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Environmental Technology
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Titanium dioxide-mediated photocatalysis of a biorefractory chloroether in

secondary wastewater effluent
Richard J. Wattsa; Sungho Kongb; Margaret P. Orrc; Glenn C. Millerd
Department of Civil and Environmental Engineering, Washington State University, Pullman, WA,
USA b Department of Chemical Engineering, Hanyang University, Seoul, South Korea c Dow Chemical,
Midland, MI, USA d Department of Environmental and Resource Sciences, University of Nevada, Reno,

To cite this Article Watts, Richard J. , Kong, Sungho , Orr, Margaret P. and Miller, Glenn C.(1994) 'Titanium dioxide-
mediated photocatalysis of a biorefractory chloroether in secondary wastewater effluent', Environmental Technology,
15: 5, 469 475
To link to this Article: DOI: 10.1080/09593339409385451


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Environmental Technology, Vol. 25. pp 469-475
Publications Division Selper Ltd., 1994



Department of Civil and Environmental Engineering, Washington State University,
Pullman, WA 99164-2910, USA
Department of Chemical Engineering, Hanyang University, Seoul, South Korea
1078 Building, Dow Chemical, Midland, MI 48667, USA
Department of Environmental and Resource Sciences, University of Nevada, Reno, NV 89557, USA

(Received 20 September 1993; Accepted 24 January 1994)

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The effects of pH, soluble chemical oxygen demand (COD), suspended solids, and ammonia -
nitrogen on the titanium dioxide (TiO2)-photocatalyzed treatment of l,2-bis(2-
chloroethoxy)ethane (BCEE) were investigated in secondary wastewater effluent. The
photochemical oxidation of BCEE was pH dependent and most rapid at pH 4. Sequential increases
in soluble COD were provided by the addition of filtered wastewater influent, and suspended
solids were varied by adding sonicated mixed liquor. Photocatalysis rates were inversely
proportional to soluble COD concentrations, and the reaction was completely quenched at a
soluble COD of 164 mg l-1. Suspended solids in concentrations up to 90 mg l-1 and ammonia -
nitrogen (0.83-70 mg 1-1) did not affect the photochemical oxidation of BCEE. The results show
that, of the water quality characteristics investigated, only soluble COD affected TiO2-mediated
photocatalysis of the chloroether under the conditions of this study. Therefore, photocatalytic
treatment of biorefractory compounds in complex matrices, such as wastewater effluents, may be
possible if the concentrations of quenching species associated with the soluble COD are not
significantly high.

Keywords: Titanium dioxide, photocatalysis, l,2-bis(2-chloroethoxy)ethane, wastewater, industrial


INTRODUCTION to its conduction band. As a result, an electron

vacancy, or hole, is left in the valence band. This
Heterogeneous photocatalysis has recently hole-electron pair process provides a
received widespread attention for the degradation mechanism by which TiO2 -photocatalysis may
of biorefractory organics, the oxidation of proceed by both electron transfer and hydroxyl
disinfection by-products, and the inactivation of radical mechanisms (3, 4).
microorganisms (1,2). A number of Extensive research has focused on the
photocatalysts have been investigated including mechanisms and pathways of TiO 2
titanium dioxide (TiC^), iron oxides, zinc oxide, photocatalysis. Mechanistic investigations using
and cadmium sulfide. Titanium dioxide has trichloroethylene (3, 4), 2-bromo-2-chloro-l,l,l-
received the most attention because to its trifluoroethane (5), and a variety of refractory
photocatalytic activity, conservative nature, and organics (6) have shown that TiC>2 -mediated
low cost. photocatalysis has potential for degrading and
Irradiation of TiC>2 suspensions by near-uv mineralizing refractory organics through
light, and the subsequent absorption of photons at various oxidative and reductive processes,
the photocatalyst surface, induces the transfer of However, most studies have used deionized water
an electron from the photocatalyst's valence band as a matrix, and only one investigation

