersi et al., 2005).
3.3. Membrane modules
For wastewater treatment, as for all
membrane application, membranes are used in
different configurations, defined in literature as
modules (Cheryan, 1998; Baker, 2004). The optimum
membrane configuration is one that has the following
characteristics (Judd, 2003 b):
- A high membrane area to module bulk volume
ratio;
- A high degree of turbulence for mass transfer
promotion on the feed side;
- A low energy expenditure per unit product water
volume;
- A low cost per unit membrane area;
- A design that facilitates cleaning;
- A design that permits modularization.
The most common membrane modules
configurations for wastewater treatment are listed
below and presented in Fig. 3:
• Plate and frame
• Spiral wound
• Tubular membranes
- hollow fiber membranes (d< 1 mm);
- capillary membranes (1<d<5 mm);
- tubular membranes (d>5 mm).
Table 5. Applications of membrane filtration in removal of POPs from textile wastewater treatment
Membrane Configuration
Nanofiltration Flat sheet
Ultrafiltration, Spiral wound
Reverse osmosis
Nanofiltration Tubular
Symbols: TDS – total dissolved solids; COD – carbon organic dissolved.
Essentially these modules provide the
structural strength and the connections, needed for
the membranes to be included in the filtration
system. For best operational performances, these
modules have to ensure (Barjoveanu and Teodosiu,
2006):
• A good fluid circulation through the
membrane in order to minimize the unwanted
effects like membrane fouling / scaling or
concentration polarization and to enable an easy
membrane cleaning;
• A very good active surface area / volume
ratio so that the filtration plant occupies as less
space as possible and also to ensure easy
assembling and replacement.
Membrane module can be operated by
using two alternatives: dead-end and cross-flow
operation.
3.4. Operational problems
For membrane processes there are two
main operational problems that inherently appear
during the filtration cycles, especially when
wastewater is used as feed (Teodosiu, 2001):
• Permeate flux decline;
• Decrease of pollutant retention capacity.
The permeate flux declines over time is
related to a series of phenomena that occur at the
membrane level during the membrane process:
fouling / scaling, concentration polarization,
membrane compacting and membrane degradation.
The first phenomena are reversible by backwashing
or chemical cleaning, while membrane degradation
is irreversible and it is responsible for the
irreversible loss of flux and also for the decrease of
pollutant retention capacity (Teodosiu, 2002).
Fouling is defined as existence and growth
of microorganisms and irreversible collection of
materials on the membrane surface which results in
a flux decline. Five principal fouling mechanisms
have been identified: concentration polarization,
cake formation, inorganic precipitation, organic
adsorption and biological fouling (Zhou and Smith,
2002). To overcome these problems, a cleaning
process must be used. Cleaning usually is
performed in three forms: physical, chemical and
biological (Mohammadi et al., 2002; Baker, 2004).
Water source Resulting effects
Textile wastewater >90% removal colour,
turbidity and TDS
Textile wastewater Absence of COD and
colour
Textile wastewater >97% for both colour and
copper
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a b

Fig. 3. Membrane modules types:

