Solar Energy 77 (2004) 635648

www.elsevier.com/locate/solener

Field solar E. coli inactivation in the absence and presence

of TiO2: is UV solar dose an appropriate parameter
for standardization of water solar disinfection?
Angela-Guiovana Rincon, Cesar Pulgarin *

Laboratory for Environmental Biotechnology, Department of Civil and Environmental Engineering,

Environmental Science and Technology Institute, Swiss Federal Institute of Technology (EPFL) School of Architecture,
CH-1015 Lausanne, Switzerland

Received 7 January 2004; revised in revised form 31 March 2004; accepted 5 August 2004
Available online 17 September 2004

Communicated by: Associate Editor Sixto Malato-Rodrguez

Abstract

Evaluation of solar treatment in the absence and presence of TiO2 has been made to assess its eectiveness in reduc-
ing bacterial load with respect to drinking water standards.
Field experiments under direct solar radiation were carried out using a compound parabolic collector (CPC) placed
at the Swiss Federal Institute of Technology (EPFL), Lausanne, Switzerland. Water contaminated with E. coli K12 was
exposed to sunlight in dierent seasons. The obtained results indicate that the presence of TiO2 accelerates the detri-
mental action of light. Total photocatalytic disinfection was obtained in both periods of year and no bacterial recovery
was observed during 24 h after stopping sunlight exposure. In the absence of TiO2, total disinfection was not always
reached; and bacterial recovery was observed, especially when inactivation was not complete. Bacterial decay was
mainly dependent on light intensity. It was also demonstrated that solar UV dose is not a pertinent parameter to stand-
ardize solar disinfection. The inuence of the following topics on solar water disinfection is also studied in this paper:
(a) UV and total solar spectra characteristics (b) volume of phototreated water (c) post-irradiation events.
2004 Elsevier Ltd. All rights reserved.

Keywords: Solar disinfection; Heterogeneous photocatalysis; TiO2; Escherichia coli; Culturability

1. Introduction pathogenic bacteria. In many places, this problem is

A primary concern of people living in developing
countries is that of obtaining drinking water free of
*
Corresponding author. Tel.: +41 216 934 720; fax: +41 216
934 722.
E-mail addresses: angela.ricon-benavides@ep.ch (A.-G.
Rincon), cesar.pulgarin@ep.ch (C. Pulgarin).
made harder by the fact that many of the available
water sources are unpotable without some form of
treatment. The most common water treatment tech-
niques are not always available to the local population
since the practice of chopping down trees for rewood
to boil water has been discouraged in many countries
for environmental health reasons and the cost of chlo-
rination may be considered prohibitive. In addition,

