A short review on recent advancements in wastewater treatment techniques

Abstract

This short review covers the recent developments and research in the advanced wastewater
treatment techniques such as nanophotocatalysis, ceramic nanoflitation membrane, biofilms. The
main objective of this review article is to provide the ready made reference for researchers and
scientists working in the field of advanced wastewater treatment. This review article is mainly
focused on the nanophotocatalyst, ceramic membrane filtration, biofilms application for
treatment of various organic pollutants such as dyes, pharmaceutical components etc. Currently
developed materials for wastewater treatment were summarized based on recent literature.

Keywords: Wastewater treatment, Biological treatment, Advanced oxidation processes,

membrane filtration, Nanocatalysts.

Review on nanophotocatalyst application in wastewater treatment

Over the past two decades, AOPs have gained an exceptional recognition concerning the
advancement of wastewater treatment technologies. Some of the methods, including Fenton,
cavitation, ozonation and photocatalytic oxidation were effectively employed for the breakdown
of recalcitrant organic contaminants at pilot scale. Research has been done beforehand on both
the homogenous and heterogeneous AOPs in the wastewater treatment domain. Catalysts such as
TiO2, ZnO, UV/visible light, various oxidants such as H2O2, O3 etc. are employed to stimulate
AOPs. At the time of activation, AOPs produce •OH radicals and react with organic composites
in the proximity of dissolved O2 of solvent media. Amid, several other industries, dyeing,
printing and paper industries are highly polluting the environment and this because of the
immense use of the organic dyes during the process. The absorption and reflection of the sunlight
will be hindered due to the presence of organic dyestuffs in water bodies. This results in an
increase in noxious concentration which eventually troubles the aquatic life. Absolute
mineralization of organic colorants can be achieved by employing the dynamic AOPs. Several
studies on different AOPs have explained the successful breakdown of the dye contaminants in
aqueous media. The photocatalytic AOP can commence the complex chain reactions and it may
also generate the uncolored organic intermediates and occasionally these intermediates are
poisonous than the initial composites. Many previous studies have revealed that, for the
breakdown of the organic composites, microsize catalysts were utilized in different AOPs. And
very few studies have explained the use of nanomaterials in AOPs for the wastewater treatment
(1,2). Until now, many kinds of semiconductors have been studied as photo catalyst including TiO 2, ZnO, CdS,
WO3, etc. (149). Zinc oxide (ZnO) is an excellent photo catalytic material since it clearly exhibit the high photo
catalytic efficiencies for the degradation of organic pollutants in comparison to other metal oxides including TiO2
(150,151,152, 153,154,155). The uses of ZnO as a photo catalytic degradation material for environmental pollutants
has also been extensively studied, because of its nontoxic nature, low cost, and high photochemical reactivity.
However, for higher photo catalytic efficiency and many practical applications, it is desirable that ZnO photo
catalyst should absorb not only UV but also visible light. In order to absorb visible light, the band gap of ZnO has to
be narrowed or split into several sub gaps, which can be achieved by implanting transition metal ions or by doping
nitrogen (156). The utilization of nanocrystalline ZnO and TiO2 as a photocatalyst for the
breakdown of organic contaminants has been increased since two decades (3-10). About 70-80%
of the literature for wastewater treatment using photocatalysis and ZnO/TiO2 as a photocatalyst
is accessible and few researchers have trialed the utilization of doped TiO2 for the pollutant
degradation. TiO2 photocatalyst is called as a semiconductor because it consists of a wide band
gap (3.2eV) and parallel to radiation in the close UV range is beneficial compared to other
photocatalysts. The ZnO/TiO2 particles get excited on UV light irradiation and also produces a
set of holes and electrons in the valence and conduction bond.
The charge carrier species can recombine, with the absorbed energy dissipated as heat, or they
can migrate to the particle surface, where the holes can react with surface-bound hydroxyl
groups (OH−) and adsorbed water molecules to form hydroxyl radicals (OH·)
.OH + h+ → .OH ------- (Eq.2)
H2O + h+ → .OH + H+ ------- (Eq. 3) (copied from RB paper).

In order to begin the photocatalytic reaction for the organic contaminants’ breakdown in
wastewater, both the light source and photocatalyst are mandatorily required. Recent studies
have focused on the feasibility usage of visible light/sunlight for commencing the photocatalytic
reaction and this will save a lot of energy, resources and also reduce the operating costs.

