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WMR0010.1177/0734242X16684383Waste Management & ResearchCoutinho de Paula and Amaral

Review Article

Waste Management & Research

Extending the life-cycle of reverse

© The Author(s) 2017
Reprints and permissions:
osmosis membranes: A review
DOI: 10.1177/0734242X16684383

Eduardo Coutinho de Paula1,2 and Míriam Cristina Santos Amaral2

The reverse osmosis (RO) technology for desalination and demineralization serves the global water crisis context, both technically
and economically, and its market is growing. However, RO membranes have a limited life-cycle and are often disposed of in landfills.
The impacts caused by the disposal of thousands of tonnes per annum of RO membranes have grown dramatically around the world.
Waste prevention should have a high priority and take effect before the end-of-life phase of a product is reached. In this review, a
summary is presented of the main advances in the performance of the RO technology and the membrane lifespan. Afterwards, this
paper reviews the most important relevant literature and summarizes the key findings of the research on reusing and recycling the
discarded modules for the purpose of extending the life-cycle of the RO membranes. In addtion, there are some recent researches that
indicated recycling RO membranes for use by the microfiltration or ultrafiltration separation processes is a promising solution to the
disposal problem. However, there are many gaps and differences in procedures and results. This article also discusses and brings to
light key parameters involved and controversies about oxidative treatment of discarded RO membranes.

Waste prevention, reuse, recycling, oxidative treatment, reverse osmosis, membranes

A semipermeable membrane is used in the reverse osmosis (RO) Most current RO systems use a thin-film composite (TFC)
separation process. The external pressure applied to the mem- polyamide-type membrane, mainly consisting of three layers,
brane allows the selective passage of water, while salts are namely: (i) an ultra-thin, dense, active or selective layer of aro-
rejected (Miller et al., 2015; Shenvi et al., 2015). A RO mem- matic polyamide; (ii) a microporous support layer of polysul-
brane system therefore comprises three fluid streams, namely, the phone; and (iii) a considerably thicker base made from polyester
feed, the permeate and the concentrate. As the feedwater passes (polyethylene terephthalate). This technology is applied to
through the membrane, a high-quality permeate is produced, remove water constituents at the ionic level, and the separation
while the concentrate is the rejected high-salt component (Baker, process follows the solution–diffusion mechanism (Baker, 2004;
2004; Habert et al., 2006). Lee et al., 2011).
The RO membrane is the most widely used desalination tech- Over the last 30 years, numerous technical and operational
nology because of its simplicity of use and relatively low energy innovations have been introduced to improve the RO process.
costs compared with distillation, which uses technology based on Significant advances, particularly in the manufacture of TFC poly-
thermal processes (Greenlee et al., 2009; IDA, 2014; Mezher amide membranes, have led to improved efficiency and a signifi-
et al., 2011; Shannon, et al., 2008; Shenvi et al., 2015). Over the cant reduction of the hydraulic pressures required to produce an
past two decades, the number of RO desalination plants has adequate permeate flowrate. The literature alludes to advances in
increased by 70% to a total of 9000 plants worldwide, which cor- the development of new designs and processes, including tech-
responds to more than 80% of the monetary value of the expand- niques for the pretreatment of the feedwater. Noteworthy is also
ing desalination market (GWI, 2014). The size of these RO plants the design of more efficient membrane modules, and pumps, as
has also increased significantly, with some reaching a production well as recovery or reduction in the consumption of energy that
capacity exceeding 600,000 m3 of water per day (IDA, 2014).
In addition to seawater desalination plants in various arid
1Federal University of Itajubá, Brazil
regions of the world, the application of RO membranes generally 2Federal University of Minas Gerais, Brazil
includes the treatment of brackish surface or groundwater,
municipal and industrial wastewater, producing demineralized Corresponding author:
Eduardo Coutinho de Paula, UNIFEI – Universidade Federal de
water, and ultrapure water for use in semiconductors and the
Itajubá, Campus avançado de Itabira, Rua Irmã Ivone Drumond, nº
pharmaceutical industries, as well as producing reuse water 200, Distrito Industrial II CEP 35903-087 Itabira – MG, Brazil.
(Harbert et al., 2006; Madaeni and Samieirad, 2010). Email:
2 Waste Management & Research

Figure 1.  Strategies on polymeric membranes considered in this review, which represent the general spectrum of
technologies available for reverse osmosis membranes.

must be used to pressurize the system (Fravel and Lindsey, 2015; of brackish water), recycling of the various separated compo-
Lee et al., 2011). These developments have resulted in a continual nents of the membrane module and energy recovery by incinera-
reduction of water desalination and desmineralization costs, tion. Another option is to convert the membrane in order to
thereby promoting the widespread use of RO membranes in water employ its microporous layer in a separation process with less
treatment systems at most competitive prices. stringent specifications.
During the operation of the RO system, several factors affect Among these recycling possibilities, oxidative treatment (a
the decline in performance, which, in practice, is indicated by a chemical conversion technique) is capable of removing the dense
decrease in the permeate flow and/or a reduced amount of selective layer of the RO membrane, consisting of aromatic poly-
rejected salt. Another common indicator of performance decline amide, to produce a porous membrane (García-Pacheco et al.,
is an increase in the pressure drop across the pressure vessel. 2015; Lawler et al., 2011, 2012, 2013; Pontié, 2014; Rodriguez-
The lifetime of a membrane is associated with the characteris- Gonzalez et al., 2002). Thus, recycling the discarded RO mem-
tics of the raw water feed and the operating conditions, such as branes for application in processes such as microfiltration (MF)
the hydraulic conditions, cycle and frequency of chemical clean- or ultrafiltration (UF) could be a feasible alternative for these and
ing, as well as the incidence of membrane fouling (Bartels et al., other types of membrane used on a large scale around the world.
2005; Pontié et al., 2005). In view of the aforementioned, this review initially seeks to
Fouling formation comprises a number of phenomena related develop a synthesis to promote the understanding of the different
to the interactions between the solute or the particles present in aspects that affect the RO membranes’ lifespan. The objective of
the water supply and the membrane. These phenomena include this review is therefore to contribute to assess the possibilities for
the adsorption of solute molecules on the membrane surface, and extending the life-cycle of the RO membrane modules for sec-
the precipitation of sparingly soluble salts on the surface of the ondary use, reuse or recycling. According to Bartl (2014), waste
membrane (Baker, 2004; Habert et al., 2006). Fouling causes a prevention and reuse should have a high priority and they take
decline in the permeate flow and affects the quality of the pro- effect before the end-of-life phase of a product is reached. In
duced water. Higher pressure and, consequently, more energy are principle, recycling processes require energy and will generate
required to overcome the resistance caused by fouling. As a side streams (i.e. waste). This text also brings to light key param-
result, the intervals between the chemical cleaning cycles are eters involved and controversies about oxidative treatment of dis-
shorter and the operating costs are higher (Kang and Cao, 2012; carded RO membranes.
Lee et al., 2011; Pontié et al., 2005; Subramani and Hoek, 2010). As discussed in this review, there is a need to find alternative
Several studies have endeavoured to improve the performance uses for discarded RO membranes to minimize the environmen-
of the process and extend the RO membranes’ lifespan. However, tal and economic impacts of their disposal of in landfill.
even with the appropriate pretreatment of the feedwater, the
membranes lifespan is generally limited to 3–5 years (Lawler
A brief overview of reverse osmosis in
et al., 2011; WHO, 2007), or 5–7 years (Ziolkowska, 2015).
Discarded RO membrane modules are currently classified
the world
worldwide as inert solid waste and are often disposed of in land- Water stress is a crucial topic on the global agenda. In accordance
fills, with limited reuse and recycling alternatives available. with a report of the United Nations, released by the United
Figure 1 shows strategies on polymeric membranes considered Nations University (UNU, 2015), on estimate, the supply of
in this review, which represent the general spectrum of technolo- water to 2.9 billion people will be insufficient to meet the needs
gies available for new and end-of-life RO membranes. Details of the population in 10 years’ time. Besides, within a decade, 48
regarding these strategies are discussed throughout this text. countries will be classified as arid, indicating water scarcity or a
Reuse possibilities for RO membranes include their direct significant lack of water. In 2030, the global demand for water is
application in systems that require lower yields (i.e. the treatment estimated to exceed the supply by 40%. Experts estimate that
Coutinho de Paula and Amaral 3

