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Article history: In the present work, a comprehensive study on the application of TiO2 photocatalysis for the removal
Received 11 October 2015 of the ame retardant tris (1-chloro-2-propyl) phosphate (TCPP) from both ultrapure water (UW) and
Received in revised form 11 March 2016 real wastewater (WW) is presented. All the photocatalytic experiments were conducted using envi-
Accepted 16 March 2016
ronmental relevant concentrations of TCPP, inherent pH and simulated solar irradiation with the view
Available online 18 March 2016
to simulate real environmental conditions. Degradation followed apparent rst-order kinetics with rate
constants varying from kapp = 14.2 102 min1 to kapp = 1.41 102 min1 for initial TCPP concentrations
Keywords:
in the range of 25500 gL1 while mineralization was accomplished in prolonged irradiation times as
Flame retardants
TCPP
monitored by the release of chlorine and phosphate ions. Scavenging studies were carried out in UW,
Photocatalysis indicating that photogenerated HO in the catalyst surface are the main species participating in the photo-
Scavengers catalytic mechanism. Experiments using secondary treated wastewater showed a signicant retardation
Transformation products of TCPP photocatalytic degradation mainly due scavenging effects and competitive adsorption of aromatic
and phenolic compounds and inorganic ions, such as HCO3 , contained in the wastewater matrix. The
transformation products were elucidated by UPLC-TOF-MS instrumentation and hydroxylation, oxida-
tion, dechlorination and dealkylation have been identied as the principal photocatalytic transformation
routes before complete mineralization. Toxicity assays in UW and WW were also conducted using Vibrio
scheri as tested organism showing a progressive toxicity decrease along the treatment till low values.
Measurements showed a higher initial toxicity and a slower decrease in WW that is attributed to the
more complex matrix regarding chemical pollutants and their transformation products formed during
the treatment as well as scavenging effects.
2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apcatb.2016.03.039
0926-3373/ 2016 Elsevier B.V. All rights reserved.
M. Antonopoulou et al. / Applied Catalysis B: Environmental 192 (2016) 152160 153
conventional wastewater treatment plants (WWTPs) [10,12]. TCPP (50 mg L1 ) was selected based on the low environmental relevant
has been detected in efuent and surface water samples at concen- concentration levels used in the irradiation experiments in order to
trations as high as 24 g L1 and 200 ng L1 , respectively [10,12]. not obtain very fast kinetics and to facilitate the study on the degra-
The main focus of the present work is to provide novel dation kinetics, mechanisms and identication of transformation
knowledge in relation to the applicability of heterogeneous TiO2 products. Prior to exposure to simulated solar irradiation, the sus-
photocatalysis to remove TCPP, a representative ame retardant pension was magnetically stirred for 30 min in the dark to ensure
pollutant, from water matrices that is studied for the rst time. adsorption equilibrium of TCPP onto the TiO2 surface. The radia-
For this purpose, the photocatalytic transformation of TCPP was tion intensity was xed at 250 W m2 for all experiments and the
investigated using concentrations similar to those detected in real incident irradiance dose for 10 min of irradiation was 150 kJ m2 as
efuents and two different aqueous matrices, ultrapure water (UW) provided by an internal radiometer of Suntest instrument. Samples
and municipal wastewater secondary treatment efuent (WW). of about 2 mL were periodically withdrawn from the reactor and
More specically, the photocatalytic transformation of TCPP in ltered for further analysis.
