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Review
Employing TiO2 photocatalysis to deal with landfill leachate: Current status and
development
Muhammad Hassan, Yapin Zhao, Bing Xie
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S1385-8947(15)01364-9
http://dx.doi.org/10.1016/j.cej.2015.09.093
CEJ 14249

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Please cite this article as: M. Hassan, Y. Zhao, B. Xie, Employing TiO2 photocatalysis to deal with landfill leachate:
Current status and development, Chemical Engineering Journal (2015), doi: http://dx.doi.org/10.1016/j.cej.
2015.09.093

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Employing TiO2 photocatalysis to deal with landfill leachate: Current status and
development

Muhammad Hassan, Yapin Zhao, Bing Xie*

Shanghai Key Laboratory for Urban Ecological Process and Eco-Restoration; School of Ecology &
Environmental Science, East China Normal University Shanghai 200241, China

* Author for correspondence; E-mail address: bxie@des.ecnu.edu.cn (Bing Xie). Tel: +86-21-54341276

Abstract
Sanitary landfilling is a low cost and well established waste disposal technique applied worldwide.
However, it also generates heavily polluted leachate. Municipal solid waste (MSW) landfill leachate
contains a wide variety of recalcitrant compounds that make it quite difficult to treat using conventional
ways of treatment due to its high chemical stability and/or low biodegradability. In the last couple of years,
photo-assisted titanium dioxide (TiO2) oxidation has shown a great potential to treat landfill leachate. This
article presents a systematic literature review of heterogeneous TiO2 photocatalysis dealing with pre and
post treatment of MSW landfill leachate.

Recent advancement of TiO2 photocatalysis in treating

recalcitrant organic and inorganic pollutants found in landfill leachate are discussed; whereas, evaluation
of the mechanism of the process, configurations of photoreactor system and influence of certain operating
factors on system efficiency are also part of the review. Finally, advantages and disadvantages of the
technology are highlighted coupled with future research perspective.

Key Words:
Sanitary Landfill; MSW Leachate treatment; Advance Oxidation Processes (AOPs); Titanium dioxide
(TiO2); Photocatalysis

1. Introduction
Municipal solid waste (MSW) generation has been increasing at an annual rate of 8 10%, with over 200
million tons of MSW being produced based on a predicted value by 2015 [1]. Solid waste generation is
linked to urbanization and economic development. That is why China in 2004 surpassed USA in terms of
waste generation, and will likely produce twice as much MSW as USA by 2030 [2]. As shown in Figure 1,
currently four major ways of MSW disposal are common, i.e. landfilling, composting or recycling in
agriculture, dumping into sea and incineration [3]. Among them, landfilling is most extensive method
especially in developing and underdeveloped countries owing to its low immediate costs. On the other
hand, it is an emerging threat to the environment as well. Its remediation is a difficult job due to its
refractory nature [4, 5], as it contains substantial amounts of dissolved organics (COD, BOD), xenobiotics,
inorganic salts, nitrogenous substances, heavy metals and other toxicants [6] and [7].
Figure 1
Percolation of rainfall through landfill sites in combination with the decomposition of the solid wastes by
simultaneous and interrelated biological, chemical and physical changes lead to the generation of a highly
contaminated liquid called leachate [8]. The composition of landfill leachate varies depending upon the
nature of the disposed wastes, climate, hydrological factors, rainfall patterns and landfill age due to the
biochemical reactions in the waste mass of landfill [9] and [10].
Many biological and physico-chemical processes have been designed for landfill leachate treatment for the
last couple of decades [11], [12] and [13]. Conventional biological treatment is hindered by the presence of
certain bio-recalcitrant compounds, especially in the case of mature leachate [14]. Similarly, physicochemical techniques such as membrane separation [15], air stripping [16], coagulation-flocculation [17]
etc. are often costly in terms of initial plant outlet, energy requirements and frequent use of chemicals.
Hence, a generalized treatment method does not exist yet because of diverse landfill leachate composition.
Advanced oxidation processes (AOPs) [processes in which oxidation of organic contaminants occur
3

primarily through reactions with hydroxyl radicals], using the combination of strong oxidants (e.g. O3,
H2O2) [18], irradiation, e.g. ultraviolet (UV) light [19] and [20], ultrasound [21] catalysts e.g. Fe2+ [15] and
photocatalyst e.g. titanium dioxide (TiO2) [22] and [23] to produce hydroxyl radicals, have been considered
as promising techniques for landfill leachate treatment.
Over the past decades, semiconductor photocatalysis has attracted much attention due to its outstanding
efficiency for environmental purification [24], [25] and [26]. So far more than 190 semiconductors have
been assayed as suitable photocatalysts [27]. TiO2 is one of the widely used semiconductor photocatalysts,
but it is often not considered a viable alternative alone. It must be irradiated with UV light to be excited
and capable of photo-oxidation. There is a growing interest in using solar energy as a photon source along
with low cost catalysts [28], but solar photocatalytic efficiency of pure TiO2 is comparatively lower than
UV source [29]. In TiO2 catalysis, two types of reactions occur, i.e. adsorption-desorption equilibrium in
dark reaction and photocatalysis under irradiation (discussed in detail in the following sections 4 and 5).
TiO2 exists in amorphous form and crystallizes in three different polymorphs in nature according to the
order of abundance i.e. rutile, anatase and brookite. As shown in Fig 2, Anatase and rutile are tetrahederal
while brookite is orthorhombic in structure. In the field of TiO2-photocatalyzed reactions, the powder
called Aeroxide P-25 has been a standard material, which has a relatively large surface area (49 m2 g-1).
Several studies have postulated that the best photocatalytic activity for TiO2 is reached with an optimum
ratio of anatase and rutile. The Degussa, P-25 contains anatase and rutile phases in a ratio of about 3:1. It is
composed of 20-30% rutile and 70-80% anatase TiO2 with particle sizes in the range of 12 to 20 nm [30].
Table 1 shows the properties of polymorphs of TiO2. The higher photo-activity of TiO2-P25 was mainly
because of its crystalline composition of rutile and anatase. It has been postulated that the smaller band gap
of rutile absorbs the photons and generates electron-hole pairs. Then the electron migration takes place
from the rutile catalyst band to electron traps in the anatase phase. Thus it inhibits recombination and
allows the hole to move to the surface of the particle and react with OH- or H2O to generate OH radical
[31].
4

Figure 2
Table 1
As illustrated in Figure 2 and Eq. 1-4, when TiO2 absorbs UV light (< 380 nm), electrons are promoted
from valence band (VB) to the conduction band (CB) to generate electronhole pairs (e/h+). Positive
holes typically oxidize organic compounds, inducing their oxidative degradation, while electrons mainly
reduce molecular oxygen to superoxide radical anions, which can lead to a number of reactive oxygen
species (OH, O2, HO2 etc.). These radicals oxidize a wide variety of organic pollutants to harmless
inorganics such as CO2, H2O and other minerals [32] and [33].

