Accepted Manuscript

Treatment of landfill leachate using electrochemically assisted UV/chlorine

process: Effect of operating conditions, molecular weight distribution and flu-
orescence EEM-PARAFAC analysis

Zhihong Ye, Hui Zhang, Xin Zhang, Dejian Zhou

PII: S1385-8947(15)01413-8
DOI: http://dx.doi.org/10.1016/j.cej.2015.10.017
Reference: CEJ 14288

To appear in: Chemical Engineering Journal

Received Date: 1 June 2015

Revised Date: 7 September 2015
Accepted Date: 7 October 2015

Please cite this article as: Z. Ye, H. Zhang, X. Zhang, D. Zhou, Treatment of landfill leachate using electrochemically
assisted UV/chlorine process: Effect of operating conditions, molecular weight distribution and fluorescence EEM-
PARAFAC analysis, Chemical Engineering Journal (2015), doi: http://dx.doi.org/10.1016/j.cej.2015.10.017

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Treatment of landfill leachate using electrochemically assisted

UV/chlorine process: Effect of operating conditions, molecular weight

distribution and fluorescence EEM-PARAFAC analysis

Zhihong Ye a, Hui Zhang a, b, *, Xin Zhang a, Dejian Zhou a

a
Department of Environmental Engineering, Wuhan University, Wuhan 430079, China

b
Shenzhen Research Institute of Wuhan University, Shenzhen 518057, China

* Corresponding author. Tel: + 86-27-68775837. Email address: eeng@whu.edu.cn.

Abstract

Leachate, a highly polluted wastewater, is generated from landfill containing

complex compositions which have great impact on the environment. The advanced

treatment of biochemically treated landfill leachate using electrochemically assisted

UV/chlorine process (UEC) in a flow reactor was investigated. The effects of pH

and current density on COD and NH3-N removal by UEC process were evaluated.

At the pH value of 5.0, current density of 60 mA/cm2, the removal efficiencies for

COD and NH3-N were observed as 77% and 87%, respectively. The electrochemical

process alone (EC) could obtain relatively high NH3-N removal but very low COD

removal, compared with which, the UEC process significantly promoted the removal

efficiency of COD while that of NH3-N increased to a very limited extent. Most of

NH3-N was converted into N2 and little nitrogen compounds and chloramines were

remained in the leachate after 8 h treatment. Moreover, the variations of active

chlorine and chloride ions were monitored in the EC and UEC systems, and a

possible mechanism was proposed for the UEC process. The in situ

1
electro-generated active chlorine and the in situ photo-generated radical species

should be responsible for the efficient degradation of landfill leachate. The total

energy consumption and current efficiency were 216.5 (kW h/kg COD) and 17.5%,

respectively, for 8 h treatment. In addition, the molecular weight (MW) percentage

distribution analysis and PARAFAC analysis of excitation emission matrix (EEM)

fluorescence spectroscopy indicated that the organic matters in the leachate were

significantly degraded into the fractions with small molecular weight.

Keywords: Landfill leachate; UV/chlorine; Electrolysis; COD; NH3-N; EEM

1. Introduction

Landfill is the primary method used to dispose solid waste in countries

worldwide due to its economic advantage [1]. However, the leachate generated from

landfill is a highly polluted wastewater containing organic pollutants, inorganic salts,

ammonia-nitrogen (NH3-N) and many other contaminants [2,3]. There are many

factors, such as landfilling age, waste composition, precipitation and weather

variation, affecting the leachate characteristics. In terms of young leachate, the value

of chemical oxygen demand (COD) can reach above 10,000 mg/L, the BOD5/COD

ratio ranges from 0.4 to 0.7 and the COD/NH3-N ratio can exceed 10:1 [4]. However,

the COD concentration and BOD5/COD ratio decrease rapidly with landfilling age,

while NH3-N still keeps fairly high. The discharge of untreated leachate can pollute

surface water, permeate the soil and contaminate ground water because of its acute

and chronic toxicity [5]. Thus the effective removal of COD, NH3-N and other

pollutants is prerequisite before the leachate is discharged into the receiving

2
environment. Biological methods are very effective, economical and widely used

processes for the treatment of raw landfill leachate. Nevertheless, they are

ineffective to degrade the recalcitrant compounds in the leachate, and the follow-up

advanced treatment is usually required. Nowadays, many advanced

physical-chemical processes have been proposed for the treatment of landfill

leachate. The advanced oxidation processes (AOPs), including H2O2/Fe2+ [6,7],

H2O2/UV [8], O3/UV [9], electro-Fenton [10], and photo-Fenton [11], are proved to

efficiently remove the recalcitrant organic contaminants in the leachate.