after 2015, the overall cost to achieve the sustainable develop- membrane modules and accessory elements, such as valves and
ment goals pertaining to water resources would be between 1.2 gauges (BCC, 2014). In accordance with GWI (2014), the current
and 2.2 trillion US dollars per annum over the next 20 years. global desalination market exceeds 11.5 billion US dollars and
The treatment and recycling of wastewater, as well the desali- the planned developments should be worth more than 14 billion
nation of brackish or seawater, could be considered very important US dollars in 2018, of which more than 80% is for the technology
feasible alternatives available to efficiently manage the worsening based on RO membranes.
global water crisis. Advanced technologies, such as membrane The vast global increase in the use of RO technology, as
separation processes, among others, represent new methods of already emphasized, has led to a drastic increase in the number of
managing urban water systems by efficiently reusing water and disposed membrane modules. Usually, the membranes are dis-
nutrients, as well as recovering energy (UNESCO, 2014). carded when the flow and quality of permeated are unrecoverable
The desalination of seawater and brackish water is common in (<15% of the initial). According to Sahuquillo et al. (2015), in
desert countries or those with a low availability of drinking water, brackish water well treatment facilities, it is considered, on aver-
as in the Middle East and North Africa, especially Saudi Arabia, age, that there is an annual replacement rate of 10%, which may
which has developed both thermal and RO technology and cur- be up to 20% depending on the pretreatment. In industrial and
rently serves 70% of the population with desalinated water (IDA, tertiary wastewater treatment facilities, the annual replacement
2014). rates are 25% and 33%, respectively.
The desalination market segment has grown over the decades, To date, a limited number of publications have been identified
both in production capacity and in monetary terms. According to that discuss the impact of this disposal. Based on an average of
the IDA (2016), more than 18,000 desalination plants are cur- 13.5 kg per 8 inch module, and a mean membrane lifespan of 6
rently in operation worldwide (of which 50% use seawater as a years, the inventory of the facilities worldwide allowed an esti-
source), using various technologies, with a production capacity mation of the total mass of modules to be disposed annually,
of around 90 million m3 of water every day, and benefiting reaching 12,000 tonnes (27,000 m3) per annum in 2015 (Lawler
approximately 300 million people in approximately 150 coun- et al., 2012). At the current rate, the disposal of RO modules pre-
tries. About 60% of the desalination market is in the Middle East, sents significant and growing environmental impacts, giving rise
where water availability is very low and is contrasted with the to the need to limit the direct discarding of these modules in the
high supply of fossil fuel sources, which are used in desalination next decade. This study is based on an approximate estimate of
by thermal processes at a low cost. However, desalination is not RO single-pass systems and could be even higher, as the large
restricted to the Middle East; it is already widespread in the power plants use multistage systems that require an even larger
Mediterranean, the Americas, Asia and the Caribbean (Victer, number of modules. Even though the polymeric membrane com-
2015). ponents are mostly inert, there is still a degradation of 1–5% of
An inventory of desalination plants (GWI, 2014) has indi- the material during the 100-year surveyable time period (Arena
cated that 59% of the installed capacity is for seawater, while that et al., 2003).
for brackish water is 22%. The trend to apply desalination tech- It is clear that although the RO desalination industry is well
niques for wastewater and water reuse is growing rapidly, repre- established and is expanding proportionate to the increasing
senting 5% of the total capacity, whereas 9% is for the treatment demand for the production of water, the industry needs to address
of river water, and 5% for pure water used in special applications, the associated environmental concerns and improve its environ-
such as power generation. As regards the type of use, approxi- mental sustainability.
mately 60% is for municipal use, 28% for industrial use, 6% for
power stations, 2% for irrigation, 2% for tourism, 1% for military
Aspects that affect the reverse
purposes and 1% for unspecified purposes (GWI, 2014). GWI
(2015) disclosed that the global contracted capacity is 92.3 mil-
osmosis membranes’ lifespan
lion m3 of water per day. Various efforts have been made over the past decades to extend
The RO membrane market is flourishing worldwide. This sit- the RO membranes’ lifespan, such as (i) combining the RO pro-
uation relates to traditional applications, such as demineralizing cess with the pretreatment process to improve efficiency, (ii)
brackish water, the treatment of water at low pressures (for boil- developing anti-fouling techniques and (iii) developing suitable
ers and cooling towers) and reuse in industrial processes, as well procedures for cleaning the membranes. It is important to under-
as to the desalination of water for public water supply purposes, stand the importance of these aspects in order avoid early dis-
particularly in the area of municipal water purification (Rovani, posal of the membranes, thus reducing the waste production,
2012; Yi and Shi, 2012). which is the first step in the waste management hierarchy.
In particular for RO membranes and components of the sys-
tem, the market reached 5.4 billion US dollars and is expected to
More efficient pretreatment processes
increase at a compound annual growth rate of 10.5%, reaching
8.8 billion US dollars in 2019 (BCC, 2014). The components A suitable pretreatment process is considered the most important
include pretreatment filter cartridges, pumps, pressure vessels, factor for the proper functioning of a RO system, as it enhances
4 Waste Management & Research