 +  ( 3.2 )
 + ( + )

(1)

 + ( ) +  
 + 

(2)

 + ( ) +  

(3)

R +  R ( ) R1 + R2 Inorganic substances (i.e.  +  O) (4)

TiO2 photocatalytic degradation has revealed a great potential as a low-cost, non-toxic, chemically stable,
high photoactivity, environmental friendly and sustainable treatment technique to fulfill the zero waste
scheme in water and wastewater industry. Thats why a number of researchers have applied TiO2 for MSW
leachate treatment [34], [35], [36] or pretreatment [37], [38], and [39] to enhance biodegradability of
refractory organic compounds in landfill leachate and post treatment [22], [23], [40] and [41] to attain an
acceptable discharge standard of MSW leachate.
Figure 3
Although many review papers have been written on advanced oxidation process and photocatalytic
technology for wastewater treatment [42], [43] and [44], but they have focused significantly on all types of
wastewaters ranging from municipal to industrial. This review paper aims to give an overview of the
applications and recent developments of TiO2 photocatalysis for MSW landfill leachate treatment,
including pre and post treatments. Moreover, types of photoreactors used along with their configurations,
5

and certain parameters that affect the efficiency of the process are also critically analysed. Major pros and
cons of this technology are highlighted coupled with future research outlook.
2. Characteristics of MSW landfill leachate
An understanding of the characteristics of MSW landfill leachate is needed to interpret the variable
performance found during leachate treatment. Organic compounds and ammonia nitrogen in landfill
leachate are considered as two key chemical characteristics of environmental concern. Organic
contaminants in leachate are described mainly using universal parameters such as chemical oxygen demand
(COD), 5-day biochemical oxygen demand (BOD5 ), and total organic carbon (TOC). As shown in Table 2,
on account of aging, three types of leachate have been distinguished: young, intermediate and mature. Each
of these is different in composition and biodegradability. Young landfills have high BOD5, COD
concentrations and BOD5/COD ratios in contrast with leachate from mature landfills, which have
comparatively low BOD5, COD concentrations and BOD5/COD ratios, but high concentration of ammonia
and certain recalcitrant compounds which are difficult to remove by conventional biological treatment
methods [19] and [45]. Leachate with a BOD5/COD ratio > 0.4 is considered as biodegradable [46],
whereas, that with BOD5/COD ratio < 0.2 is termed recalcitrant [47].
The mature landfill leachate indicates a low biodegradability due to the release of greater molecular weight
refractory organics and higher concentration of ammonia, making it difficult to treat by conventional
process [48] and [49]. Calace et al. [48] examined that mature leachate contained a broad range of
molecular weights with a large high molecular weight fraction (77% >10,000 Da) whereas, young leachate
had a narrow range with a large lower molecular weight fraction (70% <500 Da). Ammonia, released by
anaerobic hydrolysis of proteins present in the solid wastes, has been reported to be at concentrations from
500 to 2000 mg NH4N/L. It may disrupt biological units for leachate treatment due to its toxicity. Hence,
ammonia is known as the most significant factor in leachate in the long term [50]. Recently the presence of
humic substances in leachate has gained more attention. They represent the non-biodegradable fraction of
COD and show refractory properties. Owing to their structural complexity, humic substances influence the
6

behavior of some pollutants in natural environments, for example trace metal speciation and toxicity [51].
Such substances reduce the effect of UV radiation due to UV light absorption; hence they need to be taken
into serious consideration during leachate decontamination.
Table 2
3. Configuration of photoreactors used for leachate treatment
Several reactor models have been proposed and utilized in lab scale and pilot scale based TiO2
photocatalytic experiments. For example, annular photoreactor [52] falling film flow reactor [35], slurry
membrane reactor [53], thin film cascade photoreactor [54] etc. (Fig 4, 5). Depending on the principal of
photocatalysts, photoreactor models can be grouped into two broad categories i.e. mixed aqueous slurry
reactors having suspended TiO2 powders and immobilized TiO2 catalyst reactors [55]. Slurry reactor
systems have relatively high surface area for mass transfer because of the high specific surface area of the
suspended TiO2 photocatalysts. But the major drawback is the requirement for a filtration unit for
recovering the catalyst from the effluent stream. In practice, it is often hard to eliminate the smallest
catalyst particles from the effluent and this may cause turbidity downstream. The filtration requirements
also cause a significant challenge to scale up bench scale reactors into the field. Hence, much attention has
been turned in recent times towards immobilized photocatalysts. The reactors using immobilized TiO2 have
a mass transfer limitation, owing to the relatively lower external mass transfer area available [56] and [57].
Analyzing the possibility of mass transport limitations in the bulk of photocatalytic suspensions of pure
TiO2, Ballari et al. [58] noticed that the concentration profiles in the bulk will be always present unless
very good mixing conditions in the characteristic direction of radiation propagation are employed.
Moreover, when the photocatalytic reaction is not fast, employing TiO2 mass concentrations below 1 g L1,
incoming irradiation rates below 1.0 107 Einstein cm2s1 and very good mixing conditions, it will be
safe to assume that mass transport limitations in the bulk of slurry photocatalytic reactors are not important.
In flow reactors, the mass transfer limitations are almost negligible when fully developed turbulent flow
operation is achieved.
7

