Accepted Manuscript

Title: Electrolytic and electro-irradiated processes with

diamond anodes for the oxidation of persistent pollutants
and disinfection of urban treated wastewater
Author: Salvador Cotillas Mara J. Martn de Vidales Javier
Llanos Cristina Saez Pablo Canizares Manuel A. Rodrigo
PI
I:
D
OI
To appear in:

S0304-3894(16)30050-4
http://dx.doi.org/doi:10.1016/j.jhazmat.2016.01.0
50 HAZMAT 17402

Received date:
Revised date:
Accepted date:

13-10-2015
11-1-2016
19-1-2016

Journal of Hazardous Materials

ticle as: Salvador Cotillas, Maria J.Martin de Vidales, Javier

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Llanos,
Cristina Saez, Pablo Canizares, Manuel A.Rodrigo, Electrolytic and
electro- irradiated processes with diamond anodes for the oxidation of persistent
pollutants and disinfection of urban treated wastewater, Journal of Hazardous
Materials http://dx.doi.org/10.1016/j.jhazmat.2016.01.050
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1
2

Electrolytic and electro-irradiated processes with

diamond
anodes for the oxidation of persistent pollutants and
disinfection
3

of urban treated wastewater

Salvador Cotillas, Mara J. Martn de Vidales, Javier Llanos, Cristina Sez,

Pablo

Caizares, Manuel A. Rodrigo*

Department of Chemical Engineering. Faculty of Chemical Sciences &

Technology.

Universidad de Castilla-La Mancha. Edificio E. Costa. Campus

Universitario s/n 13071

Ciudad Real. Spain

Graphical abstract

10

11
12
1

Highlights

13

Coupling UV with electrolysis does not always result in synergism

for the removal

14

15

of organics

Oxidation state seems to be important parameter to foresee the

synergism of photo-

16

17

electrolysis

18

For high ThOD/TOC ratios, UV irradiation improves results attained

by electrolysis

19

Photo-electrolysis improves the disinfection as compared to the

additive effect of
20

both single technologies.

UV irradiation contributes to prevent the formation of hazardous
species during

21

22

electrolysis

23

Abstract

24

This paper analyzes the advantages and drawbacks of the combination of UV

irradiation with

25

electrolysis with the aim to give insight about the feasibility of the
application of this

26

technology for the reclaiming of conventionally-treated wastewater. The

oxidation of

27

synthetic solutions containing five selected model complex pollutants has

been compared,

28

showing that UV irradiation improves the results of electrolysis for

progesterone, metoprolol

29

and caffeine and deteriorates the performance for the degradation of

sulfamethoxazole and

30

dimethyl-phthalate. Differences observed becomes lower when

mineralization is compared

31

showing that the effects of UV irradiation are diluted when a mixture of

species is oxidized.

32

Results suggest that high ThOD/TOC (Theoretical oxygen demand/Total

organic carbon)

33

ratios improve the synergistic coupling of technologies while low values

lead to a clear

34

antagonistic effect. Because during oxidation progress this ratio is decreased,

the observed
2

35

effect on mineralization is much lower than in the oxidation of the raw

molecule. Opposite

36

to this low effect on the oxidation of organics, the improvement in the

performance of the

37

disinfection by coupling UV to electrolysis is much clearer. In addition,

UV irradiation

38

modifies significantly the chlorine speciation and helps to prevent the

formation of hazardous

39

species such as chlorate and perchlorate during the electrochemical

processes.

40
41

Keywords

42

Electrolysis, UV irradiation, photo-electrolysis, photolysis, disinfection,

reclaiming

43
44 (*) Author to whom all correspondence should be addressed:

manuel.rodrigo@uclm.es
45
3

46

1. Introduction

47

Conductive Diamond Electrochemical Oxidation (CDEO) has been proven

efficient for the

48

treatment of different types of wastewater [1-9]. According to recent

literature [10-16],

49

process efficiency seems to be improved by coupling the electrochemical

process to other

50

advanced oxidation processes such as ultraviolet (UV) irradiation, because of

the rise in the

51

generation of oxidizing agents and their better activation.

52

In this context, the role of peroxocompounds seems to be very important in

order to fully

53

understand the efficiency of the treatment. It is well-known that the

electrochemical oxidation

54

of wastewater with high concentration of sulfate leads to the formation of

peroxosulfate [17,

55

18] by the direct oxidation of the anion on the anode surface (Eq. 1),
followed by the

56

recombination of the free sulfate radicals (Eq. 2).