AOPs rely on the production of highly reactive hydroxyl radicals (•OH) (E0 =

2.73 V) for the destruction of refractory pollutants. Recently, the UV driven chlorine

process has been widely used as a potential AOP because •OH can be produced by

exposing the chlorine to UV light [12-14]. The main reactions occurring in the

UV/chlorine process are shown as follows:

HOCl ⇌ H  + OCl (pKa = 7.5 at 20 °C) (1)

HOCl + ℎ →• OH +• Cl (2)

OCl + ℎ →• Cl +• O (3)

• O + H O ⇌• OH + OH  (4)

Wang et al. [15] reported that HOCl and OCl− could efficiently absorb UV light

2.3 and 10.7 times more than H2O2 as irradiated by medium pressure UV lamps

under equal molar conditions. But the quantum yields of •OH were 0.46 and 0.28 for

HOCl and OCl−, respectively, which were much lower than 0.85 of UV/H2O2

process [16,17]. The chlorine radical (•Cl) generated in the UV/chlorine process was

3
a selective oxidant and generally was much less reactive than •OH [18]. But its

reactivity could be higher than that of •OH when reacting with some organics like

phenol. In addition, •Cl was very efficient on the degradation of NH3-N [19]. Sichel

et al. (2011) assessed that the UV/chlorine AOP was an efficient, economical and

energy-saving method in the removal of emerging contaminants [20]. However, the

feasibility of UV/chlorine AOP for the treatment of landfill leachate has not been

studied until now.

Electrochemical method (EC) has been widely applied in the treatment of

landfill leachate during the last two decades [21-23]. In EC process, the

contaminants were destroyed through two different approaches, namely direct

oxidation and indirect oxidation. The direct oxidation was attributed to the

chemisorbed and physisorbed reactive radicals generated on oxide anodes [24]:

M(H O) → M(• OH) + H  + e (5)

As high concentration of chlorine ions (Cl−) was present in the leachate,

indirect oxidation induced by the active chlorine generated via reaction (6) and (7)

played a key role in the removal of the organic pollutants [25].

2Cl → Cl + 2e (6)

Cl + H O → HOCl + HCl (7)

In addition, NH3-N could be removed by the electro-generated

chlorine/hypochlorite, and the mechanism was similar to the breakpoint reactions

[26,27]:

NH + HOCl → NH Cl + H  + H O (8)

4
NH Cl + HOCl → NHCl + H O (9)

NHCl + H O → NOH + 2HCl (10)

NHCl + NOH → N + HOCl + HCl (11)

NH Cl + NOH → N + HCl + H O (12)

NHCl + HOCl → NCl + H O (13)

When the UV irradiation was introduced into the EC process (UEC), the

electro-generated active chlorine would generate •OH and •Cl. This is different from

the conventional UV/chlorine AOP in which hypochlorite is externally applied,

while chlorine is electro-generated in UEC process. It has been reported that

photo-electrochemical method could achieve higher removal of COD, TOC and

NH3-N from the landfill leachate in comparison with the electrolysis process [28,29].

In this work, a UEC system with a 10 W UV lamp and DSA electrode was used

to simultaneously remove COD and NH3-N in the biologically treated leachate from

a two-stage anaerobic−aerobic sequencing batch reactor (SBR) system. The critical

behaviors of UEC system such as treatment efficiency, enhanced mechanism and

energy consumption, were investigated in detail to provide basic information for the

application in the treatment of landfill leachate.

2. Materials and Methods

2.1. Leachate collection and characterization

Leachate samples were taken with polyethylene bottles from a landfill at

Wuhan (China), which has been in operation since 2007. Samples taken were stored

in the refrigerator at 4°C to maintain their characteristics [30]. The leachate was first

5
pre-treated by a two-stage anaerobic−aerobic SBR system. The main characteristics

of raw leachate and biological effluent on average were summarized in Table 1. As

can be seen, the concentrations of COD and NH3-N were still high in the biological

effluent and further treatment was needed. In the meanwhile, the chloride content

varied between 2433 and 2399 mg/L, which is sufficient to generate active chlorine

during the sequent UEC process.