Figure 4
Figure 5
To configure a photocatalystic reactor, the most important factors are light distribution in the reactor and
the total irradiated surface area of the catalyst per unit volume [59]. An appropriate position of light source
is important for the distribution of photon influx within the reactor. The slurry photocatalyic reactor is still
the preferred configuration because of its high total surface area of photocatalyst per unit volume and ease
of photocatalyst reactivation [44].
In literature, the average volume of the photoreactors used for lab scale experiments ranged from 0.2 2 L,
while for pilot scale it is more than 2 L. Table 3 demonstrates various types of photoreactors, their
dimensions and process configurations. In a study, Qazaq et al. [60] used an 18 L pilot scale bubble column
photoreactor and Cho et al. [23] employed a semi-batch mode reactor with 10 L capacity, where the
suspension was circulated by a slurry pump at a flow rate of 6 L/min. Being an important component of
TiO2 catalysis, UV lamps have been either mounted over the solution or immersed in the sample. No much
research is available which could differentiate the efficiency of placing UV lamp for photo degradation, but
the immersion in the solution might be efficient as all the light might be absorbed in the solution as
opposed to suspended lamp. In two separate research works, UV lamps were immersed vertically in the
solution [32, 36], whereas, Karabelas et al. [63] employed special cylindrical photoreactor covered with
aluminum (due to its greater reflectance of UV-A irradiation) and 424 W black light lamps were
suspended over the solution.
Table 3
4. Dark reaction adsorption-driven leachate treatment
Literature validates that photocatalysis is not the only process taking place in the photoreactor [36]. One of
the important processes is dark reaction adsorption, especially of organic substances onto the catalyst
surface. It is believed to play a major role in catalytic degradation prior to irradiation. Adsorption on TiO2
is a process of formation of surface complexes and/or polar covalent, or formation of hydrogen bonds with
8

polar molecules [62]. Adsorption is more effective in acidic and alkaline medium. However in natural
medium, no correlation has been shown between dark reaction adsorption and photocatalytic degradation
[63]. Table 4 illustrates the summary of pollutants removal by TiO2 photocatalysis during dark reaction
adsorption. In an experiment [38], the adsorption capacity of TiO2 was measured under a pH range of 2-10.
For each batch of experiment, 2 g/L TiO2 were added with 800 mL landfill leachate in series and then kept
under dark reaction for 30 min. At pH 2, maximum colour removal (~28%) was observed followed by a
COD removal of 19%; whereas, maximum COD removal of 20% was noticed but slightly decreased in
colour removal (23%) after raising pH to 4. Moreover, the removal efficiency of COD and colour
diminished with increasing pH from an optimum value of 4, showing the acidic pH as favourable for
organic pollutants removal. Mansouri et al. [64] noticed a strong adsorption of the pollutants present in the
landfill leachate in the presence of 2.5 g/L TiO2 P25, where 21% TOC was reduced at an alkaline pH
during a 30 min dark reaction before sunlight irradiation. Similarly, Pobelete et al. [36] observed 45% and
57% reduction of humic acid from landfill leachate using 1 g/L and 2 g/L titania , respectively during 30
min adsorption-desorption reaction. Studies on dark reaction revealed faster adsorption rate and attainment
of the equilibrium concentration in only 30 min reaction time.
Table 4
5. TiO2 photocatalytic degradation of landfill leachate
The photocatalytic processes can either break down or rearrange molecular structures of different biorecalcitrant compounds or convert them to more readily biodegradable intermediates, improving the
efficiency and reducing the cost of further biological steps. As Table 5 illustrates, using TiO2 photocatalytic
process, certain recalcitrant organic and inorganic pollutants present in landfill leachate may be removed.
The varying removal efficiency of pollutants is due to certain factors such as types and mode of
photoreactors, operation parameters and environmental dynamics.
5.1. Organic compounds removal
9

TiO2 photocatalysis has shown efficient results in removing recalcitrant organic pollutants from landfill
leachate. In an experiment, the COD and DOC concentration were reduced to 959 mg/L and 233 mg/L
from an initial concentration of 2440 mg/L and 914 mg/L respectively, removing 60% COD and 74% DOC
during 72 h reaction time. After 72 h, the BOD5/COD ratio continued to increase up to 0.39 from initial
0.09, indicating the improvement in biodegradation ability of leachate by photocatalysis [39]. In a previous
batch experiment [38], the removal of COD, DOC and color by UV-TiO2 photocatalysis could reach above
60%, 70% and 97%, respectively. Moreover, the ratio of BOD5/COD was elevated from 0.09 to 0.39,
showing substantial improvement in biodegradability. Dealing with real Leachate, Meerof et al. [35]
removed more than 70% of COD from an initial concentration of 330 mg/L in 4 h treatment.
Adsorbent-Photocatalyst Hybrids (APHs) are bifunctional substances having adsorption and photocatalytic
properties; and proved to be more efficient than pure photocatalysts in degradation of pollutants [27]. In an
experimental study [34] organo-bentonite synthesized by organic modifier cetryltrimethyl ammonium
bromide (CTMAB) was used as an adsorbent with TiO2 photocatalyst and 82% COD was removed from
mature leachate under optimal conditions (7.5 g/L CTMAB, 1.63 g/L TiO2 dosage, 3.5 pH and 60 min
reaction time). Pobelete et al. [65] used a solid byproduct containing titania and Fe3+ and removed 86%
COD in dilute landfill leachate, which was higher than that removed by photo-Fenton (43%). Pobelete et
al. [36] also degraded around 78% TOC using 1 and 2 g/L waste titania catalyst; whereas, 60% TOC was
removed using 2 g/L commercial titania at 2 h UV irradiation. For dilute landfill leachate, 68-70% removal
of TOC was achieved using waste titania photocatalysis at 1 and 2 g/L catalyst loadings followed by
adsorption removal of 24-25%. On the other hand, TOC removal rate using commercial TiO2 after 60 min
of UV irradiation were lower (57% and 35% for 1 and 2 g/L respectively), followed by only 8% and 6%
extra TOC removal for 1 and 2 g/L, respectively. Interestingly, the waste titania proved to be efficient for
photocatalytic treatment of leachate containing high organic matter, as Fe (III) complexes demonstrated a
synergistic effect on the catalytic activity of TiO2. Chemlal et al. [37] coupled TiO2 photocatalysis with
seeded bioreactors, which allowed an abatement of 90% of initial BOD5 and 87% of the initial COD
leachate reduction with a final value of 1000 mg O2/L. The result supports the idea to recycle the irradiated
10