documented the use of TiO2 -mediated concentration of the stock titanium dioxide was
photocatalysis in wastewater (7). If TiO2 determined as total solids (8). Aliquots of 1 ml of
photocatalysis is to achieve widespread use, its the suspension were added to the wastewater
effectiveness in more complex matrices effluent (100 ml) to provide a final titanium
requires investigation. Therefore, the purpose of dioxide concentration of 250 mg I" 1 . The
this research was to determine the effects of suspensions were not sonicated during
common wastewater constituents (pH, soluble photocatalytic experiments.
chemical oxygen demand, suspended solids, and
NH3-N) on the TiC>2 -mediated photocatalytic Light Source
treatment of a biorefractory organic
contaminant. Wastewater-TiC>2 suspensions were
irradiated with Westinghouse F40BL lights,
MATERIALS AND METHODS which have an emission spectrum below 400 nm
(the range at which TiO2 absorbs most strongly)
Materials that corresponds to the solar spectrum. The light
intensity was monitored using a Spectroline long
Anatase (n-TiC>2), obtained from Fisher wave (320-380 nm) UV intensity meter to insure a
Scientific, was used without modification. 1,2- uniform and constant light flux under the bank of
Bis(2-chloroethoxy)ethane (BCEE) was purchased lamps. The lights were placed 11.3 cm above the
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from Aldrich; it was chosen as a model surface of the water.

contaminant because of its biorefractory nature,
low volatility, and high water solubility. Kinetic Studies with l,2-bis(2-chloroethoxy)
Unchlorinated effluent was obtained from the ethane
secondary clarifiers at the city of Stead, Nevada
wastewater treatment plant, an extended aeration The photocatalytic treatment of 40 mg I' 1
activated sludge facility with Q = 3790 m3 day 1 . It BCEE was investigated in unchlorinated
was stored at 4C and used within two days. The secondary effluent containing TiO2 (250 mg I' 1 )
effluent was aerated for 15 min and brought to under F40BL lights. The reactions were
room temperature 24 h prior to each experiment. conducted in 10 cm diameter x 4 cm deep
Routine nutrient analyses were performed (8), borosilicate glass dishes using 100 ml of
and the average concentrations are listed in effluent; the resulting water depth was 1.3 cm.
Table 1. The pH, soluble chemical oxygen demand (COD),
suspended solids (SS), and ammonia-nitrogen
Preparation of TiO2 Suspensions (NH3-N) were varied to determine their effects
on BCEE photocatalysis rates.
Anatase (20 g) was added to 1 1 of water The effect of pH on BCEE photocatalysis
drawn from a Milli-Q ion exchange system rates was determined by adjusting the pH of the
(Millipore Corporation) and then sonicated for effluent containing BCEE (40 mg I"1) and TiO2
30 min. The suspension was concentrated by (250 mg I'1) from 4 to 10 by 1-pH unit intervals
evaporation (103'C) for 24 h and allowed to settle using HC1 or NaOH. The effect of soluble COD on
for 2 h. The supernatant was decanted, and the BCEE photocatalysis rates was investigated using
tap water or GF/C-filtered effluent spiked with
filtered wastewater influent to provide soluble
Table 1. Nutrient data for the unchlorinated COD concentrations up to 90 mg I' 1 . To determine
secondary effluent. the effect of suspended solids, mixed liquor from
the city of Stead wastewater treatment plant was
Parameter Value added to GF/C-filtered effluent in concentrations
up to 90 mg I' 1 . The mixed liquor solids were
pH 7.1 resuspended and washed three times with
Total Alkalinity 65 mg I"1 as CaCO3 deionized water, and the final suspension was
Suspended Solids 42 mg I"1 sonicated for 30 min prior to adding the solids to
Total Dissolved Solids 313 mg I"1 the effluent. The effect of ammonia was
Ammonia-N 0.83 mg I' 1 determined by adding NH3-N (as NH4C1) at final
Nitrite-N 1.3 mg I"1 concentrations from 0.83 to 70 mg I"1 to the
Nitrate-N 13.4 mg I"1 filtered secondary effluent.
Orthophosphate 1.2 mg I' 1 Aliquots were collected during all

