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Membrane bioreactors for the removal of anionic

micropollutants from drinking water


João G Crespo, Svetlozar Velizarov and Maria A Reis

Biological treatment processes allow for the effective destroyed. A brine stream containing a high concentration
elimination of anionic micropollutants from drinking water. of ions is generated, which must then undergo additional
However, special technologies have to be implemented to treatment and disposal.
eliminate the target pollutants without changing water quality,
either by adding new pollutants or removing essential water Biological conversion is a promising technology for the
components. Some innovative technologies that combine effective and economical removal of anions from water.
the use of membranes with the biological degradation of Several bacteria capable of degrading anions to harmless
ionic micropollutants in order to minimize the secondary products have been identified. These bacteria carry out
contamination of treated water include pressure-driven anaerobic respiration using anions as electron acceptors
membrane bioreactors, gas-transfer membrane bioreactors and organic or inorganic compounds as electron donors
and ion exchange membrane bioreactors. (e.g. ethanol, acetate, hydrogen gas). Electron donors
must be added to the contaminated water; however,
Addresses the dosage must be carefully controlled in response to
CQFB/REQUIMTE, Department of Chemistry, FCT, Universidade Nova fluctuations in ion concentration, and this constitutes one
de Lisboa, P-2829-516 Caparica, Portugal

e-mail: jgc@dq.fct.unl.pt
of the serious drawbacks to the biological process.

In the presence of chemical oxidants, some organic elec-


Current Opinion in Biotechnology 2004, 15:463–468 tron donors, added in excess, can serve as precursors for
This review comes from a themed issue on the creation of novel contaminants (e.g. disinfection by-
Biochemical engineering products), which have been recognized as potential car-
Edited by Manuel Carrondo and John G Aunins cinogens [1,4]. Furthermore, any overdosing of organic
electron donors, which are readily biodegradable, can
Available online 28th July 2004
promote microbial growth in water distribution systems,
0958-1669/$ – see front matter thus requiring post-treatment to produce safe and biolo-
# 2004 Elsevier Ltd. All rights reserved. gically stable water.
DOI 10.1016/j.copbio.2004.07.001
Instead of an organic compound, hydrogen has been used
to prevent the chemical contamination of water, but it
Abbreviation
requires special hydrogen supply devices due to safety
IEMB ion exchange membrane bioreactor
reasons [11].

Introduction Most traditional techniques for the biological removal of


The contamination of drinking water sources with inor- anions from contaminated water use high cellular con-
ganic compounds is a matter of concern, because of their centration bioreactors, in which the hydraulic and cell
harmful effect on human health. Some of these com- retention times are decoupled. This type of reactor is
pounds are highly soluble in water and dissociate com- suited for the treatment of high flow rates of contami-
pletely, resulting in ions that are chemically stable under nated water with a concentration of anions in the range of
normal water conditions. Examples of polluting anions mg/L to a few mg/L, for which slow degradation kinetics
include nitrate, nitrite, perchlorate, bromate, arsenate are usually obtained. The most common configurations
and ionic mercury, for which the proposed guideline include immobilized cell reactors (e.g. packed bed, flui-
values for drinking water quality are quite low (in the dized bed or membrane-supported biofilms) [5,9,12,13],
range of mg/L to a few mg/L) owing to their carcinogenic in which cells come into direct contact with the water
effects or other risk factors to public health [1,2–5]. Some stream containing the pollutant.
of them may be present simultaneously in contaminated
water. The concept of an active layer (biofilm) is important for
understanding the functioning of membrane bioreactors.
Technologies available for the treatment of water con- In the case of the anionic compounds mentioned above,
taminated with inorganic anionic compounds include the biofilm corresponds to a reaction zone where a redox
physical, chemical and biological processes [6–10]. In process takes place involving the oxidation of the added
the first type of process, ions are concentrated rather than electron donor and reduction of the anionic pollutant

