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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.
(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.)
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
[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
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
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
0.1
0.2
0.4
1.4
11
Treated
<0.004
<0.14
water
<20
<3
20
4
150
0.1
0.1
73
55
12
60
Perchlorate
Nitrate
Nitrate
Acetate
Ethanol
Ethanol
Ethanol
Ethanol
tions.
Polyvinyldene difluoride, flat, 200 kDa cut-off
Polysulfone hollow fibres 500 kDa cut-off
Gas-transfer
Gas-transfer
Gas-transfer
Membrane
Acknowledgements
Table 1
IEMB
IEMB
gratefully acknowledged.
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