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Journal of Hazardous Materials 279 (2014) 322329

Contents lists available at ScienceDirect

Journal ofHazardous Materials

j ournal homepage: www.elsevier .com/ locate / jhazmat

New approach to solar photo-Fenton operation. Raceway ponds astertiary treatment technology

Irene Carra a,b, Lucas Santos-Juanes a,b, Francisco Gabriel Acin Fernndeza,Sixto Malato b,c,Jos Antonio Snchez Prez a,b,

a Department of Chemical Engineering, University of Almera, 04120,Almera, Spainb CIESOL, Joint Centre of theUniversity of Almera-CIEMAT, 04120,Almera, Spainc Plataforma Solar de Almera (CIEMAT), 04200, Tabernas, Almera, Spain

h i g h l i g h t s

Raceway ponds are used for the first

time as photo-Fenton reactors. Raceway ponds are effective and have

high treatment capacity (48 mg/h m2

for 360 L). The highest treatment capacity

occurs with 5.5 mg Fe/L and 15cm

liquid depth. Low iron concentrations are enough

to oxidise the pesticide mixture. Raceway ponds are a simple and low-

cost alternative for micropollutant

removal.

g r a p h i c a l a b s t r a c t

a r t i c l e i n f o

Article history:

Received 28 May 2014

Received in revised form 8 July 2014

Accepted 9 July 2014

Available online 17 July 2014

Keywords:

Acetamiprid

Thiabendazol

Photoreactor

Treatment capacity

Micropollutant degradation

a b s t r a c t

The photo-Fenton process has proven its efficiency in the removal ofmicropollutants. However, the high

costs usually associated with it prevent a spread ofthis technology. An important factor affecting costs is

the kind ofphotoreactor used, usually tubular with a reflecting surface. Tubular reactors like compound

parabolic collectors, CPCs, involve high capital costs. In comparison, the application ofless costly reactors

such as the extensive raceway ponds (RPRs) would help to spread the use ofthe photo-Fenton process

as tertiary treatment at commercial scale. As far as the authors know, RPRs have never been used in

advanced oxidation processes (AOPs) applications. This work isaimed at studying the applicability ofRPRs

to remove micropollutants with solar photo-Fenton. For this purpose, a pesticide mixture ofcommercial

acetamiprid (ACTM) and thiabendazole (TBZ) (100g/Leach) was used in simulated secondary effluent.

Iron concentration (1, 5.5 and 10 mg/L) and liquid depth (5, 10 and 15 cm) were studied as process

variables. TBZ was removed at the beginning ofthe treatment (less than 5 min), although ACTM removal

times were longer (2040 min for the highest iron concentrations). High treatment capacity per surface

area was obtained (48 mg/h m2 with 5.5 mg Fe/Land 15 cm liquid depth), proving the feasibility ofusingRPRs for micropollutant removal.

2014 Elsevier B.V. All rights reserved.

Corresponding author at: Department of Chemical Engineering, University of

Almera, 04120, Almera, Spain. Tel.: +34 950015314; fax: +34 950015484.

E-mail address:[email protected] (J.A. Snchez Prez).

1. Introduction

The detection of low concentration (g/Lng/L) of persistentpollutants, also called micropollutants, in aquatic systems has

drawn the attention of the scientific community in recent years.

http://dx.doi.org/10.1016/j.jhazmat.2014.07.010

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I. Carra et al. / Journal of HazardousMaterials 279 (2014) 322329 323

Certainly, small amounts of common substances such as caffeine,

nicotine and pharmaceuticals, among others, have been detected

in surface waters such as lakes or rivers [13].