2.2. Experimental setup

The experiments were carried out in a recirculation flow system consisting of

an electrochemical reactor and a photo-reactor, as sketched in Fig. 1. The working

volumes of the electrolytic cell (made of plexiglass) and the photo-reactor (made of

glass) were 800 mL and 300 mL, respectively. In the electrolytic cell, a

Ti/IrO2-RuO2-TiO2 plate anode (10 cm×15 cm) and a titanium plate cathode with the

same dimension were adjusted parallel at a distance of 1.5 cm. The solution was well

mixed by a magnetic stirrer (Model DW-3), and a direct current (DC) power supply

(LW-3030KD) was used to conduct the experiments under constant current

conditions. A UV lamp (10 W, main wavelength 254 nm) in a quartz glass tube was

placed at the center of the photo-reactor, and the solution temperature was kept at

about 20±3°C using a circulating water bath. 1.1 L landfill leachate was introduced

into this system, and then recirculated through the system by a peristaltic pump at a

flow rate of 91 mL/min. During the experiments, the pH value of the leachate was

kept constant using concentrated sulphuric acid and sodium hydroxide, while

leachate samples were collected for analysis at pre-selected time interval. The

6
concentrations of COD and NH3-N of the samples were determined to evaluate the

treatability of landfill leachate by the UEC process.

2.3. Analytical methods

The pH value was measured by a Mettler-Toledo FE20 pH meter

(Metttler-Toledo Instruments Co. Ltd., Shanghai). COD was determined by a fast

digestion-spectrophotometric method based on the Standard of the People’s

Republic of China for Environmental Protection [31]. Ammonium concentration was

determined using Nessler’s reagent colorimetric method [32]. Chloride was analysed

using silver nitrate method [33]. Active chlorine, NH2Cl, NHCl2 and NCl3 were

measured according to spectrophotometric method [34]. NO2−-N was determined by

a spectrophotometric method [35]. NO3−-N was measured by phenol disulfonic acid

method [36]. The molecular weight percentage distribution in leachate was analysed

using an ultra-filter apparatus employed in our previous studies [37]. Leachate

sample was initially filtered using a 0.45 µm membrane, and then separated by

membranes with nominal molecular weight cut-offs (MWCOs) of 50, 10 and 4 kDa

[38]. COD concentrations of the filtrate passing through different size membranes

were determined and then the organic matters of these samples were characterized

by excitation emission matrix (EEM) fluorescence spectroscopy on the F-4500

fluorescence spectrometer (Hitachi Co., Japan). All the samples were diluted 1:100

to prevent inner filter effects and scanned over excitation wavelengths between

220-450 nm in 10 nm intervals and emission wavelengths between 220-600 nm in 10

nm intervals.

7
2.4 PARAFAC modelling

EEM-PARAFAC analysis was conducted in MATLAB R2012a according to

the drEEM toolbox (www.models.life.ku.dk), following a tutorial of Kathlee et al.

(2013) [39]. The number, identities and relative concentrations of independent

fluorophores in EEMs were evaluated. Prior to the analysis, the EEM of a control

(Milli-Q water) was subtracted from each EEM of the studied samples and the

removal of Rayleigh and Raman scatters were conducted using the

instrument-optimized version of the EEMSCAT algorithm in the drEEM toolbox. In

the analysis, non-negativity constraints were applied to each dimension, the

PARAFAC models with two to eight components were computed for the data,

initialization of each model were derived from random values and singular value

decomposition (SVD). The appropriate number of components was determined

based on core consistency, residual analysis and loadings analysis.

3. Results and Discussion

3.1. Effect of pH

To investigate the effect of pH on the degradation efficiency of landfill leachate,

the pH values were initially adjusted respectively as 2.0, 5.0, and 8.9, and kept

constant by adding sulphuric acid or sodium hydroxide continuously during the

experiments. As shown in Fig. 3, the removal efficiencies of COD and NH3-N

decreased as pH dropped from 5.0 to 2.0. Watts and Linden [40] reported that the

quantum yields of the radicals for UV/chlorine process were predominant over a

range of pH from 4−10. The conversion of radicals was rather complex in the

8
UV/chlorine process [18]. Under strong acid condition, the abundant H+ would

greatly promote the transformation of •OH to •Cl through reaction (14) and (15), and

the accumulated •Cl could be largely scavenged by the electro-generated HOCl via

reaction (16).

