1
An Inno a i e Pho o eac o , FluHelik, To P omo e UVC/H2O2 1
Pho ochemical Reac ions: Te ia y T ea men o an U ban 2
Was ewa e 3
Jona han C. Espíndola1,2, Raquel O. C is ó ão1,*, Sa a R.F. A aújo1, Te esa Neupa h3, 4
Miguel M. San os3,4, Rosa Mon es5, José B. Quin ana5, Rosa io Rodil5, Rui A.R.5
Boa en u a1, Ví o J. P. Vila 1,*
6
7
1Labo a o y o Sepa a ion and Reac ion Enginee ing - Labo a o y o Ca alysis and Ma e ials 8
(LSRE-LCM), Depa men o Chemical Enginee ing, Facul y o Enginee ing, Uni e si y o 9
Po o, Rua D . Robe o F ias, 4200-465, Po o, Po ugal 10
2CNPq - Na ional Council o Scien i ic and Technological De elopmen , B azil 11
3CIMAR/CIIMAR - LA, In e disciplina y Cen e o Ma ine and En i onmen al Resea ch, 12
A enida Gene al No on de Ma os S/N, 4450-208 Ma osinhos, Po ugal 13
4FCUP – Depa men o Biology, Facul y o Sciences, Uni e si y o Po o, Rua do Campo 14
Aleg e, 4169-007 Po o, Po ugal. 15
5Depa men o Analy ical Chemis y, Nu i ion and Food Sciences, IIAA—Ins i u e o Food 16
Analysis and Resea ch, Uni e sidade de San iago de Compos ela, Cons an ino Candei a S/N, 17
15782 San iago de Compos ela, Spain 18
19
20
*Co esponding au ho s:21
R.O. C is ó ão: 22
Tel: +351 22 041 3606; E-mail: aquel.c is o ao@ e.up.p 23
Ví o J. P. Vila : 24
Tel: +351 91 825 7824; E-mail: [email p o ec ed] 25
Fax: +351 22 508 1674 26
This is he pos p in (accep ed manusc ip ) e sion o he a icle published in Science o he To al En i onmen .
h p://dx.doi.o g/10.1016/j.sci o en .2019.02.335
© 2019. This manusc ip e sion is made a ailable unde he CC-BY-NC-ND 4.0 license
h p://c ea i ecommons.o g/licenses/by-nc-nd/4.0/
G aphical Abs ac
*G aphical Abs ac
Highligh s
The FluHelik pho o eac o p o ed o enhance he OTC oxida ion by UVC/H2O2;
The FluHelik design showed supe io pe o mance han con en ional Je s
pho o eac o ;
FluHelik eac o + UVC/H2O2 e ec i ely educed CECs complying wi h Swiss
legisla ion;
FluHelik eac o + UVC/H2O2 e ec i ely educed CECs oxici y o zeb a ish
emb yos;
The FluHelik scale-up p o ed o be easible employing se e al eac o s in se ies.
*Highligh s ( o e iew : 3 o 5 bulle poin s (maximum 85 cha ac e s including spaces pe bulle poin )
2
Abs ac 27
An inno a i e pho o eac o , FluHelik, was used o p omo e he deg ada ion o 28
con aminan s o eme ging conce n (CECs) by a pho ochemical UVC/H2O2 p ocess. 29
Fi s , he sys em was op imized o he oxida ion o a model an ibio ic, oxy e acycline 30
(OTC), using bo h ul apu e wa e (UPW) and a eal u ban was ewa e (UWW) 31
(collec ed a e seconda y ea men ) as solu ion ma ices. Following, he p ocess was 32
e alua ed o he ea men o a UWW spiked wi h a mix u e o OTC and 10 di e en 33
pha maceu icals es ablished by he Swiss legisla ion a esidual concen a ions (CECs 34
< 660 g L-1). The pe o mance o he FluHelik eac o was analyzed bo h a lab and 35
p e-pilo scale in mul iple and single pass low modes. 36
The e iciency o he FluHelik pho o eac o , a lab-scale, was e alua ed a di e en 37
ope a ional condi ions (H2O2 concen a ion, UVC lamp powe (4, 6 and 11 W) and low 38
a e) and u he compa ed wi h a con en ional Je s pho o eac o . Bo h pho o eac o s 39
exhibi ed simila OTC emo al e iciencies a he bes condi ions; howe e , he 40
FluHelik eac o showed o be mo e e icien (1.3 imes) in e ms o mine aliza ion 41
when compa ed wi h he Je s eac o . Addi ionally, he e iciency o he UVC/H2O2 42
pho ochemical sys em using he FluHelik pho o eac o in educing he oxici y o he 43
eal e luen con aining 11 pha maceu icals was e alua ed h ough zeb a ish (Danio 44
e io) emb yo oxici y bioassays. FluHelik scale-up om labo a o y o p e-pilo o 45
p omo e UVC/H2O2 pho ochemical p ocess p o ed o be easible. 46
47
Keywo ds: FluHelik pho o eac o ; UVC/H2O2; CECs; U ban was ewa e ; Zeb a ish 48
emb yo oxici y es . 49
3
In oduc ion 50
UVC/H2O2 pho ochemical p ocess is based in he homoly ic clea age o H2O2 51
molecules by UVC ligh , esul ing in highly eac i e species (HO), able o elimina e an 52
ex ensi e a ie y o pollu an s om wa e . Howe e , due o he low alues o mola 53
abso p ion coe icien o H2O2 a 254 nm, high H2O2 o UV dose is equi ed o achie e 54
an e icien pe o mance (K ishnan e al., 2017). On he o he hand, u ban was ewa e s 55
composi ion can educe signi ican ly he sys em e iciency due o he p esence o ligh 56
abso bing species (NOM, ni i e, e c.) (Diya’uddeen e al., 2011). The e iciency o 57
UVC/H2O2 pho ochemical p ocess is also la gely in luenced by he eac o 58
hyd odynamics egime, which mus p omo e an uni o m UV luence wi hin he eac o 59
(Cambié e al., 2016). He e en e s he impo ance o he eac ion mixing condi ions o 60
he ea men e ec i eness (Ka pel VelLei ne e al., 1997). Se e al comme cial 61
eac o s inco po a e di e en mixing sys ems, such as s a ic mixe s and conical 62
dispe sion componen s, o imp o e he deg ee o mixing inside he eac o , p omo ing 63
he con ac be ween eagen s/pollu an s and he emi ed UVC pho ons. No mally, he 64