Urban wastewater treatment plants (WWTPs) are usually based

on biological treatments which are not effective in micropollutant

removal [4,5]. Likewise, WWTPs may also receive effluents from

industries with specific contamination. For instance, effluents can

easily contain low concentration of pollutants such as pesticides,

which are used in crops [6]. The small amounts in which micropol-

lutants are found in WWTP effluents can be hazardous for aquatic

systems, and their accumulation results eventually in chronic tox-

icity and other effects of environmental concern. In this regard,

advanced oxidation processes (AOPs) arise as an effective alterna-

tivethanks to the oxidationof micropollutants by hydroxylradicals

[7]. Indeed, AOPs efficiency in micropollutant removal makes them

firm candidates for tertiary treatment. Ozonation, heterogeneous

and homogeneous photocatalysis are some of the AOPs whichhave

already been studied in this sense with successful results [8,9].

Specifically, homogeneous photocatalysis or photo-Fenton process

has provento bevery efficientin this regard[10]. In this process, the

generation of radicals is catalysed by iron, with hydrogen peroxide

as the oxidant. Iron is cyclically reduced and oxidised in a redox

cycle. The oxidationtakes place in a fast reaction represented in Eq.

(1). Its reduction, though, can take place in the presence of UVvisirradiance (Eq. (2)) or in the dark (Eq. (3)). The presence of UVvis

irradiance enhances the process rate though, since Reaction (2) is

faster thanReaction(3). This factimplies thatirradiance absorption

is essential to the process performance.

Fe2++H2O2 Fe3++HO+HO (1)

Fe3++H2O+hv Fe2++HO+H+ (2)

Fe3++H2O2 Fe2++HO2

+H+ (3)

Nevertheless, the main drawback in the application of these

techniques at commercial scale is the cost. The operating costs in

the case of the photo-Fenton process may be reduced with the

use of solar light. Even so, amortisation costs are its main weak-

ness. Two factors are crucial: photoreactor cost and reaction time[11]. With regard to the first factor, the most popular photoreac-

tors are compound parabolic collectors (CPCs), developed for these

applications at the end of the nineties [12]. They are constituted by

borosilicate glasstubeson the axis of a compoundparabolic surface

(madeof aluminium).The cost forthe installation andpurchase of a

large scale CPC plant for solar photo-Fenton has been estimated as

400D/m2, including pumps, piping and accessories (Final results of

CADOX Project,Contract n EVK1-CT2002-00122) [13]. Withregard

to reaction time, long process times increase the solar collector

surface needed and energy consumption for pumping, thus, rais-

ing the costs. In this sense, 80W/m3 was reported for a 104m2

photo-Fenton plant with solar compound parabolic collectors [11].

The use of photoreactors such as CPCs comes from the need of

making the most of the solar beams that reach the system. Photoncapture is crucial whenthe need ofhydroxylradicals is largesuchas

for macropollutant (mg/Lg/L) removal, as is the case of industrial

wastewater [14]. When the treatment is aimed at micropollutant

oxidationthough, the pollutant concentrationis at leasta thousand

times lower than for macropollutant oxidation. Therefore, the pro-

cess needs less hydroxyl radicals and, consequently, less irradiance

(less photons) to achieve removal [15]. From this arises the ques-

tion whether other kind of photoreactors, less efficient in photon

capture andmore simple, could be usedfor micropollutant removal.

An interesting choice would be an extensive and non-

concentrating reactor. Some examples are the Thin Film Fixed

Bed Reactor (TFFBR) or Double Skin Sheet Reactor (DSSR) [16].

Also, shallow pond configurations and flat-plate reactors were

studied in the nineties [1820]. All of them were mainly tried for

macropollutants degradation with TiO2. Nevertheless few cases

have been published for photo-Fenton applications, Rosseti et al.,

modelled formic acid degradation in a flat-plate reactor [21]. Sim-

ilar to this kind of reactors are the Raceway Pond Reactors (RPRs),

which have been widely applied for microalgal mass culture [22].

In RPRs the liquid depth can be varied and the flow is controlled.