a. plate and frame membrane sheet; b. spiral wound module; c. tubular module

4. Removal of POPs from textile wastewater by
membrane processes
In the past, pollution control of industrial
effluents had become more stringent in Europe and
the demand for more efficient wastewater treatment
systems has increased, as a result of compliance with
the European Union legislation. The textile industry
plays a critical role in this context because: it is a
large user of water, typically 0.2-0.5 m3 are needed to
produce 1 kg of finished product, and it is well
represented in Europe (Marcucci et al., 2003).
Textile effluents contain several types of
pollutants, such as dispersants, leveling agents, salts,
various dyes etc; wastewater quality is variable and
depends on the kind of process that generates the
effluent. Table 6 presents the textile processing
categories and effluent characteristics (Judd, 2003 c).
Usually, in order to achieve the necessary
wastewater quality needed for recycling/reuse in the
textile industry, a combination of
microfiltration/ultrafiltration and reverse
osmosis/nanofiltration is needed for the removal of
dissolved organic and inorganic material.
Marcucci et al., (2003), investigated two
different approaches on a pilot scale:
• In the first case-study, a flat UF membrane
module, operating under vacuum, was placed
upstream of a spiral-wound reverse osmosis module.
A Filterpar FLAMEC filter 150.1 system with flat
polyvinylidenefluoride membranes, operating under
vacuum, was used for the UF step. The total
filtration surface of the module was 47 m2.
Membrane molecular weight cut-off (MWCO) was
70,000 Dalton (Da). Reverse osmosis process was
realized by means of a FilmTec TW30-LE-4040
spiral-wound membrane.
• In the second case-study, a MF module
was placed upstream of a NF module, containing a
spiral-wound membrane. The choice of treatment
stages depended on the different quality of the
effluents to be purified, which differed mainly in
terms of salt content. Two NADIR P150F
membranes (configuration: flat sheet in rolls),
produced by Nadir Filtration, were used for
microfiltration. Each membrane was 101.6 mm in
diameter and 1.016 mm in length. Membrane
MWCO was 150,000 Da and the filtration surface
was 11 m2. An Osmonics Desal DL4040F spiral-
wound membrane was used for nanofiltration. This
membrane has a MWCO of 150,300 Da and
filtration surface of 8.4 m2. In the first case, the RO
permeate was of excellent quality. RO significantly
achieved the removal of COD and colour of 95%.
In the second case colour removal of 94% and
COD removal of 82%.
In an extensive study, Fersi et al., (2005),
have compared different membrane process
(microfiltration, ultrafiltration, and nanofiltration).
The wastewater was supplied from a textile factory
that uses different dyes and chemical substances
such us detergents, salts and caustic soda.

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 Removal of persistent organic pollutants from textile wastewater by membrane processes

Table 6. Textile processing categories and effluent characteristics

Parameters Categories of effluents (related to production processes)

1 2 3 4 5 6 7
BOD/COD 0.0 0.29 0.35 0.54 0.35 0.3 0.31
BOD (mg/l) 6000 300 350 650 350 300 250
TSS (mg/l) 8000 130 200 300 300 120 75
COD (mg/l) 30000 1040 1000 1200 1000 1000 800
Oil and grease 5500 - - 14 53 -
(mg/l)
Total chromium 0.05 4 0.014 0.04 0.05 0.42 0.27
(mg/l)
Phenol (mg/l) 1.5 0.5 - 0.04 0.24 0.13 0.12
Sulphide (mg/l) 0.2 0.1 8.0 3.0 0.2 0.14 0.09
Colour 2000 1000 - 325 400 600 600
pH 8.0 7.0 10 10 8.0 8.0 11
Temperature (ºC) 28 62 21 37 39 20 38
Water usage (l/kg)
Minimum 4 33 111 5 20 8 3
Median 12 - 284 113 83 47 100
Maximum 78 - 657 507 378 163 557
Categories description: 1. raw wool scouring ; 2. yarn and fabric manufacturing; 3. wool finishing; 4. woven fabric finishing; 5. knitted fabric
finishing; 6. carpet finishing; 7. stock and yarn dyeing and finishing.

The effluent was treated biologically in an nanofiltration of biologically treated textile

activated sludge plant. Table 7 presents wastewater with high salt concentration (9 mg/l),
characteristics of the treated and untreated wastewater good results were obtained. More than 90% of
of the local textile industry. colour, turbidity and TSD were removed from the
treated water accompanied with a reduction of
Table 7. Wastewater characteristics COD. Based on the experiments, NF membranes
are suitable for producing permeate of reusable
Parameter Effluent Biological quality.
treated
wastewater
Table 8. Membrane characteristics
Conductivity 10300 10540
(µs·cm-1)
Membrane Geometry Composition Pore pH
Turbidity (NTU) 17.71 7.94
sizes range
COD (mg/l) 1110.4 232.0 T170-5µ TA Tubular Alumina α 5 µm 0.5-
TDS (mg/l) 8461 8658 (MF 5) 13.5
Cl - (mg/l) - 1087.7 T170-50 n Tubular Zirconium 50 0.5-
SO42- (mg/l) - 3502.8 TZ (UF 50) oxides nm 13.5
Ca2+ (mg/l) 599.0 89.0 T170-20 n Tubular Zirconium 20 0.5-
K+ (mg/l) 158.6 158.6 TZ (UF 20) oxides nm 13.5
Mg2+ (mg/l) 42.2 42.2 NF 270 Flat sheet Polyamide ~ 2 3-10
Na+ (mg/l) 2113.8 3295.1 nm