i adia ion sou ce is loca ed in he mos u bulen zone o he eac o (Masschelein, 65
1992). Nowadays he e is a g ea a ie y o pho o eac o s wi h di e se geome ies 66
leading o di e en hyd odynamics. Gene ally, he pho o eac o comp ises a cylind ical 67
shell o s ainless s eel housing a concen ic qua z slee e illed wi h an UVC lamp and 68
he wa e o be ea ed lows be ween he concen ic ubes (annula eac o ). Howe e , 69
he i adia ion sou ce may be also ex e nal, such as he pa allel pla e eac o s o 70
cylind ical eac o s epo ed by Noël (2017)). The mixing and i adia ion condi ions can 71
also be imp o ed h ough in oduc ion o a mul i-lamp design (Boyjoo e al., 2014) o 72
by usage o o a ing annula eac o s (Sub amanian and Kannan, 2010) o spinning disc 73
eac o s (Ya maz e al., 2001). The e o e, e en wi h he same lamp ype and in ensi y, 74
4
eagen s/pollu an s dosages and simila low a es, he pho ons dissemina ion as well 75
and he pollu an s emo al may be comple ely di e en (Ca is, 2011). Al hough 76
pho ochemical eac o s ha e been al eady applied in wa e /was ewa e ea men plan s, 77
he p ocess is no widely dissemina ed because o he inhe en limi a ions ha i 78
p esen s, namely in e ms o ene gy cos s and e iciency. The e o e, b eak h ough 79
designs o pho o eac o s a e equi ed o achie e a cos -e ec i e ea men solu ion (Su 80
e al., 2014). 81
The p esen wo k ocuses on he applica ion o an inno a i e pho o eac o , FluHelik, in 82
he emo al o con aminan s o eme ging conce n (CECs) om u ban was ewa e s, as a 83
polishing s ep, using a UVC/H2O2 pho ochemical p ocess. The FluHelik pho o ea o 84
comp ises a cylind ical shell o s ainless s eel, in e nally polished, wi h inle and ou le 85
pipes loca ed pe pendicula ly o he luid low and angen ially o he shell in ho izon al 86
plane and a he op in opposi e sides. A concen ic inne qua z slee e houses an UVC 87
lamp. This con igu a ion induces unique luid dynamics (high deg ee o mixing) and 88
i adia ion p ope ies (a mo e homogeneous UV adia ion dis ibu ion) by p omo ing a 89
helical mo ion o he luid a ound he UVC lamp. Fi s , syn he ic solu ions o OTC o 90
UWW o i ied wi h OTC we e used as eac ion ma ices. Two con igu a ions o 91
pho o eac o s we e employed: FluHelik and Je s ( ou inle and ou ou le pipes placed 92
in pa allel wi h he luid low di ec ion a he ends o he ube). P ocess e iciency was 93
e alua ed as a unc ion o se e al ope a ional condi ions, namely: (i) eci cula ion low 94
a e, (ii) H2O2 concen a ion and (iii) UVC lamp powe . In addi ion, he easibili y o 95
implemen ing he FluHelik eac o o he UVC/H2O2 p ocess was es ed bo h a 96
labo a o y and a p e-pilo scale ei he in mul iple o single pass low mode. Finally, he 97
ea men o a eal u ban was ewa e ma ix spiked wi h a mix u e o 11 CECs, a 98
5
esidual concen a ions, was e alua ed using he FluHelik pho o eac o and he 99
UVC/H2O2 sys em. 100
Conside ing ha oxida ion by-p oduc s migh be mo e oxic and/o pe sis en han he 101
pa en compounds, oxicological s udies a e needed o de e mine hei dele e ious 102
e ec s on ecosys ems and human heal h. Zeb a ish (Danio e io) ha e been widely used 103
in Fish Emb yo Toxici y (FET) Tes s o assess he oxici y o se e al p io i y pollu an s. 104
This emb yonic bioassay has high sensi i i y and low cos . Fu he mo e, zeb a ish 105
emb yos a e anslucen which allows o he moni o ing o emb yo de elopmen unde 106
a s e eomic oscope (Macedo e al., 2017; Zhang e al., 2015). This bioassay has ecen ly 107
been p oposed by he OECD as an al e na i e o classical acu e ish oxici y es s 108
(Lamme e al., 2009), and is an app op ia e ool o assess he dec ease in oxici y a e 109
ea men o was ewa e s con amina ed by eme ging pollu an s. 110
In his sense, emb yo oxici y bioassays wi h zeb a ish (Danio e io) we e used o 111
e alua e he ini ial e luen oxici y and possible a enua ion o he oxic e ec a e he 112
UVC/H2O2 ea men by using he FluHelik eac o . 113
2. Ma e ials and me hods 114
2.1 Chemicals 115
Oxy e acycline hyd ochlo ide (OTC, C22H24N2O9.HCl, 496.89 g/mol) was supplied by 116
Sigma-Ald ich and used as a model compound. Hyd ogen pe oxide (Fishe Chemical, 117
pu i y 49.5% (w/ )) was used as oxidan . Na2SO3 in a Na2SO3- o-H2O2 mola a io o 118
1:1 was added o CECs and dissol ed o ganic ca bon (DOC) samples o H2O2 119
elimina ion (Jeong e al., 2010). Ca alase (Sigma-Ald ich) was added o he samples o 120
elimina e esidual H2O2 be o e pe o ming eco oxicological quali y es s. Ammonium 121
mono anada e (Me ck, p. a.) was used as colo ime ic eagen o de e mine H2O2 122
concen a ion. Sul u ic acid (P onalab, pu i y 96%, 1.84 g/cm3) and sodium hyd oxide 123
6
(Me ck) we e used o pH adjus men . Ul apu e wa e was ob ained om a Millipo e® 124
Di ec -Q sys em (18.2 MΩ cm esis i i y a 25 °C). Real was ewa e sample was 125
collec ed downs eam om he seconda y ea men o an u ban WWTP om No he n 126
Po ugal in Sep embe 2017. I s physicochemical cha ac e is ics, including he CECs 127
