Bol.

Grupo Español Carbón

Using activated carbon based technologies for the removal

of emerging contaminants from water/wastewater – UQTA
(LNEC) Projects
El uso de tecnologias basadas en carbón activo para la
eliminación de contaminantes emergentes de aguas /aguas
residuales – Proyectos UQTA (LNEC)
M. Campinas1*, E. Mesquita1, R.M.C. Viegas1, M.J. Rosa1
1
Water Quality and Treatment Laboratory (UQTA), Urban Water Unit, Hydraulics and Environment Department, LNEC –
National Civil Engineering Laboratory, Av. do Brasil 101, 1700-066 Lisboa, Portugal
*Corresponding author: [email protected]

Abstract Emerging contaminants include: personal care

products and pharmaceuticals, increasingly used by
An overview is presented on the projects that are
the population and not fully retained by the wastewater
being carried out by Water Quality and Treatment
treatment plants; pesticides from agriculture and
Laboratory team of LNEC which use activated carbon
cyanotoxins produced by toxic cyanobacterial (blue-
based technologies for treating water or wastewater.
green algal) blooms in surface waterbodies. In the
Emphasis is given to the chemical enhancement of
last years, regulators and the general public have
conventional wastewater treatment using “green”
been expressing an increased concern regarding
powdered activated carbon options, hybrid adsorption/
the presence of emerging contaminants in drinking
membrane processes or biologically active carbon
water and treated wastewaters, since some of the
(BAC) filtration which are considered promising
compounds are implied in risk cancer increase,
options for upgrading the water/wastewater treatment
bacterial resistance to antibiotics and reproductive
plants for controlling emerging contaminants such as
abnormalities in aquatic organisms, based on which
pharmaceuticals, pesticides and cyanotoxins.
a more restrictive legislation is expected in a near
Resumen future.
Este artículo presenta una visión general de los For microcystin-LR (MC-LR), a potent
proyectos que se están llevando a cabo por nuestro hepatotoxin which is one of the most frequently
equipo en el Laboratorio de Calidad y Tratamiento detected cyanotoxin in toxic bloom events
[3], WHO established a guideline value of
del Agua de LNEC que utilizan tecnologías basadas
1.0 µg/L in drinking water [4], limit also adopted by the
en carbón activado para el tratamiento de agua o
Portuguese legislation (DL 306/2007). Nevertheless,
aguas residuales. Se da énfasis a la mejora química
most of the other ECs, particularly pharmaceuticals,
del tratamiento convencional de aguas residuales
are not yet legislated due to the lack of ecotoxicity
utilizando soluciones “green” con carbón activos en
data (studies not yet performed or not conclusive)
polvo y a los procesos híbridos adsorción/membrana
and analytical limitations. Besides the risk, these
o filtración con carbón biológicamente activo (BAC),
contaminants share a resistance, partial or total, to
que se consideran opciones prometedoras para
conventional treatments at the water treatment plants
la mejora de las plantas de tratamiento de agua/
(WTPs) and urban wastewater treatment plants
aguas residuales en el control de contaminantes
(WWTPs) since they are often water soluble, polar
emergentes, tales como productos farmacéuticos,
to semipolar, organic compounds, of intermediate
pesticidas y cyanotoxinas.
to low molar mass, commonly present in very low
1. The problem – emerging contaminants concentrations (pg/L to µg/L range).
Anthropogenic pressures and global climate change The control of ECs in WTPs and WWTPs is therefore
are putting increasing stress on Europe’s freshwater a priority goal that requires the assessment of the
resources, being responsible for sharp variations of raw risks involved, the improvement of the current barriers
water availability and quality, and for the degradation and, if necessary, the (W)WTP rehabilitation with
of water sources by emerging contaminants (ECs). advanced treatment technologies [2]. In this context,
Besides defying drinking water management, water in Water Quality and Treatment Laboratory (UQTA)
scarcity and asymmetric space-time distribution is of LNEC several treatment studies pursuing eco-
also driving many countries to seek non-conventional efficient barriers against microcontaminants are being
water sources. WWTPs play therefore a crucial role conducted, namely the optimization of the current
both in the safeguard of the drinking water sources sedimentation steps in wastewater treatment and
and the production of an alternative water source, the the development of advanced treatment essentially
treated wastewater which, depending on its use(s), based on adsorption, hybrid adsorption/membrane
may require an increased level of water treatment. processes and/or biodegradation. The studies are
Two of the greatest challenges for WWTPs in a near integrated in several European Projects which will be
future are the monitoring and reduction of trace presented in the following sections. Although these
pollutants and the adaptation/development of existing/ projects contain several complementary actions,
new wastewater treatment technologies in order to they will be purposely presented in the perspective of
minimize costs and optimize resource consumption activated carbon interest.
[1-2].
2. Activated carbon for improving conventional
13
nº40 / Junio 2016