the performance of the membranes, thereby improving the water such as metal oxides, proteins, polysaccharides, silicates and
quality and minimizing the chemical cleaning frequency of the clay) and microbiological (bacteria and fungi – biofouling; Kang
membranes. and Cao, 2012; Oliveira, 2007).
Henthorne and Boysen (2015) reviewed the state-of-the-art In fouling by precipitation (scaling), a common occurrence in
pretreatment for desalination using RO membranes, which has RO membranes is that calcium carbonate and barium sulphate
progressed significantly since the middle of 1990. The scientific have an extremely low solubility limit, as well as calcium sul-
pretreatment for desalination is confronted by the inherent varia- phate, strontium sulphate, calcium fluoride and complexes of
tion in water quality associated with many sources that could be silica. Moreover, iron, manganese and aluminium salts are among
desalinated by the membrane processes. The pretreatment for RO the most common contaminants in RO systems (Fravel, 2014).
systems generally consist of a series of unit operations that In accordance with Pontié et al. (2005), whereas the inorganic
addresses each of the expected fouling risks. According to the fouling of membranes by calcium salts can be controlled by pH
aforementioned authors, the state-of-the-art pretreatment has adjustment and the addition of anti-foulants, the preventing of
progressed to incorporate other unit operations, such as flotation, organic fouling, as well as colloidal and biofouling, is signifi-
and includes a vast body of knowledge on fouling mechanisms, cantly more challenging, typically requiring system-suitable
particularly on those associated with biofouling. pretreatment.
Today, in an increased number of plants, membrane-based The deposition of colloidal foulants (including both rigid inor-
pretreatments (such as MF, UF, nanofiltration [NF]) are consid- ganic colloids and organic macromolecules) on a RO or NF
ered to replace conventional RO pretreatment as coagulation and membrane forms a cake layer, which can adversely affect the
flocculation (Bartels et al., 2005; Buonomenna, 2013; Jamaly membrane flux due to (i) the cake layer’s hydraulic resistance
et al., 2014). and/or (ii) the cake-enhanced osmotic pressure (Tang et al.,
Compared with the conventional treatment, the benefits of 2011). In the case of organic foulants, Ang et al. (2011a) pro-
using membranes for the pretreatment of the feedwater in RO posed that an efficient cleaning agent and favourable cleaning
systems, especially UF, have already been recognized. According conditions could be selected by considering two important mech-
to the NAS (2008), the advantages include the production of anisms: the chemical reaction between cleaning agents and fou-
high-quality water, with a low potential for fouling regardless of lants in the fouling layer, and the mass transfer of chemical agents
the variation in the characteristics of the source water, and (from the bulk phase to the fouling layer) and foulants (from the
a decline in fouling, which results in low chemical cleaning fouling layer to the bulk phase).
frequency, increasing the membrane lifespan and minimizing Some organic compounds can adhere strongly in the RO
the overall treatment cost. Potential disadvantages include membrane surface and lead to flux decline. Besides, the organic-
higher costs and the negative environmental impacts of the rich wastewater and presence of bacteria provide a combination
concentrates. that promotes the biofouling of RO membranes. The biofilms as
In short, non-conventional pretreatment lowers the operating a result of the growing strategy of microorganisms, attached to
costs because of lesser amounts of chemical additives in the salt the surface of the membranes, restrict a rapid permeate flowrate
water feed and the lower operational maintenance required for and cause an overall reduction in the water production capacity.
the RO system. Once a biofilm is established on the membrane, its removal can
Among the efforts to extend the RO membrane lifespan, over- be extremely difficult or even impossible. It depends on the bio-
come the problem of fouling can be considered essential. Notably, film extension and age (Bartels et al., 2005; WHO, 2007).
although the pretreatment process is efficient, there will be a According to Rana and Matsuura (2010), there are no mem-
decrease in the permeate flux over the course of the operation, branes that are free from fouling under any circumstances, and
requiring the implementation of chemical cleaning procedures to the general principle is to better manage the fouling.
recover the flow. Development efforts over the past 20 years have identified the
key process parameters and membrane products needed to
achieve stable high-quality water. A clear diagnosis of the magni-
Development of anti-fouling techniques tude of fouling by feedwater analysis and membrane autopsies (a
Despite the numerous proven advantages of the TFC polyamide destructive technique that provides a comprehensive view of the
membrane, one of its limitations is its propensity to fouling and condition of the membrane elements) with appropriate combina-
consequent loss of efficiency (Bartels et al, 2005; Subramani and tion and appropriate process design and operations (pretreatment
Hoek, 2010; Tang et al., 2011). and chemical dosing), as well an efficient cleaning plan, should
Generally, four types of fouling are found on the RO mem- enable the development of an effective fouling control strategy.
branes, namely, inorganic (salt precipitation, including metal It is possible to see the great importance of fouling managing
hydroxides and carbonates – referred to as scalling), organic for the RO membranes’ lifespan. The performance of fouling RO
(deposition of natural organic materials, such as fulvic and humic membranes can be partially restored by an appropriate cleaning
acids and many organic compounds, even those used for feedwa- method, together with improved maintenance procedures, such
ter pretreatment), colloidal (particle deposition in the suspension, as air scouring, significant flux and pressure recoveries, which
Coutinho de Paula and Amaral 5

Table 1.  Categories of cleaning agents, applications and action mechanisms.

Categories Application Mechanism of action Cleaning agent

Acids Removal of inorganic salt Hydrolysis or dissolution or chelation Hydrochloric acid (HCl)
deposits (Zondervan and Roffel, 2007). Citric acid (C6H8O7)
Phosphoric acid (H3PO4)
Alkalis Removal of inorganic Hydrolysis and solubilization. Sodium hydroxide (NaOH)
colloids (silt) Electrostatic interactions between the inlay
Removal of silica and metal and the negatively charged membranes when
silicates the pH of the solution is high (D’Souza and
Removal of organic fouling Mawson, 2005).
and biofilms
Chelationg Removal of metal oxides Metal ion adsorption agents. Breaking the Tetra-sodium salt of
agents structural integrity of divalent cations, removal ethylenediaminetetraacetic
of the anchor layer on the fouling layer, acid (Na4EDTA)
which serves as binding agents for organic Citric acid (C6H8O7)
molecules (Ang et al., 2011a). Oxalic acid (H2C2O4)
Surfactants Removal of organic fouling These have both hydrophilic and hydrophobic Sodium salt of dodecyl
and biofilms groups and are semi-soluble in organic sulphate (Na-SDS)
and aqueous solvents. Can solubilize
macromolecules by the formation of micelles
around them, which help clean the surface of
the dirty membrane (Ang et al., 2011b).
Inert salts Removal of organic These promote swelling of the fouling layer in Sodium chloride (NaCl)
hydrophilic forming of gel the presence of a salt solution, and reaction Sodium nitrate (NaNO3)
and ion exchange with the Na+ polysaccharide- Sodium sulphate (Na2SO4)
calcium complex on the fouling layer (Lee and Potassium chloride (KCl)
Elimelech, 2007).
Biocides Microbiological growth Metabolic inactivation of microrganisms (Matin Sodium bisulphite
inhibition et al., 2011). (NaHSO3)
Sodium metabisulphite
Hydrogen peroxide (H2O2)

are achievable with minimal use of chemicals (Creber et al., The literature reports widely that the optimal choice of a
2010; Pontié et al., 2005). chemical cleaning procedure is a complex issue, and depends on
the membrane material and type of fouling agent, involving the
type of cleaning agent and its concentration, temperature and
Appropriate cleaning procedures for the
duration of the procedure. An insufficient dosage of chemicals
RO membranes could result in inefficient removal of the fouling and, therefore,
The membrane cleaning procedure is crucial and has significant an inadequate recovery performance. On the other hand, over-
technical and economic impacts on the RO operations process. It dosing could result in harmful effects on the selective membrane
is assumed that a cleaning process is effective when the mem- layer, including a pH range not compatible with the recommen-
brane flux is recovered, that is, when the flowrate of the permeat dations of the manufacturers (Ang et al., 2011b). Significant
reaches a value close to that at the beginning of the process. additional costs can be incurred by the excessive overdosage of
Table 1 summarizes the main categories of agents used in chemicals. In addition, there are security concerns about the use
membrane cleaning, with their applications and mechanisms of of cleaning agents, whereas the disposal of chemicals to the envi-
action. ronment can have harmful effects. For example, the discharge of
Typically, in real conditions, the volume of cleaning solution ethylenediaminetetraacetic acid (EDTA), which is non-biode-
is defined by the RO system volume and this practice is indicated gradable, into receiving waters and the environment can remobi-
by membrane manufacturers. These volumes can be discarded lize toxic heavy metal ions from soil (Pihko et al., 2004), and the
with the concentrate, depending on the situation (NAS, 2008). disposal of NaClO on effluents can lead to the formation of
Most plants clean their membranes every week. In addition to organochlorine compounds (trihalomethanes and chloramines),
this maintenance cleaning, the frequency cleaning recommended considered carcinogenic compounds that bring human health
is two to four times annually (at scheduled times). The duration risks (Silva and Melo, 2015).
of the chemical cleaning is about 2 hours, which may vary Based on the technical recommendations of the RO mem-
according to the type of fouling, and is usually performed with brane manufacturers, preferably 0.2% (w) HCl (pH 1–2) and
heating (Dow, 2012). 0.1% (w) NaOH, or 0.025% (w) sodium salt of dodecyl sulphate
6 Waste Management & Research