esidual concen a ions de ec ed in he aw e luen , a e summa ized in Table 1. The 128
ul apu e wa e and he seconda y e luen bo h spiked wi h 20 mg OTC L-1 we e used 129
as eed solu ions. Table 2 shows he 11 pha maceu ical compounds added o he eal 130
was ewa e . T icaine (1000 mg g-1) used o anes he ize zeb a ish la ae was pu chased 131
om Pha maq. Sodium hyd ogen ca bona e used as a bu e in he p epa a ion o he 132
anes he ic was supplied by Me ck KGaA. All he o he chemicals supplied by VWR-133
P olabo, Sigma-Ald ich, Pan eac, Me ck, Fishe Scien i ic and P onalab we e ei he o 134
HPLC g ade o analy ical g ade. 135
Inse Table 1 136
Inse Table 2 137
2.2 Analy ical de e mina ions 138
OTC concen a ion was ollowed by HPLC using a VWR Hi achi ELITE LaCh om LC 139
i ed wi h a Me ck LiCh oso b® RP-18 (5 µm) LiCh oCART® 125-4 column a 25 °C 140
and a diode a ay de ec o (DAD). Low-molecula -weigh ca boxylic acids (LMWCA) 141
concen a ions we e de e mined by ion-exclusion HPLC using he VWR Hi achi ELITE 142
LaCh om LC i ed wi h a Phenomenex RezexTM ROA-O ganic Acid H+ (8%) 300 143
mm × 7.8 mm column a oom empe a u e (25 ºC). A de ailed desc ip ion o OTC and 144
LMWCA analysis is gi en in Supplemen a y Ma e ial. 145
H2O2 concen a ion was de e mined by he colo ime ic (λ = 450 nm) me a anada e 146
me hod (Noguei a e al., 2005). Dissol ed o ganic ca bon (DOC), chemical oxygen 147
demand (COD), o al dissol ed ni ogen, o al dissol ed i on, o al suspended solids 148
7
(TSS), ola ile suspended solids (VSS), o al phospho ous, pH, empe a u e and 149
u bidi y, as well as ino ganic anions and ca ions concen a ions we e assessed 150
acco ding o he p ocedu es al eady desc ibed by Mo ei a e al. (2016)). Conduc i i y, 151
dissol ed oxygen and edox po en ial we e de e mined by a HANNA Ins umen s HI 152
9828 Mul ipa ame e me e . 153
CECs de e mina ion in wa e samples, a esidual concen a ions, was pe o med in an 154
Acqui y UPLC® liquid ch oma og aph sys em om Wa e s (Mil o d, MA, USA). A 155
sample olume o 45 μL was di ec ly injec ed in o a Luna C18 100A column (50 mm × 156
2 mm, 3µm pa icle size) supplied by Phenomenex (To ance, CA, USA) main ained a 157
a cons an empe a u e o 30 °C. The a ge compounds we e sepa a ed a a low a e o 158
0.2 mL min-1 using 0.1% o o mic acid in bo h, Milli-Q wa e (A) and MeOH (B) as 159
eluen s. The applied g adien was as ollows: 0–1 min, 0% B; 1–8 min, linea g adien 160
o 100% B; 7–13 min, 100% B and inally 13–20 min, 0% B. The sys em was in e aced 161
o a XEVO TQD® iple quad upole mass spec ome e equipped wi h an elec osp ay 162
in e ace (ESI). Ni ogen was used as a nebulizing and d ying gas and A gon was used 163
as collision gas. The analy es we e de e mined in he elec osp ay (posi i e and nega i e 164
pola i ies) and mul iple- eac ion moni o ing (MRM) mode o acquisi ion. Two MRM 165
ansi ions we e used as quan i ie and quali ie o each compound (see Table S1 o 166
de ailed in o ma ion). The me hod assu ed limi s o quan i ica ion (LOQ) be ween 10 167
and 100 ng L−1 o all he compounds excep o azy omicyn (LOQ 1.8 g L-1), see 168
supplemen a y ma e ial Table S1. Quan i ica ion was pe o med by he ma ix ma ched 169
calib a ion me hod using s anda ds p epa ed in ea ed was ewa e in he 1-100 g L-1 170
(2-100 g L-1 in he case o azy omicyn) ange (which was checked o be linea , 171
R2>0.99 o all he s udied analy es). Repea abili y o he de e mina ion was checked in 172
14
possible by H2O2 in he absence o adia ion, a aining deg ada ions o 20, 30 and 50% 322
a e 180 min o eac ion using 100, 300 and 500 mg L-1 o oxidan , espec i ely. As 323
expec ed, he combina ion o UVC ligh wi h H2O2 imp o ed he OTC deg ada ion 324
unde all he s udied i adia ion in ensi ies (Fig. 2). I is no ewo hy ha he 325
pho ochemical oxida ion o OTC showed o ollow a pseudo- i s o de kine ic model. 326
Fo all he UVC lamp in ensi ies e alua ed, he OTC emo al a es inc eased wi h he 327
ini ial oxidan dose, a aining he highes emo al a es (see pseudo- i s o de kine ic 328
cons an s, k, in Table 3) wi h 100 mg L-1 when using he 4 o he 6 W lamps (Fig. 2a 329
and 2b, espec i ely) and wi h 500 mg L-1 o H2O2 when he 11 W UVC lamp (Fig. 2c) 330
was employed (wi hin he es ed concen a ions ange). These esul s sugges an 331
inc easing p oduc ion o hyd oxyl adicals (●OH) o g owing H2O2 ini ial con en s (H. 332
Baxendale and A. Wilson, 1957). Fo highe oxidan dosages, he eac ion a es 333
emained cons an and, o he 11 W lamp he e was e en a dec ease o 1.3 imes in he 334
kine ic cons an when using 700 mg L-1 o H2O2 (Table 3). In ac , he H2O2 in excess 335
can ac as an hyd oxyl adicals sca enge (Mu uganandham and Swamina han, 2004). 336
This is suppo ed by he g owing H2O2 consump ion o ising ini ial H2O2 doses (Fig. 337
2). 338
Inse Figu e 2 339
Inse Table 3 340
Compa ing he OTC emo als by he UVC/H2O2 sys em unde he bes condi ions o 341
