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MEDWIN PUBLISHERS Open Access Journal of Waste Management & Xenobiotics
Committed to create value for Researchers ISSN: 2640-2718
Water Purification by a Micelle-Clay Composite Alone and its
Collaboration with other Technologies
Shlomo Nir*
Mini Review
Department of Soil and Water Sciences, Hebrew University of Jerusalem, Israel
Volume 2 Issue 1
Received Date: February 11, 2019
Published Date: March 05, 2019
DOI: 10.23880/oajwx-16000118
“Corresponding author: Shlomo Nir, Department of Soil and Water Sciences, The
Robert H. Smith Faculty of Agriculture, Food and Environment, The Hebrew
University of Jerusalem, Rehovot, 76000, Israel, Tel: +972-8949172; Fax: +972-
89475181; Email: [email protected]
Abstract
Removal of chemicals and pathogenic microorganisms by filtration may provide safe drinking water, and decrease the
risk from harmful disinfection by products. Micelle-clay complexes produced have a relatively large surface area, large
hydrophobic fractions, and are positively charged to about half of the cation exchange capacity of the clay. Their material
characteristics differ from those of organo-clays of the same composition, which are formed by adsorption of cations as
monomers. Granulated micelle-clay composites (0.4 to 2mm) formed by the organic cation ODTMA
(Octadecyltrimethylammonium), removed efficiently from water by filtration chemicals, such as herbicides, and dissolved
organic matter, pharmaceuticals, perchlorate, and microorganisms, such as bacteria, viruses and a parasite, such as
crytosporidium. Bacteria removed included (a) Escherichia coli S-17; (b) total bacteria count (TBC); and (c)
Cyanobacteria (Microcystis and Aphanizomenon). A model which considered convection, adsorption, and desorption
simulated the filtration results and yielded predictions. The emphasis in this minireview is on collaboration of this
technology with other procedures, which may enhance treated water quality and reduce the costs of treatment. Thus a
new approach intends to utilize both filtration and biocidal/biostatic activity of free cations in removal of
microorganisms from water. A two stage purification of greywater by a moving bed reactor followed by a micelle-clay
filter yielded an order of magnitude increase in the capacity of the filter. Water purification by filtration followed by solar
photocatalysis enabled removal of recalcitrant molecules and indicator bacteria from secondary treated wastewater, thus
yielding high quality water for irrigation. Other examples are reduction of membrane fouling of UF membranes and a
suggested reduction of fouling of RO membranes by a pretreatment by the micelle-clay filter, or its combination with
granulated activated carbon filter.
Keywords: Nano-Composite; Granulated Micelle-Clay; Filtration Modeling; Removal of Bacteria; Biocidal Effects;
Greywater Reuse; Combined Filtration and Photocatalysis
Water Purification by a Micelle-Clay Composite Alone and its Collaboration with other Technologies J Waste Manage Xenobio
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Open Access Journal of Waste Management & Xenobiotics
Introduction
Quite a few sources provide drinking water without a
need for treatment, which involves removal of chemicals
and pathogenic microorganisms. In the simplest cases the
authorities of health regulate the addition of disinfectants,
which have been shown to cause health problems due to
by products, which have to be monitored, and in certain
cases have to be partially removed [1]. With the
appearance of harmful residues of pharmaceuticals and
pesticides, it has become clear that one method, or
procedure is rarely sufficient, and a collaboration of
procedures is clearly essential, both in terms of water
quality, and costs [2]. In this mini review we present a few
examples of collaborations involving the micelle-clay
complex, which has been shown to be powerful in
removal of microorganisms and _ chemicals, but
recalcitrant molecules have been encountered. This
problem is mainly critical in treatment of wastewater.
Production and Characteristics of the Micelle-
Clay Complex
A dissolution of a salt ODTMA
(Octadecyltrimetyhylammonium)-Br in water at
concentrations of several mM, and elevated temperatures
of 50-60°C results in formation of micelles. The critical
micelle concentration (CMC) of the organic cation ODTMA
is 0.3 mM. Hence, at ODTMA concentrations of 10 to 30 g
per liter, most of the cation is in micellar form, in which
the positive charge of the cation is located on the external
surface of the micelle, and the internal surface, which is
devoid of water, includes the alkyl chains between which
van der Waals interactions exist. The micelle-clay
complexes produced by adding clay, such as Na-bentonite
have a relatively large surface area; they include large
hydrophobic fractions and are positively charged to about
half of the cation exchange capacity (CEC) of the clay. The
material characteristics of the micelle-clay complex
differed from those of a tested organo-clay complexes of
the same composition, which were formed by adding
ODTMA as monomers [3].