Table 2.1 reports the literature on the application of UV/Visible induced nanomaterials as a
photocatalysts for the degradation of different organic pollutants in aqueous solution.

REF
Photocatalysis/Nd- Rhodamine B Photocatalytic activity 100
doped TiO2 films of the doped TiO2 films
were assessed under UV
light by employing the
textile industry
contaminant Rhodamine
B
Photocatalysis/ Malachite green (MG) The photodegradation of 101
synthesized ZnO malachite green (MG)
dye was studied by
using ZnO
photocatalysts
synthesized by various
techniques. And also,
the impact of several
operating conditions,
including pH, catalyst
loading, light source and
initial dye concentration
on MG dye breakdown
was also analyzed.
Photocatalysis/ ciprofloxacin drug Under UV light 102
synthesized ∼2.1 nm irradiation and at
ZnO nanoparticles
various pH values
the photocatalytic
 activity of the
synthesized ZnO
nanoparticles examined
the ciprofloxacin drug
breakdown in aqueous
media. From the
obtained results it was
observed that, at pH 7
and 10 the
photocatalytic
activity/breakdown is
very effective and at pH
4 it was ineffective. In
60 minutes of time
period and at pH 10,
approximately 50% of
drug degradation was
achieved.

Photocatalytic salicylic acid (SA) and The obtained results 103

Oxidation/TiO2 sulfosalicylic acid have revealed that the
Microsphere (SSA) TiO2 microspheres
reaction rate was almost
close to TiO2 powders
in SA suspensions and
excessive in SSA
suspensions. Using the
LangmuirHinshelwood
kinetic model, the
physical and chemical
properties of TiO2
powders and
microspheres were
studied. More than 50
times the synthesized
TiO2 microsphere
materials were reused in
photodegradation
activity and observed no
change in the particle
shape and photoactivity.
And this study has
concluded that the TiO2
microsphere catalyst can
be utilized in the
wastewater treatment
process by employing
photocatalysis with ease
of catalyst recovery.
photocatalytic ozonation Pesticide (carbamate, 76.5% of TOC and 92% 104
carbaryl) wastewaters of COD reduction was
observed at pH 6, 1 g/L
of TiO2 and 0.28 g/h of
O3. Because of the self-
degradation of O3 the
synergism was strayed
at alkaline pH, but it
was observed at neutral
and acidic pH.
Photocatalysis/Mn Methylene Blue The experiments were 105
doped ZnO particles conducted separately
with the Mn doped ZnO
particles and undoped
ZnO and observed that
the doped particles have
degraded the MB dye
stuff more effectively
and quickly than the
undoped particles.

Photocatalysis/ ZnO/ Organic dyes On irradiating the textile 106

ZTO composites wastewater by sunlight,
77% of COD removal
and 50% of
photocatalytic
breakdown efficiency
was achieved by
employing ZnO/15ZTO
photocatayst. The
results were promising
when ZnO/15ZTO
catalyst was used under
solar light irradiation
and about 16%
degradation efficiency
was increased.

Photocatalysis/ ZnO/ Methyl Orange (MO) By employing porous- 107

ZTO composites ceramic-supported
catalysts
(CZnO/10ZTO) and
under UV light
irradiation 50% of MO
dye was degraded in 1
hour and approximately
95% of dye was
degraded in 3 hours.
The photocatalytic
 activity was enhanced
because of the ZTO
islands, that were
formed on the ZnO
nanorods.
Photocatalysis/ ZnO Basic Blue 11 (BB 11) From the experimental 108
results it was observed
that N-
hydroxyalkylated bi
products were generated
and BB 11 dye has
undergone oxidative
breakdown under UV
irradiation. And it was
also observed that •OH
radical was the major
oxidant in this process.
Photocatalysis/ TiO2 municipal wastewater The effect of different 109
operating conditions
including pH, type of
photocatalyst,
concentration and time
on faecal microbes’
decontamination was
analyzed. The
materialistic Degussa
P25 TiO2 photocatalyst
has worked well than
that of the pure rutile or
anatase groups

Heterogeneous leaf green dye The leafgreen dye from 110

photocatalysis/ UV-C/ the aqueous solution
TiO2(PET)/H2O2 was removed by
employing TiO2
photocatalyst
immobilized on
polyethylene
terephthalate (PET)
plates and also in in
suspension form under
UV light irradiation.
52% of TOC and 70%
of COD removal was
observed in UV-C/ TiO2
(PET)/H2O2 system.