leachate in the landfill (loop AOP + landfill). In a study, fluorescence spectroscopy was performed to
investigate the composition changes and characteristics of the leachate DOM (dissolved organic matter)
during UV-TiO2 photocatalytic treatment process. After the photocatalytic treatment process for 60 h, the
humic and fulvic acid-like substances were degraded into protein like compounds.
TiO2 photocatalysis proved efficient technique for colour removal as well. Demonstrating a pilot scale
experiment, Youngman [66] removed 55.5 % colour after treating a landfill leachate for 24 h at 4 g/L TiO2
dosage; whereas, Qazaq et al. [60] revealed 50 to 77 % decolourisation of MSW leachate.
5.2. Ammonia removal
Ammonia removal from landfill leachate is vital due to its hazardous effects to water bodies. Huge amount
of ammonia-nitrogen species in landfill leachate are in the form of ammonium ions (NH4+) because pH
levels are generally less than 8.0. Dissolved unionized ammonia is more toxic for anaerobic degradation
processes than NH4+ in a landfill leachate [67].
Using a simulated leachate having initial concentration of 1425 mg/L after 4 h contact time and catalyst
dose of 4 g/L, Meeroff et al. [35] attained 51% NH3-N removal. Moreover, similar results appeared in real
leachate, in which first order degradation constants were essentially the same (k= 0.089h-1 ; r2=0.99). It may
be due to varying TiO2 concentration based on COD loading (g TiO2/g COD) rather than volumetric
loading (g TiO2/L). More than 40% NH3-N was removed using combination of CTMAB adsorption and
TiO2 photocatalyst in 1 h reaction [34]. CTMAB due to its special structure might be considered as an
attractive substrate for TiO2 catalyst, which effectively promotes the dispersion of titania and provide easy
access for contaminants to the photocatalyst.
5.3. Total Phosphorus removal
Like for other pollutants no systematic research has been done on the removal of phosphorus in TiO2
photocatalysis. However, Wang et al. [68] reported the degradation of phosphorus in municipal landfill
leachate by photochemical oxidation at optimum conditions (TiO2 dosage: 2 g/L, pH 5) in a pyrex batch
11

photoreactor, employed with a 15 W low pressure UV lamp (wave length: 254 nm, light intensity: 48.4
Wcm-2). During the photocatalytic reaction only 37% of total phosphorus (TP) was removed from the
leachate from an initial concentration of 15.1 mg/L TP. A maximum TP degradation (almost 100%) was
observed in Fe (VI) pre-oxidization combined with TiO2 photocatalytic oxidation [Fe (VI)/TiO2/UV].
Phosphorus removal was attributed to the oxidation of hydroxyl radical generated by photochemical
reaction of Fe (VI) and coagulation of ferrate [Fe (OH) 3].
Table 5
6. Factors affecting performance of TiO2 photocatalysis
Many operating factors affect the photocatalytic degradation of landfill leachate; a brief summary is given
in Table 6. Each of these parameters will be discussed in the following sections.
Table 6
6.1. Effects of pH
The pH of the reaction medium is known to have strong influence on UV-induced degradation of organic
pollutants present in landfill leachate. It has great effect on substrate and catalyst surface charge and also
on the mechanism of hydroxyl radical generation [69]. In photolysis or photocatalysis, the ease of bond
breakage and the site of attack might be different as the pH changes due to differences in the distribution of
molecular charges. The surface charge of semiconductors, the interfacial electron transfer and the
photoredox processes occurring in their presence are also affected by pH [70]. The photocatalytic
degradation rate in acidic pH is strongly favourable for removal of organic pollutants than neutral and/or
alkaline pH [71]. In two separate studies, Cho et al. [22] and [23] explored that the removal efficiency of
pollutants was higher in acidic conditions (pH 4) compared to neutral/alkaline pH, which is in accordance
with Rocha et al. [72] where the efficiency of TiO2/H2O2/UV system increased 10 times after a preliminary
pH adjustment of 4. Using a thin-film fixed-bed reactor, Bekbolet et al. [73] reported highest degradation
of organic pollutants in acidic pH with maximum at pH 5, while at pH 9 and 11 the degradation was rather
12

slow. In a similar reactor, illuminating the leachate under three UV-C 15 W lamps for 30-50 h at an
optimum pH 5 removed 77-92% COD having initial concentration of 26,000-30,000 mg/L [74].
With rising pH, Nernstian shift of the band edges of the semiconductor to more negative values occurs
[75]. Wiszniowski et al. [76] examined that the photodegradation rate of humic acids found in mature
leachate may decline with the increase of pH above zero point charge of TiO2 at about pH 7.0. It is well
known that as pH increases above zero point charge, the decrease of hydroxyl groups on oxide surfaces
provide fewer sites for ligand exchange, resulting in lower polyelectrolyte adsorption [77].
Contrary to organic pollutant removal in landfill leachate, the photocatalytic removal rate of ammonianitrogen (NH3-N) was significantly higher at alkaline pH than that at acidic pH [72]. According to zeta
potential theory on the TiO2 surface, the adsorption of protoionised NH4+ might be difficult to occur in
acidic solution. The lower degradation at neutral pH might be because of high concentration of alkalinity in
leachate that could react with hydroxyl radicals (OH) with high reaction rate. Due to the scavenging
effects, removing alkalinity prior to photocatalytic treatment is essential to speed up the degradation rate
for other parameters [38].
6.2. Effects of photocatalyst dosage
Literature validates the fact that with increasing TiO2 photocatalyst dosage, the number of photons and the
number of pollutant molecules absorbed are increased due to an increase in the number of TiO2 particles.
The density of particles in the area of illumination also increases, and hence the rate is enhanced. The
enhanced degradation efficiency can be attributed to the increased availability of catalyst sites for
adsorption of the reactant molecules, better generation of reactive free radicals and their interactions [70].
When the amount of titania increases above the saturation level, the light absorption coefficient decreases.
The excessive TiO2 particles can create a light screening effect that reduces the surface area of titania being
illuminated and the photocatalytic efficiency [78]. At a TiO2 dosage of 4 g/L, Youngman et al. [66]
removed ~ 90% ammonia and alkalinity, 55.5% color and 37.4% COD but the degradation ratio decreased
except COD when the dosage was increased to 16 g/L. Hence, photoreactors should be operated below the
13

saturation level of titania photocatalyst used to avoid excess catalyst and ensure efficient light absorption.
In this sense, both catalyst concentration and light scattering effect can be considered as a function of
optical path length in the reactor [44]. Keeping in mind the expenses of catalyst separation and
regeneration, it is noteworthy to extend irradiation time rather than to overuse catalyst dosage in practical
application of the photocatalytic approach. Following this principle, an efficient result was obtained in one
of our recent study dealing with biologically treated landfill leachate [41]. Applying an optimum 1 g/L
TiO2 photocatalyst, 82% COD abatement was made possible which further increased to 85% with 1.5 g/L
dosage during 2 h irradiation time. The COD was degraded to 92 and 79 mg/L, respectively meeting the
national discharge standard of China for COD.
6.3. Effects of inorganic ions
A mixture of high strength inorganic ions is present in landfill leachates which could compete for the active
sites onto the TiO2 surface, and hence could decrease the photomineralisation rate of organic compounds
[73]. Many studies on the effects of inorganic anions (i.e. NO3-, Cl-, SO42-, HCO3-, HPO42-, C2O42-,
CH3COO-, CO32-, SO42-) and cations (i.e. K+, Na+, Ca2+, Mn2+, Cu2+, Mg2+, Fe2+, Ni2+, Zn2+, Fe3+, Al3+)
have been reported to date [76], [79], [80], [81] and [82]. In literature, the inhibition of photocatalytic
properties in the presence of ions is often explained by the scavenging of hydroxyl radicals by ions. For
instance, the reaction of carbonate (CO32-), bicarbonate (HCO3-) and chloride (Cl-) with hydroxyl (OH)
radical is given in the following equations:
CO32-+ OH OH- + CO3-