Figure 1. LNECs lamellar sedimentation prototype which will be Figure 2. PAC/MF prototype designed by LNEC and installed in
adapted for pilot trials in two WWTPs (LIFE Impetus). Alcantarilha WTP (LIFE Hymemb).
Figura 1. Prototipo lamelar de sedimentación que será adaptado Figura 2. Prototipo PAC/MF instalado en la planta de tratamiento
para ensayos piloto en duas plantas de depuración de aguas (LIFE de agua de Alcantarilha (LIFE Hymemb).
Impetus).

wastewater treatment - LIFE Impetus Pilot scale tests will be conducted with 3 sedimentation
prototypes which will be constructed or adapted
LIFE Impetus “Improving current barriers for controlling
(Figure 1) and installed in Beirolas WWTP (Lisbon)
pharmaceutical compounds in urban wastewater
and Faro Noroeste WWTP (Faro-Algarve): one
treatment plants” started in January 2016 and will
rapid mixer/ lamellar sedimentation prototype for
be developed during 3.5 years. It is coordinated by
the primary clarification step in Beirolas WWTP, and
LNEC and has the participation of two wastewater
two conventional sedimentation prototypes for the
management entities - Águas do Algarve, S.A. and
secondary clarification steps in both WWTPs. Pilot
EPAL, SA., one company – EHS Environment and
trials will be performed during 18 months in several
Regional Development Consulting, Lda., and three
operating conditions allowing to demonstrate the
universities – Algarve University and Science and
impact of coagulant and activated carbon addition in
Pharmacy Faculties of Lisbon University (FCUL and
the quality of the wastewater resulting from primary
FFUL).
and secondary clarification.
The project aims at demonstrating feasible
3. Activated carbon for hybrid adsorption/
improvement measures to enhance the removal of
membrane processes – LIFE Hymemb and LIFE
pharmaceuticals (PhCs) removal in urban WWTPs
aWARE
with conventional activated sludge (CAS) treatment,
the most common biological process in urban WWTPs. LIFE Hymemb Project (2014-2016) “Tailoring hybrid
The project was developed in the logic of resource membrane process for sustainable drinking water
efficiency, developing cost-effective solutions based production” is coordinated by LNEC and has the
on the existing infrastructures (many of them recently partnership of the water company, Águas do Algarve
built), as new investments are probably limited in the S.A. The project involves a 2-year field test of a
near future due to economic constraints. powdered activated carbon/ceramic microfiltration
(PAC/MF) prototype (Figure 2), designed by UQTA
LIFE Impetus involves a 3-year field test in two
team, in Alcantarilha WTP, to demonstrate the process
Portuguese CAS-WWTPs in water stressed regions
effectiveness, reliability and efficiency, and ensure a
(Lisbon and Algarve) for demonstrating improved
meaningful benchmarking between the advanced and
operation strategies and the chemical enhancement
the conventional water treatment processes.
of existing barriers for PhC control. Concerning
this last one, different clarification strategies will Figure 3 shows the target contaminants of this project
be demonstrated, at pilot scale, including the use as well as the concept of the hybrid PAC/MF process,
of absorbents and coagulants for improving the which integrates the advantages of both low pressure
clarification process, comparing commercial and membrane processes and PAC adsorption, and
newly developed materials using natural wastes and minimizes some of their disadvantages. Low-pressure
plants. membranes are not able, unless by adsorption onto
the membrane, to retain microcontaminants (e.g.
In an early phase, the project includes the preparation
pharmaceuticals, cyanotoxins), but are a safe barrier
and characterization of new adsorbents prepared
against (oo)cysts and bacteria and allow a total
from local vegetal wastes, cork and carob, and their
removal of particles (< 0.1 NTU), including PAC of
lab testing to assess the adsorption kinetics and
smaller size (< 10 µm) than usual and thus with faster
capacity for a short list of target PhCs in synthetic
adsorption kinetics. On the other hand, PAC is able
waters. The activated carbons will be prepared and
to improve the removal of microcontaminants while
characterized at FCUL, where the screening and the
enabling to control the irreversible membrane fouling
lab-scale assays will also be carried out. Adsorbent(s)
[5].
with adequate performance will be further tested by
LNEC team at lab-scale for the target PhC removal Adsorption to activated carbon is therefore the key-step
from real wastewaters and used in demonstration of adsorption/membrane processes for the removal of
14 trials at pilot-scale. low molar mass (< 300 Da) and intermediate molar
 Bol. Grupo Español Carbón