57 HSO4 (SO4 ) + H

- +

[1]
- - 2-

58 (SO4 ) + (SO4 ) S2O8

[2]
59

In addition to this direct electrolytic mechanism, it is known that conductivediamond anodes

60

promotes the production of free hydroxyl radicals at high current densities

(Eq. 3). These

61

species have a huge oxidation capability and they can react with sulfate
anions (Eqs. 4-5)

62

forming sulfate radicals [17], which can be recombined afterwards, forming

peroxodisulfate

63

(Eq. 2) and/or peroxomonosulfate anions (Eq. 5).

64 H2O OH + H+ + e- [3]
65 HSO4- + OH (SO4-) + H2O [4]
4

66 (SO )

+ OH HSO5
[5]
4

67

Similar reactivity to that observed for sulfate anions is reported for other
species such as

68

phosphates and carbonates, typically contained in urban wastewater. This

fact explains the

69

formation in the reaction media of peroxophosphates and peroxocarbonates

[19-21] during

70

electrolysis with diamond anodes. These peroxocompounds also coexist

during electrolysis

71

with hydrogen peroxide (Eq. 6) and ozone (Eq. 7) produced by the

recombination of hydroxyl

72

radicals or by the reaction of this radical with oxygen.

73 2 OH H2O2 [6]
74 O2 + 2 OH O3 + H2O [7]
75

In addition to all these oxidants, oxidation of chlorides contained in

wastewater leads to the

76

formation of hypochlorite, chlorate and perchlorate during electrolysis [22].

Opposite to the

77

formation of peroxocompounds, occurrence of these species is not always

considered to be

78

positive and often it is even aimed to be prevented.

79

Consequently, in actual wastewater with a high content of different anions,

such as urban

80

wastewater, a cocktail of different oxidants species is expected to be

formed during

81

electrolyses. Recent studies have shown that the efficiency of in-situ

electrogenerated

82

oxidants is much higher than that obtained when commercial oxidants are
added [23] and the

83

differences may only be explained by some sort of activation of the oxidants

added/produced.

84

In this context, UV irradiation is considered as a potential activation

technology [13-15, 24-

85

27] because it favors the formation of radical species by

decomposition of more stable

86

oxidants (Eq. 8-10).

87 S2O

2-

(SO -)

[8]
5

88

H2O2 h 2 OH

[9]
89

[10]

H2O2 + O3

2 OH + O2

90

This activation enhances the reaction rate of the process and, as an

example, the radical

91

sulfate reacts typically 103-105 times faster than the anion peroxosulfate [28].
Same behavior

92

is expected for peroxophosphates and peroxocarbonates. Likewise, UV

irradiation also

93

favors the activation of hypochlorite to form chlorine radical and oxygen

(Eq. 11) [29-31].

94

ClO-

(Cl) + (O-) [11]

95

It is important to note that, opposite to single electrolytic process, the effect

of these radicals

96

(such as sulfate and chlorine) can be extended to the bulk in a photoelectrolytic process

97

because, in spite of their short lifetime, radicals are produced not on the
anodic surface but

98

in the bulk by decomposition of more stable oxidants [14, 15]. This fact
can minimize the

99

well-known negative effect of the mass transfer limitations in lowconcentrated systems.

100

Several authors have studied the effect of the coupling of UV irradiation on

chemical and

101

electrochemical processes for the treatment of wastewater by photo-chemical

oxidation [16],

102

photo-electro catalysis processes [32-34], processes based on Fentons

reaction chemistry

103

[35-38] or photo-electrolysis [39, 40]. In these studies, interesting results

were obtained,

104

observing significant improvements on the process efficiency for the

removal of different

105

organic compounds, which often may be explained taking into account

the role of the

106

different types of oxidants produced. At this point, it is also important to

take in mind that

107

combination of UV irradiation and electrolysis has not only been evaluated

for the oxidation

108

of organics but also in disinfection[41][42]. The results obtained showed that

the combination

109

of both techniques allowed attaining a complete disinfection, avoiding the

bacterial regrowth.
6

110

With this background, the goal of this work is to evaluate the effect
of coupling UV

111

irradiation and CDEO for the treatment of synthetic and actual

wastewater polluted with

112

persistent pollutants (metoprolol, progesterone, sulfamethoxazole,

dimethyl-phthalate and

113

caffeine) and for the disinfection of treated wastewater in only one stage,
trying to evaluate

114

the effect of radical species on the performance of the combined treatment

and to clarify the

115

conceptual model proposed in Figure 1 which summarizes the main

reactions expected

116

(related to oxidants production and activation).