(NaC12H25SO4), known as Na-DSS, both at pH 12, should be citric acid solutions (pH 4), and by circulation, using 0.5%
used. Commonly, cleaning is performed at heating at 35°C (Dow, sodium hydroxide (pH 11) in the system, with each cleaning step
2012), and practice has shown that an improved operational cycle lasting 30 minutes. The fouling was efficiently removed and the
time and flowrate recovery can be obtained by sequential combi- permeate flowrate efficiently recovered, reaching 27.2 l m−2 h−1
nations of acidic and alkaline cleaning. (755.6×10−8 m3 s−1 m−2) with module C.
Strugholtz et al. (2005) stated that although strong mineral These conclusions among authors about the membrane chem-
acids, such as hydrochloric and nitric acids (HCl and HNO3), ical cleaning have implications for mitigating significant fouling
could solubilize deposits, organic acids, such as citric acid and in RO membranes in various applications. Careful cleaning pro-
oxalic acid, were more effective in the instance of organometallic cedures, entailing two or more chemicals being used in sequence
contaminants. or in combination, can be formulated to obtain optimal perfor-
In addition to the use of biocides in the pretreatment of RO mance recovery and high water production, minimizing fouling
system feedwater, a second general application of biocides is in after cleaning, as well as the overall consumption of chemicals.
the preservation of the polymer membranes and related module Evidently, the cleaning procedure is directly related to the
components (e.g. glues, plastic spacers, other materials of con- scaling process, so it should be evaluated case by case. The
struction) during extended periods of membrane storage or plant results obtained with specific water or effluent can hardly be used
shutdown (Matin et al., 2011). Hydrogen peroxide or a mixture of as a standard.
hydrogen peroxide and peracetic acid has been used successfully According to Fravel and Lindsey (2014), the industry has
for treating biologically contaminated RO and NF systems (Dow, responded to the adverse economic effects of fouling by adopting
2012). anti-fouling techniques specifically formulated for membranes.
Ang et al. (2011b) examined the effectiveness of various pro- Many of these formulators provide customized software pro-
cedures for chemically cleaning fouled RO membranes from a grams that will mathematically predict the percent saturation of
sewage effluent treatment plant, collected in municipal wastewa- individual compounds based on a variety of site-specific param-
ter. The procedures were applied in pairs and as individual chem- eters, including feedwater constituents, temperature, pH and
icals in four categories of chemical cleaning agent combinations. desired system recovery. The chemical is injected into the RO
This included the investigation of alkalis (sodium hydroxide, feedstream, effectively preventing the precipitation of sparingly
NaOH), a chelating agent (sodium ethylenediamine tetraacetate, soluble salts, and extending the system operating time between
EDTA), a surfactant agent (sodium salt of dodecyl sulphate, the cleaning cycles.
Na-SDS) and a concentrated salt solution (NaCl). The cleaning The above-mentioned conditions clearly indicate the strong
sessions were carried out without permeation at a crossflow interdependency among the various factors, which are the suita-
speed of 4.28×10−2 m s−1, at room temperature, for 15 minutes. ble process pretreatment of the feedwater and the effective clean-
The results illustrated the strategy of matching chemical cleaning ing of the membranes to minimize fouling. This set of strategies
agents with complementary mechanisms to achieve greater effi- is aimed at extending the lifespan of the RO membranes.
ciency. In this evaluation, the greater cleaning efficiency (94.0%)
was achieved through the use of NaCl solution in 0.5 mol con-
centration and pH adjusted to 11. As reported by Lee and
Unwanted effects of oxidatives agents
Elimelech (2007), common inert salts can be used as an effective The literature reports that various solutions employed as sanitiza-
alternative for the cleaning of RO membranes fouled by gel- tion and cleaning agents or anti-fouling agents for both porous
forming hidrophilic organic foulants. In particular, NaOH dem- and dense membranes, such as sodium hypochlorite (NaClO) and
onstrates exceptional capacity to enhance overall cleaning hydrogen peroxide (H2O2), can alter the physical integrity of
performance when introduced with other chemical agents, pos- membranes, negatively affecting their selective properties.
sibly due to its ability to loosen the fouling layer; in other words, Regarding RO, using these cleaning agents leads to a decrease in
the fouling layer matrix becomes more porous and facilitates the the salt rejection efficiency, caused by the chemical degradation
transfer of other cleaning agents into the fouling matrix. of the selective layer of the membrane (Antony et al., 2010; Cran
Frick et al. (2014) evaluated the chemical cleaning techniques, et al., 2011; Kang et al., 2007; Kwon and Leckie, 2006; Pellegrin
conservation of discarded RO membranes and dosing chemicals. et al., 2013).
Three discarded spiral modules from a water demineralization The effects of chlorination on the aromatic polyamide RO
system were compared, namely, one module without preserva- membranes have been extensively reported in the literature
tion (A), one module that was preserved in a commercial biocide (Kang et al., 2007; Kwon and Leckie, 2006; Soice et al., 2003;
solution (B) and one module taken from the unit and immediately Tessaro et al., 2005). These studies have concluded that chlorine
tested (C). The results indicated that a lower starting flowrate causes irreversible damage to the active layer of polyamide,
(0.1 l m−2 h−1, equivalent to 2.78×10−8 m3 s−1 m−2) occurred in the resulting in a loss of membrane integrity.
test condition with module A, whereas the largest flowrate (20.4 Soice et al. (2004) studied the influence of the solution con-
l m−2 h−1 or 566.7×10−8 m3 s−1 m−2) was obtained with module C. centrations on the chemical degradation of a NF polyamide
The cleaning of the membranes was done by immersion, using membrane, which had been exposed to NaClO between 10,000
Coutinho de Paula and Amaral 7