0038-092X/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2004.08.002
636 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648
combined with organic compounds naturally present
in water, chlorine yields harmful by-products like
trihalomethanes (THMs) which are mutagenic (Jolley,
1990).
Sunlight has been recently used as a method of
water disinfection where in addition to the heating ef-
fect the mechanism of treatment has been attributed
to the production of reactive oxygen species by the
UV-A photosensitization of oxygen within the water
sample (Acra et al., 1990). Most of the research into
the eectiveness of solar disinfection has focused either
into the pasteurizing eects of solar radiation at tem-
peratures higher than 4550 C, or on the synergistic
interaction, between temperature (4550 C) and solar
radiation (Wegelin et al., 1994; McGuigan et al.,
1998). One small scale approach that has gained sup-
port in recent years makes use of the disinfectant prop-
erties of sunlight to treat contaminated water in
transparent plastic bottles or plastic bags, in a process
termed solar disinfection (Joyce et al., 1996; Wegelin
et al., 2001). Experimental studies have demonstrated
that this approach is eective under conditions such
as (1) water with low levels of turbidity, (2) favorable
climate to provide sucient sunlight, (3) if the lled
bottle is left undisturbed during solar exposure, (4)
low volume, between 500 and 2000 ml (Kehoe et al.,
2001), (5) if the bottle is not completely lled and is
agitated for at least 1 min prior to exposure in order
to guarantee maximum starting dissolved oxygen level
(Reed, 1997), (6) solar disinfected water is consumed
as soon as possible after exposure.
On the other hand, heterogeneous photocatalysis is
considered one of the new Advanced Oxidation Tech-
nologies (AOT) for air and water purication treat-
ment. Some books (Serpone and Pelizzetti, 1989;
Bahnemann et al., 1994), and reviews (Mills and Le
Hunte, 1997) have been devoted to this technique. Tita-
nium dioxide (TiO2) photocatalysis is a possible alterna-
tive or complementary technology to current drinking
water treatment processes. TiO2 photocatalysis does
not require the addition of consumable chemicals and
does not produce hazardous waste products. There have
been many publications reporting the application of
photocatalysis towards water remediation with recent
review papers summarizing the photocatalytic removal
of organic, inorganic (Homann et al., 1995) and micro-
bial pollutants (Mills and Le Hunte, 1997). When TiO2
particles are illuminated with near UV irradiation
(<400 nm), electron hole pairs are generated within the
metal oxide semiconductor. The valence band hole has
a very positive reduction potential and is capable of oxi-
dising water, or hydroxide anions, to form hydroxyl rad-
icals in water (Homann et al., 1995). Hydroxyl radicals
(OH) are known to be powerful, indiscriminate oxidis-
ing agents. Mechanisms for the bactericidal action of
TiO2 photocatalysis have been proposed by a number
of authors and reviewed by Blake et al (Blake et al.,
1999). Results from the above studies suggest that the
cell membrane is the primary site of reactive oxygen spe-
cies attack. Oxidative attack of the cell membrane leads
to lipid peroxidation. The bacterial cell membrane pro-
vides an attachment site for cellular respiration and
when damaged beyond repair respiration ceases (Halli-
well and Gutteridge, 1999). The combination of cell
membrane damage, and further oxidative attack of
internal cellular components, ultimately results in cell
death (Blake et al., 1999).
Removal of several organic pollutants by photocat-
alytic treatment has been successfully tested using a
real sunlight and pilot photoreactors having capacities
of several liters (Fallmann et al., 1999; Gimenez et al.,
1999; Herrmann et al., 1999). However, very few
studies on photocatalytic bacterial inactivation at the
similar eld pilot scale as that used for organic sub-
stances have been made (Vidal et al., 1999; Vidal
and Daz, 2000). Vidal et al, reported that eld test
have showed successful destruction of Escherichia coli
and Enterococcus faecalis and have provided data for
full-scale design of water treatment systems. Some
authors (Block et al., 1997) have studied in small pho-
toreactors (25250 ml), the antibacterial eect of solar
photocatalytic reaction and the conditions that aect
it. Their work showed that several common bacteria
such as Serratia marcescens, E. coli and Staphylococcus
aureus, were killed promptly in the presence compared
to the experiments in the absence of TiO2 (Goswami,
1995).
In precedent works, our group has studied the pho-
tocatalytic bacterial inactivation via TiO2 catalyst by
using a solar simulated lamp and a batch photoreactor.
Deionized water, tap water and wastewater type have
been used to test the photocatalytic disinfection. It
was found that the eectiveness of the process depends
on the physico-chemical (Rincon et al., 2001; Rincon
and Pulgarin, 2003, 2004a,b) and biological (Rincon
and Pulgarin, 2004a,b) characteristics of treated water.
In the present study, eld experiments under direct
solar radiation were carried out using a compound par-
abolic collector (CPC) placed at the Swiss Federal
Institute of Technology (EPFL), Lausanne, Switzer-
land. Water contaminated with E. coli K12 was ex-
posed to sunlight and the bacterial cultivability was
monitored.
The goal of this work is to evaluate the solar treat-
ment in the absence and presence of TiO2 to assess its
eectiveness in reducing bacterial load respecting to
drinking water standards. The following topics are stud-
ied in this paper: (a) bacterial inactivation by sunlight in
the presence and absence of TiO2, (b) the inuence of
volume of phototreated water (c) the inuence of light
intensity and dose applied (d) the durability of the disin-
fection (post-irradiation events).
 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648
2. Experimental
2.1. Reactors
Two dierent reactors were used in this work:
2.1.1. Solar photoreactor
The conguration of the CPC is the same as that at
the PSA (Malato et al., 2001). CPC is a static collector
with a reective surface describing an in-volute around
a cylindrical reactor tube (Fig. 1a). Due to the reector
design shown in Fig. 1b, almost all the UV radiation
arriving at the CPC aperture area (not only direct, but
also diuse) can be collected and so be available for
the process in the reactor. The UV light reected by
the CPC is distributed around the back of the tubular
photoreactor and as a result, most of the reactor tube
circumference is illuminated.
The CPC has three modules (collector surface
3.08 m2, photoreactor volume 24 l, and total reactor vol-
ume ranging between 5790 l) whereas one module con-
sists of eight tubes and mounted on a xed platform 46
tilted (local latitude). The three modules are connected
in series with water directly owing through them at
20.5 l/min for some experiments and 13 l/min for the
other ones, leading nally to a recirculation tank con-
nected to a centrifugal pump.
Solar ultraviolet radiation is determined during the
experiments by means of a global UV radiometer (KIPP
& ZONEN, model CUV3) shown in Fig. 1c, also
mounted on a 46 xed-angle platform (the same angle
as the CPC). It provides data in terms of global UV
solar energy power incident per unit area, WUV m
2.
Solar-UV power varies during experiments, especially
when clouds are passing by. Data combination from
several days and their comparison with other photo-
Fig. 1. (a) View of the photoreactor used at the EPFL, Compound Parabolic Collector (CPC); (b) reective surface describing an
in-volute around a cylindrical tube on the CPC, the units of measurement are mm, and (c) view of the solar UV radiometer.
637
catalytic experiments is done by the application of
Eq. (1).
ACPC
QUV;n QUV;n
1 Dtn UVG;n 1
V TOT
where Dtn = tn
tn
1, tn is the experimental time for
each sample, UVG;n is the average UVG (global UV radi-
ation) during tn, ACPC = 3.08 m2, VTOT = 70, 90 or 57 l,
and QUV,n is the accumulated energy incident on the
photoreactor for each sample during the experiment
per unit of volume (kJ/l). For some experiments, the to-
tal solar radiation was measured by means of a radio-
meter KIPP & ZONEN, model CUV4, also mounted
on a 46 xed-angle platform.
2.1.2. Suntest lamp
A Pyrex glass bottle of 50 ml (3 cm in diameter and
5 cm high) was used as batch reactor and illuminated
by a solar simulated lamp, Hanau Suntest (AM1) lamp.
This lamp has a k spectral distribution with about 0.5%
of the emitted photons at wavelengths shorter than 300
nm (UV-C range) and about 7% between 300 and
400 nm (UV-B, A range). The emission spectrum be-
tween 400 and 800 nm follows the solar spectrum. Radi-
ation measurements were carried out with a YSI
corporation powermeter. The irradiation experiments
were started at room temperature (25 C) and progres-
sively; the temperature of the solution increases up to
32 C during irradiation.
2.2. Materials
The photocatalyst was TiO2 Degussa P-25 (Ger-
many), which contains mainly anatase, and a specic
surface area of 50 m2/g. TiO2 in suspension was used in
disinfection experiments at laboratory and large scale.
638 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648

