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In e na ional Con e ence on Disin ec ion and Disin ec ion By-P oduc s
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P5. Pho oca aly ic Deg ada ion o Disin ec ion By-P oduc s (DBPs) Using
Immobilized TiO2 Nanopa icles on Po ous Foams: A No el App oach o Wa e
T ea men
M. Miodyńska*†, O. Ca da *, P. Mazie ski*, A. Pieczyńska*, A. Zaleska-Medynska*
* Depa men o En i onmen al Technologies, Facul y o Chemis y, Uni e si y o Gdańsk, Wi a S wosza 63, 80-308 Gdańsk, Poland,
[email protected]
Abs ac :
Disin ec ion by-p oduc s (DBPs) a e unin ended chemicals o med du ing wa e ea men p ocesses, posing
heal h isks due o hei ca cinogenic and mu agenic p ope ies. Pho oca alysis, employing ma e ials like i anium dioxide
(TiO
2
), o e s a p omising solu ion o DBP emo al. This s udy in oduces a no el me hod: immobilizing TiO
2
nanopa icles on a po ous Al
2
O
3
ma ix. Pho oca aly ic expe imen s we e conduc ed on wo DBP compounds,
b omodichlo ome hane (BDCM) and monochlo oace ic acid (MCAA), con i ming high deg ada ion e iciency. Minimal
DBP adso p ion on he pho oca aly ic laye s was obse ed, wi h enhanced pho olysis o BDCM compa ed o MCAA.
S abili y es s o e i e cycles demons a ed consis en e ec i eness. These indings highligh he po en ial o TiO
2
-based
pho oca aly ic laye s o DBP emo al.
Keywo ds
: Pho oca alysis; Disin ec ion by-p oduc s; Wa e ea men
INTRODUCTION
Disin ec ion by-p oduc s (DBPs) a e chemical compounds ha o m as unin ended byp oduc s o
disin ec ion p ocesses in wa e ea men acili ies. These compounds esul om he eac ion o
disin ec an s, such as chlo ine o chlo amine, wi h o ganic and ino ganic ma e p esen in he wa e
(Xiao e al. 2023). While disin ec ion is c ucial o p e en ing he sp ead o wa e bo ne diseases, he
p esence o DBPs poses po en ial heal h isks due o hei ca cinogenic and mu agenic p ope ies
(Kimu a and O ega-He nandez 2019). E o s o mi iga e he ha m ul e ec s o DBPs ha e led o
he explo a ion o a ious emo al me hods (Mazha e al. 2020). Among hese me hods,
pho oca alysis has eme ged as a p omising app oach o he deg ada ion o DBPs in wa e (Chang e
al. 2019). Pho oca alysis in ol es he use o pho oca alys s, such as i anium dioxide (TiO
2
), which
can ha ness ligh ene gy o d i e chemical eac ions. When i adia ed wi h ligh o app op ia e
wa eleng h, pho oca alys s gene a e elec on-hole pai s, ini ia ing edox eac ions ha b eak down
o ganic pollu an s, including DBPs (Lee e al. 2023).
The pho oca aly ic emo al o DBPs o e s se e al ad an ages, including high e iciency,
en i onmen al iendliness, and he abili y o ope a e unde ambien condi ions. Mo eo e ,
pho oca alysis can a ge a wide ange o DBP compounds, making i a e sa ile solu ion o wa e
ea men applica ions.
In his s udy, we p esen a no el app oach in ol ing he immobiliza ion o a pho oca alys in he o m
o TiO
2
nanopa icles h ough he deposi ion o a homogeneous and s able laye on o a po ous Al
2
O
3
ma ix. The conduc ed expe imen s co obo a ed he ema kable e iciency o pho oca aly ic
deg ada ion conce ning wo selec ed compounds classi ied as DBPs, namely, BDCM and MCAA,
u ilizing he esul an laye s endowed wi h pho oca aly ic capabili ies.