www.sciencedirect.com Current Opinion in Biotechnology 2004, 15:463–468


464 Biochemical engineering

(electron acceptor) to harmless product(s). Two different ditions, gas-permeable membranes offer the advantage of
transport situations may occur through the biofilm: co- efficient gas transfer without bubble formation, which
transport, in which both the electron donor and acceptor prevents both the waste of excess hydrogen and the
come into the biofilm from the side of the polluted water, accumulation of explosive amounts of hydrogen in the
and counter-transport, in which they enter the biofilm headspace above water. In addition, autohydrogen-
from opposite sides. These two situations may lead to otrophic processes are attractive as they generate much
different biofilm structuring and distribution of microbial less microbial biomass than heterotrophic ones using
populations. organic electron donors. This approach has recently
received considerable attention for the treatment of
In this paper, the most promising technologies based on groundwater contaminated with nitrate [11,21,22,
membrane bioreactors for the removal of anions from 23–25] and perchlorate [26]. Up until now, research
contaminated water are presented and compared in terms has been carried out with ex situ laboratory-scale reactors;
of the treated water quality and process efficiency. however, an interesting application would be in situ water
remediation (i.e. at the contaminated site) as illustrated in
Pressure-driven membrane bioreactors Figure 1. The hydrogen gas is supplied to the inside
The integration of biological water treatment with its (lumen side) of hollow-fibre membranes and diffuses to
filtration across porous membranes, driven by a pressure the outside (shell side), where it is used by existing
difference, has already been successfully employed in microrganisms as an electron donor for the reduction of
urban and industrial wastewater treatment [14,15–17]. anionic micropollutants.
The biomass can be recycled through an external mem-
brane module, but the recent trend involves the use of There is still no general agreement concerning the role of
membranes directly immersed in the bioreactor, a con- the biofilm, which grows naturally at the outside mem-
figuration known as an ‘immersed membrane bioreactor’ brane surface, on the performance of the process. As the
[16]. The main advantage of pressure-driven systems is consumption of hydrogen in the vicinity of the membrane
the possibility of achieving high biomass concentrations guarantees a relatively high driving force for its transport,
within the bioreactor; therefore, the plant size can be some authors consider that the biofilm is an essential part
reduced. As a result of membrane separation, the biomass of the process and even designate this type of reactor as a
retention time is independent from the hydraulic reten- ‘membrane-biofilm reactor’ [22,23,24]. However, biofilm
tion time, thus allowing slow-growing microorganisms to formation hinders gas transfer to the bulk liquid, thus
be maintained in the bioreactor. This feature is of parti- decreasing the zone of influence around the membrane
cular importance for toxic compounds and/or micropollu-
tants, which usually need long periods for their complete Figure 1
biological degradation/transformation to harmless pro-
ducts. Membrane fouling may affect the performance
Gas-permeable H2
of the process, either due to the deposit of a layer at
membrane
the membrane surface and/or by partial or complete Microorganism
blockage of the pores; however, fairly efficient solutions Biofilm
(e.g. periodic membrane backwashing) can be implem- Water table
ented so that relatively high amounts of water may be
treated per unit area of membrane [12,18]. H2 H2
Groundwater X–
Several attempts, all aimed at nitrate removal, have been flow
Harmless products
made to extend this approach to the production of drink-
ing water [12,18–20]. The main concern is the treated
water quality. Although microbial contamination of water
can be avoided, the retention of ions and low molecular
mass compounds (such as metabolic by-products) by Confining layer Contaminant plume
porous membranes is generally insufficient to meet the Current Opinion in Biotechnology
stringent drinking water criteria; therefore, either process
modifications or water post-treatment are necessary.
A schematic representation of an in situ hydrogen gas supplying
membrane system installed across a contaminant plume. Hydrogen gas
Gas-transfer membrane bioreactors is supplied to the lumen of a gas-permeable hollow-fiber membrane,
Hydrogen can serve as an inexpensive, non-polluting while groundwater flows past the membrane. The figure shows that, as
and non-toxic electron donor for reducing different hydrogen is transferred, it dissolves into the water and serves as an
electron donor for hydrogenotrophic microorganisms, thus reducing the
oxy-anions by autotrophic microorganisms, although its anionic micropollutants (X ). The pressure of the gas in the lumen can be
direct injection is not acceptable because of its low adjusted independently so as to control the desired hydrogen delivery
solubility and high flammability. Under appropriate con- rate. (Figure adapted from [11] with permission from Elsevier.)