They are extensive reactors withchannels through which the water

is recirculated. They are made of low cost materials, mainly plastic

liners, giving rise to low construction costs of about 100,000 D/ha,

that is 10 D/m2 [23]. Additionally, the power requirements for

mixing are also small over 4 W/m3. Due to their flexibility

and easy scale-up, raceway reactors are the most used devices

for microalgal applications [22] and production costs have been

reported to be markedly lower than for tubular photobioreactors,

such is the case for fuel production from microalgae [24,25] and

much lower than CPCs. Effective, extensive and low-cost (per

surface unit) photoreactors such as RPRs would spread the use of

the photo-Fenton process as tertiary treatment.

In the light of these facts this work was aimed at studying the

applicability of extensive RPRs to remove micropollutants with

solar photo-Fenton. For this purpose, a mixture of commercial

pesticides, acetamiprid (ACTM) and thiabendazole (TBZ), 100g/Leach, was used in simulated secondary effluent as model pollutant

mixture, avoiding the disturbance of daily variations in real efflu-ents. Both pesticides are commonly applied to citrus crops in the

Mediterranean area. To assess the best process conditions, first the

effect of iron concentration (1, 5.5 and 10mg/L) and liquid depth

(5,10 and15 cm, which correspondedto the same illuminatedarea

but different water volume, up to 360L) was studied using tap

water as matrix instead of simulated secondary effluent to avoid

disturbances due to other organics but with a ionic composition

close to secondary effluents. Results were confirmed in simulated

secondary effluent.

2. Materials and methods

2.1. Chemicals

Sulphuric acid (9597%) and hydrogen peroxide (35%) were

obtained from J.T. Baker and ferrous sulphate (99%) from Fluka.

CaSO42H2O, MgSO4, KCl, (NH4)2SO4, NaHCO3, beef extract,

peptone, humic salts, sodium lignin sulfonate, sodium lauryle

sulphate, acacia gum powder, formic acid and Arabic acid were

acquired from SigmaAldrich. Commercial formulations of pesti-

cides were used: EPIK (20%, w/w ACTM) and TEXTAR (60%, w/v

TBZ). HPLC grade acetonitrile from Carlo Erba Reagents andMilli-Q

grade water were used in the chromatographic analysis.

2.2. Experimental set-up

Theexperiments were carried outin a fibreglass-RPR pilot plantat pH 2.8. This pH value was chosen because it is the optimum

for the photo-Fenton process [22] and allows a higher solubility

of iron, allowing evaluating properly the efficiency of RPRs. Future

work will be focused on working at circumneutral pH in RPRs, rec-

ommended to treat micropollutants [26]. The fibreglass-RPR has

a maximum capacity of 360 L , a length of 3.85 m and width of

0.64m. It is separated by a central wall, forming two canals. The

RPR includes a paddle wheel connected to an engine to obtain a

mixed and homogeneous system. The engine was linked to a vari-

able frequency drive to control the paddles speed. A scheme of the

plant is presented in Fig. 1.

Iron concentration and liquid depth (treated volume) were the

process variables studied. A one-factor-at-a-time strategy was

followed, changing an individual variable and keeping the other


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324 I. Carra et al. / Journal of HazardousMaterials 279 (2014) 322329

Fig. 1. RPR scheme.

one constant. Iron concentration was kept to low values, from 1

to 10mg/L, typically used for micropollutant removal [27,28]. Low

concentrations of iron contribute to prevent large generation of

iron sludge when neutralising the effluent after the treatment.

Liquid depth, which determines irradiance path length, was varied

from 5 cm to 15 cm. The first value was taken as the common

diameter used in tubular reactors such as CPCs [29]. The last depthvalue is the maximum allowed by the configuration of the RPR

reactor. The Reynolds number wasestimated for each liquid height

[22] and a turbulent regime was used: 6105, 7105 and 7105

for 5cm, 10cm and 15cm liquid depth, respectively.

The central operating condition (5.5mg Fe/L and 10cm height)

was replicated five times to determine the experimental error.