• OH + Cl → ClOH• 4.3×109 M-1s-1 (14)

ClOH• + H  →• Cl + H O 2.1×1010 M-1s-1 (15)

• Cl + HOCl → H  + Cl +• ClO 3.0×109 M-1s-1 (16)

Thus the UV/chlorine process would be inhibited at pH 2.0, resulting in the

relatively low treatment efficiency of landfill leachate. On the other hand, •OH could

be derived from •Cl at high pH by the following reactions:

• Cl + OH  → ClOH• 1.8 ×10 10 M-1s-1 (17)

ClOH• → • OH + Cl 6.1×109 s-1 (18)

The production of •OH enhanced by increasing pH to a certain range may

further explain the higher COD removal obtained at pH 5.0 than pH 2.0. Some

literatures indicated that the optimum pH for the UV/chlorine AOP was 5.0 [12,16],

which was consistent with the results obtained in this study.

When pH rose from 5.0 to 8.9, the highest NH3 -N removal (91.2%) and the

lowest COD removal (67.8%) were obtained. The dissociation of hypochlorite acid

at basic condition of pH 8.9 may explain the lowest COD removal. The dominant

species were OCl− in alkaline solution since the components of aqueous active

chlorine were pH dependent (pKa for HOCl/OCl− was 7.5); the quantum yield of

9
HOCl photolysis by 254 nm light was 1.45, which was higher than that of OCl−

(0.97) [18]. On the other hand, OCl− scavenged more •OH than HOCl [15],

• OH + HOCl → H O +• ClO 8.46×104 M-1s-1 (19)

• OH + OCl →• ClO + OH  9.0×109 M-1s-1 (20)

The increment in NH3-N removal at pH 8.9 might be caused by the combined effect

of indirect oxidation, direct oxidation and air stripping (including O2, Cl2, H2, etc)

[41].

3.2. Effect of current density

Generally, current density was the most frequently referred term in an

electrochemical process as it controlled the reaction rate. Figure 4 presented the

effect of current density on COD and NH3-N removal in the UEC process. The

removal efficiencies of both COD and NH3-N significantly increased with the

increase of current density from 20 to 60 mA/cm2. An increase in current density

would lead to a more rapid generation of chlorine via reaction (6), which promoted

the subsequent UV/chlorine process to degrade the landfill leachate. Chiang et al.

[26] reported that contaminant removal efficiency at the same charge loading was

independent of current density in a direct electrochemical oxidation process, and

proved that indirect oxidation played an important role in UEC process.

When the current density further increased from 60 to 80 mA/cm2, NH3-N

removal efficiency still slightly increased from 87.3% to 93.5%, while the COD

removal efficiency decreased from 77.0% to 69.1%. In the UEC process, COD was

degraded by indirect oxidation via HOCl, •OH and •Cl as well as direct oxidation via

10
M(•OH). However, ammonium was removed only by indirect oxidation via HOCl

and •Cl since •OH could not oxidize ammonium efficiently. At higher current

density of 80 mA/cm2, the side reaction of oxygen evolution would become

significant [42]:

2H O → 4H  + O + 4e (21)

This reaction would compete with the electrolysis of water to generate

chemisorbed and physisorbed reactive radicals via reaction (5), and less M(•OH)

would be produced. Therefore, COD removal was hindered at current density of 80

mA/cm2. It indicated that the contribution of direct oxidation to COD removal could

not be neglected. On the other hand, the DSA anode (Ti/IrO2-RuO2-TiO2) is an

efficient electrode for chlorine evolution, and the oxygen evolution reaction may

have little influence on the generation of active chlorine. As a result, ammonium

removal by hypochlorite continued to increase when current density reached to 80

mA/cm2.

3.3. Comparative study on degradation of landfill leachate in different systems

To verify the enhancement effect of UV light on the electrochemical process,

the leachate was treated by the electrochemical oxidation (EC), UV irradiation (UV)

and electrochemically assisted UV/chlorine system (UEC), respectively. As shown

in Fig. 2, UV irradiation led to a very limited removal of COD or NH3-N from the

leachate. When EC process was employed instead, 52.1% of COD removal was

achieved within 8 h electrolysis. This is attributed to direct oxidation with M(•OH)

and indirect oxidation with active chlorine. The active chlorine is also responsible

11
for the removal of NH3-N, and there is a competition between NH3-N removal and

COD removal. When indirect oxidation is prevalent, the higher NH3-N removal

would be obtained than COD removal [22,26,27]. As illustrated in Fig. 2, the

removal efficiency of NH3-N reached 82.1% while only 52.1% of COD was

removed after 8 h electrolysis.