MATERIALS AND METHODS
A pho oca aly ic ma e ial, comp ising a po ous Al
2
O
3
ma ix (p e- ea ed wi h isop opanol deg easing
and subsequen d ying), was u ilized in conjunc ion wi h a pho oca aly ic pas e (as de ailed in pa en
applica ion PCT/PL2021/050011). The pas e inco po a ed TiO
2
pa icles (P25, Ae oxide) and was
applied on o he Al
2
O
3
ma ix ia a con en ional deep coa ing echnique, wi h an applica ion du a ion
o 3 minu es. Following applica ion, excess pas e was elimina ed by ni ogen blowing om all
di ec ions o he ma ix. The esul ing pho oca aly ic laye s we e hen d ied o e nigh a 60 ℃ and
subsequen ly calcined a 450 ℃. As p epa ed pho oca aly ic oam is depic ed in Figu e 1a.
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Pho oca aly ic measu emen s we e conduc ed wi hin a e lon eac o (as shown in Figu e 1b). The
eac o con ained he pho oca aly ic laye , along wi h 25 mL o an aqueous solu ion o DBP wi h an
ini ial concen a ion o 20 mg/L, alongside a magne ic ba , and was he me ically sealed. P io o
i adia ion, he eac o was s i ed in da kness o 30 minu es o es ablish adso p ion-deso p ion
equilib ium be ween he pho oca aly ic laye and DBP molecules. Following his, a e e ence sample
was collec ed, and he sys em was subjec ed o 1 hou o i adia ion, wi h con ol samples (0.5 mL)
wi hd awn ia a silicone sep um e e y 20 minu es. The samples unde wen il a ion h ough a
sy inge il e (wi h a po e size o 200 µm) and we e p omp ly analyzed using high-pe o mance liquid
ch oma og aphy (HPLC, Nexe a XR SIL-20AC by Shimadzu) and ion ch oma og aphy (Me ohm
AG 940 P o essional IC Va io). To minimize he in luence o empe a u e on DBP emo al, he
sys em was cooled o 16 ℃ du ing whole expe imen . The e alua ed DBPs included
b omodichlo ome hane (BDCM) and monochlo oace ic acid (MCAA). Addi ionally, he s abili y o
he sys em was assessed o e i e pho oca aly ic cycles, wi h each cycle in ol ing he emo al o he
DBP solu ion om he ba ch eac o and subsequen eplenishmen wi h a esh 25 mL po ion o
DBP solu ion (C
0
=20 mg/L). These p ocesses we e conduc ed unde iden ical condi ions as desc ibed
abo e, and sample analysis ollowed he same p o ocol.
Figu e 1
a) Pho oca aly ic laye , b) Te lon ba ch eac o o pho oca aly ic expe imen s.
RESULTS AND DISCUSSION
The ob ained pho oca aly ic laye s we e applied in a pho oca aly ic eac ion aimed a decomposing
molecules o BDCM and MCAA. Figu e 2 p esen s he esul s along wi h he pho olysis o hese
compounds in he UV-Vis i adia ion ange (p ocess wi hou he pho oca aly ic laye ) as well as
conduc ed in da kness (90 minu es) o de e mine he abili y o DBP molecules o adso b.
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Figu e 2
a) Pho oca aly ic deg ada ion o BDCM (C
0
=20 mg/L), b) Pho oca aly ic deg ada ion o MCAA (C
0
=20 mg/L).
The deg ada ion e iciency o BDCM and MCAA was egis e ed a app oxima ely 45 % and 90 %
a e 60 minu es o i adia ion, espec i ely. In bo h cases, minimal adso p ion o DBPs molecules on
he pho oca aly ic laye s in da kness was obse ed. Howe e , inc eased pho olysis o BDCM in he
UV-Vis i adia ion ange (abou 25 %) compa ed o he ob ained pho olysis o MCAA (abou 13 %)
was also no ed. None heless, he s abili y o he pho oca aly ic laye s was in es iga ed in i e
consecu i e pho oca aly ic cycles using he deg ada ion o BDCM as an example. Figu e 3 p esen s
he ob ained esul s, clea ly indica ing he consis en e ec i eness o employing he p oposed
pho oca aly ic ma e ials in he deg ada ion eac ion o he DBPs ep esen a i e, BDCM.
Figu e 3
Tes ing he s abili y o he pho oca aly ic laye in i e BDCM (C
0
=20 mg/L) deg ada ion cycles.
The conduc ed expe imen s demons a e a emendous po en ial o he applica ion o pho oca aly ic
emo al o DBPs in he p esence o he p oposed pho oca aly ic laye s con aining TiO
2
.