117

At this point, it is important to note that, when the effluent of the

secondary treatment of a

127

118

municipal wastewater treatment plant is treated by electrochemical

oxidation for the

119

degradation of persistent pollutants looking for wastewater reclamation,

both removal of

120

organics and disinfection take place simultaneously and hence, the

electrochemical oxidation

121

of persistent pollutants from a real wastewater entails the disinfection

process. This could

122

open up the way for an efficient reclamation of urban wastewater. In

this context, this

123

manuscript looks for the clarification of the mechanisms of photoelectrochemical oxidation

124

of reclaimed wastewater trying to elucidate if the irradiation of UV can lead

to improvements

125

in the efficiency of the treatment.

126

Material and Methods

Chemicals
128

Progesterone/2-hydroxypropyl--cyclodextrin, sulfamethoxazole,
metoprolol tartrate salt

129

(2:1), caffeine and dymethylphtalate (analytical grade > 99% purity)

were supplied by

130

Sigma-Aldrich Laborchemikalien GmbH (Steinheim, Germany). Anhydrous

sodium sulfate,

131

used as supporting electrolyte, was analytical grade purchased from Fluka.

Sulfuric acid and
7

132

sodium hydroxide used to adjust the solution pH were analytical grade

and supplied by

135

133

Panreac Qumica S.A. (Barcelona, Spain). High-purity water was obtained

from a Millipore

134

Milli-Q system, with resistivity > 18 M cm at 25 C.

Target effluents
136

Synthetic wastewater was prepared with high-purity water, 100 mg dm -3

of the persistent

137

organic pollutant and 5000 mg dm-3 of sodium sulfate as supporting

electrolyte. On the other

138

hand, actual wastewater was collected at the secondary clarifiers of

the Wastewater

139

Treatment Plant (WWTP) of Ciudad Real (Spain). The influent of this

Municipal WWTP is

140

domestic wastewater without a significant industrial contribution. The

chemical and

141

microbiological composition characteristics of the samples used in this

work are shown in

142

Table 1. It is important to note the low concentration of organic mass

(TOC 13 mg dm-3)

143

and the relatively high concentration of chloride and sulfate, which were
above 110 and 120

144

mg dm-3, respectively. In addition, to study the removal of persistent organic

pollutants in

145

this wastewater, 100 mg dm-3 of caffeine was added to this effluent.

146

147

Experimental set-up

148

Bench scale electrolysis, photolysis and photo-electrolysis were carried

out in a single

149

compartment electrochemical cell equipped with a Boron Doped Diamond

(BDD) plate as

150

anode (surface area: 78 cm2) and a perforated Stainless Steel (SS) plate as
cathode (diameter:

151

100 mm). The electrode gap between both electrodes was 6 mm and the
internal volume of

152

the cell was 60 ml. The applied current intensity was provided by a Delta
Electronika ES030-

153

10 power supply (0-30 V; 0-10 A). For the photolysis and photo-electrolysis
processes, a UV
8

154

lamp VL-215MC (low-pressure Hg vapor lamp) with 254 mm was used to

irradiate 4 W

155

directly to the quartz cover. A detail of the electrochemical cell has been
described by the

156

authors [10].

157

Wastewater was stored in a glass tank with a total capacity of 5 dm 3. The

system operates in

158

discontinuous mode with a peristaltic pump (JP Selecta Percom N-M328). A

heat exchanger

159

with a thermostatized bath (Digiterm 100, JP Selecta, Barcelona, Spain) was

used to maintain

160

the temperature. The desired set point was 25C.

161

Experimental procedure

162

All the tests (bench scale: 1.0-4.0 dm3) were carried out under
galvanostatic mode. The

163

current density applied was 0.13-300 A m-2 for bench scale electrolysis.
Prior to use in

164

electrochemical assays, the electrode was polarized for 10 min with 5,000
mg dm-3 Na2SO4

165

(pH: 2) at 300 A m-2 to remove any kind of impurity from its surface.
Operation conditions

166

of every experiment are clearly described in the R&D section.

167

The sample volume was 100 cm3 and 20 cm3 for the experiments of
disinfection and

168

electrochemical oxidation, respectively. The measure of E. coli and

disinfectant species (free

169

and combined chlorine compounds) were carried out immediately. In this

context, it is not

170

necessary the addition of chemical reagents to stop the reaction between

microorganisms and

171

disinfectants.

172

Analytical techniques

173

E. coli was determined by most probable number (MPN) technique [43]

(confidence level:

174

95 %). This method consists of an incubation at 44C during 24 hours.