Review on ceramic membrane filtration in wastewater treatment

Recently, the ceramic membranes are gaining the attention of researchers because of their
superior characteristics like long operating cycle, simple cleaning and regeneration, good
chemical reliability and pollution free in the application of wastewater treatment. In the past, the
ceramic membrane had limited application range and also it was expensive. Advancements in
membrane research have resulted in the utilization of membrane technology for various purposes
and also it has become inexpensive (111). Because of the fouling issue, the influent water
standards are to be analyzed before the ceramic membrane is utilized in the industrial wastewater
treatment process. In removing the pollutants from the wastewater the ceramic membrane
follows two methods. All the particles that are larger than the membrane size are blocked by the
membrane; this is known as the self-retaining activity of the membrane. The smaller molecular
weight particles will be adsorbed by the membrane due to electrostatic forces, chemical bonds
and Vander Waals forces and this is known as the adsorption capacity of the membrane. Based
on the pore size of the ceramic membrane, these membranes are classified into four types
namely; microfilteration, ultrafilteration, nanofilteration and reverse osmosis. Excluding RO, the
other three different membranes are employed in industrial wastewater treatment applications
(112). Based on the shape, ceramic membranes can be classified into four types namely; single-
channel tubular, multi-channel tubular, flat and hollow fiber membrane. In the wastewater
treatment process, the hollow fiber membrane is mostly employed. The flat membrane is widely
used in the water resources area and the tubular membrane is used in solid-liquid separation
methods (113). The previous studies on application of ceramic membrane filtration in
wastewater treatment were discussed here.

Xu et al. investigated the treatment of dyeing waste water by combining different treatment
methods such as flocculation, cross flow microfiltration and ceramic membranes. The results
have shown the decline of absorbency of sulfur black, DSD acidic, 3-acidic wastewater and
CODcr. This study has concluded that the utilization of ceramic membrane has exceptional
advantages compared to the other organic membranes (119).

Pizzichini et al. investigated the reuse of Italian paper mill wastewaters by employing different
membrane filtration technologies. Out of all the membrane systems, ceramic microfiltration
membrane has shown the best results with a stable productivity of 150–200 L/m2h. More than
80% of the original wastewater was recycled and reused by employing the tubular ceramic MF membrane method,
followed by a RO filtration (118).

Khemakhem et al. investigated the cuttlefish effluent treatment by employing new microfiltration
membranes, which are developed by using Tunisian natural materials. The results have revealed
that the chemical oxygen demand (COD) and turbidity were declined at a higher rate after
treating the cuttlefish effluent by using the developed new microfiltration ceramic membrane.
Hence this new microfiltration was declared as worthy for wastewater treatment (120).

Damas et al. studied the working condition of the ceramic membranes by conducting the
experiments with three materialistic ceramic membranes of different molecular weight cut-offs.
The experimental results have shown, increase in permeate flux, a very little cake layer
formation on the membrane and minimal flux decline. Moreover, at lowest cross-flow velocity,
higher conductivity retention coefficients and COD were acquired. The color and turbidity
rejections were observed between 98 % and 84 % respectively. From the obtained results it was
concluded that the ceramic UF membranes can be considered as the constructive pre-treatment
substitutes (114).

Tewari et al. investigated the filtration performance of inexpensive ceramic filters (nylon mesh
and ash) in a submerged membrane bioreactor (MBR) for wastewater treatment. From the results
it was observed that both the ash and nylon mesh filters are fine solid-liquid separators and also
the ash filters have shown greater critical flux compared to the commercial membranes (115).

Abadi et al. investigated the oily wastewater treatment by utilizing the tubular ceramic MF (α-
Al2O3) system. The various initial operating conductions including temperature, fouling
resistance, cross flow velocity and Trans membrane (TMP) were examined. The proposed
operating conditions are temperature 32.5 °C, TMP 1.25 bar and CFV 2.25 m/s. The particulates
and the oil droplets were removed by back washing. 95% of TOC removal was observed after
the treatment (117).

Zielińska and Galik et al. demonstrated the removal of color, organic compounds, turbidity and
suspended solids from the anaerobically treated dairy wastewater by employing various ceramic
membrane filtration systems such as direct microfiltration (MF), ultrafiltration (UF), MF-UF and
a combination of UF with coagulation. The COD removal in various systems was observed as,
89 ± 2% in MF, 95 ± 1% in UF and 99% in MF-UF respectively, and also 96–98% of color
removal was observed in all the systems. 96–97% of COD, 98% of color and more than 99%
of turbidity was removed on the integration of UF with coagulation (116).