Tubular membranes purchased from TIA Ultrafiltration and reverse osmosis on

(France) and composed of several layers of porous
ceramic with a well defined texture were used in
microfiltration and ultrafiltration and a Filmtech NF
270 flat sheet polyamide based thin film composite
membrane was used in NF.
Table 8 indicates the main characteristics of
the different membranes. The membrane based
separation processes performance was controlled by
measuring the permeate flows and the operating
pressure during experiments. Permeate samples were
collected for water quality analyses. The membrane
permeability to water was measured before the
beginning of experiments and it was verified after
membrane cleaning. The results of this study show
that microfiltration seems to be a realistic method in
the pretreatment of the textile wastewater. For direct
dyeing and fulling textile wastewater was studies
by Ciardelli et al., (2000). Fig. 3 presents two
plants for wastewater treatment (present and
proposed) for a dyeing and finishing textile.
Effluents were first pre-treated by means of a
biological activated sludge plant. A Trisep 8040-
UE50-TXA membrane, of the spiral wound type
(with fiberglass outer wrap), was used for the
ultrafiltration step of textile wastewater. The
membrane is 200 mm in diameter and 1000 mm in
length and has a filtrating surface of 23 m2.
Characteristic molecular weight cut-off is 100 kDa.
A module, with two Toray polyamide membranes
of the spiral wound type was placed in series, and
used for reverse osmosis. Each membrane is of 100
mm diameter and 1000 mm length and has a

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 Musteret and Teodosiu /Environmental Engineering and Management Journal 6 (2007), 3, 175-187

filtrating surface of 54 m2. The pilot plant installed
consisted of three stages: sand filtration, ultrafiltration
and reverse osmosis.
A part of the effluent from the biological
plant was sent to the sand filter (3 bar pressure) which
had an output of 800 l/h. The filter was washed every
15 h. Water from sand filtration was stored in a tank
and then sent to the ultrafiltration module at 4 bar
relative pressure. A total of 10% of the total flow was
the permeate of the ultrafiltration step, while the rest
was sent back to the storage tank. The average flow
of the ultrafiltration step was 550–600 l/h. The
membrane was chemically washed as soon as the
hydraulic performance worsened. The ultrafiltrated
effluent was stored in a second tank and sent at 8 bar
pressure to the reverse osmosis module at an inlet
flow of 500 l/h (40% concentrate for discharge;
60% of permeate for reuse). The analytical
parameters of the reverse osmosis permeate is of a
high quality (~95% reduction of salt content,
practical absence of COD and colour) and can be
therefore reused without problems since the quality
of water presently used in textile wet processes
(usually drained from wells and in part softened) is
usually worse (conductivity of ~800 µs/cm, absence
of COD and colour).
Efficiency of advanced treatment process
(ATP) was studied by Nandy et al., (2006). Fig. 4
present a scheme of the advanced treatment
processes, while the technical details of the
membrane systems are given in Table 9.

20% wells’ draining

(a) (b)
100% wells’ draining
50% 30%
PLANT

PLANT
ACTIVATED SLUDGE TREATMENT

ACTIVATED SLUDGE TREATMENT 50% 50%

OZONATION MEMBRANE
100% discharge PLANT PLANT

20% discharge

Fig. 3. Present (a) and proposed (b) wastewater management for a dyeing and finishing textile plant

Rejects Dechlorination

Antiscalant dosing Reject

UF

Multi -
grade
Chlorine dosing filter RO

UF
Permeate Permeate
Tertiary collection HP
effluent
treatment P

UF-Ultrafiltration unit
RO-Reverse osmosis unit
HP-High pressure pump
P-Pump

Fig. 4. Schematics of advanced treatment system for textile wastewater

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 Removal of persistent organic pollutants from textile wastewater by membrane processes

Table 9. Technical details of ATP (ultrafiltration and reverse osmosis)

Sr. Particulars Ultrafiltration Reverse osmosis

no.
Membrane
Material Polyacrylonitrile (PAN) Polyamide (TFC)
Module Hollow fiber Spiral wound
Pore size (MWCO) 0.01 µm (50,000) 0.0001 µm
1
Size 30m2 33.91m2
Life 4–5 years 3–5 years
Flux 105 l/m2 25.8 l/m2
Numbers 3 8 (2 per module)
Operational parameters
Capacity (product) 9.5m3/h 7m3/h
Mode of operation Automatic Semi-automatic
Operating pressure 2–3 kg/cm2 13–16 kg/cm2
Feed flow rate 10–10.5m3/h 9.5m3/h
2
Permeate flow rate 9.5m3/h 7m3/h
Rejects flow rate 0.5m3/h 2.5m3/h
Percentage recovery 90–95% 75%
Percentage rejection 5–10% 95–98%
Power consumption 1.5 units/h 11 units/h
Pretreatment Chlorination multi-grade filter Dechlorination antiscalant
3
dosing SMBS dosing