The samples are

175

diluted 1:10, 1:100 and 1:1000 (multiple tube fermentation: 5 tubes at

each dilution).
9
-+

176

Inorganic ions (Cl-, ClO-, ClO3-, ClO4-, NO2-, NO3 , NH4 ) were
measured using ion

177

chromatography (Shimadzu LC-20A). A shodex IC I-524A column was used

to determine

178

the anions (eluent: 2.5 mM phtalic acid at pH 4.0; flow rate: 1 ml min-1) and
a shodex IC YK-

179

421 column was used to analyse the cations (eluent: 5.0 mM tartaric acid, 1.0
mM dipicolinic

180

acid and 24.3 mM boric acid; flow rate: 1 ml min -1) (concentration accuracy:
0.5 %). The

181

measurement of hypochlorite was carried out by titration because the peak of

this compound

182

interferes with that of chloride. A solution of As2O3 in 2.0 M NaOH was

used to determine

183

the hypochlorite concentration [44, 45]. Inorganic chloramines were

determined following

184

the DPD standard method described in literature [43]. The Total Organic
Carbon (TOC)

185

concentration was monitored using a Multi N/C 3100 Analytik Jena analyser
(standard error

186

< 2 %). Measurements of pH and conductivity were carried out with an

InoLab WTW pH-

187

meter and a GLP 31 Crison conductimeter, respectively. The concentrations

of the persistent

188

pollutants were quantified by HPLC (Agilent 1100 series). The detection

wavelength used to

189

detect POPs depends on the compound studied (sulfamethoxazole: 245 nm,

metoprolol: 223

190

nm, progesterone: 248 nm, caffeine: 205 nm, dimethyl-phthalate: 274 nm).
For the HPLC

191

measurements, the column temperature was set to 25 C and the injection

volume was set to

192

50 L. The analytical column used was a Phenomenex Gemini 5 m C18

column, and the

193

solvent solution was a mixture of 25 mM of formic acid and acetonitrile

(linear gradient

194

chromatographic elution was performed from 10 to 100% acetonitrile in 40

min) (detection

195

limit: 0.01 mg dm-3). Samples extracted from electrolysed solutions were

filtered with 0.20

196

m Nylon filters before analysis.

197

Synergy coefficient
10

198

The synergy coefficient (%) is used to evaluate the effect of the

coupling of different

199

processes. For the photo-electrolysis process (studied in this work), it

can be calculated

200

according to Eq. 12 where k is the kinetic constant calculated for the

different studied

201

processes (electrolysis, photolysis and photo-electrolysis).

202

Synergy coefficient (%)=

203
kphoto-electro -kphoto -kelectro kphoto+kelectro

100 [12]
204

Results and Discussion

205

Figure 2 compares the removal of metoprolol and progesterone and

their mineralization

206

during the photolysis, electrolysis and photo-electrolysis of synthetic

solutions containing

207

5000 mg dm-3 of sodium sulfate in addition to 100 mg dm-3 of the

pollutant carried out to

208

evaluate the effects of UV irradiation on the performance of the

electrolysis of organics in

209

low concentration solutions.

210

As it can be observed, electrolysis is more efficient than photolysis at 254 nm

in the removal

211

of the raw molecule and this trend becomes even more important in
the case
of

212

mineralization, because for the two compounds tested, photolysis is

completely inefficient in

213

the complete transformation of the two molecules into carbon dioxide.

214

The combined effect of the UV irradiation and electrolysis applied

simultaneously is more

215

efficient that the addition of the two single processes and, in comparison
with electrolysis,

216

metoprolol is depleted in a 54.35% lower period and mineralized in a

59.26% shorter time,

217

while for progesterone, the saving in the electrolysis time (and hence in
the current charge

218

applied) is 42.31 and 26.92%, respectively.

11

219

Data of Figure 2 can be fitted to a pseudo-first order kinetic [46, 47] in order
to calculate the

220

kinetic constant of each process and the values obtained can be used to
calculate the synergy

221

coefficients according to Eq. 12. Results show that photo-electrolysis of

metoprolol entails a

222

synergy effect of 158.95 and 77.23% for pollutant removal and

mineralization, respectively,

223

and of 132.79 and 4.15% for progesterone. Hence, there is clearly a

synergistic combination

224

of processes and improved performance cannot only be explained in terms of

the addition of

225

the same processes that occurs during the electrolytic and photolytic
processes but by newer

226

and interesting processes resulting from their combination.