Hydrogen peroxide concentration was added at the beginning of

the process in a concentration of 50mg/L in all cases to ensure

excess. As the liquid depth changes, so does the treated water vol-

ume in each case. To ensure similar mixing times the paddle wheel

speed waschangedaccording to thetreated volume. Theresult was

a 2.5min mixing time for all cases.

UV radiationwas measured using a global UV radiometer (Delta

Ohm, LP UVA 02 AV) with a spectral response range from 327 to384nm, mounted on a horizontal platform,providing data in terms

of incidentUV radiation(W/m2).Also,theplantisequippedwithpH

and temperature probes. The variables were monitored on-line by

means of a LabJack USB/Ethernet data acquisition device connected

to a computer.Prior to thebeginning of theexperiments,the reactor

was covered and pH was adjusted to 2.80.05 with sulphuric acid.

A recirculation time of 5 min was allowed for homogenisation after

the addition of the pesticide mixture and iron salt, corresponding

to twice the mixing time in the photoreactor. Then the reactor was

uncoveredand hydrogenperoxidewas added, starting thereaction.

The reactor was continuously mixed during the experiments with

the paddle wheel. The experiments were always run at noon (from

12 to 13.30 p.m.), when solar irradiance was practically constant.

The average UV irradiance was 153W/m2. Average temperaturewas 282 C.

Both ACTM and TBZ are commonly used in citrus crops which

predominate in the Mediterranean agriculture (e.g. lemon, orange

trees) [30,31]. ACTM is a neonicotinoid insecticide and it has been

reported to be more resistant to oxidation than other pollutants

typically found in WWTP effluents [15,32]. TBZ is a widely used

benzimidazole fungicide. Thus, ACTM and TBZ serve the purpose of

model pollutants.

To study the effect of iron concentration and liquid depth, tap

water was used as matrix. The main properties of tap water are

presented in Table 1. Dissolved organic carbon (DOC) due to the

tap water was negligible. The small concentration of commercial

ACTM and TBZ (100g/L each) did not result in significant DOC

concentration either (less than 1 mg DOC/L).

Table 1

Tap water properties.

Parameter Concentration (mg/L)

Sulfate 29.5

Chloride 206.1

pH 7.9

Conductivity 0.85 mS/cm

To confirm the best operating conditions obtained in tapwater, experiments were carried out in simulated secondary

effluent from an urban WWTP used in previous works [15].

The constituents of the simulated secondary effluent were

CaSO42H2O (60 mg/L), MgSO4 (60mg/L), KCl (4mg/L), (NH4)2SO4(23.6 mg/L), K2HPO4 (7.0mg/L), NaHCO3 (96mg/L), beef extract

(1.8mg/L), peptone (2.7mg/L), humic salts (4.2mg/L), sodium

lignin sulfonate(2.4 mg/L), sodium lauryle sulphate (0.9mg/L),aca-

cia gum powder (4.7mg/L), and Arabic acid (5.0mg/L) [33]. The

dissolved organic carbon, DOC, of the initial water was 14mg/L.

2.3. Determination of the optical thickness

Regarding the absorption of the incident radiation, the ferric

iron species in solution are dominant for UV-light absorption ashydrogen peroxide and ferrous iron do not absorb any radiation

over 300 nm [21]. Absorption of ACTM, TBZ and generated inter-

mediates was checked and found negligible at the concentration

used in the experiments.

The absorption spectra of ferric iron in tap water were obtained

at different iron concentrations and making use of solar power

emission spectrum the spectral-averaged specific absorption coef-

ficient kA(mM1 m1) of solution species was determined, Eq. (4):

kA =

maxmin

Id

maxmin

Id(4)

where I is the solar power at the corresponding wavelength and

is the specific absorption coefficient of the solution at the cor-responding wavelength (mM1 m1). The wavelength limits in

Eq. (4) were those corresponding to radiometer spectral response

(327384nm). The specific absorption coefficient for ferric iron

species at pH 2.8 in tap water was 46mM1 m1.