UW and WW, in terms of pollutant abatement and mineraliza-
tion and the effect of the matrix on the transformation process
were evaluated. The contribution of oxidative and reductive species 2.3. Analytical determinations
generated during the process was studied in detail using vari-
ous well-established scavengers. Emphasis was also placed on the TCPP quantication and identication of transformation prod-
identication of the transformation products using ultra pressure ucts was performed by means of UPLC coupled to a time of ight
liquid chromatography coupled to time-of-ight mass spectrome- mass spectrometry (UPLC-TOF-MS) system in positive ionization
try (UPLC-TOF-MS). Finally, the study focused also on the integrated mode. Samples (20 mL) were pre-concentrated by means of solid
evaluation of the treatment process by assessing the evolution of phase extraction (SPE) as reported in our previous study to a
ecotoxicity during the treatment. nal volume of 0.2 mL [5]. The UPLC-TOF-MS system consisted
of an Ultra-High Performance LC pump (Dionex Ultimate 3000,
Thermo) equipped with a C18 AcclaimTM RSLC 120 column, 100 mm
2. Experimental
x 2.1 mm, 2.2 m particle size (Thermo Fisher Scientic, San Jose,
USA), thermostated at 30 C and a microTOF Focus II time of ight
2.1. Chemicals
mass spectrometer (Brker Daltonics, Germany). A and B mobile
phases were methanol and water with 5 mM ammonium formate
TCPP (mixtures of isomers), analytical standard was obtained
respectively, at a ow rate of 0.4 mL min1 . The following program
by Sigma-Aldrich (USA). TiO2 P25 (Evonik, Germany; particle
was adopted: 1% A/99% B at 0 min to 99% A/1% B in 10 min and
size 2030 nm; crystal structure, 80% anatase and 20% rutile;
back to the initial ratio in 13 min. The injection volume was 10 L.
surface area, 56 m2 g1 , zero point of charge 6.36.8) was
The TOF mass analyzer with an electrospray interface was oper-
employed as the semiconductor catalyst in the photocatalytic
ated under the following conditions: dry gas ow rate 8 L min1
experiments. All reagents used (sodium azide (NaN3 ), KI, p-
(nitrogen), nebulizer pressure 2.4 bar, capillary voltage at 4500 V,
benzoquinone (BQ), NaF, K2 Cr2 O7 and Folin Ciocalteu) were
end plate offset at 500 V, hexapole RF 100.0 Vpp, dry temperature
obtained from Sigma-Aldrich. LCMS-grade solvents (acetonitrile,
at 200 C using otof control software. The mass accuracy (5 ppm)
isopropanol, methanol and water) were supplied by Merck and
of the TOF mass analyzer was ensured by an externally calibra-
used for UPLC-TOF-MS analyses. In order to remove the TiO2
tion using sodium formate, in the scan range m/z 501000, prior
particles of the solution samples during the experiments, HA
to analysis. Under the adopted chromatographic conditions, TCPP
0.45 m lters were supplied by Millipore (Bedford, USA). Oasis
retention time was 8.1 min The limit of detection (LOD) and limit
HLB (divinylbenzene/N-vinylpyrrolidone copolymer) cartridges
of quantitation (LOQ) was 50 and 165 ng L1 , respectively.
(60 mg, 3 mL) from Waters (Mildford, MA, USA) were used for the
Aromatic compounds content in WW sample was evaluated
extraction of water samples and the identication of transforma-
by means of the absorbance at 254 nm that was monitored using
tion products. TCPP solutions were prepared both in ultrapure
a UVvis spectrophotometer (Hitachi, U-2000). The total phenols
water (Milli-Q) and secondary (conventional activated sludge)
were determined by the FolinCiocalteau method. The phenolic
treated municipal wastewater samples (WW). Samples of WW
content (TPh) was expressed as mg L1 of equivalent phenol, using
were collected directly from the treatment plant of Patras Univer-
a calibration curve based on standard solutions of phenol. Cl and
sity, West Greece. After collection, the samples were transferred
PO4 3 ions, released during the oxidation of TCPP, were determined
to the laboratory immediately and ltered to remove particulate
by a Dionex ICS-1500 Ion Chromatography system incorporated
matter. Mean values of physicochemical parameters of the WW
with an ASRS Ultra II suppressor. Analysis was performed on an Ion-
were: pH 7.85 0.04; conductivity = 310.51 25.3 S cm1 ;
Pac AS9-HC using an aqueous sodium carbonate (9 mM) solution as
Total suspended solids = 1.07 0.013 mg L1 ; Chemical
mobile phase was at a ow rate of 1 mL min1 .
