Desalination 199 (2006) 405407

Removal of heavy metals from drinking water supplies

through the ion exchange membrane bioreactor

Adrian Oehmen*, Rui Viegas, Svetlozar Velizarov,

Maria A. M. Reis, Joo G. Crespo
CQFB/REQUIMTE, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
email: adriano@dq.fct.unl.pt
Received 19 October 2005; accepted 6 March 2006

Abstract
Arsenic (As) and mercury (Hg) are two highly toxic heavy metals that must be removed to very low levels in
drinking water supplies. A novel treatment method for the removal of both compounds is the ion exchange
membrane bioreactor (IEMB) process, which incorporates pollutant transport through an ion exchange membrane
by Donnan dialysis, with biological removal of the pollutant. As detailed in this study, the IEMB process has a
high potential for use in drinking water treatment systems, and offers numerous advantages over currently
implemented processes, such as minimising the risk of secondary pollution of the drinking water.
Keywords: Anion exchange membrane (AEM); Cation exchange membrane (CEM); Arsenate (H2AsO4);
Arsenite (H2AsO3); Ionic mercury (Hg2+); Biological removal

1. Introduction the World Health Organization are 10 ppb and

Heavy metals have been found in poten-
tially harmful concentrations in numerous
drinking water systems due to natural or indus-
trial pollution sources. Two of the most toxic
heavy metals are arsenic (As) and mercury
(Hg), and thus each compound must be
removed to very low levels in order to prevent
health problems. The maximum concentrations
of arsenic and mercury recommended by
*Corresponding author.
1 ppb, respectively.
The main limitations of existing treatment
technologies are secondary contamination
by microbial cells, nutrients, and metabolic
by-products in biological processes; difficul-
ties in disposing the brine solution from pres-
sure driven membrane processes; high energy
demands in distillation processes; competition
for adsorption sites in ion-exchange systems by
other ions that are usually present in much
higher concentrations; and the undesirable
addition of chemicals, as well as difficulties in

Presented at EUROMEMBRANE 2006, 2428 September 2006, Giardini Naxos, Italy.

0011-9164/06/$ See front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2006.03.091
406 A. Oehmen et al. / Desalination 199 (2006) 405407
Cation exchange
membrane Treated water
Biofilm
Biocompartment Water
Stripping compartment
and Anions
recovery
Cations H+
H+ Cationic
micropollutants
Hg0 Hg2+ Hg2+
Nutrients + Driving counterions
Polluted water
e.g., H+, Na+
(a)
Fig. 1. Ion exchange membrane bioreactor description with Hg2+ (a) and H2AsO4 (b) as target pollutants.
achieving very low limits, in coagulation pro-
cesses.
One possible means of overcoming these
problems is through the ion exchange membrane
bioreactor (IEMB) [1], illustrated in Fig. 1. This
approach allows for the isolation of the microbial
culture from the feed stream through a membrane
barrier (in the biocompartment), avoiding con-
tamination of the treated water with cells, meta-
bolic by-products and excess levels of carbon.
The charged ion exchange membrane excludes
similarly charged ions, while permitting the flow
of oppositely charged ions. The transport of
charged micro-pollutants to the biocompartment
can be stimulated by supplying an excess of a
harmless ion to the biocompartment for counter
transport, according to Donnan dialysis princi-
ples. The conversion of the pollutant in the bio-
compartment keeps its concentration at low
levels and consequently ensures an adequate
driving force for transport. Since Hg is often
present in the cationic form (Hg2+), a negatively
charged cation-exchange membrane is required
for pollutant transport; while arsenic is often
present as negatively charged arsenate (H2AsO4)
or arsenite (H2AsO3), thus permeable through
positively charged anion-exchange membranes.
This technology has shown excellent perfor-
mance for the removal of pollutants such as
nitrate and perchlorate from drinking water,
Anion exchange
membrane Treated water
Biofilm
Biocompartment Water
compartment
Cations
Cl- Anionic
Cl-
micropollutants
As2S3 H2As3O4- H2AsO4-
Precipitation Electron donor + Nutrients +
and Polluted water
Driving counterion (e.g., Cl )
recovery
(b)
however, the IEMB potential for the removal of
Hg and As has not yet been investigated. This
paper explores the use of the IEMB system for
mercury and arsenic removal from drinking
water treatment systems.
2. Materials and methods
Ionic mercury and arsenate transport through
11 cation- and 11 anion-exchange membranes,
respectively (models include Nafion, Neosepta,
Ionac, Selemion, Fumatech, Ionics, among others),
were assessed in a stirred diffusion cell operated in
batch mode. For the transport of Hg2+ from the
water compartment, a 1 mM HCl solution was ini-
tially added to the biocompartment side to
ensure a sufficient driving force (0.01 mM of
HgCl2 was initially present in the water compart-
ment). A 10 mM NaCl solution was initially added
to the biocompartment and 0.1 mM of Na2AsO4)
was added to the water compartment during
the arsenate transport tests. Elemental Hg and As
were analysed using inductively coupled plasma
spectroanalysis (ICP).
3. Results and discussion
Mercury transport is illustrated in Fig. 2a for
the case of the Nafion 112 (Dupont, USA) mem-
brane, and clearly display the good permeability of
 A. Oehmen et al. / Desalination 199 (2006) 405407 407

2000 8000

1500 6000

As (ppb)
Hg (ppb)

1000 4000
Water compartment Water compartment
Biocompartment Biocompartment
500 2000

0 0
0 100 200 300 0 500 1000 1500 2000
(a) Time (min) (b) Time (min)

Fig. 2. Ionic mercury (Hg2+) transport through the Nafion 112 cation exchange membrane (a) and arsenate (H2AsO4)
transport through the Ionac MA3475 anion exchange membrane (b).

this membrane for Hg2+ transport. Similarly, As (in
the form of H2AsO4) was transported well through
an Ionac MA3475 membrane (Sybron Chemicals
Inc, USA), as shown in Fig. 2b. The flux of ionic
mercury and arsenate through the respective mem-
branes were calculated as 2.5 108 mmol cm2 s1
(0.18 g m2 h1) and 2.7 108 mmol cm2 s1
(0.14 g m2 h1), respectively, under the test condi-
tions. The optimal membranes for the transport of
ionic mercury and arsenate will be determined
from further testing.
Additionally, a strain of Pseudomonas putida
has been shown to biologically convert mercurial
compounds such as Hg2+ to Hg0, while arsenic can
be precipitated by sulphate-reducing bacteria and
removed using conventional solidliquid separa-
tion techniques. The capacity of these bacteria to
convert mercury and arsenic compounds will be
clearly displayed in future studies.
In conclusion, the IEMB system appears to
be a promising technology for ionic mercury
and arsenate removal from drinking water without
the risk of secondary contamination by bacteria
or metabolic by-products. We will clearly dem-
onstrate the IEMB capacity for Hg and As removal
to achieve very low target limits for these toxic
compounds, while optimisation of the integrated
process will be performed using experimental
and modelling techniques.
Acknowledgements
The financial support by Fundao para a
Cincia e a Tecnologia (FCT), Portugal through
Project POCI/AMB/57356/2004 is gratefully
acknowledged. Adrian Oehmen acknowledges
FCT for the post-doctoral grant SFRH/BPD/
20862/2004.
Reference
[1] J.G. Crespo and M.A.M. Reis, European Patent,
EP 1 246 778 B1, (2003).