each o he lamp powe s s udied (Fig. 2d), no signi ican di e ences be ween he 342
eac ion a es (in e ms o ene gy) we e obse ed. Fo all he sys ems, an OTC emo al 343
abo e 90% is al eady achie ed wi h 0.4 kJ L-1. On he o he hand, a di e en beha iou 344
was obse ed in ela ion o he OTC mine aliza ion: DOC decays o 13, 50 and 45% 345
a e 60 min o eac ion we e obse ed a he bes condi ions when using he 4, 6 and 11 346
15
W lamps, espec i ely. I is wo h men ioning ha , du ing his eac ion pe iod, simila 347
oxidan consump ions we e no iced o he 4 and 6 W lamps (c.a. 35 mg H2O2 L-1); 348
howe e , when using he 11 W lamp a 5- old inc ease in hyd ogen pe oxide 349
consump ion (highe ini ial H2O2 dose) was obse ed. These esul s p o e ha he 350
highe H2O2 consump ion associa ed o he 11 W lamp is no ela ed wi h a highe 351
mine aliza ion, bu p obably o pa asi e eac ions. The e o e, he 6 W lamp p o ided he 352
mos sui able pho on low o he expe imen al se -up used: he 4 W lamp showed o no 353
supply he necessa y UV dosage and, in u n, using he 11 W UVC lamp a possible loss 354
o he emi ed pho ons is occu ing, p obably due o he low mola abso p ion 355
coe icien o H2O2 a 254 nm, equi ing highe amoun s o H2O2 o abso b all hose 356
pho ons. 357
As abo e-men ioned, al hough he o al deg ada ion o he pa en compound (OTC) is 358
achie ed in sho eac ion imes, ela i ely low mine aliza ion is obse ed. Ac ually, o 359
longe eac ion imes (360 min), a mine aliza ion o 62% was eached (6 W UVC lamp; 360
100 mg H2O2 L-1), consuming 87 mg L-1 hyd ogen pe oxide, a highe alue han he one 361
p edic ed by he eac ion s oichiome y o comple ely mine alize 20 mg L-1 o OTC (77 362
mg H2O2 L-1). In ac , 38% o he esidual DOC co esponds o low-molecula -weigh 363
ca boxylic acids (LMWCA) in solu ion, namely oxalic and oxamic acids. 364
The H2O2/UVC p ocess led o highe OTC deg ada ion a es wi h he inc emen o Q 365
om 50 o 100 L h-1 (Table 3), indica ing a change in he hyd odynamic condi ions 366
inside he pho o eac o . A Re numbe o 446 (Q = 100 L h-1) allowed o a 2.3- old 367
inc ease on OTC oxida ion a e compa ing wi h a Re o 223 (Q = 50 L h-1). A hose 368
condi ions, an OTC emo al abo e 90% is achie ed a e 5 min o eac ion wi h 0.4 kJ 369
L-1. 370
16
3.2 OTC deg ada ion by an UVC/H2O2 pho ochemical sys em using an inno a i e 371
FluHelik pho o eac o in mul iple pass low mode 372
An ini ial H2O2 dose o 300 mg L-1 led o a maximum OTC oxida ion a e and 373
mine aliza ion, co esponding o a 9- old inc emen on eac ion a e when compa ed o 374
di ec pho olysis (Table 3). A highe oxidan dose (400 mg L-1) led o a sligh ly dec ease 375
in he OTC oxida ion a e, due o hyd oxyl adicals quenching by he hyd ogen pe oxide 376
molecule i sel . This is also suppo ed by he g owing H2O2 consump ion o ising 377
ini ial H2O2 doses (Fig. 3). Using 300 mg L-1 o oxidan , a 77% mine aliza ion was 378
a ained a e 360 min wi h a inal esidual H2O2 concen a ion o 17 mg L-1. 50% o he 379
emaining DOC was om oxalic and oxamic acids. In u n, he ni ogen con en o he 380
OTC compound was con e ed o ni i es, ni a es and ammonium, wi h ammonia 381
ep esen ing he la ges ac ion. The un-mine alized ac ion o ni ogen p o ed o be 382
p esen as oxamic acid, as also obse ed by Pe ei a e al. (2013)). 383
Inse Figu e 3 384
The OTC emo al a e showed a 1.6- old inc ease when he low a e inc eased om 50 385
o 75 L h-1. A u he inc ease on low a e om 75 o 100 L h-1 esul ed in an inc emen 386
on he eac ion a e o only 1.2 imes (see Table 3). This indica es ha he 387
hyd odynamic condi ions do no conside ably change be ween 75 o 100 L h-1. Unde 388
his condi ion (100 L h-1), an OTC emo al >90% is eached a e 5 min o eac ion (0.4 389
kJ L-1 o accumula ed ene gy), wi h a pho onic e iciency (ξ) (numbe o OTC 390
ans o med molecules di ided by he numbe o inciden pho ons) o 13.7%. 391
Compa ing he deg ada ion o he OTC molecule in UPW ma ix by he wo eac o s 392
unde s udy in he bes condi ions ound o each one (Fig. 4), i was p ac ically simila 393
in bo h eac o s. On he o he hand, FluHelik eac o showed o be mo e e icien (1.3 394
imes) in e ms o mine aliza ion (77%) when compa ed wi h he Je s eac o (61%), o 395
17
he same accumula ed UVC ene gy (14.4 kJUV L-1). This indica es ha he limi ing s ep 396
o he eac ion is he by-p oduc s emo al, which is imp o ed by he unique luid 397
dynamics and i adia ion p ope ies o FluHelik eac o . 398
Inse Figu e 4 399
3.3 E ec o u ban was ewa e (UWW) ma ix 400
OTC emo al by he UVC/H2O2 pho ochemical sys em was also e alua ed o an UWW 401
o i ied wi h 20 mg OTC L-1. Fig. 5a shows an inc emen on OTC emo al a e o 402
highe H2O2 doses using he Je s pho o eac o . In ac , a 29- old inc ease on OTC 403
oxida ion a e is obse ed o he UVC/H2O2 sys em ([H2O2]0 = 500 mg L-1) when 404
compa ed o di ec pho olysis (Table 3). Likewise, i was ound ha he highes OTC 405
oxida ion a e using he UWW and he FluHelik pho o eac o was eached wi h he 406