The optical thickness, , was calculated as follows:

= kA CFe D (5)

where CFeis the iron concentration (mM) and D is the liquid depth

(m).

2.4. Chemical analysis

The sample volume was 10mL. All samples were immediately

filtered (nylon filters from Millipore with pores of 0.20m-diameter) and the filter was washed with 1 mLof acetonitrile and

mixed with the filtered water sample. This is because acetoni-

trile acts as an HO scavenger, stopping the reaction [34], and also

sweeps out any trace of pollutant that may have been retained by

the filter and avoid any possible adsorption.

Hydrogen peroxide was measured by a colorimetric method

using ammonium metavanadate, measuring the absorbance at

450nm [35]. The concentration of iron was determined accord-

ing to the o-phenantroline standardised procedure (ISO 6332) and

the red complex formed was determined spectrophotometrically

at 510 nm. DOC determinations were carried out in a Shimadzu-

V CPH TOC analyser. Anion concentrations were determined using

ion chromatography (Metrohm 881 Compact IC pro). The column

was an anionic MetroSep Supp 7 column (250/4.0mm5m) from


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Metrohm. The eluent used was a solution of 3.6 mM Na2CO3 and

the flow rate was 0.8 mL/min.

ACTM and TBZ concentrations were determined by means of

liquid chromatography (UPLC Agilent 1200 Series equipped with

a column oven, degasser, autosampler and diode array detec-

tor) with a reversed-phase column (Agilent XDB-C18). The mobile

phase consisted of a gradient mixture of acetonitrile and 1% (v/v)

formic acid in water. Retention times were 6.1 min for TBZ, 9.6

for ACTM. The detection wavelengths were 300nm for TBZ and

248nm for ACTM. The gradient used was initially set at 5% ace-

tonitrile, progressively increasing the concentration to 100% in a

12-min method. The limit of detection (LOD) was 2g/L for ACTMand 1g/L for TBZ.

3. Results and discussion

3.1. Effect of liquid depth and iron concentration on pesticide

removal

In this work the solar photo-Fenton process was applied as

tertiary treatment, focusing on the effects of liquid depth and

iron concentration in the RPR operation. The degradation profilesobtained for the commercial pesticide mixture during the photo-

Fenton process are shown in Figs.2 and 3. The experimental error,

obtained from five replicates of the central operating condition

(5.5mg Fe/L10 cm liquidheight) waslowerthan 5% forACTM, TBZ

and hydrogen peroxide concentrations.

Either for ACTM or TBZ, two oxidation steps were clearly

detected, regardless of the liquid depth. The first step was always

marked by high and fast oxidation of the compounds due to the

initial reaction of Fe2+ with hydrogen peroxide (Eq. (1)) (Fenton

effect). It is rather fast, directly proportional to Fe2+ concentration

andgenerates a great amount of hydroxylradicals[36]. In said reac-

tion, Fe2+ is oxidised. On the second reaction step, Fe3+ is reduced

(Eq. (2)), establishing a continuous iron redox cycle (Eqs. (1) and

(2)). In this step, degradation is progressive, not as fast as in thefirst step because the ferric iron reduction is rate limiting.

Of the two compounds, ACTM presented slower degradation

rate than TBZ. As the most persistent compound of the mixture,

ACTMwas theone which gavefurtherinsight intothe results.Fig.2a

illustrates ACTM oxidation with 1 mg Fe/L for all liquid depths (5,

10 and 15cm). The first oxidation step, previously described, gave

rise to 19% removal. As this step is dependent on iron concentra-

tion, it was the same for all liquid depths. The second oxidation

step fitted an exponential decrease with similar degradation rates

for the three liquid depths. In all cases approximately 75% ACTM

removal was measured after 90min of solar photo-Fenton.