Sodium chloride was supplied by Fluka (Buchs, Switzer- 1.E+05

land). Yeast extract and tryptone were supplied by dark 1000 33

Merck AG (Darmstadt, Germany). 900

Total radiation W/m 2

UV radiation W/m2
29
1.E+04 800 UV 25
700 21
600 17
2.3. Bacterial strain and growth media 500 13

Bacterial survival (CFU/ml)

total rad.
400 9
1.E+03 300 5
11 12 13 14 15 16 17
The bacterial strain used was E. coli K12 (ATCC Real time (h)

23716) and was supplied by DSM, German Collection 1.E+02

of Microorganisms and Cell Cultures. E. coli K12 was
inoculated into Luria Bertani (LB) medium and grown Without TiO 2
overnight at 37 C by constant agitation under aerobic 1.E+01
th
8 August 2003
conditions. Components of LB medium included so-
dium chloride (10 g), tryptone (10 g) and yeast extract 1.E+00
(5 g) in 1 l of deionized water; this solution was then ster- 0 2.5 5 7.5 10 12.5 15
(a) Q ( kJ/l )
ilized by autoclaving for 20 min at 121 C. Aliquots of
the overnight culture were inoculated into fresh LB med- 1.E+05

ium and incubated aerobically at 37 C. Bacterial growth

was monitored by optical density at 600 nm. At an expo- 1.E+04 dark
nential growth phase, bacterial cells were collected by 1000
UV 34

Bacterial survival (CFU/ml)

Total Radiation W/m 2

UV Radiation W/m2
centrifugation at 500 g for 10 min at 4 C and the bac- 960 32
30
920
1.E+03
terial pellet was washed three times with a tryptone 880
28
26

solution (1% W/V). Finally, the bacterial pellet was 840

24
22
resuspended in tryptone solution and diluted in natural 1.E+02 800 20
11 11.5 12 12.5 13 13.5 14 14.5 15
water to the required cell density corresponding to Real time (h)

104106 colony forming units per milliliter (CFU/ml).