When UV irradiation was introduced into the EC process, NH3-N removal was

slightly improved to 87.4%, whereas COD removal efficiency significantly

increased to 77.1%. This indicated that UV/chlorine AOP with the generation of

reactive radicals, such as •OH and •Cl, via reactions (1) – (4) should be responsible

for the better degradation of COD from the leachate.

3.4. Conversion of NH3-N in the UEC process

In the sequence of oxidation of NH3-N with in situ generated active chlorine,

the intermediate products known as chloramines, mainly including monochloramine

(NH2Cl), dichloramine (NHCl2) and trichloramine (NCl3), are formed. Finally most

of ammonium is converted to N2, while the rest is transformed to various

nitrogenous compounds such as NO3− and NO2− [43,44].

NH + 4HOCl → NO + HO + 6H  + 4Cl (22)

4NH Cl + 3H O → 4Cl + 3NH + NO + 5H  (23)

NO + 2e + 2H → NO

 + H O (24)

When the UV light was introduced, the overall reactions occurring in the UEC

process could be summarized as follows:

2NH + 3HOCl → N + 5H  + 3Cl + 3H O (25)

12
2NH + 6 • Cl → N + 8H  + 6Cl (26)

The concentrations of intermediates and nitrogenous compounds are

determined during the UEC process (current density = 60 mA/cm2, pH = 5.0) as

shown in Fig. 5. The concentration of NHCl2 was maximized in the first 1 h (43.2

mg/L), and then gradually declined to 3.91 mg/L after 8 h treatment. The

concentrations of another two intermediates (NH2Cl and NCl3) kept very low during

the whole experiment. The maximum concentration of NO3− formed in the UEC

process was 8.9 mg/L, which might be caused by the accelerated degradation of

NH2Cl under the UV irradiation [42]. Nitrite was produced through reaction (24),

and its content reached a maximum value of 0.29 mg/L at the first hour. Then nitrite

was further converted to nitrate and ammonia and its concentration decreased to a

very low level (0.1 mg/L) after 8 h of UEC process. The low content of chloramines

as well as nitrate and nitrite in the effluent indicated that NH3-N in the leachate

could be transformed into nitrogen gas efficiently under the UEC process.

3.5. Determination of active chlorine and chloride ions in different system

Indirect oxidation played a key role in the treatment of landfill leachate by EC

and UEC processes, which was mainly caused by the electro-generated active

chlorine via aforementioned reactions (6) and (7). The evolution of active chlorine

was monitored when the leachate or NaCl solution with the same Cl− concentration

as that present in the leachate was subjected to EC and UEC processes. As shown in

Fig. 6 (a), in the case of the pure NaCl solution, the concentrations of active chlorine

in the EC and UEC processes reached as high as 712.5 and 278.8 mg/L, respectively.

13
The much lower concentration of active chlorine in the UEC process than that in the

EC process indicated indirectly that active chlorine was dissociated under UV

irradiation. In the case of the leachate, active chlorine was kept at very low level

during the first 5 h in both processes. This could be attributed to the significant

consumption of active chlorine by the organics and NH3-N in the leachate, and it

was proved again that active chlorine was the major oxidant for the treatment of

landfill leachate. In particular, In the UEC process, the concentration of active

chlorine in the UEC process accumulated rapidly after 5 h due to the significant

reduction of contaminants in the leachate.

The variation of chloride ions was also monitored as illustrated in Fig. 6 (b),

and the decreased concentration of chloride ions might be caused by the Cl2

stripping into the air. The rates of decrease of Cl− in the EC process were higher than

those in the UEC process, and higher rates were obtained in NaCl solution than in

the leachate. This implied that the presence of UV light and pollutants could

accelerate the recycle of chloride ions and retard the escaping of Cl2.

Based on the results, the mechanism of the UEC process was proposed as

shown in Fig. 7. The UEC oxidation of the leachate is considered as an

electrochemically assisted UV/chlorine AOP, and the reactions take place not only

in the bulk of solution, but also on the DSA anode. The degradation of organics is

fulfilled by either direct oxidation on the anode or indirect oxidation by the active

species (including HOCl, •OH and •Cl), among which •OH oxidation was the main

approach. The NH3-N removal is attributed to the oxidation by HOCl and •Cl.