Figure 3. The target contaminants and the concept of LIFE Hymemb project.
Figura 3. Los contaminantes objetivo y lo concepto de proyecto LIFE Hymemb.

mass contaminants (300-1000 Da), and also for with or without PAC addition, in dead-end operation,
viruses, and should allow the adaptation to space- minimizing the operating costs, or in cross-flow when/
time specificities, presenting solutions for a wide if necessary (semi dead-end operation).
range of applications. For such purpose, one of the
The selection of the powdered activated carbons
innovation pillars of this project is the “tailoring”, i.e.
adequate to control the project’s target contaminants
the adjustment of PAC type and dosing to specific
through PAC conventional addition and the hybrid
contaminants and the high flexibility of membrane
PAC/MF process followed a 3-step methodology
process. Therefore, pretreatment is easily adjustable
developed in UQTA/LNEC [6]: i) selection of a short-
to water quality (PAC and/or coagulant addition and
list of ECs representative of the target contaminants;
pH adjustment), low-pressure membranes may work

Figure 4. Laboratory tests for selecting PACs and optimizing PAC dosing.
Figura 4. Ensayos de laboratorio para selección de los PAC y la optimización de la dosificación. 15
nº40 / Junio 2016

ii) pre-selection of commercial PACs with the Two activated carbons were preselected for performing
adequate chemical and textural properties for each the adsorption kinetics until equilibrium of the target
application (classification/elimination process based pharmaceuticals and, through the analysis of the PAC
on average particle size, surface charge and pore capacity and removal rate, one activated carbon was
volume distribution); iii) performance of adsorption chosen to perform the lab PAC/NF trials. For the
kinetics (Figure 4) with the selected PACs and a short- evaluation of the adsorption capacity complementary
list of ECs in model waters and in natural waters from adsorption isotherms of the 4 target PhCs in mineral
Alcantarilha WTP. matrix were performed, as well as kinetics and
isotherms with micro screened secondary effluent of
The preselected PACs were characterized, including
El Prat WWTP. Adsorption isotherms were modeled
their elemental analysis, porosimetry and point of
with the Freundlich model, for single solutes, or with
zero charge (pHpzc). Adsorption kinetic assays were
the Fritz & Schlünder model in competition scenario
performed with the short-list of ECs (5 pharmaceuticals,
[8], and the adsorption kinetics were modeled with
1 pesticide and 4 microcystins, natural organic matter).
the Homogeneous Surface Diffusion Model – HSDM
Four PACs were tested for PAC conventional addition
[9]. Combining the calibrated models of competitive
and five for PAC/MF application. This methodology
adsorption isotherms and kinetics batch numeric
allowed selecting one PAC for each application – PAC
simulations of the PhC removal vs PAC dose and
conventional addition and PAC/MF – which are being
contact time were performed for predicting removals
tested/demonstrated at pilot scale for EC removal.
for different PAC concentrations and contact times.
PAC/MF prototype is working at Alcantarilha WTP
The PAC/NF configuration tests were performed in
since July 2015. The membrane module (KleanSep,
a laboratorial unity dimensioned and built by UQTA
Orelis) contains three tubular ceramic membranes
team. Two configurations were tested: i) one with
with a total area of 0.75 m2 and a pore diameter of
a single PAC dose at the beginning of the filtration
0.1µm. One of the main objectives of the project is to
cycle (pulse dosing) and ii) other with continuous PAC
identify PAC/MF optimal pre-treatment and optimize
dosing (step dosing). The membrane (X-FLOW HFW