oxygen demand = 18.9 1.82 mg L1 ; Total organic car-
bon = 6.2 0.18 mg L1 ; TPh = 1.03 0.015 mg L1 ; PO4 3 = 1.85
0.017 mg L1 ; SO4 2 = 30 0.96 mg L1 ; NO3 = 20.5 0.48 mg L1 . 2.4. Scavenging experiments
2.2. Photocatalytic experiments The role of HO , h+ , e aq and O2 in the degradation mech-
anism was assessed by the addition of 1 103 M isopropanol
Photocatalytic experiments were carried out in a solar simu- (i-PrOH), 1 103 M I , 50 103 M K2 Cr2 O7, 1 103 M p-BQ
lator Suntest XLS+ apparatus (Atlas, Germany) equipped with a and 1 103 M N3 , respectively. Photocatalytic experiments with
2.2 kWatt xenon lamp jacked and special glass lters cutting the the addition of 1 103 M methanol as well as using MeCN as reac-
irradiation with wavelengths below 290 nm. In each experiment tion media were also conducted for discrimination between the
250 mL of aqueous solutions with the desired concentration of TCPP oxidation by HO and h+ . To wash HO ads into solution as bulk
and the appropriate amount of catalyst (50 mg L1 ) were loaded in HO bulk , NaF at 0.1 103 mM was used. Finally, aqueous solu-
Pyrex glass UV-reactor at ambient conditions (temperature = 23 C tions of TCPP degassed with high-purity N2 were also subjected
and pH 6.5) under continuous stirring. The catalyst loading level to photocatalytic treatment [13,14].
154 M. Antonopoulou et al. / Applied Catalysis B: Environmental 192 (2016) 152160
C/C0
TCPP
C/C0
A/A0
i-PrOH
MeOH
0.4 0.4 0.4 NAF
p-BQ
ACN
-
0.2 0.2 I
0.2
Cr (VI)
-
I +i-PrOH+N2
-
N3
0.0 0.0 0.0
0 40 80 120 160 200 240 0 10 20 30 40 50 60
Irradiation time (min) Irradiation time (min)
1
Fig. 2. Degradation kinetics of TCPP (C0 = 25 g L ) and TPh and evolution of Fig. 3. Degradation kinetics of TCPP (C0 = 100 g L1 ) in the presence of scavengers
absorbance at 254 nm, in aqueous TiO2 suspensions (50 mg L1 ) under simulated in aqueous TiO2 suspensions (50 mg L1 ) under simulated solar light (I = 250 W m2 ).
solar light (I = 250 W m2 ) in WW.
Table 1 Table 2
Kinetic Parameters (Rate constants, correlation coefcients (R2 ), Half-Life (t1/2 )) LCMS-TOF retention times, high resolution accurate mass data ([M + H+ ], molecular
of TCPP in the presence of scavengers ([TCPP]0 = 100 g L1 , [TiO2 ] = 50 mg L1 , formulas and relative error (ppm)) for TCPP and the identied transformation
I = 250 W m2 ). products.