highes oxidan concen a ion applied ([H2O2]0 = 500 mg L-1) (Fig 5b, Table 3). An 407
inc ease in he low a e alue om 50 o 100 L h-1, achie ed a 1.2- old imp o emen in 408
he OTC eac ion a e (Table 3), associa ed wi h an highe deg ee o mixing inside he 409
sys em. Unde hose condi ions (500 mg H2O2 L-1; 100 L h-1), 90% o OTC emo al 410
was achie ed a e 7.5 min o eac ion and using 0.6 kJUV L-1 and a inal mine aliza ion 411
o 71% was a ained a e 180 min o eac ion and 14.4 kJUV L-1. Pa alleling he eac ion 412
a es in bo h ma ices, a dec ease o abou 1.7 imes was pe cei ed when in he p esence 413
o he UWW, using he same ini ial H2O2 dosage, mainly due o inne il e and 414
hyd oxyl adicals sca enging e ec s (Wols and Ho man-Ca is, 2012). The e o e, a 415
highe amoun o oxidan is equi ed o o e come hose e ec s o ob ain simila OTC 416
emo als. In ac , when using he FluHelik pho o eac o o bo h ma ices, a he bes 417
condi ions, simila pho ochemical space ime yield (PSTY) we e obse ed (0.50 and 418
0.53 m3wa e m-3 eac o day-1 kW-1 using he UPW and UWW, espec i ely). This shows 419
he abili y o he FluHelik eac o design o o e come ma ix e ec s due o i s unique 420
18
cha ac e is ics. I should be no ed ha he high H2O2 concen a ions used in hese 421
expe imen s we e due o he low pho on lows p o ided by he a ailable UVC lamps. I 422
highe pho on lows a e p o ided (able o o e coming he was ewa e inne il e 423
e ec s), lowe ini ial doses o oxidan would be equi ed o achie e he same OTC 424
oxida ion a es. 425
Inse Figu e 5 426
The FluHelik pho o eac o showed a be e pe o mance han he con en ional Je s 427
eac o du ing he OTC oxida ion when in he p esence o he UWW ma ix a he same 428
ope a ing condi ions (500 mg L-1 o H2O2 and 100 L h-1) (Fig. 6, Table 3). In his case, 429
he helical mo emen o he luid a ound he adia ion sou ce allows a mo e 430
homogeneous UV adia ion dis ibu ion, enhancing he eac ion a e. In ac , he Je s 431
eac o p esen s a solu ion low pa e n pa allel o he adia ion sou ce, and 432
consequen ly, he liquid s eams a highe dis ance om he ligh sou ce ecei e a less 433
UV dose. FluHelik’s unique luid hyd odynamics also p o ided a mo e e icien oxidan 434
homoly ic clea age, allowing u he emo al o he emaining by-p oduc s. In ac , a 435
1.4 imes highe hyd ogen pe oxide consump ion was obse ed when using he 436
FluHelik eac o (Fig. 6), eaching a mine aliza ion o 71% ins ead o 56% o he Je s 437
eac o , using he same accumula ed UVC ene gy (14.4 kJUV L-1). 438
Inse Figu e 6 439
The FluHelik pho o eac o was also e alua ed o he ea men o an UWW ma ix 440
spiked wi h OTC and 10 addi ional CECs (desc ibed in Table 2) om he 12 es ablished 441
by Swiss legisla ion (Hochs a e al., 2015) a esidual concen a ions (60 μg L-1) using 442
he UVC/H2O2 pho ochemical p ocess. The Swiss legisla ion es ablishes 80% emo al 443
o 5 ou o 12 indica o compounds (11 pha maceu icals and 1 biocide) (Hochs a e 444
al., 2015). An OTC emo al o mo e han 80% can be achie ed using only 10 mg L-1 o 445
19
H2O2 (Table 2) a e 30 min. In o de o comply wi h he Swiss legisla ion, an oxidan 446
amoun o 250 mg L-1 is equi ed o achie e 80% emo al o 5 compounds a e 30 min. 447
Howe e , using a H2O2 dose o 500 mg L-1, a e 30 min o eac ion, a emo al 448
e iciency o 80% is ob ained o all he 11 CECs. 449
3.4 CECs emo al by an UVC/H2O2 pho ochemical sys em using FluHelik/Je s 450
pho o eac o s in single pass low mode 451
In o de o es ima e he e iciency in a eal scale implemen a ion, es s we e pe o med 452
in single pass low mode (one passage h ough he eac o ) ins ead o eci cula ing he 453
solu ion be ween he eac o and he eed ank (mul iple passage). In his way i is also 454
ensu ed ha only he hyd odynamic e ec o he eac o s is e alua ed, excluding he 455
addi ional mix u e p omo ed by he eci cula ion. Fig 7a shows an imp o emen on he 456
OTC emo al om an UWW ma ix, a he s eady s a e condi ions (5 imes he 457
esidence ime), by he UVC/H2O2 p ocess (500 mg H2O2 L-1; 6 W; 100 L h-1), using he 458
FluHelik pho o eac o (18% OTC emo al) ins ead o he Je s eac o (15% OTC 459
emo al). In ac , he longe esidence ime o FluHelik eac o (0.4 min) when 460
compa ed o ha o he Je s eac o (0.3 min), along wi h he highe accumula ed ene gy 461
(in a single passage) and wi h he lowe dead olume zones due o he FluHelik helical 462
mo emen o he luid con ibu ed o he highe OTC emo al. 463
Table 2 shows ha much smalle emo als o all he 11 CECs spiked in he UWW we e 464
achie ed by ope a ing he FluHelik ea o in single passage mode (low esidence ime): 465
none o he compounds each he emo al imposed by Swiss legisla ion. The design o 466
he FluHelik pho o eac o s ongly a o s he implemen a ion o a ious eac o s in 467
se ies, p omo ing i s applica ion in indus y. The e o e, wo FluHelik pho o eac o s 468
associa ed in se ies we e es ed o he emo al o 20 mg L-1 o OTC unde he same 469
condi ions p e iously es ed wi h only one eac o . Howe e , i was no iced ha when 470