1.E+01
Thereafter, bacterial suspension was exposed to the sun- With TiO2
th
light irradiation in the presence or absence of TiO2. 13 August 2003

Samples were taken during illumination period and after 1.E+00

24 h in the subsequent dark period. Serial dilutions were
prepared if necessary in tryptone solution and the sam-
ples plated on agar Plate-Count-Agar (PCA, Merck,
Germany) plates; samples were not ltered prior to plat-
ing. Colonies were enumerated after a 24 h incubation
at 37 C. The detection limit was 1 CFU/ml.
In the curves of the experiments performed under
sunlight irradiation, the reported results are the arithme-
tic means of values from four samples collected at the
same time interval. The error bars (Figs. 26) indicate
standard deviation (SD) of these samples. Experiments
performed under articial sunlight were carried out
three times and each point in the Figs. 7 and 8 represents
the average of the repetitions. SD was calculated as
follows:
s used.
P
X
X
2
SD
n
P 3. Results
where = sum of; X = each value in the data set,
X
= average of all values in the data set and n = the
number of value in the data set.
2.4. Water sources
Two dierent water types were used in this work. For
outdoor experiments, natural water coming from the
Leman Lake was tested. Table 1 shows some physico-
0 2.5 5 7.5 10 12.5 15
(b) Q ( kJ/l )
Fig. 2. Inactivation of E. coli by sunlight with (b) and without
(a) TiO2. The inset contains the UV () and total (. . ..)
irradiation measured during the period of the experiments. 8th
(a) and 13th (b) August, 2003, in Lausanne, Switzerland. Dark
control (p) with and without TiO2 (w). Conditions:
TiO2 = 0.02 g/l, VTOT = 70 l, recirculation rate = 13.5 l/min, illu-
mination time = 4.5 h on August 8th, 2003 (a), 3 h on August
13th, 2003 (b). Each point represents an average value of four
samples taken at the same time. The bars show the standard
deviation.
chemical characteristics of this water source. For indoor
experiments, both deionized and natural water were
3.1. E. coli inactivation by sunlight with a CPC reactor
E. coli inactivation by sunlight occurs in the absence
or presence of the catalyst as shown in Fig. 2a and b.
The bacterial inactivation by sunlight is strongly en-
hanced by the presence of TiO2 (Fig. 2b). In the latter
case, the number of active (cultivable) bacteria decreases
to non-detectable levels (<1 CFU/ml) when an accumu-
 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648 639

1.E+06 dark 800 18

Total radiation W/m 2

700

UV radiation W/m2
40 1.E+04 600 13

UV radiation W/m 2
35 500
1.E+05 30 UV
400 8
25 300

Bacterial survival (CFU/ml)

20 1.E+03
Bacterial survival (CFU/ml)

200 3
15 100
1.E+04
10 0 -2
12 13 14 15 16 17 18 16.5 17 17.5 18 18.5 19 19.5 20
Real time (h) Real time (h)
1.E+02
1.E+03

1.E+01 With TiO 2

1.E+02
th
13 August 2003
Without TiO2 1.E+00
1.E+01
th
16 May 2002
0 1 2 3
Q ( kJ/l )
1.E+00
0 5 10 15 20 25 Fig. 4. Inactivation of E. coli by sunlight with TiO2 (q). The
(a) Q ( kJ/l ) insert contains the UV () and total irradiation (- -) measured
1.E+06 during the period of the experiment. Conditions: TiO2 = 0.02 g/
dark l, VTOT = 70 l. Recirculation rate = 13.5 l/min, illumination
40
time = 3 h on August 13th, 2003. Each point represents an
1.E+05
average value of four samples taken at the same time. The bars
UV radiation W/m2

30

20 show the standard deviation.