Treatment system k x 102 (min) t 1/2 (min) R2 % k Rt (min) TPs code Molecular formula [M + H+ ] (ppm)
Control 5.11 13.6 0.9982 8.1 TCPP C9 H19 Cl3 O4 P 327.0083 0.6
i-PrOH 0.32 216.6 0.9419 93.74 7.5 TP343 C9 H19 Cl3 O5 P 343.0029 0.3
MeOH 0.2 346.5 0.966 96.08 7.3 TP307 C9 H18 Cl2 O5 P 307.0270 2.2
NaF 3.47 20.0 0.9756 32.1 7.1 TP211 C8 H20 O4 P 211.1092 0.8
p-BQ 1.5 46.2 0.9175 70.6 6.8 TP323 C9 H18 Cl2 O6 P 323.0213 0
ACN 0.38 182.4 0.8691 92.56 6.7 TP251 C6 H14 Cl2 O4 P 250.9996 2.2
I 0.33 210.0 0.9427 93.54
Cr (VI) 4.03 17.2 0.9882 21.13
I + i-PrOH + N2 0.14 495.0 0.9903 97.26
N3 0.6 115.5 0.9291 88.30 the proposed elemental composition and the exact mass values of
the major TPs identied during the degradation of TCPP. In Fig. 4,
UPLC-ESIMS chromatographic proles after 30 min of photocat-
scavenger, kHO = 1.1 1010 ) [27] ions and MeCN as reaction media alytic treatment for full scan and scan ltered m/z ions are depicted.
were used to discern the participation of holes and HO in the reac- The TCPP molecule (m/z [M + H]+ = 327.0083, C9 H19 Cl3 O4 P+ ) is
tion mechanism. Iodide ion is strongly bound to the TiO2 surface an aliphatic chlorinated organophosphate compound and the
and has been used to estimate the quantum yield of photogen- results clearly demonstrated that the main structural alterations
erated holes [37] while it scavenge also efciently the resulted took place in the chlorinated isopropyl moieties. HO attack at
HO ads radicals. The rate constant decreased by 93.74%, 96.08% one CH3 group of isopropyl chain resulted in the formation of
and 93.54% when i-PrOH, methanol and I ions were added to the hydroxylated derivative with m/z [M + H]+ = 343.0029 (TP 343) and
photocatalytic system, respectively. An inhibition of 92.56% was molecular formula C9 H19 Cl3 O5 P+ . The formation of TP307 with [M
observed when TCPP photocatalytic degradation was performed + H]+ at m/z 307.0270 can be explained by the loss of one Cl atom
in MeCN solution. In the presence of NaF a rate constant equal from TCPP molecule followed by the oxidation of CH3 group. The
to 3.47 102 min1 was obtained, decreasing by 32.1%, due to formation of TP323 ([M + H]+ = 323.0213) indicates the cleavage of
the transformation of HO ads to HO bulk [38]. Based on the above one Cl atom and the simultaneous hyrdoxylation and oxidation of
results, the degradation of TCPP can be proposed to take place at TCPP molecule and can formed from either TP307 or TP 343.
the surface or at least in the intimate proximity of the TiO2 parti- Previous research on the reaction of hydroxyl radicals with tri-
cles whereas the participation of HO in bulk water can be assumed alkyl phosphates has highlighted the preferential H-abstraction at
minor. The above results clearly show the major contribution of the -position relative to the phosphate functions [40,41]. Based
HO to TCPP degradation, the indirect participation of holes for the on the effect of chlorine substitution for the reaction of chloroalka-
generation of HO ads and the limited direct reaction of holes (about nes with HO radicals [42] the chlorine substitution in the alkyl
67%) with TCPP. groups of TCPP has two different effects: (a) an inductive which
A reduction in the rate constant of TCPP degradation of 88.30% decreases the reactivity for H-atom abstraction at least extending
was observed with azide addition, a well-documented 1 O2 and to the carbon relative to the chlorine position and (b) a mesomeric
HO scavenger (k1 O = 4 108 M1 s1 ; kHO = 1.2 1010 ), indicat- effect increasing the reactivity at the a carbon relative to the chlo-
2
rine position with the rst case to be the dominant effect [42].