20
using he wo eac o s in se ies an OTC emo al o only 31% was ob ained a e 471
eaching he s eady s a e (Fig. 7b), a lowe alue han he one expec ed (36% - wice he 472
one achie ed wi h only one eac o ). In ac , when using 2 FluHelik eac o s in se ies, 473
di e en eloci y p o iles can be ound in he each eac o due o an inc ease in luid 474
ene gy dissipa ion (p essu e d op). The e o e, a new es was ca ied ou doubling he 475
low a e (200 L h-1), co esponding o a esidence ime o 0.4 min. A hese condi ions, 476
an OTC emo al o 36% was a ained a s eady s a e condi ions. The e o e, when using 477
2 FluHelik eac o s in se ies he e is a minimum low a e alue o be used o achie e 478
luid eloci ies p o iles inside bo h pho o eac o s simila o when using only one 479
FluHelik eac o . 480
Inse Figu e 7 481
Finally, a pilo -scale FluHelik eac o (95 W UVC lamp) unde mul iple pass low mode 482
was also e alua ed o he OTC emo al using ei he UPW and UWW as solu ion 483
ma ices. This sys em was ope a ed a a low a e o 7500 L h-1, a aining a u bulen 484
egime inside he pho o eac o (Re = 15000). Fig. 8a and 8b show ha he highes OTC 485
oxida ion a e was eached when using 500 mg L-1 o H2O2 o bo h eac ion ma ices. 486
Howe e , a 1.5- old dec ease in he OTC kine ic a e (Table 3) was ob ained o he 487
UWW when compa ed wi h UPW, as well as a sligh ly lowe mine aliza ion (52% 488
ins ead o 58%) using 4.6 kJUV L-1. I should be no ed ha , a he bes condi ions, when 489
using UPW, a highe pho ochemical space ime yield (PSTY) a p e-pilo scale (0.85 490
m3wa e m-3 eac o day-1 kW-1) when compa ed wi h he one a lab scale (0.50 m3wa e 491
m-3 eac o day-1 kW-1) was no iced. This dissimila i y is mainly associa ed o he di e en 492
low a es and UV luence inside he eac o s (dis inc pa h leng h and UVC lamp 493
powe ). In addi ion, when using UWW, simila PSTY we e obse ed a bo h scales 494
(0.57 and 0.53 m3wa e m-3 eac o day-1 kW-1 a he p e-pilo scale and lab scale, 495
21
espec i ely). These da a a e in ag eemen wi h he esul s ob ained by Mo ei a e al. 496
(2019)) when compa ing he deg ada ion o a model compound, 3-amino-5-497
me hylisoxazole, using he FluHelik a he lab and p e-pilo scale; and indica e he 498
easibili y o scaling-up he FluHelik eac o . 499
Inse Figu e 8 500
3.5 Toxici y 501
The pe cen age o emb yo mo ali y a he end o he bioassays was simila among 502
ea men s and emained a low le els, below 3% (da a no shown). The o al 503
abno mali ies, he leng h and he yolk sac pe ime e obse ed on zeb a ish emb yos 504
exposed o he ini ial and ea ed e luen s a e p esen ed in Fig. 9. A signi ican inc ease 505
o o al abno mali ies (sum o ail abno mali ies, lo dosis anomalies and pe ica dial 506
oedema) was obse ed in emb yos exposed o he UWW + 11 CECs, wi h 12.5% o 507
abno mal emb yos in compa ison wi h 1.4% o he con ol (p < 0.05). These 508
abno mali ies we e signi ican ly educed a e he FluHelik pho ochemical ea men 509
(UWW + 11 CECs + T ea men ), wi h alues simila o he con ol (4.7% - p > 0.05). 510
The exposu e o he UWW wi hou he 11 CECs addi ion did no cause signi ican 511
abno mali ies in he emb yos (p > 0.05). 512
Inse Figu e 9 513
I was also e i ied ha he exposu e o he UWW + 11 CECs signi ican ly dec eased 514
he leng h o he la ae and inc ease he yolk sac pe ime e when compa ed wi h con ol 515
(p < 0.05). These endpoin s e u n o con ol le els a e he FluHelik pho ochemical 516
ea men (UWW + 11 CECs + T ea men ). The yolk sac pe ime e was also 517
signi ican ly inc eased by he UWW wi hou he 11 CECs. 518
When compa ing he oxici y e ec s o he UWW + 11 CECs wi h hose o he UWW + 519
11 CECs + T ea men (Fig. 9), i is e iden ha he UVC/H2O2 pho ochemical sys em 520
22
using he FluHelik pho o eac o led o a signi ican dec ease o he oxici y on zeb a ish 521
emb yos. In his sense, he ea ed was ewa e had no signi ican e ec s on he o al 522
abno mali ies incidence, in he leng h o he la a and in he yolk sac pe ime e . Thus, i 523
may be assumed ha he deg ada ion o pollu an s p esen in he UWW o i ied wi h 11 524
CECs by he UVC/H2O2 pho ochemical sys em wi h he FluHelik pho o eac o did no 525
esul in oxic ans o ma ion p oduc s o zeb a ish emb yos. 526
4. Conclusions 527
The FluHelik pho o ea o showed o be an in e es ing sys em o UVC/H2O2 528
pho ochemical p ocess applied o he emo al o CECs om u ban was ewa e s, as a 529
polishing s ep, being able o o comply wi h he Swi ze land legisla ion and o 530
e ec i ely educe CECs oxici y o zeb a ish emb yos. Due o i s unique con igu a ion, 531
he FluHelik p omo es an helical mo emen o he luid a ound he i adia ion sou ce, 532
p o iding a mo e homogeneous UV adia ion dis ibu ion (each luid pa icle ecei es a 533
simila UVC adia ion dosage), being able o o e come ma ix e ec s in was ewa e s 534
wi h low o mode a e ansmissibili y (inne il e e ec s). Ano he ad an age o his 535
eac o echnology is i s easy scalabili y, h ough i s e y simple and compac 536