experiments at 0, 15, 30, 60, and 90 min. The Other studies (4, 6) have shown empirical first-
aliquots were extracted with ethyl acetate and order loss of organic substrates during
analyzed by gas chromatography. Control heterogeneous photocatalysis, and such
samples without anatase and dark controls with experimentally-determined rate constants were
anatase were run in parallel. used in this study to compare the treatment of
BCEE in the presence of different wastewater
Analyses constituents.
The effect of pH on the photocatalytic
Ammonia-nitrogen concentrations were treatment of BCEE is shown in Figure 1. These
monitored using low- and high-level indophenol data show that the removal of BCEE was dependent
methods (9). Chemical oxygen demand was on pH; the most effective treatment was at the
analyzed by the low-level closed reflux procedure lower pH regimes with the highest rate constant
(8). Ethyl acetate extracts were analyzed for for BCEE loss (0.009 min"1) at pH 4. Other studies
BCEE with a Hewlett-Packard 5890 gas have shown that photocatalysis rates are pH
chromatograph fitted with a 15 m x 0.53 mm DB-1 dependent; for example, the Ti02-photocatalyzed
capillary column and flame ionization oxidation of phenol was also greatest at pH 4 (10).
detection. The nitrogen carrier gas flow rate was The alkalinity of the effluent was 65 mg I' 1 as
10 ml min" 1 ; chromatographic conditions CaCO3 (0.65 mM) which consists primarily of
included an initial oven temperature of 60C, HCO3- at neutral pH (Table 1). The higher
final oven temperature of 180cC, program rate of
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photocatalysis rates at the lower pH regimes may

15C min' 1 , injector temperature of 180C, and be due to the loss of HCO3' as CO2 because the
detector temperature of 190C. equivalence point between the two species is at a
pH of approximately 4.5. Bicarbonate is an
RESULTS AND DISCUSSION important hydroxyl radical quencher that can
significantly lower TiO2 -mediated
Experimental data obtained throughout this photocatalysis rates (1, 11). In addition, other
study showed exponential loss of BCEE. Plots of species commonly found in wastewater, such as
the natural logarithm of BCEE concentration as a weak organic acids (in which the pKa varies as a
function of time yielded straight lines with r 2 > function of chain length), may also affect the pH
0.90 which indicates pseudo first-order kinetics. response of photocatalytic activity (11, 12).


0.008 -


0.004 -

0.002 -

1 1. 1 1 I I I
3 4 5 6 7 8 9 1 0 11
Figure 1. First-order rate constants for BCEE degradation as a function of pH.