227

At this point, it is worth to take in mind that in the synthetic supporting

media used in both

228

synthetic wastewater solutions, only sulfate may produce oxidants (in

addition to water, see

229

Eq. 1-5). Therefore, it is remarkable to remind persulfate formation with

anodes consisting

230

on coatings of conductive diamond, has been well studied in previous

works [17, 18]. As

231

happens with other peroxocompounds such as peroxophosphates

[17, 23, 48] and

232

peroxocarbonates [49], the peroxo group makes the peroxosulfate a very

powerful oxidant

233

from the view point of thermodynamics (with a standard reduction

potential of 2.07 V vs

234

0.17 V respect to standard hydrogen electrode, SHE). However, this oxidant

is not kinetically

235

very efficient at room temperature. For this reason a controversy appears

when its role in the

236

electrolysis of organics with diamond anode is discussed at the light of

the
present

237

knowledge, because its effect seems to be much important than that can be
obtained by the

238

single chemical reaction of organics and this oxidant in a tank cell [23].
As in the case of

239

peroxodiphosphate, this can be easily explained in terms of the activation of

the oxidants, in

240

particular of peroxodisulfate with the formation of radicals (SO -). This

activation can be

241

attained either by the combination with another oxidant such as OH in the

nearness to the

12

242

surface of the anode, H2O2 or even O3. Both hydrogen peroxide and ozone
have been detected

243

in the water undergoing electrolysis with diamond anodes and their efficient
production has

244

been explained by the action of the OH radicals on water or oxygen [5052].

245

In addition to chemical activation [53], a very interesting way to activate

peroxocompounds

246

is by UV irradiation, such as Eq. 8. This method has a great advantage.

Radicals are not only

247

formed on the surface of the diamond coating but on the whole electrolyte
volume, making

248

the process being much more efficient because mass transport, the main
limitation of this

249

process is overcome.

250

Hence, this attack of radicals (SO4-) to organics in the whole bulk volume
can explain the

251

much higher efficiency found in the treatment of metoprolol and

progesterone synthetic

252

solutions. Radical oxidation of organics with persulfate has been previously

studied by many

253

authors [54-58] and main conclusions are that the activation of persulfate
to carry out the

254

radical oxidation of organic compounds in wastewater allows a removal

of the pollutant

255

higher than 80% in all cases, independently on the activation method (but
with an significant

256

influence of the operation conditions) being very efficient in the breakage

of the aromatic

257

rings and less efficient in the mineralization of carboxylic acids.

258

Figure 3 shows the results of the three evaluated technologies in the

treatment of plasticizer

259

dimethyl-phthalate and antibiotic sulfamethoxazole. In this case results

are completely

260

different to those observed in Figure 2 because there is a clearer effect of UV

irradiation on

261

the degradation of the raw molecules and combination of UV irradiation and

electrolysis does

262

not result in a faster depletion of the molecule but even in a slower

removal rate. Anyhow,

263

almost no effect on the mineralization rate is observed by the irradiation of

UV light during
13

264

electrolysis of the electrolyte. Again, results have to be explained in terms

of the chemistry

265

of sulfate radicals, because this is the only species that can be produced
in the combined

266

process and not in the single ones.

267

According to the literature [59, 60], (SO -) radicals attack easily the
aromatic ring and the

268

insaturations of the aliphatic carbon chains and are not very efficient in
the oxidation of

269

carboxylic acids. Last stages in the oxidation of organics involve formation

and oxidation of

270

these carboxylic acids and the main difference between the species shown in
Figure 2 and 3

271

is the mean oxidation of carbon, which is clearly higher for the species
shown in the second

272

figure, and hence closer to the expected values for carboxylic acid
compounds. Anyhow,

273

both electrolyses and photo-electrolyses can cope with the complete

oxidation of pollutants

274

to carbon dioxide while photolysis can only produce limited and soft
oxidation for some of

275

the species. The improved removal of aromatics as compared to carboxylic

acids has been

276

previously described by Vicente et al., Guo et al. and Pardo et al. [59-61].

277

These experimental data can be fit to a pseudo-first order kinetic and to use
these values to

278

calculate the synergy coefficient for the experiments of degradation of

sulfamethoxazole and

279

dimethyl phthalate by photo-electrolysis process. Results show that for

sulfamethoxazole

280

there is a synergy coefficient of -16.72 and -0.63% (antagonism) in

terms of compound

281

removal and mineralization, respectively, and -33.67 and -10.39% for

dimethyl phthalate.

282

Figure 4 focuses on caffeine and compares results obtained in the

treatment of real

283

wastewater intensified with caffeine (100 mg dm-3 of caffeine were added

to a secondary

284

treatment effluent of a Municipal WWTP) and synthetic solutions.

14

285

It can be observed a similar behavior although differences are less clearly

observed in the

286

real wastewater, perhaps because of the more complex matrix of inorganic

ions, which may

287

result in a more complex mixture of oxidants.

288

Real wastewater contains chloride (approx. 150 mg dm-3), nitrates (approx.

5 mg dm-3) and

289

sulfates (approx. 250 mg dm-3). Lower concentration of sulfate ions and the
very important

290

role expected for chlorinated intermediates can help to understand these

smaller differences.