and 100,000 ppm h (10 and 100 g l−1 for 1 hour). They observed NF membranes, including an increase in the permeability of 1.0–
the complete removal of the dense membrane layer with the 2.1 l h−1 m−2 bar−1 (equivalent to 2.8–5.8×10−12 m3 s−1 m−2 Pa−1)
increased concentration. According to Kang et al. (2007), the and a decrease in the rejection of NaCl (which had been more
active layer of the polyamide membrane exhibits low tolerance than 95%) to 35–50%. Consequently, the authors proposed that
(average 1000 ppm h or 1.0 g l−1 for 1 hour) for exposure to free the discarded membranes can be utilized in wastewater treat-
chlorine. ment, the pretreatment of seawater or the demineralization of
Besides the harmful effects of chlorine on the TFC polyamide selective brackish water, with little or no treatment.
membranes, the presence of transition metal ions, such as alu- Similar results were obtained in a study conducted by Prince
mina, can catalyse the degradation processes (Causserand et al., et al. (2011) that compared the performance of discarded RO
2008; Tessaro et al., 2005). The oxidation of the polyamide mem- membrane elements with new membranes. It was concluded that
brane, using a monochloramine solution in the presence of iron although the sample membranes did not conform completely to
compounds, was studied by Gabelich et al. (2005), demonstrating the criteria of the manufacturer (salt rejection of 99.5%), all the
the catalytic effect of iron. tested membranes showed a superior rate (96%) of rejection. In
From the above reports it is evident that the useful life of the view of this high rate of salt rejection, the authors proposed the
RO membranes is dependent on the quality of the water supply reuse of the membranes for applications such as brackish water
and several operational aspects. The need for cleaning and the treatment.
use of anti-fouling agents can compromise the integrity of the Kraemer (2009) and Rosa (2012) studied the application of
membranes, reducing their useful life and ending in disposal. discarded RO membranes from water demineralization processes
The philosophy of waste prevention and reuse really tackles for use in the treatment of the drain current of a cooling tower in
the causes. Whereas disposal represents the least favourable a petrochemical company. The permeate produced served as
option, recycling can help to decrease the consumption of pri- makeup water to the cooling tower. They evaluated chemical
mary resources but it does not tackle the causes, only the symp- cleaning procedures, the influence of the preservation of mem-
toms (Bartl, 2014). brane modules and the dosage of chemicals by testing in a pilot
system next to the cooling tower. A higher initial permeate flux
was obtained with a membrane module from the water deminer-
Reuse and recycling of discarded
alization unit that had been installed in the pilot system. The
reverse osmosis membranes combined chemical cleaning acid–base (citric acid pH 4 and
Membranes are considered inert municipal solid waste because sodium hydroxide pH 11) was shown to be effective for remov-
of their mostly polymeric composition in the case of landfill dis- ing deposits on the membrane surface and the subsequent recov-
posal. The inert components are not toxic and, thus, the main ery membrane flowrate. Laboratory tests indicated that the
problem associated with their existence in landfill is due to land quality of the permeate produced and used as makeup water for
occupation and transportation. the cooling tower was superior to that of clarified water produced
The alternatives for reuse and recycling of discarded RO by the company.
membranes include the direct reuse of modules in other separa- A comparative evaluation of the permeability of wet and dry
tion processes with less stringent specifications, recycling of membranes by Lawler et al. (2013) has revealed that appropriate
components, including incineration associated with energy storage conditions for RO membranes destined for direct reuse
recovery, and chemical conversion by means of oxidative treat- was crucial. The evaluation indicated that only partial recovery
ment. This section shows some results to extend the life-cycle of the performance was feasible after drying the membranes.
and improve a sustainable technology. Manufacturers generally recommend soaking the element in
sodium bisulphite or sodium metabisulphite solution and storage
in a sealed bag to maintain membrane hydration and to preserve
Direct reuse of discarded RO membranes
performance (Dow, 2012). Failure to adequately preserve and
A small number of publications identified the direct reuse poten- store can lead to premature drying of the membrane and perme-
tial of RO membrane modules. In this context, direct reuse ability loss resulting from increased interchain hydrogen-bond-
implies using membranes that were considered unsuitable in the ing replacing the water–polymer bonds, which facilitate
main application after transporting them for use to a secondary permeation (Louie et al., 2011).
application. Lawler et al. (2015) indicated that the most viable secondary
A survey conducted by Mohamedou et al. (2010) followed an application involves harsh feedwater conditions that require regu-
integrated autopsy approach for discarded RO membranes. The lar membrane replacement. Based on a survey of the condition of
parameters determined were the hydraulic permeability, salt the reused membranes, the manufacturer’s specifications and the
rejection, morphological and topographical variations (changes expected lifespan, these authors estimated the potential second
in average roughness) and verifying the presence of chemical life of the membranes. The authors concluded that a membrane
and/or biological contaminants. The authors concluded that some reused in harsh brackish water RO conditions would have a virgin
old RO membranes presented behavior similar to that of the new membrane production offset of 33%, followed by disposal in
8 Waste Management & Research

Table 2.  Composition of a typical reverse osmosis membrane element.

Membrane element component Composition Approximate carbon content (%)

Outer casing (12%) Fibreglass 30–50
Feed spacer (9%) PP 85.7
Permeate spacer (13%) Polyester 62.5
Membrane sheet Aromatic polyamide (0.2 μm) 71.6
(thin-film composite) (41%) Microporous polysulphone 73.7
(40 μm)
  Polyester support (120 μm) 62.5
Permeate tube/end caps (17%) ABS 88.3
Glues (7%) Epoxy resin 62.2
Rubber ring (1%) EPDM (ethylene-propylene-diene) 83.6

Source: Adapted from Lawler et al. (2012), Pontié (2014) and Prince et al. (2011).
PP: polypropylene; ABS: acrylonitrile butadiene styrene.

landfill. While the membrane reuse will offset production, it also RO membranes recycling
requires an additional cleaning, packaging and preservation step
prior to transport. Recycling of materials is a general term that involves physically
Lawler et al. (2012) suggested the development of standard transforming the material or its components (so that they can be
protocols for chemical cleaning to efficiently remove most of the regenerated into other useful products) and the recovery of energy.
fouling that occurred during the original application of the mem- The recycling of solid polymeric residues is widely known.
branes. In addition, these authors believe that a crucial step in this The various recycling technologies of plastic solid waste
process is to verify that the cleaning membranes conformed to (PSW) used in recent years have contributed greatly to the eco-
the requirements for clean membranes, such as permeability and image of waste management and particularly to PSW recycling,
integrity for salt rejection, before proceeding to reuse them. This treatment and recovery (Al-Salen et al., 2009).
verification could be facilitated by means of a detailed perfor- A study on the management and recycling of solid waste gen-
mance report on the RO membranes at the end of their usage time erated by desalination plants based on RO membranes was devel-
in the initial application. oped by Rattanakul (2012). The membrane spiral wound elements
Sahuquillo et al. (2015) reported the experience of the of different models and brands, used by the industries, were sub-
Remembrane project developed by a consortium of companies in jected to dissection for the purpose of extracting the individual
Spain in order to recover RO membranes (BW-F) to reduce costs components, in order to establish the weight ratio of each compo-
and increase the overall efficiency of the desalination process. nent. The results showed that the RO membrane module compo-
The aim of the project is to improve the feasibility of water reuse nents consisted of recyclable material, corresponding to about
plants and stimulate, at a lower cost, other applications requiring 80% (weight), and were mostly plastic. The author has proposed
a lower quality specification of water, such as in industry or in a business plan for the recycling of disposed modules to reduce
irrigation. In accordance with the authors, after diagnosis by the environmental impact of the solid waste of RO plants.
autopsy, the membranes are chemically cleaned in a pilot plant The membrane modules are complex structures, consisting of
recovery. The results show a permeate flow of 1000 l h−1 and a a number of different polymeric components and, potentially, the
NaCl rejection greater than 96%. Subsequently, the recovered individual components can be recovered for other purposes.
membranes are tested in other pilot plant as the tertiary treatment Table 2 shows the composition of a typical RO membrane
of secondary effluent decanting, preceded by filtration and MF. element.
Microbiological analyses of treated water indicated that is meets Table 2 shows that there are several types of materials that
the requirements for total coliforms, Escherichia coli and make up the membrane module. In addition, there are contamina-
Legionella spp. Recovery costs of the membranes were less than tions inherent in the use of membranes in the desalination/demin-
95 euros per module. A reduction of 2000 tonnes per year of eralization process.
modules disposed of in landfills, waste disposal savings of 80,000 The main aspects of RO membrane mechanical recycling,
euros per year, excluding shipping costs, based on 40 euros per incinaration and recovery energy, are discussed in the following.
ton removal rates are expected.
In view of these studies, the importance of reusing discarded Mechanical recycling. In order to accomplish the mechanical
RO membranes is evident. However, direct reuse is not always recycling of discarded membranes, the module removal and sepa-
possible due to the high or irreversible fouling of membranes. ration of the components of interest is required, prior to the wash
Therefore, following the waste management hierarchy, recycling steps and grinding the plastics. Because of the mechanical recy-
of membrane modules should be the next step to be prioritized. In cling requirements, only the ABS components (acrylonitrile buta-
the following, the possible techniques focused on recycling will diene styrene) are suitable, including the central tube, the end caps
be addressed. and the spacers, with all the other components having to be
Coutinho de Paula and Amaral 9