the PAC/MF operating conditions under different feed
1000 da Pentair) has a molecular weight cut-off of
water qualities. Up to this moment very promising
1000 Da, which is high for nanofiltration, allowing to
results have been obtained in terms of treated water
remove dissolved organic compounds of intermediate-
fluxes and quality.
high molecular weight (e.g. natural organic matter),
LIFE aWARE (2013-2016) “Innovative hybrid MBR- but working at a relatively low pressure (around 1 bar)
(PAC-NF) systems to promote Water Reuse” is being with relatively high fluxes (20- 25 L/m2.h). The tests
developed in El Prat WWTP (Barcelona, Spain), included NF trials (no PAC addition) and PAC/NF trials
combining the technology of membrane bioreactors (single and step PAC dosing) with the evaluation of the
(MBR) with the hybrid adsorption/membrane process removal of the four pharmaceuticals supplemented
of PAC/nanofiltration (PAC/NF). The project is to the micro screened secondary effluent of El Prat
coordinated by CETAqua (Barcelona), and the UQTA WWTP. No pressure increase was observed with PAC
team was responsible for: i) selecting the adequate addition and the higher removals (between 68-98%)
PAC for controlling ECs and ii) evaluating, at lab scale, were observed for a pulse dosing of 100 mg/L PAC
of different PAC/NF configurations to be implemented [10].
at a pilot scale in El Prat WWTP.
4. Biological actived carbon (BAC) filtration
PAC selection followed the methodology developed
Due to MC-LR chemical stability and the strong
by UQTA/LNEC and already presented in this section.
competition with natural organic matter (NOM) (µg
For the short-list of ECs, the starting point was the
MC-LR/L vs mg NOM/L) for adsorbents and oxidants,
contaminants previously detected in campaigns in El
conventional drinking water treatment may not
Prat WWTP and Llobregat river [7] and afterwards
guarantee the absence of MC-LR in the distributed
a classification according to the properties that are
water [4]. Adsorption-based processes, as hybrid
important for PAC adsorption, namely size, charge
adsorption/ low-pressure processes [5] or biological
and hydrophobicity. Four classes were identified and
activated carbon (BAC) filtration [11] are promising
a compound representative of each class was chosen.

Figure 5. Laboratory unit of PAC/NF Figure 6. BAC filters assembly.

16 Figura 5. Unidad PAC/NF de laboratorio Figura 6. Ensamblaje de filtros BAC
 Bol. Grupo Español Carbón

options for upgrading the water treatment plants. BAC Union LIFE programme under grant agreement LIFE14
filters are typically robust systems, simple to assemble ENV/PT/000739 (www.life-impetus.eu), LIFE12 ENV/
and with low energy requirements, representing an PT/001154 (www.life-hymemb.eu) and LIFE11 ENV/
interesting alternative technology for controlling NOM ES/000606 (www.life-aware.eu ).
MC-LR [12] and other microcontaminantss [13].
BAC investigation work was supported by the
Granular activated carbon (GAC), besides being an Portuguese Foundation for Science and Technology
excellent adsorbent material, is a good support media (FCT - Fundação para a Ciência e Tecnologia)
for the attachment and growth of microorganisms and through the project PTDC/ECM/69610/2006 and the
biofilm development. Activated carbon biofilters take PhD fellowship SFRH/BD/21941/2005. FCT is also
advantage of the accumulation of substrates in the acknowledged for the Post-Doctoral research grant
GAC particle surface and of the roughness the carbon SFRH/BPD/91875/2012 provided to R.M.C. Viegas.
granules which protects microbial cells from the fluid
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[8]

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5. AcknowledgementsThe investigation projects
herein presented have received funding from European
17