ing negligible participation of 1 O2 in degradation mechanism. A rate
Watts and Linden [28] studied the advanced oxidation (UV/H2 O2
constant of 1.5 102 min1 corresponding to 70.6% decrease of
and O3 /H2 O2 ) kinetics of four different alkyl-phosphates namely
rate constant was observed with the addition of p-BQ (O2 and HO
tris-2-chloroethyl phosphate (TCEP), tris-2-butoxyethyl phosphate
scavenger, kO = 1.0 109 ; kHO = 1.2 109 ) [27,39], proving a
2 (TBEP), tributyl phosphate (TBP) and TCPP. They have concluded
partial contribution of O2 to TCPP degradation. that the addition of a Cl atom on the alkyl chain (e.g. TCEP) signi-
K2 Cr2 O7 was used to trap e aq produced at TiO2 conduc- cantly reduces H-atom availability relative to TBP and TBEP and the
tion band leading to a slight decrease of the rate constant to phosphate with the chain structure having the most carbons (TBEP)
4.03 102 min1 . For the elucidation of direct or indirect contri- had the fastest rate of reaction. However, TCPP with one more car-
bution of e aq , experiments in aqueous TCPP solution with I ions, bon on each chain than TCEP, scavenged HO at a slower rate, most
i-PrOH and N2 gas ow were conducted in order to exclude all other likely due to the inuence of the alkyl branched chain of TCPP [28].
species except reductive e aq. Experimental results showed that The H-abstraction is followed by O2 trapping resulting in the for-
the direct participation of e aq was limited (about 3%) as a rate mation of peroxy-radicals that recombines giving rise to hydroxy-
constant equal to 0.14 102 min1 was obtained. These results [43] and keto derivatives [44] or in another mechanism the gener-
are in agreement with the inhibition effect observed with the addi- ated hydroperoxide intermediate dehydrates to the corresponding
tion of p-BQ, proving the indirect contribution of e aq to form O2 aldehyde or ketone derivatives [45]. Finally, H-abstraction and the
after the effective capturing by oxygen (k = 1.9 1010 M1 s1 ). It is resulting carbon-centered radicals could be also followed by the
well established that e aq can react with O2 an electron acceptor addition of water leading to the formation of hydroxy-derivative
adsorbed on catalysts surface or dissolved in water, reducing it to according to the reaction pathways proposed for the isopropyl-
O2 [1,2]. function photocatalytic degradation [45].
The loss of one chloro-isopropyl group leads to the formation of
3.4. Identication of major transformation products by TP251 ([M + H]+ = 250.9996, C6 H14 Cl2 O4 P+ ). One potential mecha-
UPLC-TOFMS and catalyst reuse nism for the formation of TP251 is the direct dealkylation of the
phosphate triester to the corresponding di-ester could be assigned
The screening of the photocatalytically treated samples in UW to an addition of HO radical to the phosphorus center and the
in positive (+) ESI mode allowed the identication of ve TPs with subsequent elimination of the alkoxide radical [43,46]. In an alter-
a high degree of certainty (mass error < 2.2 ppm). The presence of native mechanism, acid catalyzed hydrolysis of the phosphate ester
the characteristic isotopic chlorine pattern in the mass spectrum through the addition of photogenerated H+ to the P = O bond could
of TPs facilitated their identication, as well. Table 2 summarizes be also proposed [43]. Finally, a less probable pathway via grad-
M. Antonopoulou et al. / Applied Catalysis B: Environmental 192 (2016) 152160 157
0
Intens. TPS_TCPP_30min_RA2_01_405.d: EIC 343.0029 +
x104
2
0
Intens. TPS_TCPP_30min_RA2_01_405.d: EIC 307.0270 +
x104
4
2
0
Intens. TPS_TCPP_30min_RA2_01_405.d: EIC 211.10920.02 +
x105
2
0
Intens. TPS_TCPP_30min_RA2_01_405.d: EIC 323.02130.02 +
x105
0.5
0.0
Inten s. TPS_TCPP_30min_RA2_01_405.d: EIC 250.99960.05 +
x105
2
1
0
3 4 5 6 7 8Time [min]
Fig. 4. UPLC-ESIMS chromatographic proles after 30 min photocatalytic treatment for full scan and scan ltered m/z ions.