disposed of in landfill (Goodship, 2007). Thus, the mechnical the discarded modules could potentially be used in electric arc
recycling scenario still requires the disposal of 8 kg of material as furnaces. Although the chemical composition and the structure of
40% by mass of the membrane module is unsuitable for this appli- plastic waste are known to influence the reactivity of coke and
cation (Lawler et al., 2015). After the crushing and screening the subsequent combustion performance, it would be necessary
phase (assuming a loss of 5% of material), the plastic has to pass to test the other plastics that comprise the modules. The same
through the melting and extrusion process, and an additional loss tests would allow a full assessment of the feasibility of using
of 10% of material is assumed (UNSW, 2010). The main advan- some or all of the RO membrane elements in the specific applica-
tage of this process is that it displaces virgin plastic production. tion (Lawler et al., 2012). The main advantages of using this
technique are the diversion of the polymeric materials from land-
Incineration and energy recovery. Incineration is commonly fills and the reduction of coke consumption, as well as the ensu-
used in countries with strict land use requirements, and in some ing environmental and economic benefits.
cases has been shown to be environmentally favourable to land-
fill (Assamoi and Lawryshyn, 2012; Merrild et al., 2012). The
literature generally indicates that the combustion of solid plastic
Conversion of membranes by oxidative
waste can reduce the volume of plastic sent to landfills by 90–
99%. Furthermore, energy can be recovered and used for produc- In fact, due to the nature of the TFC membrane used in the RO
ing electricity, or the thermal processes of other products (Yassin process, and particularly because of the structure of the support
et al., 2005). With regard to the thermal decomposition of the layer (Baker, 2004), the conversion from the RO membrane to a
polymeric components of RO membranes, the membrane com- porous membrane is possible by degrading the dense layer of pol-
ponents, with the exception of the outer housing made of glass yamide. The relative vulnerability of the polyamide layer to con-
fibre, consist of synthetic polymers containing C, N, H, O and S ventional oxidizing agents, observed during the chemical cleaning
as the main constituents. of the membranes, can be used as the conversion method.
As indicated in Table 2, the carbon content of the polymers is Pioneering studies were conducted in Spain by Rodriguez-
between 62.2% and 88.3% by mass, pertaining to the main com- Gonzalez et al. (2002) and Veza and Rodriguez-Gonzalez (2003).
ponents of the membrane. With a total mass of 13.5 kg, a RO These authors verified the possibility of converting RO mem-
membrane element, typically 8 inches in diameter (equivalent to branes by chemical treatment with different oxidizing solutions,
2×10−1 m), contains 9.1 kg of carbon. aimed at removing the active layer of the polyamide membrane,
Although high-performance polymers are used as energy intended for reuse in applications such as MF. Assessments were
sources, it has been repeatedly mentioned in the literature that the performed in various conditions, such as with different oxidizing
process of incineration of such waste requires good operating reagents, various doses and contact times, as well as different
practices. Inadequate management and control could lead to methods of contact. Tests have shown that the best results were
greenhouse gas (GHG) emissions and attendant health risks. The obtained with the oxidizing agent in recirculation for 1–2 hours at
health risks are attributable to the generation of toxins and carci- a pressure of 5–10 bar (5 to 10×105 Pa). The following solutions
nogenics, for example, dioxins from the polymers that contain presented the best options, namely, 7.7 g l−1 sodium hydroxide
chlorine (Achilias et al., 2012; Al-Salem et al., 2009). (NaOH), 6.0 g l−1 sodium hypochlorite (NaClO) and 0.9 g l−1
Consequently, implementing additional technologies to cap- potassium permanganate (KMnO4). The membranes were previ-
ture and treat atmospheric emissions, in accordance with current ously washed with water and cleaned with a sodium bisulphite
legislation, should be considered. Moreover, energy recovery solution (NaHSO3) in recirculation for about 18 h. According to
from the process could compensate for GHG emissions from tra- the authors, the dosage of 0.9 g l−1 KMnO4 demonstrated a highly
ditional power generation, further expanding the sustainability of positive result, by reducing the salt rejection properties of RO
the incineration process (Assamoi and Lawryshyn, 2012). membranes from a value above 95% to 2%, as desired.
Evidently, the incineration process should be considered as an In addition, in the study by Veza and Rodriguez-Gonzalez
integrated solution. (2003), the converted membranes were tested in the pressure ves-
In addition, using polymeric residue is possible, for instance sel, which had also been used in the RO systems and recovered
as a coke substitute in the electric arc furnaces employed in the for a new purpose. A pilot plant was designed to reduce sus-
steel-making process. Worldwide, worn tires and plastic waste pended and dissolved solids in secondary wastewater, with a
nowadays are burned as a partial substitute for coke (Sahajwalla designed production capacity of 1.6×10−3 m3 s−1. The converted
et al., 2011). The use of waste polymer in electric arc furnaces membranes were applied as pretreatment for RO after the filter
provides several advantages, such as an increase in furnace effi- cartridge, and proved able to reduce suspended solids (93.9%
ciency, reduction in power consumption and a decrease in coke average reduction in turbidity), and the total separation efficiency
consumption (Sahajwalla et al., 2011), as well the diversion of reached 97%. The authors indicated that fouling has been identi-
polymeric materials from landfill. fied as the most important disadvantage of the operating charac-
In respect of the RO membrane modules, as the feed spacers teristics. The converted membranes developed a significant drop
are often made from PP (polypropylene), this fraction of in pressure and required frequent cleaning by washing with
10 Waste Management & Research