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ACKNOWLEDGEMENTS
The esea ch was inanced by he Ho izon Eu ope P og am o he Eu opean Union as pa o he p ojec No.
101081963 “Inno a i e In eg a ed Tools and Technologies o P o ec and T ea D inking Wa e om
Disin ec ion Byp oduc s (DBPs)”, ac onym “H2O o All”.
REFERENCES
Chang, Xueming, Xiaolong Yao, Ning Ding, Xiu eng Yin, Qinmin Zheng, Songliu Lu, Danmeng Shuai, & Yingxue Sun.
2019. Pho oca aly ic Deg ada ion o T ihalome hanes and Haloace oni iles on G aphi ic Ca bon Ni ide unde Visible
Ligh I adia ion.
STOTEN
,
682
, 200–207.
Hassaan, Mohamed A, Mohamed A El-Nem , Ma wa R Elka o y, Sa aa Ragab, Viole a-Ca olina Niculescu, & Ahmed
El Nem . 2023. P inciples o Pho oca alys s and Thei Di e en Applica ions: A Re iew.
Top. Cu . Chem. (Z).381
, 31.
Kimu a, Susana Y, & Alejand o O ega-He nandez. 2019. Fo ma ion Mechanisms o Disin ec ion Byp oduc s: Recen
De elopmen s.
Cu en Opinion in En i onmen al Science & Heal h
,
7
, 61–68.
Mazha , Mohd Aami , Nadeem A Khan, Si ajuddin Ahmed, A zal Husain Khan, Azha Hussain, Rahisuddin, Fazlollah
Changani, Mahmood Youse i, Shahin Ahmadi, & Viola Vambol. 2020. Chlo ina ion Disin ec ion By-P oduc s in
Municipal D inking Wa e – A Re iew.
J. Clean. P od.
273
, 123159.
Lee, Dong-Eun, Mo-Keun Kim, Moh a am Danish, and Wan-Kuen Jo. 2023. S a e-o - he-A Re iew on Pho oca alysis
o E icien Was ewa e T ea men : A ac i e App oach in Pho oca alys Design and Pa ame e s A ec ing he
Pho oca aly ic Deg ada ion.
Ca al. Comm.
183
, 106764.
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Pho oca aly ic Deg ada ion o Disin ec ion
By-P oduc s (DBPs) Using Immobilized TiO2
Nanopa icles on Po ous Foams: A No el
App oach o Wa e T ea men
Magdalena Miodyńska-Melze , Onu Ca da , Paweł Mazie ski, Aleksand a Pieczyńska,
Ad iana Zaleska-Medynska
Depa men o En i onmen al Technology, Facul y o Chemis y, Uni e si y o Gdansk, Wi a S wosza 63 S ee , 80-308 Gdańsk, e-mail: magdalena.miodynska-melz[email p o ec ed]
Disin ec ion by-p oduc s (DBPs) a e chemical compounds o med unin en ionally du ing wa e ea men when disin ec an s like chlo ine o chlo amine eac wi h o ganic and
ino ganic ma e [1]. While disin ec ion p e en s wa e bo ne diseases, DBPs pose heal h isks due o hei ca cinogenic and mu agenic p ope ies [2]. To educe DBP le els,
a ious emo al me hods ha e been explo ed [3], wi h pho oca alysis showing p omise o DBP deg ada ion [4]. Using pho oca alys s like i anium dioxide (TiO2), pho oca alysis
ha nesses ligh o d i e eac ions ha b eak down DBPs [5]. In his s udy, we p opose immobilizing TiO2 nanopa icles on a po ous Al2O3 ma ix, demons a ing e ec i e
pho oca aly ic deg ada ion o selec ed DBPs.
CONCLUSIONS
4 h In e na ional Con e ence on Disin ec ion and DBPs | Oc obe 21s –24 h 2024 | Alme ía, Spain
Acknowledgemen : The esea ch was unded by he Ho izon Eu ope P og am o he Eu opean Union as pa o he p ojec No. 101081963
“Inno a i e In eg a ed Tools and Technologies o P o ec and T ea D inking Wa e om Disin ec ion Byp oduc s (DBPs)”, ac onym
“H2O o All”.h ps://h2o o all.eu/
Re e ences:
[1] R. Xiao e al., Disin ec ion Byp oduc s and Thei P ecu so s in D inking Wa e Sou ces: O igins, In luencing Fac o s, and En i onmen al Insigh s, Enginee ing., 36 (2024)36–50.