(8)

HCO3- + OH H2O + CO3-

(9)

Cl- + OH Cl+ OH-

(10)

The anions (such as NO3-, Cl-, HCO3-, SO42-, NO2- and PO43-) pose a detrimental effect on photocatalytic
activity [80] and [83], and may hinder the hydroxyl radical production and prevent substrates from
reaching surface active sites. Especially, Cl- scavenges the valence band holes and radicals during
14

photocatalysis; and chloride radical (Cl) can be generated from these reactions [84]. Wiszniowski et al.
[76] investigated the effect of inorganic anions commonly found in landfill leachate such as HCO3-, SO42-,
Cl- on photocatalytic degradation of humic acid (HA) as a model of refractory organic substance. Although
SO42- (7.75 g/L) and Cl- (4.5 g/L) didnt pose any effect individually on the photocatalytic process but their
mixture significantly delayed the degradation process; whereas, the presence of HCO3 - (3.05 g/L) in the
solution matrix strongly inhibited the photocatalytic degradation. It is due to the fact that HCO3- acted as
radical scavenger and effectively consumed hydroxyl radicals.
A study showed that the effectiveness of photocatalytic TiO2 was significantly decreased in the presence of
HPO42-, C2O42-, CH3COO-, CO32-, SO42- and citrate ions at acidic pH, while the adsorption of dye on TiO2
particles was slowed down in the presence of these ions. On the other hand, there was no effect on photodegradation in the presence of NO3-, Cl- and SO4 2- ions [82]. Guillard et al. [85] correlated the effect of
inorganic anions (CO32-, PO43-, SO42-, Cl- and NO3-) on the amount of initially adsorbed dyes with its
photocatalytic degradation efficiency. Moreover, the inhibition by inorganic salts of the decomposition of
methylene blue at neutral and alkaline pH is in the following decreasing order:
CO32- PO43- SO42- Cl- NO3Among inorganic cations, Cu2+, Al3+ and Fe2+ at a certain level may decrease the photo-degradation rate
whereas, Mg2+, Ca2+, and Zn2+ have very minor effects. This is because the Ca2+, Mg2+ and Zn2+ are at their
maximum oxidation states resulting in their inability to inhibit the photocatalysis reaction [44].
6.4. Effects of radiant power and irradiation time
The apparent rate constant of degradation increases with an increase in UV irradiance because more
photons fall on the catalyst, which enhances production of hydroxyl radicals [63]. At low intensity of
illumination, the degradation rate is of first order in intensity, while at high intensity, the reaction rate
increases with the square root of the intensity level [86]. Pera-Titus et al. [87] has remarked that by
increasing light intensity, the photon quantity emitted by the system into the solution also increases; hence
15

more TiO2 particles are activated. Treating municipal landfill leachate, at constant density of 31.5 mA cm-1,
a maximum of 57.3 % COD was degraded with a 400 W lamp, while only 37.7 % removal was achieved
when 125 W UV lamp was employed [14]. Uyguner and Bekbolet [88] investigated the photocatalytic
mineralisation of humic acids (HA) at low radiant power from 0.98 to 3.4410-6 Einstein min-1 and
concluded that the photocatalytic HA degradation rate was a linear function of irradiance. Palmer et al. [89]
described that for radiant power of less than 1.2210-5 Einstein sec-1, the rate of initial HA degradation
increased linearly with irradiance.
Although pollutant removal is directly proportional to irradiation time in photocatalytic process, but the
pollutants degradation efficiency ceases beyond a certain irradiation time. During an investigation [23],
concentrations of organics (COD and TOC) in the landfill leachate decreased exponentially as a function of
illumination time. During 5 h irradiation, 52% of COD and 79% TOC degradation was observed and at 10
h UV illumination the removal efficiency was 56% and 88% respectively.
6.5. Effects of Dissolved Oxygen
Dissolved Oxygen (DO) has a vital role in TiO2 photocatalysis to make sure sufficient electron scavengers
are present to trap the excited conduction band electron from recombination [90]. Aeration also provides
the energy necessary to keep titania particles in suspension [44]. According to Cho et al. [23], landfill
leachate was photocatalytically degraded in the presence of DO, and removal rate of COD was 1.5 times as
large as the rate of accumulation of DO, but after 5 h of irradiation time, the DO level declined, and
photocatalytic oxidation rates were nearly zero.
7. Comparative evaluation of TiO2 photocatalysis with other AOPs
A number of AOP techniques (heterogeneous and homogenous) have been used to treat landfill leachate.
Their effectiveness depends on the removal rate of recalcitrant pollutants, cost effectiveness, technical
viability and environment friendliness. The use of certain oxidants (O3, H2O2, S2O82-), catalysts (TiO2,
ZnO, Fe2+) and their combination were reported in the literature. Ozonation, Fenton oxidation, electro16