Ebrahimi et al. investigated the utilization of various ceramic membranes for the
treatment of oil-field generated wastewater. Few steps were involved in this treatment
process which includes; a) pre-treatment step employing microfiltration, b) simulated
batch dissolved airflotation (DAF), c) multistage post-treatment step employing cross-
flow ultra and nanofiltration. From the results it was observed that, 99.5% of total oil and
49% of carbon was removed and the mean permeate flux was altered from 3.4 to 3300
l/h m2 bar (163).

Sentana et al. studied the removal of chlorination byproducts from the surface water by
employing two ceramic nanofiltration membranes of different molecular weight cut off of 450 Da
(NF450) and1000 Da (NF1000). The various initial operating factors including pH, conductivity and pressure were
examined. From the experimental results it was observed that the NF1000’s permeation flow rate was higher than the
NF450 membrane. The efficiency of organic matter removal was surpassed and the formation of disinfection by products
declined on increasing the operating pressure. The NF450 membrane has removed about 75% of trihalomethanes and
NF1000 generated smaller decreases in trihalomethanes. For NF1000 membrane, 51 to 22% and for NF450, 80 to 39% of
trihalomethanes reduction was observed on increasing the conductivity from 900μS/cm to 4000μS/cm. On decreasing the
pH of the solution from 8.3 to 4.5 the flow through NF450 and NF1000 was decreased. At pH 8.3, for NF450 and NF1000
membranes, 79% and 58% of trihalomethanes were rejected and at pH 4.5 it declined to 65% and 40% (164).

Zaviska et al. investigated the treatment of pharmaceutical compounds by utilizing a nanofiltration membrane bioreactor
(NF-MBR). This experiment was performed for approximately 4 months. Even with the acclimated sludge, the two
compounds are weakly decomposed and when the membrane fouling has increased, only a little amount of these
compounds are retained. The colour, total suspended solids (TSS) and COD were removed effectively. Additionally, the
retention, biodegradability and adsorption techniques were also analyzed (165).

Review of Biofilm applications in wastewater treatment

Biological methods, in particular biofilm technologies play a vital role in treatment of various
wastewaters. Biofilm is the cluster of several microbial communities bound in self-generated
extracellular polymeric substance (EPS) matrices. The biofilm development involves in five
important phases. 1) The early bonding of planktonic microbes with the subjection of a surface to
an aqueous media; 2) Absolute fixation consequent to the generation of microorganism-
moderated EPSs as polyhydroxyl groups and along hydrogen bonding these polyhydroxyl groups
seize bacteria to the surface (121); 3) Development of monolayer mini colonies on the firm
surface because of the replication of initial colonizers; 4) Biofilm development into 3D form by
utilizing the new planktonic bacteria and also by binding the detritus from the adjoining
surroundings; 5) diversification or scattering by passive and active methods in which the matrix-
encased biofilm cells transform into planktonic bacteria through a cell-to-cell signaling
procedure (122,123). Factors that affect the formation of biofilm are nutrients, pH, temperature,
the surface topology of support media, velocity, turbulence, hydrodynamics, production of EPS
and divalent cations (124,125). In order to allocate the appendage surfaces for the biofilm
development, the solid support media (SSM) are included to the suspended growth reactors. The
addition of SSM enhances the microbial concentration and breakdown the pollutants as well
(126). The carbonaceous materials, phosphorous, trapped pathogens, nitrogen-containing
compounds and nutrients from the wastewater are degraded by the various microbial populations
present in the biofilm matrix. Advantages offered by the biofilm-based wastewater treatment
plants are flexibility in operation, less space required, decrease in hydraulic retention time, the
less effect over the environment, increase in biomass weight, low sludge production, superior
biomass residence time, and superior capability to degrade complex compounds (127,128). The
previous studies on application of biofilms in wastewater treatment were discussed here.

Boelee et al. examined the ability of the micro algal biofilms for the municipal wastewater
effluent treatment. From the experimental results it was observed that, at loading rates of 0.13
g/m2/day phosphorus and 1.0 g/m2/day nitrogen, the micro algal biofilm ingestion capacity
reached maximum. On increasing the initial loading rate, the internal nitrogen to phosphorus ratio declined
from 23:1 to 11:1. This study has concluded that, for the elimination of phosphorus and nitrogen from the municipal
wastewater effluent, the micro algal biofilms can be utilized (129).