291

Thus, in addition to the well-known direct electrolysis of chlorides to

yield chlorates,

292

electrolysis with diamond coatings can produce other highly oxidized

chlorine species by the

293

action of hydroxyl radicals such as it is pointed out in Eqs. 13 to 18.

294 2 Cl Cl2 + 2e [13]

295 Cl2 + H2O HClO + Cl + H [14]

-

296 HClO ClO- + H+ [15]

-

297 ClO + OH ClO2 + H + e [16]

2

298

ClO

ClO

+ OH ClO

+ H+
+ e[17]
3
299
4

+ OH ClO

+ H+
+ e[18]
300

Anyhow, general trends are the same and they clearly indicate enhanced
removal of caffeine

301

but not of intermediates with a very low influence on the mineralization rate.
As commented

302

before, experimental results were fitted to first order kinetics, taking

into account that

303

electrolysis is known to fit well this type of processes because this is the
expected kinetic for

304

mass-transport controlled processes and also for mediated electrolytic

processes [62]. As it

305

can be seen in Figure 5, kinetic constants for the depletion of the raw
species tested ranged
15

from 0.4 to 1.3 h-1, while for the complete mineralization they ranged in
between 0.2 and 0.8

306

307 h-1.
308

Lower values obtained for the mineralization as compared to the

oxidation of the raw

309

pollutants clearly indicate that oxidation of highly oxidized species like the
carboxylic acids

310

is much slower than that of aromatic species. It is important to take in mind

that values are

311

compared in a relative way, because values obtained for k in the fitting

procedure have to be

312

related to the current intensity and should not be compared to other in the
literature unless

313

they were obtained just at the same conditions (300 A m -2; T: 25C). The
higher the ratio, the

314

lower is the oxidation state of carbon. Clearly it can be seen a relationship.

For electrolysis,

315

the higher the ThOD/TOC ratio, the lower is the oxidation and mineralization
rate. For photo-

316

electrolysis, there is a clear increase in the k with the ratio ThOD/TOC,

meaning that highly

317

oxidized carbon is most easily oxidized by (SO4-) radicals as the lowly

oxidized carbon.

318

Anyhow, values for photo-electrolysis at high ThOD/TOC values are

clearly over those

319

obtained by electrolysis. This also explains the slightly higher value of

kmineralization in photo-

320

electrochemical processes.

321

Figure 6 shows the effect of the ThOD/TOC ratio on the synergy coefficient.
It is important

322

to note that not only carbon is oxidized (that explains the dispersion of data),
but it is possible

323

to observe a direct relation between synergism and a difficult

mineralization. As it can be

324

observed, the higher the ratio, the higher is the synergy. For low
ThOD/TOC ratios (highly

325

oxidized carbon) not synergy but antagonisms are observed.

326

Disinfection seems to be a more important process for the combination of

UV irradiation and

327

electrolysis, because opposite to the mineralization of organics (as it has

been shown in
16

328

Figure 2, 3 and 4), homogeneous photolytic processes are known to be very

efficient in the

329

killing of microorganisms. Thus, Figure 7 shows the effect of the irradiation

dose (expressed

330

in W m-3) on the UV disinfection of secondarily treated wastewater (Figure

7a).

331

As expected the higher the specific power irradiated, the faster is the
disinfection. Results are

332

fitted to a first order kinetic and as it can be seen in the part (b) of the
figure, the kinetic

333

constant depends linearly on the specific power irradiated.

334

Combination of electrolysis and photolysis should be carried out in a

different way in this

335

case, because during electrolysis with diamond, the production of highly

undesirable species

336

such as chlorates and perchlorates are formed [63, 64] and their
occurrence prevents its

337

application. The formation of these species could be avoided by applying

very low current

338

densities, and thus, the combined process is not an UV irradiation assisted

electrodisinfection,

339

but an electrochemically assisted UV disinfection.

340

Figure 8 compares the results of the single electrolysis, the UV disinfection

and the combined

341

process. As it can be observed, performance of the combined process

overcome the additive

342

effects of the two single disinfection processes, although in this case the
synergy coefficient

343

reach a value of only 10%. This clearly advantage, as well as the lower
energy consumed by

344

the combined process as compared to single UV disinfection (1.22 vs. 3.87

kWh m-3), show

345

a promising technology, worth to be studied.

346

An additional interesting point is the chlorine speciation. Figure 9

compares the species

347

produced in the electrolytic and photo-electrolytic disinfection.

348
17

349

As it can be seen, hypochlorite is the only oxochlorinated anion and

no chlorates or

350

perchlorates are formed. In addition, maximum concentration of hypochlorite

is lower in the

351

combined process. However, chloramines concentration is slightly higher in

the case of the

352

combined technology. As already known, chloramines are very important

disinfectants which

353

can be well-combined with hypochlorite and lead to a broader spectra of

microorganisms.