oxidation etc were regarded as well known oxidation processes in wastewater treatment. However, the
complexity of landfill leachate makes their utilization alone unsatisfactory unless they are photo-irradiated.
Table 7 shows the comparative efficiency of various AOPs for pollutants removal. Fenton related
processes i.e. electro-Fenton and photo-Fenton/photoelectro-Fenton are efficiently used for the
degradation of organic compounds. Electro-Fenton process has been applied less frequently to treat landfill
leachate than conventional Fenton process. Using Fenton oxidation, Zhang et al. [91] removed 71-76%
COD from old landfill leachate, whereas, 83% COD was degraded using photo-Fenton by Bauer et al. [33],
respectively at acidic pH. In a study, Cortez et al. [92] compared operating costs of Fenton and O3/H2O2
techniques. Fenton process showed to be the most economical system (8.2 m-3 g-1 of COD removal) to
treat landfill leachate followed by O3/H2O2 (25.6 41.5 m-3 g-1 COD) at different H2O2 concentrations
and O3 oxidation (36.3 101 m-3 g-1 COD). One of the major environmental problems in the final
effluent discharge during Fenton related processes including ozone/Fenton is the release of a considerable
amount of iron sludge, which can be separated from the leachate but requires additional investment and
operating costs [92] and [93].
Electrochemical assisted photocatalysis is a new approach integrating two techniques i.e. electrochemical
oxidation and photocatalytic degradation. Photoelectrochemical treatment is more promising than
electrolysis for remediation of recalcitrant biodegradable in landfill leachate. Employing electrochemical
oxidation, Bashir et al. [94] abated 70% BOD5, 68% COD and 84% colour, whereas, 94% COD, 97%
colour and 96% phosphate were successfully removed by Altin [95] applying photoelectrochemical Fenton.
The key challenges which hinder widespread adoption of electrochemical AOPs (EAOPs) are formation of
perchlorate (ClO4-) and halogenated organic compounds by products during oxidation of waste streams and
the low electroactive surface area for electrode material [96].
TiO2- mediated photocatalysis is a powerful tool for the total mineralization of a wide range of organic
compounds caused by the in situ generation of hydroxyl radicals upon photo- irradiation [38]. The
preferential use of TiO2 for the photocatalytic degradation of recalcitrant organic compounds is based on its
low-cost, non-toxic, and photochemical stability. Dealing with landfill leachate as pretreatment, Chemlal et
17

al. [74] degraded 92% COD at pH 5, whereas; in our recent study Hassan et al. [41] 82% COD was
removed using an optimum 1g/L TiO2 dosage at the same pH, consuming 900 kJkg-1 of leachate (43 kWh
kg-1 COD). Post-separation/reclamation of TiO2 photocatalyst after leachate treatment is the key challenge
towards commercialization of the process (discussed in the following section).
7. Post separation/recovery and reuse of TiO2 photocatalyst
The applicability of heterogeneous photocatalytic process for landfill leachate treatment is inhibited by
several technical challenges that need to be further investigated; among them, the post-separation of
semiconductor TiO2 catalyst after leachate treatment is the most important obstacle towards practicality of
the process [44]. In a study [98], the post separation of TiO2 photocatalyst dispersed was successfully
achieved with an optimal coagulant dose, proper flocculation, and sand filtration. Maximum separation


occurred at an optimized G value [The G value is defined as  (s  ), where P is the power (W), is the
liquid viscosity (Pas), and V is the liquid volume (m3)] of < 34 s1 with a coagulant concentration of > 8
mg/L as Al2O3. Sand filters had the capability to remove residual turbid materials and thus, the turbidity of
the final product water declined to as low as 0.1 NTU when the coagulation/flocculation process was
carried on. The final effluent quality was comparable to that of a 0.45 m membrane filter. Szabo et al.
[99] separated photocatalyst from aqueous dispersion using graphene oxide/TiO2 nano-composites.
Although the presence of exfoliated graphene oxide was linked with a loss of photocatalytic efficiency, it
has induced an accelerated sedimentation of catalyst slurry as compared to pure TiO2, resulting in the
complete separation of photocatalyst from the treated water in a highly reduced time scale. The loose
physical network of weakly adhered particles can be shattered by sonication or other strong mechanical
means, but spontaneous aggregation occurs upon mild re-dispersion. Therefore, hetero-coagulation is
reversibly induced and can be used to collect the finely suspended catalyst particles worn off from the
composite.
Gandhi et al. [100] tested the regeneration of used Degussa P25 from the photocatalytic degradation of
phthalic acid (C8H6O4) by using three regeneration techniques: washing with methanol, thermal treatment,
18

and treating with hydrogen peroxide. Moreover, it was subsequently used again for a second and third
treatment cycle. In an experiment, [101] the recovery method of titania involved simple sedimentation of
the catalyst after each run was carried out. It was discovered that using tap water instead of deionized water
led to more coagulation of titania particles which delivered greater catalyst settling for reuse, but resulted
in lower degradation efficiency of the catalyst. The additional electrolytes in the tap water neutralized
charged species on the catalyst surface and reduced repulsion.
8. Conclusion and future perspectives
Photocatalysis operates under ambient conditions provided an appropriate light source is available, while
TiO2 is still the foremost photocatalyst, since no adequate alternatives have emerged. This study revealed
that TiO2 photocatalysis is a viable technique to remove certain recalcitrant pollutants found in landfill
leachate. It also pointed out that the efficiency of TiO2 mediated photocatalysis has a direct or indirect
dependence on certain operating conditions. For example, the increasing catalyst dosage enhances the
photocatalytic effect but is limited to a certain level, beyond that it could be diminished. The same
phenomenon is prevalent for irradiance time. Acidic and alkaline pH is favourable for organic pollutants
and ammonia removal respectively. Presence of certain ions (both anions and cations) in the landfill
leachate can limit the photomineralisation rate of organic pollutants, as they compete for active sites on to
the TiO2 catalyst. Among the various forms of TiO2 catalysts, anatase and/or anatase/rutile mixture is most
favorable for photocatalytic applications.
Despite relatively good efficiency of TiO2 photocatalysis to deal with landfill leachate, several technical
challenges are needed to be addressed, like post separation methods of titania after water treatment, depth
of light penetration into aqueous titania suspension and low quantum efficiencies of the degradation
process on irradiated catalyst. Moreover, the catalyst turnover number and catalyst poisoning also needs to
be further investigated. Use of UV irradiation is also an obstacle to scale-up this technology. Certain
modifications of TiO2 semiconductor may resolve this issue to an extent by reducing the band gap of TiO2.
However, most of these modifications are achieved by doping or by making composite catalysts. Synthesis
19

of new phases of titania having potentially significant photocatalytic can minimize the short comings of
this technology. Covering all these aspects, it is believed that further research is needed toward sunlight
irradiated TiO2 photocatalysis based on charge transfer mechanism in order to make this technology more
cost effective and commercialized.

Acknowledgment
This work was supported by the Natural Science Foundation of China (31370510, 21577038,
31411130123) and Shanghai project of international cooperation of science and technology (1352072600).