Li et al. investigated the elimination of pollutants such as ammonium, phenols and thiocyanate
from coal gasification wastewater by employing moving bed biofilm reactor. 89% of phenol,
93% of ammonia, 81% of COD and 94% of thiocyanate were removed after the treatment. With
decrease in hydraulic residence time (HRT), the effluent ammonia and thiocyanate concentration increased.
Based on the obtained results this research was concluded as the appropriate method for the treatment of coal
gasification wastewater (130).

Posadas et al. investigated the assessment of carbon and nutrient removal at the time of centrates
and domestic wastewater treatment in an open bacterial biofilm reactor and an open algal–
bacterial biofilm reactor. At 10 days of HRT, 70 ± 8% of nitrogen, 91 ± 3% of carbon and 85 ±
9% of phosphorous removal was achieved by the algal–bacterial bioreactor. The micro algae
based method was concluded as an environmental feasible method after observing the water
footprint as 0.5–6.7 L m-2 d-1 (131).

Francisco Osorio and Ernesto Hontoria et al. examined the performance of immersed biological
aerated filter poised of a double layer bed prepared by using plastic and ceramic waste materials.
The obtained results found to be highly adequate. 3.0 kg SS/m3/d and 4.87 kg TBOD5/m3/d could
be applied to attain the effluent concentrations below 25 mg SS/L and 20 mg TBOD5/L. And
1.0kg O2/kg TBOD5,eliminated was acquired for the maximal TBOD5 volumetric load.
Corresponding to SS removal and TBOD5 the counter-current flow system surpassed the co-
current flow system (132).

Sukačová et al. Investigated the potential for phosphorous elimination from the micro algal
biofilm at various light regimes. In 24 hours of uninterrupted artificial irradiation, 97 ± 1% of
total phosphorus from wastewater was removed by the algal biofilm. On irradiating the algal
biofilm by natural light, 36 to 41 of phosphorous was removed. 5.6 ± 1 g dry weight (DW) m−2
d−1 with natural light and 12.21 ± 10 g dry weight m−2 d−1 with uninterrupted artificial irradiation
was the experimentally obtained biomass generation rate. The obtained outcomes of this study
designate the capacity of microalgal biofilms in the tertiary wastewater treatment (133).

Hao et al. studied the removal of nitrate from the municipal wastewater effluent by using a three-
dimensional biofilm-electrode reactor (3D-BER). At HRT of 7 hours and C/N ratio of 3.0, 98.3%
of nitrate removal was achieved. And at HRT of 10 hours and C/N ratio of 1.5 85.0–90.0% of
nitrate removal was achieved, this was because of the cooper-ative autotrophic and heterotrophic
denitrification. The biofilm found to be ample with enterobacter-like and thauera-like bacteria.
From the obtained results it was concluded that 3D-BER is an efficient and viable method for the
municipal wastewater effluent denitrification (134).
Dong et al. investigated the oilfield wastewater treatment in a movable bed biofilm reactor
(MBBR) by employing a novel suspended ceramic biocarrier. In order to feed the MBBRs, two
distinct carriers, sepiolite-modified and unmodified suspended ceramic carriers were utilized.
The obtained results have revealed that at HRT of 10 h, the highest COD removal was found in
the sepiolite-modified reactor. Likewise, the aromatic hydrocarbons and ammonia nitrogen
removal was found more in the sepiolite-modified reactor. This experimental research has
concluded that the sepiolite-modified reactor was more shock resistant than the unmodified
reactor and also specified the suspended ceramic carrier as a fine MBBR carrier (135).

Naz et al. investigated the wastewater treatment under aerobic and anaerobic conditions by
employing the biofilms developed on the Tire derived Rubber (TDR). In 4 weeks of time period,
notable movement of bacterial population from pathogenic to autotrophic was noticed. BOD,
COD and bacterial count found to be decreased and certain changes in nutrients and pH were
also observed after 7 weeks of experiment. Abundant bacterial growth was observed in SEM
images. Overall, This study has concluded that, the TDR solid support media is inexpensive and
durable, and it is best usable for the wastewater treatment using biofilms under aerobic
conditions (136).