354

Regarding the formation of other disinfectant species, the presence of

persulfate was

355

discarded during the process due to the low current densities applied. Hence,
the generation

356

of sulfate radicals, from the photo-activation of persulfate, does not

take place in the

357

electrodisinfection process.

358

Thus, UV irradiation coupled to electrolytic processes allows improving

the degradation of

359

raw pollutants and disinfection process. However, there is a low influence of

this irradiation

360

on the degradation of highly oxidized compounds (such as carboxylic

acids), usually less

361

dangerous. These results suggest worthwhile to conduct further studies on

the use of UV

362

radiation on the treatment of wastewater polluted with

microorganisms and organic

363

compounds in different oxidation state, in order to look for the application of

electrolysis in

364

Municipal WWTPs.

365

Conclusions

366

From this work, the following conclusions can be drawn regarding the
combination of UV

367

irradiation and electrolysis with diamond for the treatment of secondary

effluents for

368

reclaiming:
18

UV irradiation during the electrolysis of organic compounds does not

always lead to

369

370

an improvement in the performance of the treatment as compared to

results obtained

371

in the single electrolysis.

The mean oxidation state of the molecule (quantified as ThOD/TOC
ratio) seems to

372

373

be a good parameter to foresee the synergistic/antagonistic behavior

of UV irradiation

374

on electrolysis. The higher the ratio, the higher is the improvement

obtained in the

375

oxidation by applying UV irradiation to the electrolysis.

As the mean oxidation state decreases during the electrolysis (and it
is particularly

376

377

low in the last stages corresponding to the oxidation of carboxylic

acids), effect of

378

UV irradiation on mineralization is low.

Combination of UV irradiation and electrolysis is more efficient
that the additive

379

384

380

effect of both single processes. UV irradiation contributes

to minimize the

381

concentration of hypochlorite available in the system and it has a

positive effect on

382

the prevention of the formation of the undesirable and

hazardous chlorate and

383

perchlorates during the electrodisinfection process.

Acknowledgements

385

The authors acknowledge funding support from the EU, Spanish

Government and JCCM

386

(Junta de Comunidades de Castilla-La Mancha) through the MINECO

Project CTM2013-

387

45612-R, PEII-2014-039-P, FEDER 2007-2013 PP201010 (Planta Piloto

de Estacin de

388

Estacin de Regeneracin de Aguas Depuradas) and INNOCAMPUS.

389

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580

581

582 Figure 1. Mechanisms expected for the photo-electrolytic reclamation of

secondarily treated
583 wastewater.
24

(a)

(b)
100 100

TOC removal / % Pollutant removal / %

10 10

1 1

0.1

591
0 100 200 300 400 500 600

Time / min
0.1
0 100 200 300 400 500 600

Time / min

592 Figure 2. Evolution of pollutant (a) and TOC (b) removal with the time during

UV irradiation
593 (, ), electrolysis (,) and photo-electrolysis (,) of metoprolol

(square symbols) and

-3
594 progesterone (circle symbols) synthetic wastewater. C 0: 100 mg dm ; j: 30 mA

cm-2; V: 1
3

-3

595 dm ; T: 25C; electrolyte solution: 5000 mg dm Na2SO4; anode: BDD;

cathode: SS; UV254

596

nm:

4 W.
25

(a)

(b)

TOC removal / % Pollutant removal / %

100 100

10 10

1 1

0.1

603
0 100 200 300 400 500 600

Time / min
0.1
0 100 200 300 400 500 600

Time / min

604 Figure 3. Evolution of pollutant (a) and TOC (b) removal with the time during

UV irradiation
605 (, ), electrolysis (,) and photo-electrolysis (,) of

sulfamethoxazole (diamond
606 symbols) and dimethyl phthalate (square symbols) synthetic wastewater. C0:

100 mg dm-3; j:
-2

-3

607 30 mA cm ; V: 1 dm ; T: 25C; electrolyte solution: 5000 mg dm Na2SO4;

anode: BDD;
608 cathode: SS; UV254 nm: 4 W.
609

610
611
612
613
26

(a)

(b)

TOC removal / % Pollutant removal / %

100 100

10 10

1 1

0.1

614
0 100 200 300 400 500 600

Time / min
0.1
0 100 200 300 400 500 600

Time / min

615

Figure 4. Electrolysis and photo-electrolysis of synthetic solutions of

caffeine and of actual

616

wastewater intensified with caffeine. () photolysis of synthetic solution,

() electrolysis

617

of synthetic solution, () photo-electrolysis of synthetic solution, ()

electrolysis of actual

618

619

wastewater and () photo-electrolysis of actual wastewater. C 0: 100 mg dm3

; j: 30 mA cm

; V: 1 dm ; T: 25C; electrolyte solution in synthetic wastewater: 5000

mg dm
620

-3

Na2SO4;

anode: BDD; cathode: SS; UV254 nm: 4 W.