Current Opinion in Biotechnology 2004, 15:463–468 www.sciencedirect.com


Membrane bioreactors for water purification Crespo, Svetlozar and Reis 465

[21,27]. This problem appears to be more important Figure 2


for in situ remediation, as natural convection in ground-
water may be poor. Moreover, in some cases, mineral Anion exchange
precipitation on the membrane surface can reduce the gas membrane
Treated water
transfer rate [27]. Biofilm

The most serious concern for further research is water


Biocompartment Water
quality, which has still not reached acceptable levels.
compartment
Indeed, the main problems include a significant increase Cations
in water turbidity as a result of biomass sloughing [25] and
an increase in the total organic content due to soluble Cl–
microbial products leaking from the microbial cells Cl–
[21,25,28]. Anionic micropollutants
Harmless X– X–
products
The ion exchange membrane bioreactor
A new process has recently been proposed [29–31,32] for
the removal and bioconversion of ionic micropollutants Electron donor + nutrients +
driving counterion (e.g. Cl–) Polluted water
from water streams. In this process, the ionic micropol-
lutant is transported from the water stream through a non- Current Opinion in Biotechnology

porous ion-exchange membrane into a biological com-


partment where it is simultaneously converted by a A schematic diagram of the ion transport mechanism in the ion
suitable microbial culture into harmless products. exchange membrane bioreactor (IEMB). A non-porous, anion exchange
membrane serves as a selective barrier between the water stream,
The mechanism of ion-transport and co-ion exclusion
containing one or more anionic micropollutants, represented as shaded
(Donnan dialysis) in the ion exchange membrane bior- circles (X ). The addition of a suitable counterion (e.g. Cl ) to the
eactor (IEMB) is represented in Figure 2, illustrating biocompartment at a sufficiently high concentration results in a chloride
the transport and bioconversion of an anionic pollutant. flux to the water compartment. To preserve electroneutrality, an
The microbial culture is fed with an adequate carbon equivalent back flux of X to the biocompartment is generated where it
undergoes bioreduction to harmless product(s) within the biofilm, which
source and other required nutrients in a continuous develops on the membrane surface and/or in the biomedium. Due to the
mode. The Donnan dialysis type of operation re- Donnan exclusion effect, co-ions (cations in the case presented) are
quires the addition of a so-called driving counter-ion to rejected by the positively charged membrane, thus maintaining their
the biocompartment, which is transported in a direction original levels in the two compartments. (Figure adapted from [32] with
permission from Wiley.)
opposite to that of the polluting ion to maintain electro-
neutrality.

This process has been tested for the removal and bio- it allows for the isolation of the microbial culture from the
conversion of nitrate, nitrite and perchlorate from drink- feed stream behind a dense membrane barrier, avoiding
ing water, even if they are present simultaneously in the contamination of the treated water with cells, meta-
different concentration ranges [29–31,32,33–35,36,37]. bolic by-products and excess carbon source. This in turn
Other anionic micropollutants are presently under study, prevents the secondary contamination of the treated
namely bromate, arsenate and cyanide. This concept water. Secondly, the process of removing the charged
may be extended to the removal and bioconversion/ target pollutant can be enhanced by providing a selected
bioaccumulation of cationic micropollutants such as ion for counter transport, whereby the conversion of the
ionic mercury. pollutant in the biocompartment keeps its concentration
at low levels and consequently guarantees an adequate
A microbial biofilm develops naturally at the membrane driving force for transport. Lastly, the hydraulic residence
surface in contact with the biological compartment. The time can be independently adjusted in the two compart-
development of an active biofilm also guarantees that the ments to optimise the degree of extraction of the pollu-
concentration of the carbon source is rather low near tant.
the membrane surface, avoiding the penetration of this
compound into the water stream compartment. Excess Other attempts have been made to separate the microbial
biofilm growth may become a problem because it reduces culture from water to be treated using micro-porous
the transport rate of the pollutant. hydrophobic membranes, based on a simple dialysis mode
of operation [38,39]. However, secondary water contam-
This approach — the transport of a target ionic micro- ination by methanol, used as the carbon source, was not
pollutant through a dense membrane followed by its avoided [38]. Furthermore, in this process, the rate of ion
bioconversion in an isolated compartment — presents transport is controlled by the size of the water-filled pores
some interesting advantages over other processes. Firstly, together with a given ion concentration gradient across

www.sciencedirect.com Current Opinion in Biotechnology 2004, 15:463–468


466 Biochemical engineering

the membrane, thus reducing the process selectivity

[21]

[26]

[36]
Ref.