high-flow recirculation, such as chemical cleaning. Recirculation 4% HNO3 for 1–100 h. According to Jezowska et al. (2006) and
was recommended to maintain a significant flow and avoid the Louie et al. (2011), pre-soaking dry aromatic polyamide mem-
deposition of solids, as well as for optimizing the cleaning proce- branes in short-chain aliphatic alcohols results in a significant
dures (Veza and Gonzalez-Rodriguez, 2003). increase in the water flowrate, which is attributed to wetting of
Lawler et al. (2011) evaluated the degradation capacity of pores in the selective polyamide layer and to changes in the poly-
three solutions to remove the active layer of RO membranes, mer structure.
namely, NaOH, KMnO4 and NaClO. Using the concept of expo- In addition, Lawler et al. (2013) proposed a conversion opti-
sure intensity (in ppm h), the oxidizing agent concentration was mization method (NaClO, 300,000 ppm h) to determine the ini-
maintained constant during the research. The exposure intensities tial condition of the membrane and its corresponding performance
were varied at different times to obtain the desired intensity. After to permeability, salt rejection, rejection of proteins and humic
treatment, the RO membranes were tested for permeation of pure substances, removal of pathogens and the fouling level. The
water and for salt rejection (2.0 g l−1 NaCl feed solution). The results for the converted membranes demonstrated that the per-
effects of the different exposure intensities of the solutions on the meability performance ranged from 9.3 to 116.3 l h−1 m−2 bar−1
membranes were compared. In accordance with the authors, (equivalent to 25.8–323×10−12 m3 s−1 m−2 Pa−1) for pre-wetted
treatments with KMnO4 and NaOH resulted in a significant low- samples, with lower salt rejection than 1% in all instances. The
ering effect on the rejection of salt, which indicated damage to converted membranes demonstraded a 2.4 log removal of virus-
the membrane surface. However, the most promising results were sized particles, and were comparable to UF membranes (molecu-
obtained for NaClO. RO membranes treated with at least 300,000 lar weight cutoff estimated at 10 kDa) in terms of proteins and
ppm h of NaClO by immersing at room temperature showed an humic substance rejection and fouling propensity. Characterization
increased permeability of 4–175 ± 4 l h−1 m−2 bar−1 (equivalent to techniques used for the surface of the membranes, such as
11 to 486 ± 11×10−12 m3 s−1 m−2 Pa−1) and salt rejection of less Scanning Electron Microscopy (SEM) and Fourier Transform
than 4%. Studies by Raval et al. (2012) and Pontié (2014), using Infrared Spectrometry(FTIR), indicated the removal of the active
NaClO solution in similar conditions, reached similar results. layer of polyamide.
Note that the method of degradation of RO membranes used A study by Ambrosi and Tessaro (2013) evaluated the effects
in the research by Lawler et al. (2011) considered exposure inten- of the chemical treatment with 2 g l−1 KMnO4 solution in combi-
sities between 28,000 and 500,000 ppm h, whereas the study by nation with chemical cleaning of old RO membranes in order to
Rodriguez-Gonzalez et al. (2002) addressed dose ranges (in mg make then reusable in applications other than RO and to increase
l−1) of oxidizing agents at significantly lower strengths, of the their life-cycle. The performance of membrane samples was
order of 12,000 ppm h. This could explain the differences in the evaluated in terms of water permeate flux and salt rejection. The
results and the conclusions reached. samples were given a pretreatment with sodium bisulphite solu-
Correspondingly, Lawler et al. (2013) assessed the various tion (NaHSO3) for recirculating at 4 bar (4×105 Pa) for 1 hour.
kinds of membrane available on the market, focusing on the stor- After oxidative treatment, the selective layer was degraded,
age methods of the membranes and the pre-wetting action to pro- improving the water permeate flux of at least 15% from its initial
mote the conversion of the membranes. They stated that all the value at the expense of decreased salt rejection. Citric acid solu-
tested membranes invariably benefited from pre-wetting. In addi- tion was used as a cleaning agent after the oxidation step in order
tion, it was found that an increase in the applied pressure led to an to remove a manganese oxide layer formed on the surface of the
increase in the permeability of the membrane. For pre-wetting membrane. The result was an enhanced oxidative process, which
purposes, a pressure of 15 bar (15×105 Pa) was adopted, with increased the permeate flux even more and decreased the salt
Milli-Q™ water, for 30 minutes. The importance of properly rejection to 85%. However, the authors did not disclose that this
storing the membranes to maintain the hydraulic performance technique completely removed the active membrane layer and
was emphasized, because the average permeability of the dehy- therefore had limited possibility for conversion from RO to UF or
drated membranes was less than that of the wet stored mem- MF.
branes (or the virgin membrane samples). García-Pacheco et al. (2015) also studied the recycling of end-
Drying polyamide membranes has a negative impact on the of-life RO membranes (used in the desalination of brackish
membrane–water interactions, causing a large decrease in the water). Membrane samples were subjected to chemical attack by
permeate flowrate. Preventing drying of membrane modules immersion of NaClO (124 ppm free chlorine), acetone solution
after use is an important warning in the technical manual of the (10,000 ppm) or N-methyl-2-pyrrolidone solution (10,000 ppm).
manufacturers. For example, the technical manual from the man- An important consideration in this respect is that the best water
ufacturer (Dow, 2012) recommends a typical method for effec- permeability results were achieved with NaOCl solution, and that
tive membrane rewetting that requires pressurization to 10 bar other agents did not cause substantial changes in membrane per-
(10×105 Pa), with a closed permeate valve. Other recommended meability. When comparing different pH conditions (pH 3, 7 and
methods for moistening dry elements include immersion in a 10.5), the alkaline condition was the most effective to increase
solution of ethanol–water or propanol–water, at a ratio of 50% by the permeability; the experiments were carried out up to 410 h
volume, for 15 minutes or, alternatively, in 1% HCl solution or exposure time. The process was repeated for five commercial
Coutinho de Paula and Amaral 11

membrane brands, stored wet. Membrane permeability and rejec- In accordance with Muñoz and Navia (2011), there are two
tion characteristics were tested with synthetic brackish water main fields for LCA application in waste management strategies:
containing NaCl (2000 ppm), magnesium sulphate (MgSO4, assessing the environmental performance of specific waste man-
2000 ppm) and glucose (250 ppm, 180 Da). According to the agement systems and comparing different waste management
authors, most of the transformed membranes achieved permea- scenarios for a specific waste type. Moreover, a novel field of
bility and rejection like NF membranes up to 50 hours’ exposure application in municipal solid waste management seems to be
time, while performed like UF membranes after 242 hours’ expo- GHG emissions assessment and the comparison of scenarios with
sure time indicating, respectively, partial removal and complete and without energy recovery using LCA.
removal of the aromatic polyamide layer. Coventry et al. (2016) state that many solid waste LCA meth-
It is noted that García-Pacheco et al. (2015) used an intensity ods have been previously proposed; however, research suggests
of exposure of the membrane NaClO ranging between approxi- that the applicability of a given method is limited by geography.
mately 4200 and 50,000 ppm h, much smaller than those used Some studies have shown that the exclusion of a detailed trans-
by Lawler et al. (2011, 2013), Raval et al. (2012) and Pontié portation model in a LCA study can result in a severe underesti-
(2014). A comparison of the membrane characteristics after mation of the environmental impacts of disposal scenarios
chemical oxidation with UF membranes is common among (Brambilla Pisoni et al., 2009; Merrild et al., 2012).
these authors, although García-Pacheco et al. (2015) had report Lawler et al. (2015) looked at the environmental impact of a
characteristics of NF membranes as a product of a partial number of proposed end-of-life disposal options for membranes
removal of aromatic polyamide layer. within the context of the Australian desalination industry, as fol-
In the context of the recycling process of RO membranes, the lows: landfill, incineration, gasification, electric arc furnace,
permeability of the dense membranes, converted to porous mem- direct reuse, recycling and chemical conversion. The effect of
branes, as well as the fouling phenomenon of the converted variation in membrane lifetimes after reuse and recycling, as well
membranes, along with their reapplication in other processes the required transportation distance, were explored through a
(MF, UF or NF) are the fundamental parameters that reflect the sensitivity analysis and the mass sent to landfill was estimated for
overall effectiveness of the process. each end-of-life option. According to this authors, the reuse sce-
Providing converted RO membranes, such as low-cost UF narios are highly environmentally favourable across the studied
membrane substitutes, for use in water treatment service projects, impact categories, namely, climate change, fossil depletion,
pretreatment in low-cost RO systems or wastewater treatment ozone depletion, ecotoxicity, human toxicity, freshwater eutroph-
operations has several benefits (Lawler et al., 2013). Lawler et al. ication, marine eutrophication and terrestrial acidification. Direct
(2015) stated that the RO membranes converted into UF mem- RO reuse has both the greatest reduction in CO2-e emissions and
branes and applied in the RO systems pretreatment had an esti- fossil fuel depletion of all the scenarios, with the oxidative treat-
mated extended life-cycle of two years, followed by disposal in ment scenario only slightly behind, due to the extra chemical
landfill. treatment steps involved. While the reuse scenarios gain benefit
The recycling processes presented here can be acceptable for from avoiding the production of virgin membranes, the recycling
RO membranes. However, for large-scale applications, the qual- scenario gains environmental credit from the offset of virgin
ity and performance of the process obviously have to be opti- plastic production.
mized, controlled and standardized appropriate to the different The results showed that after the reuse scenarios, recycling
types of RO membranes. The fouling behaviour of the converted has the greatest environmental benefit. For the end-of-life sce-
RO membranes in the long-term operation should be assessed. narios where the used membranes require substantial relocation,
It is evident that the options for recycling discarded RO mem- transportation emissions have the potential to play a significant
brane modules offer numerous study possibilities. role in the scenario's environmental sustainability. Therefore,
membranes directly reused, which last at least 11 months, and
membranes converted by oxidative treatment, lasting at least 1.4
A life-cycle perspective years, will be more environmentally beneficial than landfill at all
A life-cycle perspective is necessary when discussing alterna- possible transportation distances (Lawler et al., 2015). The
tives related to the extension of the RO membranes’ lifespan. greater emission offsets that the recycling scenario offer mean
While some alternatives could expand the lifespan of a product, that substantially shorter distances or longer lifespans are
unintended environmental impacts in other phases of its life- required to make reuse comparably more beneficial.
cycle should be discussed. Life-cycle assessment (LCA) method- Clearly, the use of NaClO, KMnO4, NaOH and other chemical
ology is a systematic tool for assessing potential environmental agents will show an environmental impact, require an effective
consequences and has been applied to recycling, treatment and cleaning of contaminated chemicals, and has to be compared to
disposal scenarios for all PSW (Al-Salem et al., 2009; Rajendran the use of new membranes. LCA or similar tools available to
et al., 2013; Simões et al., 2011; Turconi et al., 2011) and, evaluate the massive use of chemicals was identified in a small
recently, to membrane industries (Plappally and Lienhard, 2012; number of studies, in different types of applications. According
Zhou et al., 2011). to Bindra et al. (2015), the manufacture of sodium hydroxide and
12 Waste Management & Research