10
1.E+04
Bacterial survival (CFU/ml)

1.E+03
1.E+02
Without TiO2
15
th
August 2002
1.E+01
1.E+00
0 5
(b)
Fig. 3. Inactivation of E. coli by sunlight: (a) May 16th 2002 in
Lausanne, Switzerland ( ). Dark control (d). Conditions:
VTOT = 70 l, Recirculation rate = 20.5 l/min, illumination
time = 5 h. Inset contains a UV radiation vs. time from 12:20
to 17:20. Each point represents an average value of four
samples taken at the same time. The bars show the standard
deviation. (b) On August 15th, 2002. Summer in Lausanne,
Switzerland ( ). Dark control (d). Conditions: VTOT = 70 l,
Recirculation rate = 20.5 l/min, illumination time = 5 h. Inset
contains a UV radiation vs. time from 11:30 to 17:30. Each
point represents an average value of four samples taken at the
same time. The bars shows the standard deviation.
lated solar energy incident on the photoreactor per unit
of volume of 12.5 kJ/l is applied, contrary to that ob-
served when TiO2 is absent The inset contains the plot
of solar spectra corresponding to each experiment. Con-
trol experiments of Fig. 2a and b shows that after 4 h of
stirring, in the dark, all E. coli survive in the presence or
absence of TiO2. This indicates that disinfection with
TiO2 in the dark does not occur. These controls also
showed that the transfer of E. coli from the culture
media to the lake water do not cause a detrimental
impact on their cultivability.
0
11 13 15 17 19
Real time (h)
In the absence of TiO2 (Fig. 2a) active E. coli concen-
tration decreases as the accumulated energy increases up
to 7.5 kJ/l, thereafter, bacterial concentration slightly re-
increases. This tendency has been conrmed in several
supplementary experiments not shown here and carried
out in conditions dierent from those of Fig. 2a, some
of these results are illustrated in Fig. 3a and b.
10 15 20 25 30
In the absence of TiO2 (Fig. 2a), water temperature
Q (kJ/l ) increased from 36.6 C (at 11:52), up 38.6 C (at 16:26)
and in the presence of TiO2 (Fig. 2b) from 32.6 C (at
11:45), up to 39.0 C (at 14:45). The pH increases from
7.2 to 7.5 during both phototreatments.
3.1.1. Discussion about the eect of sunlight on E. coli in
the absence of TiO2
In the absence of TiO2 active E. coli decreases with
the amount of accumulated energy up to a plateau and
reincrease thereafter as shown Figs. 2a and 3a and b.
It is well known that sunlight is able to inactivate micro-
organisms due to the synergistic eect of the UV and
heating of water by infrared radiation. Very little dier-
ence in water temperature was measured throughout.
Therefore, inactivation was predominantly due to opti-
cal, rather than thermal eects.
UV wavelengths which reach the earths surface are
classied as UV-A (320400 nm) and UV-B (290
320 nm). The UV-A (or far-UV) wavelengths typically
cause only indirect damage to cellular DNA through
catalyzing the formation of chemical intermediates such
as reactive oxygen species such as  O