[12]
[19]
[18]

[28]

[37]
towards target micropollutants.

TOCb (mg L 1)

Not detectedd
Not detectedd
Table 1 compares the results obtained with different

Not reported
pollution as
Secondary

membrane bioreactor systems for the removal of nitrate


1.5–2.1

1.5–2.0
and perchlorate from drinking water. As can be seen,
5–10

0.9c
pressure-driven membrane bioreactors allow for the high-
0.5
est treated water production rate per unit of membrane
area. However, the IEMB system is most appropriate if
production rate
Treated water

high water quality is envisaged; compared with pressure-


(L m 2 h 1)

driven and gas transfer membrane bioreactors, the former


system produces water with a much lower carbon content,
100
21
80
10

10

11
3
avoiding problems of secondary contamination and dis-
8

infection by-products.
Target anion
removal rate
(g m 2 h 1)

Detection limit ~0.01 mg NO3 L 1; bTOC, total organic carbon; cMeasured as dissolved organic carbon; ddetection limit ~0.5 mg carbon L 1.
0.9  10

0.3  10

The main difficulties regarding this process are associated


with the fact that commercially available ion selective
3.1
4.5
0.8

0.1

0.2
0.4

1.4
11

membranes are expensive in comparison with mem-


branes typically used in pressure-driven processes.
Not detecteda
Target anion content

Treated

Conclusions and perspectives


<0.004

<0.004
<0.14
water
<20

Until recently, membranes in bioreactors were essentially


<2
<1

<3
20
4

regarded as micro/ultra porous barriers to promote high


cell concentrations for process intensification and to avoid
(mg L 1)
Polluted
water

contamination of the treated water with the biocatalysts.


120
150
148

150
0.1

0.1
73
55
12

60

The growing concern about drinking water quality is


Comparison of performance of membrane bioreactors for removal of anions from drinking water.

focusing nowadays not only on the removal of macro-


Perchlorate

Perchlorate

pollutants and nutrients but also on the elimination of


acceptor
Electron

micropollutants, which may have dramatic consequences


Nitrate
Nitrate
Nitrate
Nitrate
Nitrate
Nitrate

Nitrate
Nitrate

for human health. The need for water treatment systems


able to deal with specific micropollutants has been iden-
tified and new problems and/or opportunities are becom-
Hydrogen
Hydrogen
Hydrogen
Electron

Acetate
Ethanol
Ethanol

Ethanol
Ethanol

ing apparent. To deal with these problems, catalytic


donor

reactors able to combine selective transport steps (selec-


tive membranes are a good example) with (bio)catalytic
compartments may offer flexible target-oriented solu-
Derivatized cellulose hollow fibres, 0.01 mm pores

tions.
Polyvinyldene difluoride, flat, 200 kDa cut-off
Polysulfone hollow fibres 500 kDa cut-off

This comment applies not only to ionic compounds, but


also to a variety of other situations where catalytic reactors
may deal with micropollutants, such as endocrine dis-
ruptors and pesticides among others. In this context, we
Dense anion-exchange; flat
Dense anion-exchange; flat

anticipate that a new generation of membrane bioreactors


Membrane configuration

Composite hollow fibres


Composite hollow fibres

will develop in the near future; these bioreactors will


Silicone-coated fibers

combine selective membranes, exploring different types


of affinity and transport mechanisms (electrostatic inter-
actions/ion-exchange and chiral affinity) with specific
catalysts able to deal with defined compounds. These
bioreactors will be complementary and should be inte-
grated with existing treatment units to offer complete
water treatment solutions.
Pressure-driven
Pressure-driven
Pressure-driven
bioreactor type

Gas-transfer
Gas-transfer
Gas-transfer
Membrane

Acknowledgements
Table 1

IEMB
IEMB

Financial support from Fundação para a Ciência e Tecnologia, Portugal


(Projects POCTI/EQU/39482/2001 and POCTI/BIO/43625/2000) is
a

gratefully acknowledged.

Current Opinion in Biotechnology 2004, 15:463–468 www.sciencedirect.com


Membrane bioreactors for water purification Crespo, Svetlozar and Reis 467

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