The recovery of BCEE in control solutions below its detection limit with over 60% reduction
was greater than 95%, indicating that the loss of in TOC were observed, which is expected because
BCEE by volatilization or sorption was minimal. of the nonspecific nature of the hydroxyl radical
A pH of 6 was chosen for subsequent experiments oxidations.
because it provided a relatively high rate of The TiO2 -mediated photocatalytic treatment
reaction (Figure 1) and is representative of the of BCEE was unaffected by suspended solids
pH of industrial and municipal waste streams. concentrations up to 90 mg I'1 (Figure 4). These
First-order rates for BCEE degradation as a data show that suspended solids did not
function of soluble wastewater COD are shown in significantly reduce the available light, quench
Figure 2. Photocatalytic rates of BCEE the titanium dioxide excited states, or reduce the
degradation were inversely proportional to availability of the photochemically-produced
soluble COD concentrations. 1,2-Bis(2- reactants which oxidize BCEE when short light
chloroethoxy)ethane degraded most rapidly at the paths (e.g., 1.3 cm) are used. Although suspended
lower COD concentrations (k = 0.029 min'1 with solids concentrations up to 90 mg I' 1 were
COD of 10 mg I"1), and the oxidizing species evaluated, the soluble COD concentrations were
generated by the illumination of titanium dioxide nearly equal (80-100 mg I"1) because the COD
were completely quenched at a soluble COD added through the addition of the sonicated mixed
concentration of 164 mg I' 1 (Figure 2). The liquor suspended solids was primarily in the
effects of hydroxyl radical quenchers have been particulate state. The rate constants for BCEE
well documented (11-13). Common quenchers, removal shown in Figure 4 range from 0.004 to
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such as organic acids, alcohols, ascorbic acid, 0.006 min'1. These results are in agreement with
and amino acids, react with hydroxyl radicals at the first-order rate constant of 0.006 min' 1
rates > 109 M'1 sec -1 (14). These species are obtained for the soluble COD concentration of 92
commonly found in municipal and industrial mg I"1 without the addition of suspended solids
wastewaters, and may affect the oxidative (Figure 2).
treatment of these waste streams if they are Figure 5 describes rates of TiO2-mediated
present in high enough concentrations. BCEE photocatalysis as a function of NH3-N
A reduction of 50% in total organic carbon concentration. These data show that the
(TOC) and BCEE was observed within 15 min photocatalytic degradation of BCEE was
(Figure 3). After 90 min, the oxidation of BCEE to unaffected by NH3-N concentrations up to 70 mg


0 50 100 150 200
Soluble COD (mg I 1 )
Figure 2. Effect of soluble COD on the TiO 2 -mediated photocatalysis of BCEE.

300" -[ 50

250 -,

- 30
I 150"
- 20

50" - 10
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0 20 40 60 80 100
Time (min)
Figure 3. Titanium dioxide-mediated photocatalysis of BCEE and total organic carbon in secondary
wastewater effluent.

0.008 -1

0.007 -


0.001 "

0 I I 1
20 40 60 80 100
Suspended Solids (mg I'1)
Figure 4. Effect of suspended solids on TiO2-mediated BCEE photocatalysis in secondary
wastewater effluent.

I' 1 . The concentrations of NO3-N and NO2-N did provided similar results; for example, Langlais
not increase during these reactions, which et al. (15) reported that ozone-generated hydroxyl
confirms that NH3-N was not oxidized during the radicals reacted slowly with NH3-N, especially
photocatalytic treatment. Other studies have at neutral pH--the regime at which the

0.008 -

0.007 -

0.006 -

0.005 -

0.004 -

0.003 -

0.002 -

0.001 -

i I
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10 20 30 40 50 80
60 70

Figure 5. Effect of NH3-N on BCEE photocatalysis by TiO2 suspensions in secondary wastewater


concentration of NH4+ predominates over NH3. BCEE removal when the reaction is conducted at
The results of this research show that near-neutral pH.
significant rates of TiO2 photocatalysis may be If TiO2 photocatalysis is to be applied to
achieved in dilute wastewater at neutral pH, more complex matrices than previously
although higher rates were found at acidic pH investigated, the results of this study show that
regimes. Soluble COD, which is common to soluble COD is the most significant water quality
nearly all municipal and industrial waste characteristic that controls TiO2 -mediated
streams, significantly affected the TiO2 - photocatalysis. Therefore, TiO 2 -mediated
photocatalyzed treatment of BCEE. Alcohols, photocatalysis of biorefractory compounds in
organic acids, ascorbic acid, and other quenchers complex matrices, such as wastewater, may be
and scavengers of oxidants are common to practical if the quenching and scavenging
municipal wastewater, and probably caused the compounds characteristic of soluble COD are
decrease in BCEE removal with increased present in low concentrations.
soluble COD concentrations. If a photocatalysis
reactor is designed with a short pathway for light ACKNOWLEDGEMENTS
absorption, suspended solids will not
significantly affect heterogeneous photocatalysis Funding for this research was provided by
rates. In addition, NH3-N concentrations to 70 the U.S. Geological Survey through Grant No. 14-
mg I' 1 did not affect the rate of photocatalytic 08-0001-G1238.


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