14
3.6. Calculation of current efficiency and energy consumption

Current efficiency (CE) and total energy consumption (TEC) are the key

parameters to the field application. The CE and TEC in terms of COD removal are

defined as Eq. (27) and (28), respectively [45,46]:

' (COD) − COD+ ),
CE (%) = × 100% (27)
28800-.
<
1000 78. + 9) :-;.=
TEC (kW h/kg COD) = (28)
(COD) − COD+ )'

here COD0 and CODt are the chemical oxygen demands at times 0 and t (in g

O2/L), respectively, V is the volume of electrolyte (L), F is the Faraday constant

(96487 C/mol), I is the current (A), t is the reaction time (h), U is the voltage (V) and

P is the power of UV light (W).

As can be seen in Fig. 8 (a), the current efficiency decreases gradually with an

increase in COD removal. For example, when the COD removal efficiency increased

to 77.0%, the current efficiency decreased into 17.5%. High proportion of refractory

organics in the biological treated landfill leachate might be responsible for the

relatively low current efficiency. The continuously decreasing current efficiency was

due to the fact that hardly oxidizable products were formed and the side reactions

such as O2 or H2 evolution became significant [10]. The relationship between TEC

and COD removal was displayed in Fig. 8 (b). A 131.8 (kW h/kg COD) of TEC was

needed to remove 62.4% COD, and then the TEC value increased sharply with

further increase in COD removal. This was in agreement with the continuously

decrease of current efficiency and the formation of hardly oxidizable products like

short chain organic acids was responsible for this trend [40]. Therefore, an extension
15
of reaction time could improve the removal efficiency to some extent, but it

decreased the current efficiency and increased the energy consumption accordingly.

Since TEC is related to the operation cost, the balance of increasing removal

efficiency, decreasing current efficiency and increasing TEC should be considered to

select an appropriate treatment time.

3.7. Molecular weight distribution of organics during UEC process

A comparison of the COD distribution among different fractions was performed

using an ultra-filter apparatus. The leachate was first pre-filtered by 0.45 µm

membrane to remove suspended solid and coarse colloids [38], and then was filtered

by 50 kDa, 10kDa and 4kDa membranes, orderly. The result is shown in Fig. 9.

Although the components contributed to COD are mainly distributed in the fractions

smaller than 4 kDa membrane, the portion of 4~50 kDa fractions is as high as 26.3%.

After being treated by UEC process, the COD concentrations of each fraction are

efficiently decreased, the COD content of the fractions smaller than 4 kDa is

significantly decreased to 209.7 mg/L, while the proportion of which was increased

to 80.7%, and all the other fractions were less than 20%. Li et al. [47] reported that

the truly dissolved organic matter was mainly distributed in the < 1 kDa fractions,

and the organic matter with molecular weight less than 500 Da was primarily

volatile fatty acids (VFAs). In contrast, organic matter of medium and high MW

(1~10 kDa and 10~100 kDa) is mostly consisted of humic acids (HA) and fulvic

acids (FA). The results obtained in our study indicated that the fractions with large

molecular weight such as HA and FA were efficiently decomposed into fractions

16
with small molecular weight, and organics with low molecular weight were

significantly degraded into inorganics during UEC process.

3.8. PARAFAC analysis of EEMs

The filtrate passing through different size ultra-filtration membranes was

analysed by excitation emission matrix (EEM) fluorescence spectroscopy before and

after UEC treatment. As shown in Fig. 10, although the EEMs of all the samples

(S1-S8) were already treated by eliminating the scatter peaks and interpolation, some

EEM peaks still overlapped considerably. PARAFAC was then used to decompose

EEMs into various individual fluorescent compounds. The number of components in

the PARAFAC model was obtained from the core consistency diagnostic and

residual analysis. It can be seen from Fig. 11 that three components were appropriate

to fit the PARAFAC model. Fig. 12 showed the EEM contours of components 1−3

and the corresponding excitation and emission loadings. The peaks of component 1

(Ex/Em 250/450 and 360/450) were identified as the typical signals of fulvic-like

substances according to Stedmon et al. (2005) [48], Component 2 was comprised of

two peaks that were similar to the hydrophobic fraction (Ex/Em 241/410) and

hydrophilic fraction (Ex/Em 330/410), which was referred to as humic-like

substances [49]. Component 3 was suggested to be tryptophan-like substances since

it was characterized by two main peaks of Ex/Em 230/345 and 280/345 [50].