of
Laboratory and Pilot Experiments have Yielded
Efficient Removal from water of
e Hydrophobic and anionic organic molecules, such as
herbicides; humic acid, dissolved organic matter;
pharmaceuticals [2-13].
e Inorganic anions, e.g., perchlorate, ferricyanide (Nir,
unpublished) [14].
e Microorganisms, whose external surfaces are net
negatively charged. Such as bacteria, viruses, and
parasites, e.g., cryptosporidium, which is resistant to
chlorination? Low cost regeneration of used filters after
Shlomo Nir. Water Purification by a Micelle-Clay Composite Alone and its Collaboration
with other Technologies. J Waste Manage Xenobio 2019, 2(1): 000118.
bacteria adsorption is described in Shtarker-Sasi, et al.,
Rakovitsky, et al. and Kalfa, et al. [15-17]. The
experimental results coupled with model calculations
have indicated that the micelle-clay filter is very
economical in removal of microorganisms from water
by filtration. However, we will present cases where the
economy and quality of water purfication by the
micelle- clay filter purification are enhanced
significantly by other elements and technologies. Vice
versa, the micelle-clay technology can provide a polish
to water purification by other technologies. Briefly, we
advocate collaboration between technologies.
Biocidal Effects of Quaternary Amine Cations
(QACs)
Biocidal and biostatic effects of cations, (mainly QACs)
have been widely reported [18-21]. Sukenik, et al.
demonstrated that addition of 75 ug/L ODTMA cations
abolished completely the photosynthetic activity of
Aphanizomenon (cyanobacteria) cells within 20 to 40 min.
Kalfa, et al. suggested that a micelle-clay complex which
released during filtration a larger number of QACs was
more efficient in removing from water bacteria, due to the
biocidal/biostatic effect of the released cations [17,22].
This might suggest that removal of bacteria from water by
filtration is expected to be more efficient by a small
increase of the ratio of ODTMA/ clay in the complex,
which will enhance the concentrations of cations released
during filtration. Preliminary results of Margalit and Nir
(unpublished) gave support to this suggestion by
filtration of tap water which included total count bacteria.
The released cations are removed from water before
consumer use by another filter containing activated
carbon. Drinking water from lakes is forbidden during
cyanobacteria bloom, due to harmful toxins. Filtration by
the granulated micelle-clay complex and killing of
cyanobacteria by ODTMA cations are described in
Sukenik, et al. [22].
A Two Stage Purification of Greywater by a
Moving Bed Reactor Followed by a Filter
Reuse of grey water (GW) enables to save significant
amounts of fresh water. Grey water from sinks outside the
kitchen, showers and baths amounts daily to 150-300 L
per household. Use of inadequately treated GW can be a
potential health hazard [23]. A moving bed reactor (MBR)
was used by Winward, et al. [24]. Bani-Melhem and Smith
used a submerged MBR for removal of anionic surfactants
and coliforms [25]. Friedler, et al. combined biological
treatment using a rotating biological contactor (RBC) with
a sedimentation stage, a sand filtration stage and a
Copyright© Shlomo Nir.
Open Access Journal of Waste Management & Xenobiotics
hypochlorite disinfection stage [26]. RBCs combined with
sand filtration and UF membranes and combined with UV
disinfection were tested for treatment of GW. Constructed
wetlands have been employed for GW treatment. Gross, et
al. and Benami, et al. employed a recirculating vertical
flow constructed wetland (RVFCW), whereas Travis, et al.
examined the use of an anaerobic pretreatment stage
before treatment of GW by RVFCW [24,27-33, 35]. Santos,
et al. tested purification of GW by a hydraulically, self-
cleaning mesh filter followed by UV disinfection. Thus it
follows that in the area of grey water treatment,
collaboration of technologies has been considered about a
decade ago [33]. Brook, et al. indicated that an activated
carbon filter yielded poor removal of bacteria even after
the passage of 5 L [34]. A comparison of these results with
those of several recent studies which employed a variety
of technologies for treatment of greywater demonstrated
the advantage of the micelle-clay complex in reducing
significantly the number of pathogenic bacteria, despite
the relatively small amounts of the complex.
The biological reactors, which were introduced with
the aim of reducing the amount of organic material in the
grey water, also significantly reduced the number of fecal
coliforms [16,36]. The two-stage purification procedure,
i.e, preincubation of GW in a bioreactor followed by
filtration, increases the purification capacity of the filter
filled with the complex by an order of magnitude. The
bioreactor was effective in reducing the concentration of
the organic material and the numbers of fecal coliforms in
the GW. Regeneration of the micelle-clay granules could
be accomplished by NaOCl (0.5 %), or HCl (0.05 mM), or
by heating at 120 °C for 3h. The capacity of the granulated
complex to purify grey water from showers baths and
sinks amounts to 20 m3 per kg of the granulated complex,
and when two regenerations are considered the capacity
becomes 47 m3 per kg of the complex. The two - stage
procedure yields a safe and economical reuse of GW, since
the plan is to have <1 per 100 mL of fecal coliforms or
other indicator, or pathogenic bacteria in the filtered
water.