20

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28

Figure Legends
Fig 1: Disposal of worldwide total municipal solid waste
Fig 2: The crystal structures of TiO2; (a) Rutile, (b) Anatase, (c) Brookite
Fig 3: Mechanism of TiO2 photocatalytic oxidation
Figure 4: Experimental set-up of the slurry membrane photoreactor.
Fig 5: Schematic diagram of lab scale batch mode photassisted electrochemical oxidation reactor

29

Figure 1: Disposal of worldwide total municipal solid waste [2]

30

Figure 2: The crystal structures of TiO2: (A) Rutile, (B) Anatase, (C) Brookite
[http://ruby.colorado.edu/~smyth/min/tio2.html]

31

Figure 3: Mechanism of TiO2 photocatalytic oxidation

32

Figure 4: Experimental set-up of the slurry membrane photoreactor. Adopted from Laohaprapanona et al.
[53]

33

Figure 5: (a) Schematic diagram of the pilot scale cascade photoreactor. A: TiO2-coated plates; B: tank
with drain valve; C: control; D: centrifugal pump; E: cooling coil in water bath; F: flow meter; G: liquid
reservoir. (b) The pilot scale cascade photoreactor. Adopted from Chan et al. [54]

34

Table legends
Table 1: Properties of polymorphs of TiO2
Table 2: Landifill age versus leachate quality
Table 3: Types of reactors and their configurations
Table 4: Removal of different organic pollutants by TiO2 catalytic dark reaction adsorption
Table 5: Summary of TiO2 photocatalysis for the removal of landfill leachate pollutants
Table 6: Effect of operating factors in TiO2 photocatalytic degradation of landfill leachate
Table 7: Pollutants removal performance of various AOPs dealing with landfill leachate

35

Table 1: Properties of polymorphs of TiO2 [102, 103, 104, 105, 106]

36

Properties

Anatase

Rutile

Brookite

Aeroxide P-25

Density (g/cm3)

3.90

4.27

4.13

3.8

Energy band gap (eV)

3.2

3.0

>3.0

Refractive Index

2.52

2.72

2.63

2.49

Threshold wavelength (nm)

380

413

< 400

Permittivity

48

114

78

78.5

Hardness

5.5-6

6-6.5

5.5-6

Average size (nm)

85

25

21-25

Table 2: Landifill age versus leachate quality [19, 20, 107, 108, 109, 110]
Parameter
Age (Years)

Young
<5

Intermediate
5 10

pH

6.5

6.5 7.5

>7.5

COD (mg/L)

>10,000

5,000 10,000

< 5,000

BOD5 (mg/L)

10,000 -20,000

50 100

TOC (mg/L)

9,000 15,000

< 1000

BOD5/COD

>0.3

0.1 0.3

<0.1

TOC/COD

< 0.3

0.3 - 0.5

> 0.5

Ammonia (mg/L)

100 - 600

>400

SO4 (mg/L)

50-1000

< 50

Cl (mg/L)

200 - 3000

< 400

Organic compounds (%)

80 % VFA

5-30%VFA+humic &

Humic & fulvic acids

Mature
>10

fulvic acids
VFA (as acetic acid)
(mg/L)

37

9,000 - 25,000

50 100

Table 3: Types of reactors and their configurations

Reactor type

Dimensions

Made of

Volume

UV light source

References

Buble column photoreactor

18 L

[60]

Pilot scale tube shaped reactor/

Lab scale cylindrical shaped
reactor
Self designed photocatalytic
reactor

Quartz and steel/

Quartz

10 L /
190 mL

5 cm id 6
cm h

Pyrex

1.0 L

Bench scale
photoelectrochemical reactor

3.0 L

Cylindrical photoreactor

250 mm h
90 mm id

Jacket glass
cylinder with
quartz tube
Stainless steel

Primac (AVP06C)
lamp with 200-400 W
UV source
2 UV lamps (25 nm)/
Philips, model G8TS
with 8W UV lamp
15W Low pressure
UV mercury vapor
lamp exerted in the
centre
Mercury vapour (125,
250, 400 W) lamps

[32]

Slurry reactor

4 2.5
2.5

1.0 L

Tube-shaped reactor

Wrapped with
galvanized
aluminum sheet
Borosilicate glass

Cylinder photoreactor

12.5 cm id
31.8cm h

Covered with
aluminum

2.3 L

250 W Mercury lamp

was immersed in the
solution
840 W black
fluorescent UV lamps
were fitted at the top
150 W UV lamp was
immersed in the
solution
424 W black light
lamps were suspended

Cylindrical glass reactor with

two circular windows

5cm id 2.75
cm l

0.5 L

Halogenated mercury
lamp, Powerstar HQI

[112]

Lab scale photo-assisted

electrochemical oxidation
reactor
Annular shaped photocatalytic
reactor

Glass cell with

quartz tube

600 mL

10 W low pressure
mercury lamp

[113]

Quartz

375 mL

450 W medium
pressure mercury
vapor lamp mounted
auxiliary

[35]

id: Inner diameter; h: Height; l: Length, cm: Centimeter

38

1.25 L

600 mL

[23]
[38]

[14]

[111]
[36]
[61]

Table 4: Removal of different organic pollutants by TiO2catalytic dark reaction adsorption

Photocatalyst dosage

Surface area

Particle

Pollutant removal by

Dark reaction

(m /g)

size (nm)

dark reaction

time (h)

20 nm

20% COD

2g/L P25 TiO2

pH

References

0.5

4.0

[38]

0.5

2.0

[36]

~25% Colour

1g/L P-25 TiO2

50

30

2g/L P-25 TiO2

45% HA
57% HA

1g/L Degussa P25

20

42 ppmC TOC

1.0

3.0

[22]

1g/L Mesoporous

74.3

12.2

12% CODcr

10

3.0

[71]

12% Chroma

12

93% DOC

2.0

[76]
[111]

0.7 g/L TiO2

0.2 g/L TiO2

86% DOC

2g/L Degussa P25

5015

30

74 g/L dye

3.0

4.5

1g/L Degussa P25

50

40% dye

0.5

3.0

2.5g/L Degussa P-25

55

21 % TOC

0.5

alkaline

39

[64]

Table 5: Summary of TiO2 photocatalysis for the removal of landfill leachate pollutants
Leachate
type

Pollutant
removal (%)

Catalyst
Concentration
(g/L)

Reactor
mode

pH

UV irradiation details

Irradiation
time (h)

Reference

Diluted
(10%)
stabilised
Landfill
Leachate

68 /TOC

1g/LWTiO2
(mixture of TiO2
and Fe III)

Batch

150 W UV-A, medium

pressure mercury lamp,
365 nm; light intensity 5
kW/m2

[36]

Mature
Landfill
leachate
Biologically
pre-treated
Landfill
Leachate
MSW natural
leachate

60/COD
>70/DOC
97/Colour
88 /TOC
56/ COD

2 g/L/P25 nanoTiO2 (70% rutile)

Batch

4-5

15 W low pressure UV-

72

[38, 39]

3g/L TiO2 (Degussa

P-25) 70% anatase

Batch

10

[23]

50-77 /Colour

5g/L TiO2 particles

(average
dp=120m)

Batch

n.r.

n.r.