4 mum area in the rst stages of the process (15 min) and gradually
7x10 TP343
TP323 decreased their abundance until the end of the photocatalytic
4 TP307 treatment. TP323 and TP251 can be considered as secondary trans-
6x10
TP251 formation products as they peak up at 30 min, following after a
5x10
4 TP211 progressively decay. Finally, the formation of TP211 is likely a
slower pathway reaching its maximum area at 60 min. At 120 min,
4x10
4
all TPs were completed abated.
Area
The identied TPs and their proles are in agreement with the
4
3x10 slow release of PO4 3 , proving the preservation of phosphate core
of TCPP molecule till more prolonged irradiation times. On the other
4
2x10 hand, more rapid release of Cl is proved once more by the iden-
4
tication of dechlorinated TPs. Combining the above results on the
1x10 identied TPs and their evolution proles as well as the evolu-
tion of ions release the degradation could be considered to proceed
0
0 20 40 60 80 100 120 through hydroxylation, oxidation, dealkylation and dechlorination
pathways and a proposed degradation mechanism is given in Fig. 6.
Irradiation time (min) Taking into account the aliphatic structure of TCPP and the
results obtained in the present study, as nal TPs, compounds such
Fig. 5. Evolution proles of identied TPs ([TCPP] = 100 g L1 , [TiO2 ] = 50 mg L1 ,
I = 250 W m2 ).
as the methyl esters of phosphoric acid, formic, acetic, glycolic,
oxalic acids and phosphates can be considered [18,51]. A great effort
was also devoted to elucidate TPs generated during the photocat-
ual demethylation by oxidation and decarboxylation reactions [47] alytic removal of TCPP using wastewater as matrix. In this case,
could be also proposed. only TP307 and TP251 have been identied. Both TPs emerged at
A dechlorination reaction pathway can be proposed for the for- prolonged treatment times (120 min) and remained abundant in
mation of TP211 ([M + H]+ = 211.1092, C8 H20 O4 P+ ) exhibited the the reaction solution until 360 min showing once more the notable
absence of chlorine isotopic pattern in the mass spectra. A reductive effect of water matrix composition on the photocatalytic process.
dechlorination by superoxide radical ions could be proposed based Since the stability and recyclability of photocatalysts are of great
on previous results dealing with the photocatalytic degradation of importance for industrial applications, the photocatalytic degrada-
chlorinated aliphatic compounds [48], pentachlorophenol [49] and tion of TCPP for three consecutive cycles was investigated and the
halogenated disinfection by-products [50]. In contrast, reductive kinetics proles are presented in Fig. 7. TCPP removal after 60 min
dechlorination by e is supposed to be a minor pathway. of irradiation decreased only about 10% probably due to the accu-
Due to the lack of analytical standards of the identied TPs, mulation of end-product in the surface of the catalyst. The observed
an accurate determination of the exact concentrations was not loss of efciency is similar with that reported in other studies for
possible, thus the relative area of TPs versus irradiation time was
followed. As depicted in Fig. 5, TP343 and TP307 attained its maxi-
158 M. Antonopoulou et al. / Applied Catalysis B: Environmental 192 (2016) 152160
H3C
Cl
O
O
H3C P O TCPP
O
Cl Cl
CH3
H3C H3C
Cl
CH3
O OH O O
OH
O O
O
H3C P O H3C P O
H3C P O
O O
O
Cl Cl Cl
Cl Cl Cl
TP343 CH3 TP251* TP307* CH3
CH3
H3C H3C
CH3
O O O
O O
H3C P O H3C P O
OH CH3
O O
CH3
Cl Cl
Fig. 6. Proposed degradation pathways of TCPP photocatalytic degradation in the presence of TiO2 and simulated solar light in UW (*TPs identied in WW, as well).
Acknowledgments
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