For 5.5mg Fe/L (Fig. 2b) the first oxidation due to Eq. (1) is

more significant as there was more initial Fe2+, reaching54% ACTM

removal in 2.5 min. In addition, there was a significant increase inthe process rate and complete removal was achieved in 40min for

all liquid depths with solar photo-Fenton. This short reaction time

is animportant factas it is one of the factors which affects costs the

most [11]. As observed with 1 mg Fe/L, the profiles were analogous

for the three liquid depths. This is also a significant effect. When

the liquid depth was 5cm, the treated volume was 120L. When

the liquid depth was increased to 10cm and 15cm, the treated

volumes were 240 and 360 L, respectively. So, the number of iron

ions present that needed to be photoactivated in the system was 2

and 3 times greater and so was the number of pesticide molecules.

However, the photons reaching the system remain the same as the

photoreactor surface did not change. Even so, the oxidation rate

with solar photo-Fenton was the same, regardless of the volume.

This meant that all iron ions were photoactivated for the three

Fig. 2. ACTM degradation by solar photo-Fenton and Fenton with 1, 5.5 and 10mg

Fe/L(243 WUV/m2 and 282 C).

liquid depths and the concentration of hydroxyl radicals generated

was similar.

When 10mg Fe/Lwas used(Fig.2c), there was an increase in the

process rateas well. However,it wasnot linearly proportionalto the

increase in iron concentration. The first degradation step involved

69%ACTMremovalfor allliquid depths, incomparisonwiththe 54%

achieved with 5.5mg Fe/L. This first degradation step wasthesame

for all liquid depthssince it is independent of irradiation.However,

in the second degradation step, there was a remarkable difference

with respect to the two lowest iron concentrations: the oxidation


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326 I. Carra et al. / Journal of HazardousMaterials 279 (2014) 322329

Table 2

Kinetic constantsfor ACTMand H2O2.

Fe concentration (mg/L) Liquid height (cm) kACTM(min1) kH2O2 (mMmin

1)

Mean Standard deviation Mean Standard deviation

1 5, 10 and 15 0.02 0.002 0.003 0.0003

5.5 5, 10 and 15 0.08 0.004 0.012 0.0008

10 10 and 15 0.08 0.003 0.013 0.0009

10 5 0.13 0.021

of ACTM was faster in 5c m than in 10c m or 15c m liquid depth.

Indeed, complete removal time was 20min in 5cm liquid depth

and 40min in the other two.

This can be explained as follows, taking into account that the

amount of photons reaching the surface is the same for all liquid

depths but not the amountof iron ions: in 5 cmdepth with10 mg/L

of Fe there are 1.31022 iron ions in 120L which need certain

amount of photons to be photoactivated. When the treated volume

is increased to 240L or 360L, the number of iron ions is 2.61022

or 3.91022, respectively, but the amount of photons reaching the

system remains the same. Another approach to study this effect is

the optical thickness,which was calculated according to section 2.3

for every iron concentration and liquid depth. The maximum opti-cal thickness for 1 mg Fe/L was 0.12, and for 5 mg Fe/L, it was 0.68.

An optical thickness of 1 means that 90% of the photons entering

the reactor are absorbed. Therefore, there were enough photons

for both iron concentrations. Thus, for 1 and 5.5mg Fe/L all iron

ions were photoactivated for the three different depths as shown

in Fig.2a andb. Althoughthe highest optical thicknesswas obtained

for10mg/L(itrangedfrom0.41to1.24),solarradiationstillreached

the bottomof the reactor. However, with 10 and15 cm liquiddepth

theprocesscould become photo-limited. Nonetheless, these optical

thickness values are below the optimal range reported for photo-

catalytical reactors (1.83.4), pointing out that liquid depth could

still be increased keeping low iron concentration [37].

Fig.3 shows TBZdegradationprofilesfor 1 mg Fe/L and thethree

liquid depths. As previously mentioned, it was oxidised faster thanACTM and difficult to evaluate any effect at concentration >1mg

Fe/L. For 5.5 and 10mg Fe/L degradation was so fast it could not

be tracked. Indeed, for 5.5mg Fe/L complete removal was achieved

in 5min; while for 10mg Fe/L, the first degradation step (Fenton

effect) was already enough to completely remove all TBZ. This is

likely due to differences between the reactivity of hydroxyl radicals

towards ACTM and TBZ (hydroxyl radical is more reactive towards

Fig. 3. TBZ degradation by solar photo-Fenton and Fenton with 1 m g Fe/L

(24WUV/m2 and 282 C).