Artiga et al. has developed a novel biofilm suspended biomass hybrid bioreactor for the
wastewater treatment. The wastewater with excessive organic content and nitrogen from the fish-
canning and tannery industries were used for the treatment purpose in this experiment. On
treating the fish canning wastewater at an loading rate (OLR) of 6.5 kg COD/m3.d and an NLR
of 1.8 kg N-N𝐻4+ /m3.d, 99% of COD removal was obtained. 97% of ammonia and 95% of COD
removal were acquired with the gradual increase in ALR and OLR up to 1.2 kg N-N𝐻4+ /m3.d and
4.5 kg COD/m3.d. Because of the membrane filtration the reactor was successfully operated at
high OLRs without any drawbacks (137).

Punzi et al. investigated the textile azo dyes breakdown by the combination of anaerobic biofilm
method with photo-fenton oxidation. On using the primary fenton reagent concentration less than
10 mM hydrogen peroxide and 1 mM ferrous ions, COD was reduced to less than 18 mg/l.
Eventually the toxicity was also reduced by the photo-Fenton oxidation, but the final effluent
consisted of high concentrated Nacl. The obtained experimental outcomes of this research work
has recommended the utilization of photo Fenton oxidation after biological treatment for the
elimination of toxic and organic pollutants from the textile effluents (138).

Review on nanophotocatalysis coupled with ceramic membrane filtration for wastewater

treatment
Due to adsorption and precipitation of large molecules on to the membrane surface leads to fouling and it ultimately
reduce the further separation and life of the membrane (143, 144). This issue is more pronounced in case of
polymeric and ceramic membranes. The fouling issue in the membrane processes can be resolved by combining
photo catalytic based degradation process prior to membrane separation (145,146). The ceramic membranes may
reject the degraded organic pollutants along with the suspended photo catalysts whenever it combines with the photo
catalysis.
Integration of photo catalysis and membrane separation have been applied for removal of various dyes such as
methylene blue, direct black, methyl orange, congo red, etc. The design configuration of the hybrid system is also
different in most of the studies. Few studies were integrated into the ceramic membrane and photo catalysis in a
sequential manner, whereas some studies shown submerging of membrane in the photo catalytic reactor. However,
very few studies have been applied the ceramic membranes rather than the polymeric membranes along with photo
catalysis for the removal dyes from waste water (copied from RB paper).

Damodar et al, studied the degradation of reactive black 5 (RB5) dye by using submerged flat poly tetra fluoro
ethylene (PTFE) membrane module in TiO2 slurry photo catalytic reactor. They found that the, nearly 82–100%
color, 45–93% TOC and 50–85% COD removal was achieved at a hydraulic retention time (HRT) of 4 h, depending
on the initial RB5 concentration (139) (copied from RB paper).

Buscio et al. studied the heterogeneous photo catalytic process combined with microfiltration for the removal of C.I.
Disperse Red 73 from synthetic textile effluents. Titanium dioxide (TiO2) and P25 were used as the photo catalysts
in the hybrid system. Their studies found that, photo catalysis alone shows 60 to 90% of dye degradation and up to
98% chemical oxygen demand (COD) removal based on the initial dye concentration and operation time (140)
(copied from RB paper).

Athanasekou et al. synthesized and stabilized the novel materials such as modified TiO2 with an organic shell layer
and reduced graphene oxide-TiO2 (rGO/TiO2) on the surface and pore structure of the monoliths. Their study
involves the degradation of methylene blue (MB) and methyl orange (MO) by continuous flow photo catalytic
filtration under near-UV/Vis and visible light irradiation. The influence of several parameters, such as feed pressure,
feed concentration and flow rate, on the pollutant degradation efficiency and membrane permeability was
investigated and analyzed (141) (copied from RB paper) .

Hairom et al. studied the effect of various zinc oxide nano particles in membrane photo catalytic reactor (MPR) for
Congo red dye treatment. Four types of ZnO were synthesized (7–30 nm) of ZnO without any agglomerations,
especially under stirring conditions in the presence of PVP (ZnO-PVP-St).They found that, the ZnO-PVP-St
presented the greatest potential in MPR in terms of the highest photo degradation efficiency and lesser membrane
flux decline (142) (copied from RB paper) .

Cui et al. (2006) attempted the combination of photo catalysis along with ceramic membrane as a case in point.
Combining photo catalysis with membrane separation in a single module shows many potential benefits in terms of
compactness of the system and also lower investment (147,148) (copied from RB paper).