sodium hypochlorite are energy-intensive processes and the recycling alternatives, not only based on efficiencies, but also on
potassium permanganate can also be very expensive; thus, this the environmental impact associated with the treatment of emis-
would make it impractical for use in large facilities. sions. Besides that, the membranes, even after been reused or
Phong et al. (2012) showed that an alkali treatment had high recycled, will eventually end up in landfill.
impacts on the environment due to high toxicity. Dedpakdee The finding that the conventional oxidizing agents cause a
et al. (2015) similarly reported that using a high concentration of gradual degradation of the active layer of the TFC aromatic poly-
NaOH could lead to a high potential impact on toxicity as the amide membrane can be used in favour of new alternatives for
consequences of chemical production and wastewater treatment recycling end-of-life membranes. This could be considered a
afterwards. Boonterm et al. (2016) reported that high NaOH practical illustration of converting the problem into the solution.
consumption contributes to the impact on the human toxicity, ter- Various studies have demonstrated the possibility of removing
restrial eco-toxicity, marine eco-toxicity and freshwater eutrophi- the thick active layer of the RO membrane, with the converted
cation categories, while Alfonsín et al. (2015) had previously membranes exhibiting satisfactory performance, especially in
reported that the use of large amounts of NaClO presented high terms of permeability. However, other discussions have alluded to
impacts in freshwater eutrophication, photochemical oxidant for- inconsistent performance results for various types of membrane.
mation, human toxicity and ecotoxicity. Furthermore, the requirement for pre-wetting and the application
In addition to the above and according to Rajendran et al. of high pressures or high doses of chemical oxidants could limit
(2013), many LCA studies have focused on individual impact the feasibility of the large-scale implementation of the method.
categories rather than the aggregated single score, and a compari- Therefore, various technical and operational parameters need
son of LCA results between individual and aggregated impacts to be considered, evaluated and discussed. Among these are the
and integration of the performance of recycled plastics in LCA efficient cleaning of the membranes after disposal, the selection
are necessary for the decision making. of the respective oxidant and the appropriate concentrations of
the oxidizing agent solutions. It must be noted that the operating
pressure parameters of the chemical attack and the pH of the oxi-
Considerations and conclusions dizing solutions certainly have a strong influence on the removal
This review provides an overview of the main advances in RO mechanisms of the polyamide layer, but these aspects have not
technology that aimed to improve system performance and been sufficiently assessed in the literature. As regards the chemi-
extend the membranes’ lifespan. These advances include the cal conversion of the membrane, it is necessary to investigate
feedwater pretreatment adjustment, anti-fouling management whether the recycled membranes have overall performance char-
and suitable procedures for membrane chemical cleaning. The acteristics and application capabilities compatible with the MF,
significant interdependence of all these factors was evident. UF or NF, and also under what conditions.
Because of the sensitivity of RO systems to fouling, good pre- One important issue that should be considered is related to the
treatments need to be coupled to continuous monitoring to avoid morphological characteristics of TFC membranes, mainly from
irreversible fouling. Since feedwater quality and operating condi- the polysulphone support layer. Thus, the tendency of the recy-
tions can change from time to time, optimized cleaning methods cled membranes to fouling in the new application is another
need to be applied. Thus, the discussed set of strategies could important aspect to be evaluated in depth.
lead to an increased lifespan for the RO membranes, with atten- Added to these aspects is the need for immediate care after the
dant operational, economic and environmental benefits. Avoiding disposal of the modules, such as proper storage and moistening,
early disposal of the membranes is the first step in the waste man- prior to the membrane recycling process. It must be noted that
agement hierarchy. each batch of membranes for recycling requires individual char-
Subsequently, as regards the aim of extending the life-cycle of acterization and assignment to an appropriate application.
the RO membranes, the possible reuse options and the recycling In addition, after confirming the technical feasibility of adopt-
of discarded membrane modules were discussed. These alterna- ing the oxidative conversion of discarded RO membranes as a
tives include the direct reuse of the disposed modules in other method to extend the life-cycle of the membranes, the economic
separation processes with less stringent specifications, the recy- and environmental viability has to be assessed.
cling of the membrane module components, including incinera- Another important issue that previous studies did not discuss
tion (for energy recovery), and chemical conversion by oxidative refers to the specific environmental impacts associated with the
treatment of the membranes. chemical effluents produced after the oxidative treatment tech-
Current waste and resource management lacks an integrated nique. Therefore, the reuse of the oxidative solutions should be
approach covering the whole chain of product design, raw mate- evaluated to minimize effluent production during membrane
rial extraction, production, consumption, recycling and waste recycling. Last but not least, the treatment of wastewater pro-
management. Efforts related to the re-design of RO membranes duced must also be evaluated.
based on recycling purposes, to the best of our knowledge, have Finally, the choice of strategies to reuse and recycle depends
not been reported elsewhere. on integrated criteria that are of importance to the user, involving
It is very important to consider that the assessment should cost, system operation and environmental friendliness from a
provide consistent guidelines for the selection of reuse and sustainability perspective.
Coutinho de Paula and Amaral 13

Employing more sustainable alternatives rather than simply Baker RW (2004) Membrane Technology and Applications. 2nd ed.
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Minas Gerais (FAPEMIG), Brazil, for financial support for the revi- ated using magnetic resonance imaging. Journal of Membrane Science
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