The distribution of three components in eight samples was illustrated in Fig. 13.

It can be seen that the fulvic-like and humic-like substances represented by

component 1 and 2 occupied a dominant proportion of dissolved organic matter

17
(80.0%, 80.6%, 80.3% and 81.9%, respectively, in S1−S4). This indicated that the

biological effluent was refractory before UEC process. The peaks of component 1

and 2 were almost disappeared after UEC process, and the corresponding reduction

efficiencies were 96.9% and 98.9%, respectively. It showed the fulvic-like and

humic-like substances were preferentially degraded into the substances without

fluorescence characteristics. These results were consistent to that obtained by MW

distribution analysis. The tryptophan-like substances which occupied a relatively

low proportion were also degraded significantly, but the proportion of component 3

increased after UEC process. It may attribute to the higher reduction efficiencies of

fulvic-like and humic-like substances than those of tryptophan-like substances. Since

tryptophan-like substances are most likely to relate to the biodegradable fraction of

leachate [51], the increased proportion of which indicated that the biodegradability

of the effluent was improved after UEC process.

4. Conclusions

A chloride-based photo-electrochemical process was proposed for the

post-treatment of biorefractory landfill leachate, and it was more promising and

effective than single electrolytic method. At a current density of 60 mA/cm2 and pH

5.0, about 77% of COD and 87% of NH3-N were removed in the UEC process

without addition of electrolyte. Most of NH3-N was converted into N2 as well as a

little NO3-, NO2- and chloramines in the solution. In the UEC process, both the

concentration of active chlorine and the decreasing rate of chloride ions were lower

than those in EC process because of the improved Cl−/Cl2 recycling. The reduction

18
of pollutants was primarily due to indirect oxidation; the in situ electro-generated

active chlorine and in situ photo-generated radical species should be responsible for

the synergetic effect on the landfill leachate treatment. Consequently, the MW

distribution and PARAFAC-EEM analysis indicated that the dominant fulvic-like,

humic-like and tryptophan-like substances in the leachate were mostly transformed

into small organic fractions or inorganic matter.

Acknowledgements

This study was supported by Human Settlements and Environment Commission

of Shenzhen Municipality.

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26
 Figure Captions

Fig. 1 Scheme of the experimental setup for the UEC process.

Fig. 2 Effect of pH on the degradation of (a) COD and (b) NH3-N in the UEC process

(j = 60mA/cm2).

Fig. 3 Effect of current density on the degradation of (a) COD and (b) NH3-N in the

UEC process (pH = 5).

Fig. 4 The removal of (a) COD and (b) NH3-N in different processes (pH = 5, j = 60

mA/cm2).

Fig. 5 Conversion of NH3-N in the UEC process (pH = 5, j = 60 mA/cm2).

Fig. 6 (a) Production of active chlorine and (b) variation of Cl- concentration in

different systems (pH 5, j = 60 mA/cm2).

Fig. 7 Schematic diagram of the mechanism of UEC process for the treatment of

landfill leachate.

Fig. 8 Evolution of (a) current efficiency and (b) energy consumption during the UEC

process (pH 5, current density 60 mA/cm2).

Fig. 9 Relationship between COD and molecular sizes; inset, percentages of the COD

concentration in each fraction.

Fig. 10 Original EEM contour of effluent samples (S1-S8) from different units.

Fig. 11 Core consistency and residual test for determining the components numbers.

Fig. 12 The PACAFAC model output with three components (a-c) and the excitation

and emission loadings (d-f).