621
622
623
624
27

(a)

(b)

2 1.2
1.8
1

1.6

kpollutant / h-1

1.4

1.2

kTOC / h-1

0.8

1 0.6
0.8
0.6
0.4
0.4
0.2
0.2
0

625
2.5 2.7 2.9 3.1 3.3 3.5 3.7

ThOD / TOC
0
2.5 2.7 2.9 3.1 3.3 3.5 3.7

ThOD / TOC

626 Figure 5. Plot of the kinetic constants vs. the ration ThOD/TOC (Theoretical

Oxygen
627 Demand/Total Organic Carbon), in terms of pollutant removal (a) and

mineralization (b), for

628 the different evaluated pollutants in synthetic wastewater. () photo-

electrolysis and ()
-3
-2
3
629 electrolysis. C0: 100 mg dm ; j: 30 mA cm ; V: 1 dm ; T: 25C; electrolyte

solution: 5000

-3

630 mg dm Na2SO4; anode: BDD; cathode: SS; UV254 nm: 4 W.

28

150

Synergy coefficient / %

100

2 2.5 3 3.5 4

ThOD / TOC

637 Figure 6. Effect of the pollutant ThOD/TOC ratio on the observed

synergism/antagonism of
638 UV irradiation on electrolytic processes in terms of pollutant removal () and

mineralization
639 (). C0: 100 mg dm-3; j: 30 mA cm-2; V: 1 dm3; T: 25C; electrolyte solution

in synthetic
640 wastewater: 5000 mg dm-3 Na2SO4; anode: BDD; cathode: SS; UV254 nm: 4 W.

641
642
643
644
645

646
29

(a)

(b)
1 0.2

k / min-1 [E. coli] / [E. coli]0

0.1 0.15

0.01 0.1

0.001 0.05

0.0001

647
0 50 100 150 200

Time / min
0
0 500 1000 1500 2000 2500

UV dose / W m-3

648 Figure 7. Disinfection of secondarily - treated wastewater using UV

irradiation. (a) Influence

649 of the UV irradiation dose. () 2000 W m-3; () 1000 W m-3; () 500 W m-3;

() 0 W m-3.
-1
-2
650 (b) Elimination rate constants. [E. coli]0: 5400 CFU 100 ml ; j: 0 mA cm ; V:

4; 2; 1 dm3;
651 UV254 nm: 4 W.
652
653
654
655
656
30

k = 1.4 h-1

k = 2.9 h-1

k = 4.6 h-1
1

[E. coli] / [E. coli]0

0.1

0.01

0.001

0.0001

657
0 50 100 150 200

Time / min

658 Figure 8. Disinfection of secondarily - treated wastewater using electrolysis

(), photolysis
-1
659 () and photo-electrolysis (). [E. coli]0: 16,000; 5,400; 9,100 CFU 100 ml ;

j: 0.13 mA
-2
3
660 cm ; V: 4 dm ; T: 25C; anode: BDD; cathode: SS; UV254 nm: 4 W.

661
662
663
664
665
31

(a)

(b)

0.05 0.01

Cl-NHxClx / mmol dm-3

-3

ClOx / mmol dm

0.04 0.008

0.03 0.006

0.02 0.004

0.01 0.002

666
0 50 100 150 200

Time / min
0
0 50 100 150 200

Time / min

667 Figure 9. Chlorine speciation during the electrolysis (filled symbols) and photo-electrolysis
668 (empty symbols) of actual wastewater (discontinuous process). a) oxochloranions ( ClO-;

- - -2 3

669 ClO3 ; ClO4 ); b) chloramines ( NH2Cl; NHCl2 ; NCl3). j: 0.13 mA cm

; V: 4 dm ;
670 T: 25C; anode: BDD; cathode: SS; UV254 nm: 4 W.

671 Table 1. Characteristics of secondary treatment effluent.

Parameter

Value

Cl- (mg Cl dm-3)

110-180

NO3- (mg N dm-3)

3-12

SO 42- (mg S dm-3)

120-400

NH 4+ (mg N dm-3)

10-28

Turbidity (NTU)

10-11

TSS (mg dm-3)

7-10

TOC (mg dm-3)

12-14

COD (mg O2 dm-3)

35-42

E. coli (MPN 100 ml-1)

5,400-9,100

672
32