a angemen in se ies, s ongly p omo ing i s use in indus ial applica ions. 537
Acknowledgmen s 538
This wo k was inancially suppo ed by: Associa e Labo a o y LSRE-LCM - 539
UID/EQU/50020/2019 - unded by na ional unds h ough FCT/MCTES (PIDDAC). 540
V.J.P. Vila acknowledges he FCT In es iga o 2013 P og amme (IF/00273/2013). 541
J.C.A. Espíndola acknowledges CNPq (B azil) o his schola ship (205781/2014-4). R. 542
Mon es, R. Rodil and J.B. Quin ana acknowledge he inancial suppo o Spanish 543
“Agencia Es a al de In es igación” ( e . CTM2017-84763-C3-R-2) and Xun a de 544
Galicia ( e . ED431C2017/36), bo h con ounded by FEDER/ERDF. 545
23
Re e ences 546
Ba os S, Mon es R, Quin ana JB, Rodil R, And é A, Capi ão A, e al. Ch onic 547 en i onmen ally ele an le els o sim as a in dis up emb yonic de elopmen , 548 biochemical and molecula esponses in zeb a ish (Danio e io). Aqua ic 549 Toxicology 2018; 201: 47-57. 550 Boyjoo Y, Ang M, Pa eek V. CFD simula ion o a pilo scale slu y pho oca aly ic 551 eac o and design o mul iple-lamp eac o s. Chemical Enginee ing Science 552 2014; 111: 266-277. 553 Cambié D, Bo ecchia C, S aa ho NJW, Hessel V, Noël T. Applica ions o 554 Con inuous-Flow Pho ochemis y in O ganic Syn hesis, Ma e ial Science, and 555 Wa e T ea men . Chemical Re iews 2016; 116: 10276-10341. 556 Ca is CHM. New concep s o UV/H2O2 oxida ion: KWR, 2011. 557
Diya’uddeen BH, Daud WMAW, Abdul Aziz AR. T ea men echnologies o 558 pe oleum e ine y e luen s: A e iew. P ocess Sa e y and En i onmen al 559 P o ec ion 2011; 89: 95-105. 560 H. Baxendale J, A. Wilson J. The Pho olysis o Hyd ogen Pe oxide a High Ligh 561 In ensi ies. Vol 53, 1957. 562 Hochs a R, Scha e M, Bleny H. Elimina ion o mic opollu an s – he Swiss app oach. 563 TAPES Final Con e ence, B ussels, 2015. 564 Jeong J, Song W, Coope WJ, Jung J, G ea es J. Deg ada ion o e acycline an ibio ics: 565 Mechanisms and kine ic s udies o ad anced oxida ion/ educ ion p ocesses. 566 Chemosphe e 2010; 78: 533-540. 567 Ka pel VelLei ne N, Le B as E, Foucaul E, Bousga bies JL. A new pho ochemical 568 eac o design o he ea men o abso bing solu ions. Wa e Science and 569 Technology 1997; 35: 215-222. 570 K ishnan S, Rawind an H, Sinna hambi CM, Lim JW. Compa ison o a ious ad anced 571 oxida ion p ocesses used in emedia ion o indus ial was ewa e laden wi h 572 ecalci an pollu an s. IOP Con e ence Se ies: Ma e ials Science and 573 Enginee ing 2017; 206: 012089. 574 Kuhn HJ, B asla sky SE, Schmid R. Chemical ac inome y (IUPAC Technical Repo ). 575 Pu e and Applied Chemis y. 76, 2004, pp. 2105. 576 Lamme E, Ca GJ, Wendle K, Rawlings JM, Belange SE, B aunbeck T. Is he ish 577 emb yo oxici y es (FET) wi h he zeb a ish (Danio e io) a po en ial 578 al e na i e o he ish acu e oxici y es ? Compa a i e Biochemis y and 579 Physiology Pa C: Toxicology & Pha macology 2009; 149: 196-209. 580 Leblebici ME, S e anidis GD, Van Ge en T. Compa ison o pho oca aly ic space- ime 581 yields o 12 eac o designs o was ewa e ea men . Chemical Enginee ing and 582 P ocessing: P ocess In ensi ica ion 2015; 97: 106-111. 583 Liu Y, He X, Duan X, Fu Y, Dionysiou DD. Pho ochemical deg ada ion o 584 oxy e acycline: In luence o pH and ole o ca bona e adical. Chemical 585 Enginee ing Jou nal 2015; 276: 113-121. 586 Macedo S, To es T, San os MM. Me hyl- iclosan and iclosan impac emb yonic 587 de elopmen o Danio e io and Pa acen o us li idus. Eco oxicology 2017; 26: 588 482-489. 589 Masschelein WJ. Ul a iole disin ec ion o wa e . In : Uni P ocesses in D inking 590 Wa e T ea men . Vol Chap. 4, 1992. 591
Mo ei a FC, Bocos E, Fa ia AGF, Pe ei a JBL, Fon e CP, San os RJ, e al. Selec ing he 592 bes piping a angemen o scaling-up an annula channel eac o : An 593
30
Figu e 3 700
701
702 703
704
705
706
0 2 4 6 8 10 12 14 16 18 20
0.0
0.2
0.4
0.6
0.8
1.0
[OTC]/[OTC]0
Time (min)
020 40 60
0
50
100
150
200
Consumed H
2O2 (mg L-1)
Time (min)
31
Figu e 4 707
708
709
710
711
712
713
714
715
716
717
718
719
720
721
722
723
724
725
0.0 0.4 0.8 1.2 1.6
0.0
0.2
0.4
0.6
0.8
1.0
0 4 8 12 16 20 24 28
0
50
100
150
200
250
300
QUV (kJ L-1)
Consumed H
2O2 (mg L-1)
0
20
40
60
80
100
Mine aliza ion (%)
je
lu
[OTC]/[OTC]0
QUV (kJ L-1)
32
Figu e 5 726
727
(a)
(b)
728
729
020 40 60
0.0
0.2
0.4
0.6
0.8
1.0
020 40 60
0
25
50
75
100
Consumed H
2O2 (mg L-1)
Time (min)
[OTC]/[OTC]0
Time (min)
020 40 60
0.0
0.2
0.4
0.6
0.8
1.0
020 40 60
0
50
100
150
200
Consumed H
2O2 (mg L-1)
Time (min)
[OTC]/[OTC]0
Time (min)
33
Figu e 6 730
731
732
0.0 0.4 0.8 1.2 1.6 2.0 2.4
0.0
0.2
0.4
0.6
0.8
1.0
04812
0
50
100
150
200
250
300
350
400
450
QUV (kJ L-1)
Consumed H
2O2 (mg L-1)
0
20
40
60
80
100
Mine aliza ion (%)
[OTC]/[OTC]0
QUV (kJ L-1)
34
Figu e 7 733
734
(a)
(b)
735
736
737
738
739
740
741
742
0.0 0.1 0.2 0.3 0.4
0.80
0.84
0.88
0.92
0.96
1.00
[OTC]/[OTC]0
QUV (kJ L-1)
0 1 2 3 4 5
0.64
0.68
0.72
0.76
0.80
0.84
0.88
0.92
0.96
1.00
[OTC]/[OTC]0
Time (min)
35
Figu e 8 743
(a)
(b)