TBZ than ACTM). This is important since if only TBZ had been used

the effect of photo-limitation would not have been detected. The

first degradation step for 1mg Fe/L by Reaction 1 was more sig-

nificant as TBZ is likely more reactive towards hydroxyl radicals

than ACTM; andthe secondoxidation step also follows a fast expo-

nential decrease. Nevertheless, the profiles tendency proved to be

analogous to ACTM in the same conditions: the degradation rate

was similar for the three treated volumes. The discussion of TBZ

degradation follows the explanation given for ACTM above.

In addition to the photo-Fenton tests, the Fenton process was

alsocarriedoutasblank(Figs.2and3). The Fenton process is mainly

dependenton theconcentrationof iron andthe liquiddepth is nota

variable in this case. Additionally, the reduction of Fe3+ takes placethrough Eq. (3) instead of Eq. (2). As Eq. (3) is very slow [38], so the

most significant degradation occurred in the first degradation step,

which also happened in solar photo-Fenton. In no case was com-

plete ACTM removal accomplished in 90min, but high percentage

was obtained with 10mg Fe/L, 90%. This means the Fenton effect is

rather important in micropollutant removal only if high iron con-

centration is used. As a result, a combination of solar photo-Fenton

and Fenton (for cloudy days and nights) could be made to operate

continuously. This is essential for the commercial development of

this technology: extensive, less costly reactors which can operate

in continuous mode.

Aside from micropollutant concentration, hydrogen peroxide

consumption is crucial to corroborate the effects observed. In this

case, the reactant concentration was in light excess, 50mg/L, toensure that the micropollutant oxidation was not conditioned by

lackof hydrogenperoxide. Theevolution of hydrogenperoxide con-

centration with time is shown in Fig. 4. At first glance it can be

appreciated that the effects observed in ACTM degradation were

reflected in H2O2 concentration.

The factthat ACTMandH2O2profiles matched is especiallyclear

for10mg Fe/L, whereprofiles forthe 5-cm liquiddepth were differ-

entwithrespectto10cmand15cm(Fig.4c). H2O2 consumptionfor

different liquid depths with 10mg Fe/L corroborates the idea that

not all iron ions are photoactivated for 10-cm and 15-cm depth.

With 1 and 5.5mg Fe/L the degradation of H2O2 was similar

for all liquid depths (Fig. 4a and b). At the end of the test, 10%

H2O2 was still in the system for 5.5 m g Fe/L. When 1mg Fe/L

was used, only 30% H2O2 was consumed. This is consistent sinceH2O2 consumption rate is proportional to the concentration of

catalyst.

These results show the efficiency of the RPRs as extensive sys-

tems for micropollutant removal. A kinetic analysis was also made

to compare the value of the constants. For the calculation of the

kinetic constants, the first degradation step (Fenton) was omitted

since it was mainly a result of the first ferrous iron oxidation, as

described in Eq. (1), yielding a great amount of HO. It isin the sec-

ond degradation stage (photo-Fenton) whenthe Fe redoxcycle was

established as iron reductionis theslowestreaction inthe cycle and

is seriously affected by radiation absorption and, therefore, liquid

depth [15].