The UF was operated at a feed flow rate of monovalent salts, mainly NaCl. This will limit the
8.0m3/h and the RO system at a feed flow rate of reuse possibility for the permeate. Permeate after
7.0m3/h and pressure of 13 kg/cm2, achieved nanofiltration can be used for rinsing. Reverse
permeate recovery of 5.0m3/h (71.4%) and rejects of osmosis produces a permeate that can be used in
2.0m3/h (28.6%). The system ATP (ultrafiltration and the production process as technological water.
reverse osmosis) implemented achieved 100%
removal of suspended solids (SS), dissolved organics Table 10. Effect of initial dye concentration on flux and
(expressed as BOD and COD), and 98.2% total dye rejection at different pressures and flowrates
dissolved solids removal (TDS) removal.
Tang and Chen, (2002), investigated the Dye Pressure, Flowrate, Flux, Dye
concentration, kPa L/min L/m2h rejection,
mechanisms of controlling flux and permeate
ppm %
pollutants rejection by varying the operating pressure, 82 200 3 23.85 97.2
NaCl concentration and dye concentration in a 147 200 3 25.07 97.2
simulated dye effluent. A flat sheet polysulfone based 398 200 3 23.5 97.1
thin film composite (TFC-SR2) nanofilter, supplied 705 200 3 24.27 97.4
by Fluid Systems, California, USA was selected to 448 200 5 23.12 97.6
perform the dye separation. Synthetic dyebaths 92 500 5 59.58 97.5
consisting of CI reactive black 5 (Bayer, Sydney), salt 188 500 5 62.72 97.8
(NaCl), and Milli-Q water were made up for each 455 500 5 55.75 98.1
filtration test. Nanofiltration experiments operated in 708 500 5 59.76 98.4
crossflow mode were carried out in a single flat sheet 890.8 500 5 59.58 98.5
stainless steel membrane module with a channel with 1583 500 3 78.4 98.1
the following characteristics: 1.4 mm height, 25 mm
width and 232 mm length. The effective membrane 5. Conclusions
surface area was 58 cm2. Pressure and crossflow
velocity were modified depending on the Pollution control of persistent organic
experimental specification, and varied between 100- pollutants from textile effluents has become more
500 kPa and 3-5 l/min respectively. In table 10 the stringent and demand for more efficient wastewater
effects of initial dye concentration on flux and dye advanced treatment. Combination of physico-
rejection at different pressure and flowrates are chemical and biological treatment with membrane
presented. processes represents an efficient solution for the
The recovery of indigo dye by ultrafiltration removal of POPs from textile wastewater.
and reverse osmosis was studied by Sójka- Utilization of membrane processes
Ledakowicz et al., (1998). More than 99% of colour successfully depends on several factors such as:
was removed by reverse osmosis. The lab and the material composition membrane selection, type of
pilot scale tests proved that nanofiltration will modules, wastewater characteristics and the
produce permeate comparable to permeate from interactions between pollutants and the membrane.
reverse osmosis except for the contents of Membrane processes use, for the removal priority

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 Musteret and Teodosiu /Environmental Engineering and Management Journal 6 (2007), 3, 175-187
organic pollutants from textile wastewater are
ultrafiltration, reverse osmosis and nanofiltration. For
economical reasons, such applications are still limited
to the cases where contaminants and/or water can be
recovered for recycle or reuse.
Membrane processes using polymeric
membranes for the removal of persistent organic
pollutants with high removal rates but inherent
operational problems appear: fouling and
concentration/polarization phenomena. These
phenomena determine the decrease of the permeate
flux, which is the main operational parameter of
membrane processes and thus the membrane
productivity decreases. Membrane cleaning through
different physical and chemical processes partially
recovers the permeate flux between the membrane
processes cycles, but inherently irreversible fouling
may occur.
The operational efficiency of membrane
processes may be improved through adequate
selection of membrane materials, considering issues
such as: permeability, selectivity, chemical and
mechanical resistance.
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