Fig. 13 Distribution of relative fluorescence intensities of component 1-3 among

different samples.
Fig. 1
 a
1.0

0.8
CODt/COD0

0.6

0.4
pH 2.0
0.2 pH 5.0
pH 8.9
0.0

0 2 4 6 8
Time (h)

b
1.0

0.8
[NH3-N]t/[NH3-N]0

0.6

0.4
pH 2.0
0.2 pH 5.0
pH 8.9
0.0

0 2 4 6 8
Time (h)

Fig. 2
 a
1.0

CODt/COD0 0.8

0.6

0.4 20 mA/cm2
40 mA/cm2
0.2
60 mA/cm2
0.0 80 mA/cm2

0 2 4 6 8
Time (h)

b
1.0

0.8
[NH3-N]t/[NH3-N]0

0.6

0.4 20 mA/cm2
40 mA/cm2
0.2
60 mA/cm2

0.0 80 mA/cm2

0 2 4 6 8
Time (h)

Fig. 3
 a
1.0

0.8
CODt/COD0

0.6

0.4
UV
0.2
EC
UEC
0.0

0 2 4 6 8
Time (h)

b
1.0

0.8
[NH3-N]t/[NH3-N]0

0.6

0.4
UV
0.2 EC
UEC
0.0

0 2 4 6 8
Time (h)

Fig. 4
 50
NH2Cl
40
NHCl2
30 NCl3
20
10
C/ mg L-1

10

5
NO3-N
0.4
NO2-N
0.2
0.0
0 2 4 6 8
Time (h)

Fig. 5
 Active Chlorine (NaCl solution)/ mg L-1
800 120

Active Chlorine (leachate)/ mg L-1

700
100
600 EC (NaCl solution)
500 UEC (NaCl solution) 80
UEC (leachate)
400 60
EC (leachate)
300
40
200
100 20

0 0
0 2 4 6 8
Time (h)

b
2400
Concentration of Cl-/ mg L-1

2200
2000
1800
1600
UEC (leachate)
1400
UEC (NaCl solution)
1200 EC (leachate)
EC (NaCl solution)
1000
0 2 4 6 8
Time (h)

Fig. 6
Fig. 7
 a 100 100
90 Current efficiency 90

COD removal efficiency (%)

80 COD removal efficiency 80
Current efficiency (%)
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 2 4 6 8
Time (h)

b 250

200
TEC (kWh/kg COD)

150

100

50

30 40 50 60 70 80 90
COD removal (%)

Fig. 8
 900
800 Before UEC
After UEC
700 1.0
0.9
600 0.8
COD (mg/L)

0.7

500 0.6
0.5

Rate
0.4
400 0.3
0.2
300 0.1
0.0
200 <4KDa
Before UEC
4~10KDa
After UEC
10~50KDa >50KDa

100
0
<4KDa 4-10KDa 10-50KDa >50KDa

Fig. 9
Fig. 10
 ×107
100 3.5
Core Consistency
3.0
Sum of squared error

Sum of squared error

Core Consistency(%)
80
2.5
60 2.0
1.5
40
1.0
20
0.5

0 0.0
0 1 2 3 4 5 6 7 8 9

Number of components

Fig. 11
 600
(a) Component 1
550 0.6 (d)
Em
500 0.5 Ex

450 0.4
Em. (nm)

Loadings
400 0.3

350 0.2

300 0.1

250 0.0
200 250 300 350 400 450 500 550 600
200 250 300 350 400 450
Ex. (nm) Wavelengh (nm)

600

550 (b) Component 2

0.5 (e)
Em
500
0.4 Ex
450
Em. (nm)

Loadings
0.3
400
0.2
350

300 0.1

250 0.0
200 250 300 350 400 450 500 550 600
200 250 300 350 400 450 Wavelengh (nm)
Ex. (nm)

600
(c) Component 3 (f)
550
0.4
Em
500
Ex
0.3
450
Em. (nm)

Loadings

400
0.2
350
0.1
300

250 0.0
200 250 300 350 400 450 500 550 600
200 250 300 350 400 450
Ex. (nm) Wavelengh (nm)

Fig. 12
 1800
Component 1
1600 Component 2
1400 Component 3
Fluorescence intensity

1200
1000
800
600
400
200
0
S1 S2 S3 S4 S5 S6 S7 S8

Fig. 13
Table 1 Average characterization of the raw and biologically treated landfill
leachate.

Parameter Raw leachate Biological effluent

COD (mg/L) 14768 1273

NH3-N (mg/L) 1441 750

Cl− (mg/L) 2433 2399

pH 7.9 8.9

43
 Highlights

A novel electrochemically assisted UV/chlorine AOP was used in leachate

treatment.

The optimal conditions were obtained as current density of 60 mA/cm2 and pH

5.0.

Active chlorine and radical species were responsible for the leachate treatment

PARAFAC analysis indicated fluorescence organic matter was efficiently

degraded

44