ACTM and TBZ profiles adjusted an exponentially decreasing

function, following a pseudo-first order degradation. ACTM


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Fig. 4. Hydrogen peroxide concentration profiles during pesticide degradation by

solar photo-Fentonand Fentonwith 1, 5.5 and 10mg Fe/L.

pseudo-first order kinetic constants were calculated as well after

the first degradation stage and included in Table 2. Hydrogen per-

oxide profiles adjusted a linear decrease after the first degradation

stage, so pseudo-zero order kinetic constants were calculated

(Table 2). As kinetic constants for TBZ could not be obtained for

5.5 and 10mg Fe/L due to fast degradation, only ACTM constants

are presented. Since the degradation rate for 5, 10 and 15cm liq-

uid depth was the same for 1 and 5.5mg Fe/L, a mean value was

calculated. Standard deviation of ACTM and H2O2 constants were

Fig. 5. ACTM degradation and hydrogen peroxide consumption in simulated sec-

ondary effluentby solarphoto-Fentonin 15 cm liquid-depth-RPR with5.5 and10 mg

Fe/L, and in 5cm diameter-CPC with 5.5mg Fe/L.

included. For 10mg Fe/L and 5 cm, there was only one experiment,

so the kinetic values were not averaged.It could be seen that either for ACTM and H2O2 an increase in

catalyst concentration from 1 to 5.5 mg/L raised the kinetic con-

stant values four times: from 0.02min1 to 0.08min1 in the case

of ACTM; and from 0.003 mMmin1 to 0.012 mMmin1 for H2O2.

However, when the catalyst concentration was increased to 10mg

Fe/L, the kinetic constants were over 1.5 times greater only for

5 cm liquid depth (0.13 min1 and 0.021mM min1 for ACTM and

H2O2, respectively); while at the higher liquid depths the constants

remainedpractically the samethan for 5.5 mg Fe/L.This contributes

to the explanation given above that there was excess of catalyst for

10mg Fe/L at 10 and 15cm liquiddepth. Therefore, with the fastest

operating conditions (10 mg Fe/L and 5cm liquid depth) 120L of

water were treated in 20min. On the contrary, using 5.5mg Fe/L

with 10cm depth, 240L of water were treated in 40min and 360 Lwith 15cm liquid depth. As a result, the best operating condition

was 5.5 mg/L of Fe concentration and 15cm liquid depth.

3.2. Micropollutant removal in simulated secondary effluent

In simulated secondary effluent, the RPR was operated at the

highest liquid depth, 15cm, and two iron concentrations, 5.5 and

10mg Fe/L. Thefirst as the best operatingcondition obtained in tap

water and the second, to check if the use of a different matrix

with organic matter (14 mg/L DOC) could have an effect on the

process, for example, decreasing reaction rate as DOC scavenges

HO or augmenting water light absorption. In bothcases, increasing

Fe concentration would produce a clear effect increasing reaction

rate.Additionally, for comparison purposes, the same pesticide mix-

ture was degraded in a CPC photoreactor of 5 cm diameter, 0.48m2

collector area and 7L total volume, with 5.5mg/L of iron. More

CPC details and operation procedure are described elsewhere [39].

ACTM and hydrogen peroxide concentrations are shown in Fig. 5.

TBZ concentration is not shown as its degradation was too fast (it

was removed in less than 5 min).

Inthe RPR, ACTM as well as hydrogenperoxide degradationpro-

files were analogous for both iron concentrations, validating the

effects observed in tap water and excluding a detrimental effect

provoked by scavengers of HO or light absorption. Nevertheless

the acetamiprid degradation kinetic constantwas 0.01min1 inthe

secondaryeffluent;while theconstant intap water was0.08min1.

This is dueto thedifference inorganicmatterandsalts inbothwater


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[40] S. Malato Rodrguez, J. Blanco Galvez, M.I. Maldonado Rubio, P. FernandezIbanez, D. Alarcon Padilla, M. Collares Pereira, J. Farinha Mendes, J. Correia deOliveira, Engineering of solar photocatalytic collectors, Sol. Energy 77 (2004)513524.

Further reading

[17] F.G. Acin Fernndez, J.M. Fernndez Sevilla, E. Molina Grima, Photobioreac-tors for the production of microalgae, Rev. Environ. Sci. Biotechnol. 12 (2013)131151.
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