In passing, it might be of interest to test a
collaboration of Constructed Wetlands with filtration by
the granulated micelle-clay complex, or with the two-
stage treatment by a moving bed reactor followed by a
filter.
Water purification by Filtration Followed by
Degradation
A few molecules denoted recalcitrant are not removed
efficiently from water by filtration, e.g., carbamazepine. It
turns out that such molecules as well as others can be
Shlomo Nir. Water Purification by a Micelle-Clay Composite Alone and its Collaboration
with other Technologies. J Waste Manage Xenobio 2019, 2(1): 000118.
removed from secondary treated wastewater by photo
degradation. The efficiency of removal of such molecules
by photo degradation from pools of treated wastewater is
small, due to the presence of other molecules and loss of
intensity of radiation, which penetrates into deeper
depths. The combination of filtration and degradation can
on one hand enable to remove recalcitrant pollutants
from water, and on the other hand purify the water from
several other pollutants and enhance the efficiency of
removal of many pollutants by degradation.
In a recent pilot experiment a tertiary treatment of
effluent from a secondary treated wastewater was tested
by combining filtration and solar photocatalysis [37, 38].
The water to be purified included 26.3 mg of TOC. Such a
load of organic materials might reduce significantly the
capacity of the micelle-clay filter to capture the ECs in the
water and the bacteria: 105 and 104 of Escherichia Coli and
Enterococcus faecalis per mL, respectively. The filtration
system included a first filter (2 cm: 50 cm) with 70 g of
GAC, followed by a second filter (2 cm: 40 cm) which
included 20 g of granulated micelle (ODTMA)-
montmorillonite mixed with 100 g of sand (grain size of
0.8-1.5 mm). Wastewater effluent (45 L) was pumped at a
flow rate of 10 mL/ min. Thirteen ECs were selected as
representatives of the most common micropollutants in
wastewater: Ketoprofen, caffeine, carbamazepine,
sulfamethoxazole, atenolol, amoxicillin, venlafaxine,
tamoxifen, sulfamethazine, fenofibric acid, mepanypirim,
chlotianidin and diclofenac.
The applied solar advanced oxidation process was
homogeneous’ photo-Fenton photocatalysis using
peroxymonosulfate (PMS) as oxidant agent. This
combination of technologies aimed to ensure water
disinfection and removal of emerging contaminants (ECs,
mainly pharmaceuticals). The filtration step showed good
performance in removing dissolved organic matter mostly
by the GAC filter and also by the micelle-clay filter. On the
other hand a practically complete removal of the bacteria,
from the secondary treated water was achieved by the
micelle-clay filter, whereas the GAC filter had low
efficiency of bacterial removal. Solar advanced oxidation
processes were efficient in elimination of trace levels of
ECs. The final effluent presented an improved sanitary
level with acceptable chemical and__ biological
characteristics for irrigation.
Additional Possible Collaborations of
Technologies
The WWTP in the Campus of the University Al-Quds
includes a sequence of treatment elements, 2 UF
membranes, a GAC filter and a RO membrane. It was
Copyright© Shlomo Nir.
Open Access Journal of Waste Management & Xenobiotics
suggested in several publications, e.g., Karaman, et al. that
it would be beneficial to add a filter based on granulated
micelle-clay complex before the UF element denoted SW
(20 kD cut off) and another one before the RO, in order to
reduce membrane fouling in these two elements, thus
save on the needed energy The rationale was that the
micelle-clay filter is efficient in removal of bacteria, which
are a main cause of membrane fouling by sorption and a
formation of a biofilm [2]. The study of Brienza, et al. also
demonstrated that a GAC filter placed before the micelle-
clay filter removed a great deal of the dissolved organic
material, thus making the micelle- clay filter more
efficient in removing bacteria from the water entering the
RO membrane [37].
Conclusions
This articles advocates collaboration between
technologies for enhancing the quality of treated water
and the economy of the process. Examples for the
usefulness of such collaboration are presented in several
cases. 1. Filtration by the granulated micelle-clay complex,
where a consideration of biostatic and biocidal effects of
QACs may enhance dramatically the capacity of
purification of water from microorganisms. The residues
of QACs can be removed by activated carbon. 2. Water
purification by filtration by means of (i) activated carbon
followed by a micelle-clay and (ii) photodegradation. This
process is promising for removal of recalcitrant molecules,
TOC and microorganisms at a low cost.
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with other Technologies. J Waste Manage Xenobio 2019, 2(1): 000118.