[60]

MSW
Landfill
leachate
Biologically
pre-treated
Landfill
Leachate

70
/Sulfonamides

0.5gL-1TiO2+ 1.0
mmolL-1FeCl3

Batch

3.10

200-400W Primarc
(AVP06C) UV lamp,
250-400 nm; 110-4
Einstein s-1
4 UV lamps (TL-

11-18

[114]

0.08

40W/05), 366 nm

78 /COD
72/ TOC

TFBR

[73]

86 /COD

[65]

Biologically
pre-treated
Landfill
leachate
MSW
Landfill
Leachate

30 /COD

500W Xenon lamp

(OSRAM HBO), 320
nm; Light intensity 5.3
Wm-2
Solar UV irradiation,
350nm; Light intensity 30
W m-2
8WUV-C, 254 nm;
Light intensity 21 Wcm-2

MSW
Landfill
Leachate

5g/L Hombikat
UV100
(SachtlebenChemie
)
1g/L WTiO2
(mixture of TiO2
and Fe III)
3g/L TiO2 (Degussa

12

[22]

35-57 /COD

Aging
Leachate
Young
Landfill
Leachate
Aged landfill
leachate

mercury lamp; 254 nm

8 W UV-C, mercury
lamp, 254 nm

Batch

Batch

8.7

1-2g/L TiO2
(Degussa P-25)

Batch

7.5

150 W, medium pressure

mercury lamp, 365 nm;
5 kW/m2

[36]

86 /COD
41 /NH3-N
76-92 /COD

1.63+7.5g/L
TiO2+CTMAB
TiO2 coated sheet

Batch

3.5

[34]

TFBR

18 W UV lamp, 365
nm; 57 Wcm-2
3 UVC 15 W UV lamps

2.5

[74]

~ 100/TP

2g/L TiO2 + 16
mM/L Fe(OH)3

Batch

Low pressure 15W lamp,

254 nm, light intensity
48.4 Wcm-2

[68]

P-25)

MSW: Municipal Solid Waste; : wavelength; n.r.: Not reported; CTMAB: Cetyltrimethyl ammonium bromide; TFBR: Thin Film
Bed Reactor

40

Table 6: Summary of the effect of operating factors in TiO2 photocatalytic degradation of landfill leachate
Operating factors

Effect

pH

Removal rate of organic pollutant and ammonia accelerate at acidic and alkaline pH,
respectively.

TiO2 dosage

Increasing TiO2 photocatalyst dosage increases the pollutant removal efficiency but decreases
beyond a certain limit.

TiO2 phases

Anatase is favorable for photocatalytic application followed by rutile, but currently TiO2
aeroxide P25 has been proved to be an viable alternate having both anatase and rutile (~3:1)

Crystal facets

The {0 0 1} facet of crystalline TiO2 has more photocatalytic activity than thermodynamically
stable {1 0 1} facets.

Inorganic ions

High strength inorganic ions in landfill leachate inhibit the photomineralisation rate of organic
compounds by scavenging hydroxyl radicals

Irradiation time

Pollutant removal rate accelerates with irradiation time but decline and/or ceases beyond a
certain point.

Irradiant power

The rate constant of pollutant degradation speeds up with increasing UV irradiance because
more photons fall on the catalyst, which enhances the hydroxyl radicals

Dissolved oxygen (DO)

DO makes sure the presence of sufficient electron scavengers to trap the excited conduction
band electron from recombination

41

Table 7: Pollutants removal performance of various AOPs dealing with landfill leachate
Process
UV/TiO2

Leachate type
MSW landfill leachate

Ozone /Fenton

Stabilized leachate

UV/TiO2

MSW landfill Leachate

Electrochemical
oxidation

Stabilized landfill
Leachate

Fenton

Old MSW landfill

leachat
MSW Landfill leachate

H2O2/UV
Photoelectro
Fenton

MSW Landfill Leachate

Photo- Fenton

Landfill Leachate

Ozone/Persulfate

Mature MSW Landfill

Leachate

UV/persulfate

Operating conditions
TiO2: 1 g/L; UV lamp power:125 W;
pH 5; RT: 2 h; V: 1 L
0.05 molL-1 H2O2, 0.05 molL-1 Fe2+;
RT: 90 min; O3: 80 g/m3
TiO2 source: TiO2 catalyst paper
sheet; UV lamp power: 15 W; pH
5;V: 3 L ; RT: 3 h
Current density: 79.9 mA/cm2; RT: 4
h; Na2SO4 (as electrolyte): 1 g/L
FeSO4.7H2O: 0.01-0.05 M; H2O2:
0.06 M; pH 4
H2O2: 5g/L; RT: 360 min; UV lamp
power:15 W; V: 1 L; pH 3
H2O2: 3 g/L; pH 3; Current: 2.5 A;
RT: 20 min; UV power 8W; UV
intensity: 14 Wm-2;V: 1 L
H2O2 : 1.9 10-1 mol/L; FeSO4.7H2O:
1.51 10-3 mol/L; V: 8 L; RT: 6 h
Na2S2O8: 35 g; RT: 4 h; pH 10; V: 2
L; Temperature: 15C

Efficiency (%)
82% COD

References
[41]

65% COD;
98% Colour;
12% NH3-N
92% COD

[115]

70% BOD;
68% COD;
84% colour
71-76% COD

[94]

91% COD

[116]

94% COD;
97% Colour;
Phosphate 96%
83% TOC

[95]

72% COD;
92% Colour;
55% NH3-N
90% NH4-N

[93]

[74]

[91]

[33]

Bilogically treated
K2S2O8 : 1.5 g/L; UV lamp power: 8
[41]
MSW landfill leachate
W; RT: 30 min; pH 5; V: 1 L
RT: retention time; V: Leachate volume; Na2SO4: Sodium sulfate; Na2S2O8: Sodium persulfate; K2S2O8 : Potassium persulfate

42

Graphical Representation

43

Highlights

Photo-assisted TiO2 semiconductor is a viable alternative for landfill leachate treatment

Acidic and alkaline pH are favourable for organic and ammonia removal, respectively

High strength of inorganic ions could decrease photomineralisation rate of pollutants

Post separation of TiO2 photocatalyst after wastewater treatment is a major obstacle towards
scaling up of the process

44

Photocatalytic activity of TiO2 can be enhanced with doping by inorganic or metal elements