Zhang et al. investigated the photooxidation of organic pollutants present in the wastewater by using silica/titania
nanotubes composite membranes. By utilizing porous alumina support membranes, the silica/titania membranes
were formulated from silica/titania sols. The water contact angle has declined from 62° to nearly 5° in 80 minutes
because of the surface membranes, which has shown a high affinity for water under UV irradiation. For Direct Black
168 dye at 100 min of experimental operation, 73% and 66% of degradation was achieved in individual membrane
separation and photocatalysis. On integrating both the systems, i.e., the photocatalysis and the membrane separation
process, 85% removal efficiency was achieved. The obtained results have concluded that the silica/ titania nanotubes
used in this study had multi functions such as breakdown, refinement of membrane flux in photo oxidation and
separation of organic pollutants present in wastewater (157).

Zhu et al. investigated the removal of organic contaminants from the secondary effluent by employing tubular
ceramic membrane (α-Al2O3 or TiO2) filtration integrated with the ozonation. Upon filteration, the flux of the
effluent was reduced to 45% and 60% for α-Al2O3 and TiO2 respectively over a 2 hour time period. The membrane
filteration efficiency was surpassed for the reduction of TOC, color and A254 (organic absorption). TiO2 membrane
integrated with ozonation gave good results; 43% of TOC, 88% of color and 75% of A254 reduction was observed in
this integrated system. The researchers have concluded that integrating TiO2 membrane with ozonation gave
beneficial outcomes (158).

Song et al. developed a hybrid system (combined ceramic membrane filtration with photocatalytic oxidation) for the
secondary effluent treatment of wastewater. After 60 min of filtration, 30 and 50% of flux decline of CMF
Membrane with and without TiO2/UV photocatalytic treatment was observed. The obtained results have revealed
that the existing ions in the SE behave as scavengers and which eventually leads to decline in photocatalytic
oxidation reactions efficiency. And also 50% of biopolymers were removed by the CMF membrane alone. The
researchers in this study have assumed the apparent correlation between the biopolymers quantity in SE and
filterability of water samples in CMF (159).

Romanos et al. studied the effective wastewater purification method by employing the double-side active
TiO2-modified nanofiltartion membranes in continuous flow photocatalytic reactors. In this method, the
titanium tetraisopropoxide (TTIP) vapors are decomposed pyrolytically and through the aggregation of
generated transistional species and homogenous gas phase reactions, the TiO2 nanoparticles are formed. By
applying UV irradiation on both membrane sides, the membrane efficiency to photodegrade distinctive water
contaminants were assessed. The results indicated that, the high water permeability and low adsorption-
fouling propensity were observed during the decomposition of methyl organge in the composite NF
membranes (160).

Ke et al. investigated the removal of organic contaminants from the drinking water by combining the
photocatalysis method with membrane filtration. In this method, by insitu hydrothermal reaction, the
alumina nanofibers (AF) of pore size 10 nm were synthesized. In this combined system, the dyes are
maintained on the surface of the membrane and the concentration of the dyes close to the AgNPs are
excessive and hence under UV light irradiation they can be degraded effectively. This study has concluded
that the integrated system (photocatalysis and membrane filtration) performed well in removing the organic
contaminants from the drinking water (161).
Wang et al. studied the Acid Red 4 dye photocatalytic degradation combined with TiO2 membrane supported
on a porous ceramic tube. The physical operating conditions such as light intensity, flow rate, catalyst loading,
flow configurations (dead-end and cross-flow) and initial dye concentration were examined in this study. In
addition, the concurrent effect of catalyst loading and light intensity were experimentally resoluted. The
conclusions of this research work include; a) Three and five times higher decomposition ratios for dead-end
system than the cross-flow system, b) With increasing light intensity and catalyst loading, the decomposition
ratio has enhanced, but at higher catalyst loading it remained constant, c) And with increasing flow rate the
decomposition ratio declined (162).

Conclusion
This short review conluded that this technologies may be effectly employed in the treatment of
variety of wastewater. The techniques cited in this report are feasible options for use in the
developing world and even more apparent that, these technological options can be used effectly
in real industrial wastewater at large scale. In current scenario, these treatment technologies are
attracting a significant level of interest by environmental managers. These technologies are
considered viable because of their low capital costs, their ease of maintenance, their potentially
longer life-cycles and their ability to treat a variety of organic pollytants in wastewater. This
report examined the recent developments in photocatalytic materials and biofilms options related
to the wastewater treatment.