744
0 5 10 15 20 25 30 35 40 45
0.0
0.2
0.4
0.6
0.8
1.0
[OTC]/[OTC]0
Time (min)
020 40 60
0
10
20
30
40
50
60
70
Consumed H
2O2 (mg L-1)
Time (min)
0 5 10 15 20 25 30 35 40 45
0.0
0.2
0.4
0.6
0.8
1.0
020 40 60
0
10
20
30
40
50
Consumed H
2O2 (mg L-1)
Time (min)
[OTC]/[OTC]0
Time (min)
36
Figu e 9 745
746
(a)
(b)
747
0
20
40
60
80
100
Con ol
UWW
UWW + 11 CECs
UWW + 11 CECs +
T ea men
To al abno mali ies (%)
a
b a
a
0
20
40
60
80
100
120
140
Con ol
UWW
UWW + 11 CECs
UWW + 11
CECs +
T ea men
Pe ime e (%)
a
b a
a
+
*
# +
a a
b
a
37
Table 1. Main physicochemical cha ac e is ics o he eal u ban was ewa e collec ed 748
a e seconda y ea men . 749
Pa ame e (uni s)
Values
Colo
Pale/Yellow
Odo
n.d.a
pH
6.5
Tempe a u e (°C)
24.7
Tu bidi y (UNT)
1.0
Conduc i i y (µS cm-1)
883
Dissol ed oxygen (mg L-1)
3.8
Redox po en ial (mV)
-10
To al dissol ed ca bon (mg L-1)
51
Dissol ed ino ganic ca bon (mg L-1)
33
Dissol ed o ganic ca bon (mg L-1)
18
Chemical oxygen demand (mg O2 L-1)
56
To al dissol ed i on (mg L-1)
0.26
Abso bance a 254 nm (AU)
0.21
To al suspended solids (mg L-1)
1.7
Vola ile suspended solids (mg L-1)
1.7
To al dissol ed ni ogen (mg L-1)
3.9
To al dissol ed o ganic ni ogen (mg L-1)
2.7
Ammonium - N-NH4+ (mg L-1)
1.1
Ni i e - N-NO2- (mg L-1)
<0.02
Ni a e - N-NO3- (mg L-1)
0.09
B omide - B - (mg L-1)
0.1
Chlo ide - Cl- (mg L-1)
174
Phospha e - PO43- (mg L-1)
12
Sul a e - SO42- (mg L-1)
76
Calcium - Ca2+ (mg L-1)
57
Li hium - Li+ (mg L-1)
<0.02
Magnesium - Mg2+ (mg L-1)
9.1
Po assium - K+ (mg L-1)
29
Sodium Na+ (mg L-1)
136
To al phospho ous - P (mg L-1)
4.8
A enolol (μg L-1)
1.1
Ca bamazepine (μg L-1)
4.8
Diclo enac (μg L-1)
2.8
Me o min (μg L-1)
2.1
Sul ame hoxazole (μg L-1)
2.4
T ime hop im (μg L-1)
3.7
a n.d. - No de ec ed. 750
38
Table 2. E ec o H2O2 ini ial concen a ion in he emo al o 11 pha maceu icals spiked in a eal u ban was ewa e by UVC/H2O2 751
pho ochemical sys em using a FluHelik pho o eac o in mul iple o single pass low mode. 752
Name
Chemical Fo mula
Company
% Remo al o CECs in mul iple pass low mode
(a e 30 min)
% Remo al
o CECs in
single pass
low mode
[H2O2]0
10 mg L-1
25 mg L-1
50 mg L-1
250 mg L-1
500 mg L-1
500 mg L-1
Azy omicyn
C38H72N2O12
TCI
9.3
19
23
> 95
> 95
24
Nap oxen
C14H14O3
Al aAesa
60
68
79
> 99
> 99
26
A enolol
C14H22N2O3
Al aAesa
27
42
62
> 99
> 99
35
Me o min
NH2C(=NH)NHC(
=NH)N(CH3)2.HCl
Al aAesa
1.9
6.0
6.7
72
90
15
Beza ib a e
C19H20ClNO4
Al aAesa
40
51
66
> 99
> 99
18
Ibup o en
C13H18O2
Al aAesa
30
38
63
> 99
> 99
35
T ime hop im
C14H18N4O3
Al aAesa
19
29
43
> 99
> 99
17
Ca bamazepin
C15H12N2O
ACROS
o ganics
25
30
45
> 99
> 99
19
Sul ame hoxazole
C10H11N3O3S
TCI
98
99
> 99
> 99
> 99
25
Oxy e acycline
C22H24N2O9.HCl
AppliChem
Pan eac
92
96
98
> 99
> 99
32
Diclo enac
C14H10ClN.NaO2
Sigma
Ald ich
96
98
97
> 99
> 99
31
753
39
Table 3. Pseudo- i s o de kine ic cons an s along wi h he co esponding coe icien o de e mina ion (R2) and esidual a iance (S2 ), pho onic 754
e iciencies ( and pho ochemical space ime yields (PSTY) o deg ada ion o 20 mg L-1 o OTC a pH 7.5 and 25 ºC. 755
Expe imen
[OTC]0
(mg L-1)
[H2O2]
(mg L-1)
Q
(L h-1)
pH
k×101
(min-1)
k
(L kJ-1)
R2
S2
(mg L-1)2
0×102
(mg L-1 min-1)
×102
PSTY
(m3wa e m-3 eac o day-1 kW-1)
Je s pho o eac o - UVC lamp o 6 W
1.1
5.1
0
100
4.5
0.17 ± 0.01
0.21 ± 0.01
0.989
0.02
0.018 ± 0.001
0.11
0.02
1.2
5.0
0
100
7.5a
0.30 ± 0.02
0.37 ± 0.03
0.963
0.08
0.032 ± 0.002
0.19
0.03
1.3
5.0
0
100
7.5
1.1 ± 0.1
1.4 ± 0.1
0.976
0.07
0.12 ± 0.01
0.70
0.12
Je s pho o eac o - UVC lamp o 4 W
2.1
21.3
0
100
7.5
0.41 ± 0.04
1.2 ± 0.1
0.963
2.0
0.19 ± 0.02
2.6
0.10
2.2
20.9
20
100
7.5
1.3 ± 0.1
4.0 ± 0.3
0.976
1.3
0.6 ± 0.1
8.5
0.34
2.3
21.8
50
100
7.5
1.5 ± 0.2
4.6 ± 0.5
0.963
2.0
0.7 ± 0.1
10.3
0.40
2.4
19.9
100
100
7.5
2.7 ± 0.1
7.8 ± 0.4
0.988
0.6
1.2 ± 0.1
16.1
0.69
2.5
20.0
200
100
7.5
2.8 ± 0.1
8.2 ± 0.3
0.999
0.1
1.23 ± 0.04
17.2
0.73
Je s pho o eac o - UVC lamp o 6 W
3.1
20.9
0
100
7.5
0.52 ± 0.05
0.65 ± 0.06
0.961
2.0
0.24 ± 0.02
1.4
0.06
3.2
22.0
20
100
7.5
2.4 ± 0.3
3.1 ± 0.3
0.968
2.1
1.2 ± 0.1
6.9
0.26
3.3
22.9
50
100
7.5
4.0 ± 0.3
5.0 ± 0.4
0.972
1.6
2.0 ± 0.2
11.7
0.43
3.4
20.2
100
100
7.5
5.0 ± 0.2
6.3 ± 0.2
0.998
0.1
2.2 ± 0.1
13.0
0.54
3.5
21.0
200
100
7.5
4.7 ± 0.2
5.9 ± 0.3
0.996
0.3
2.1 ± 0.1
12.6
0.51
3.6
20.8
100
50
7.5
2.2 ± 0.1
2.8 ± 0.2
0.992
0.5
1.0 ± 0.1
5.9
0.24
3.7
21.4
100
75
7.5
3.0 ± 0.3
3.7 ± 0.4
0.982
0.8
1.4 ± 0.1
8.2
0.32
Je s pho o eac o - UVC lamp o 11 W
4.1
21.5
0
100
7.5
0.58 ± 0.04
0.61 ± 0.05
0.962
1.8
0.27 ± 0.02
1.3
0.05
4.2
21.0
20
100
7.5
2.0 ± 0.2
2.1 ± 0.2
0.983
1.2
0.9 ± 0.1
4.4
0.18
4.3
22.0
50
100
7.5
3.5 ± 0.2
3.6 ± 0.2
0.974
1.2
1.7 ± 0.1
8.2
0.32
4.4
21.3
100
100
7.5
5.18 ± 0.02
5.40 ± 0.02
0.999
0.1
2.40 ± 0.01
11.8
0.47
4.5
21.3
200
100
7.5
6.4 ± 0.1
7 ± 1
0.986
0.9
2.94 ± 0.03
14.4
0.57
4.6
20.6
500
100
7.5
7.2 ± 0.2
7.5 ± 0.2
0.999
0.1
3.2 ± 0.1
15.9
0.65
4.7
20.0
700
100
7.5
5.7 ± 0.3
5.9 ± 0.3
0.996
0.2
2.5 ± 0.1
12.1
0.51