[2] Kimu a e al.,Fo ma ion Mechanisms o Disin ec ion Byp oduc s: Recen De elopmen s. Cu en Opinion in En i onmen al Science & Heal h, 7 (2019)61–68.
[3] Mazha e al., Chlo ina ion Disin ec ion By-P oduc s in Municipal D inking Wa e –A Re iew. Jou nal o Cleane P oduc ion, 273 (2020)123159.
[4] Chang, e al., Pho oca aly ic Deg ada ion o T ihalome hanes and Haloace oni iles on G aphi ic Ca bon Ni ide unde Visible Ligh I adia ion. Science o The To al En i onmen , 682 (2019)200–207.
[5] Lee, e al., S a e-o - he-A Re iew on Pho oca alysis o E icien Was ewa e T ea men : A ac i e App oach in Pho oca alys Design and Pa ame e s A ec ing he Pho oca aly ic Deg ada ion. Ca alysis
Communica ions, 183 (2023)106764.
Figu e 3 – E iciency o pho oca aly ic deg ada ion o di e en ype o DBPs compound in he p esence o
pho oca aly ic laye s.
RESULTS
Label Name
BDCM
B omodichlo ome hane
MCAA
Monochlo oace ic
acid
CSA
5
-Chlo osalicylic acid
CP
4
-Chlo ophenol
DCP
2,4
-Dichlo ophenol
TCP
2,4,6
-T ichlo ophenol
CNP
4
-Chlo o-3-ni ophenol
METHODOLOGY
Pho oca aly ic oams p epa a ion
Pho oca aly ic expe imen s
Figu e 1 – Scheme o pho oca aly ic oam p epa a ion.
➢Sou ce o ligh : 1000 WXe lamp
➢Ligh in ensi y: 100 mW/cm²
➢Reac o olume: 25 mL
➢Ini ial concen a ion o pollu an solu ion: 20 mg/L
➢Volume o pollu an solu ion: 25 mL
➢P ocess empe a u e: 16 °C
➢Equilib ium ime: 30 minu es
➢I adia ion ime: 60 minu es (samples we e collec ed e e y 20 minu es)
➢Concen a ion analysis o DBPs: The concen a ions o BDCM, CSA, CP, DCP,
TCP, and CSA in he collec ed samples we e analyzed using HPLC/DAD, while
MCAA was analyzed using IC.
➢Fil e : ABK7 il e was used o block adia ion below 300 nm, p e en ing excessi e
pho olysis o he es ed DBPs.
➢Pho oca aly ic oam size: 2 x 2 x 1 cm
The exac con en o he pho oca aly ic pas e wi h TiO2pa icles
and pa ame e s o pho oca aly ic laye s p epa a ion is pa en ed
(no PL433102A1)
1. Cleaning ce amic oam
2. D ying he ce amic oam in he
d ye
3. Dipping he oam in o he
pho oca aly ic pas e con aining
TiO2 pa icles
4. Remo ing he pho oca aly ic
laye om he pas e and
emo ing he excess pas e
wi h an ai s eam
5. D ying he pho oca aly ic oam
in a d ye
6. Calcina ion o he oam
Figu e 2 – Pho o aly ic oam and he pho o eac o used o expe imen s o DBPs
pho odeg ada ion.
INTRODUCTION
➢A s able pho oca aly ic pas e con aining TiO₂ nanopa icles wi h e ec i e pho oca aly ic p ope ies was success ully o mula ed.
➢A eliable p ocedu e was de eloped o applying his pas e on o he su ace o comme cially a ailable po ous Al₂O₃ ce amic ma ices.
➢The esul ing pho oca aly ic laye s we e e ec i ely u ilized in he deg ada ion o selec ed DBPs unde pho oca aly ic condi ions, demons a ing excellen p ocess e iciency.
➢The highes e iciency o pho odeg ada ion was obse ed o haloacids (MCAA and CSA).
➢The weakes e iciency o pho odeg ada ion was de e mined o halome hanes (BDCM).
➢These indings p o ide a solid ounda ion o u he ad ancemen in he applica ion o he de eloped pho oca aly ic ma e ials, pa icula ly om a p ocess enginee ing
pe spec i e.