2 , H2O2 and OH.
In contrast, UV-B (or near-UV) radiation can cause di-
rect DNA damage by inducing the formation of DNA
photoproducts, of which the cyclobutane pyrimidine
dimer (CPD) and the pyrimidine(64) pyrimidinone
640
1.E+01
1.E+00
1.E-01
Bacterial survival N/No
1.E-02
1.E-03
1.E-04
1.E-05
1.E-06
1.E-07
0 1
Fig. 5. E. coli inactivation by sunlight using a CPC photoreactor in Lausanne, Switzerland. Conditions: VTOT = 70 l (d), 57 l ( ), 90 l
( ). Recirculation rate = 20.5 l/min, illumination time = 1.5 h. Insert contains a plot of the quotient of active bacteria and initial
bacterial load vs. time. Each point represents an average value of four samples taken at the same time. The bars show the standard
deviation.
(64PP) are the most common (Pfeifer, 1997). The accu-
mulation of DNA photoproducts can be lethal to cells
through the blockage of DNA replication and RNA
transcription (Harm, 1980; Britt, 1996). Bacteria have
evolved four main mechanisms in the repair or damage
tolerance of UV radiation-damaged DNA, including
photoreactivation, nucleotide excision repair (NER),
mutagenic DNA repair (MDR), and recombinational
DNA repair (Friedberg et al., 1995).
In the absence of TiO2 (i.e. in Figs. 2 and Fig. 3), the
concentration of active (culturable) bacteria decreased
as the energy increased up to a certain amount of accu-
mulated solar energy but the concentration of active E.
coli increased again from this point even if the illumina-
tion was continued. Note that, the light intensity (insert
in Figs. 2a and 3) diminishes approximately to 50% at
the end of each experiment; which is one of the reasons
why the complete E. coli inactivation was not reached
(Rincon and Pulgarin, 2003). An increase of E. coli con-
centration was observed after a certain treatment time
even without stopping of illumination, which could be
due to dierent reasons summarized as:
(a) Some bacteria recover their culturability after a
certain time of phototreatment. Recently, it has been
suggested that some readily culturable species of bacte-
ria, when subjected to prolonged starvation or other
stress, may enter a survival state in which they are not
detectable by culturability tests (Bogosian and Bour-
neuf, 2001). Authors (Bogosian et al., 1996) suggest that
A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648
0.8
Bacterial survival N/N 0
0.6
0.4
0.2
0
0 30 60 90
Time (min)
90 l
70 l
57 l
2 3 4 5 6 7 8 9 10 11 12
Q ( kJ/l )
the non-culturable cells are in a viable but non-cultur-
able (VBNC) state in which they remain viable but can-
not be cultured. Figs. 2a and 3 show that during the rst
stage of illumination, bacteria lost their culturability due
to the stress induced by light. But these non-culturable
cells of E. coli could not be dead, they are damaged
and their cellular damage is reversed probably favored
by the decrease of light intensity (see inserts of Figs.
2b and 3) to enable the injured cell to resume growth.
Therefore, there was probably a conversion of non-cul-
turable cells into culturable ones without any change
in overall cell numbers due to regrowth.
Moreover, some bacteria are susceptible to counter-
act the UV-B photoinactivation of dierent cell process
(i.e. respiration, reproduction) by a UV-A phoreactiva-
tion. Photoreactivation is thought to be an important
component of the bacterial arsenal in the repair or rever-
sal of UV-B-mediated DNA damage (Harm, 1980). Pho-
toreactivation in bacteria involves a single enzyme called
photolyase which binds CPDs and, in a light-dependent
step, monomerizes the CPD and dissociates from the re-
paired lesion (Yasui and Eker, 1998). Therefore, UV-A
is essential for photoreactivation, although it also has
lethal and sublethal eects on organisms. Most strains
of E. coli, are known to be capable of photoreactivation.
(b) Decrease in UV intensity and modication of the
visible spectral composition of sunlight. This point sug-
gests that there is a disinfection mechanism associated
with the visible part of the spectrum. Light eects at
 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648 641

Sample Illumination
1.E+05
time ( h )

Bacterial survival (CFU/ml)

before dark period
1.E+04 1 0.00
24h after dark period
2 0.50
1.E+03
3 0.72
4 1.00
1.E+02 5 1.50
6 2.00
1.E+01
7 2.50
8 3.00
9 4.20
1.E+00
1 2 3 4 5 6 7 8 9 10 10 4.53
(a) Samples

Sample Illumination
1.E+05 time ( h )
before dark period
1 0.00
Bacterial survival (CFU/ml)

1.E+04 24h after dark 2 0.083

3 0.25
1.E+03 4 0.33
5 0.50
1.E+02 6 0.75
7 1.00
8 1.25
1.E+01 9 1.50
10 2.00
1.E+00 11 2.50
1 2 3 4 5 6 7 8 9 10 11 12 12 2.75
(b) Samples

Fig. 6. (a) Durability of solar disinfection without TiO2. On August 8th, 2003. E. coli concentration of illuminated samples ( ) and the
same samples after 24 h in the dark ( ). Each point represents an average value of four samples taken at the same time. The average
standard deviation was 3%, between four samples taken at the same time. Sample 1 was not illuminated (time zero). (b) Durability of
solar disinfection with TiO2. On August 13th, 2003. E. coli concentration of illuminated samples ( ) and the same samples after 24 h in
the dark ( ). TiO2 0.02 g/l. Each point represents an average value of four samples taken at the same time. The average standard
deviation was 3%, between four samples taken at the same time. Sample 1 is not illuminated (time zero).

1.E+07 1.E+09
control in the dark
dark
1.E+06 1.E+08
Bacterial survival CFU/ml

1.E+05 1.E+07 control in dark

Bacterial survival CFU/ml

1.E+04 1.E+06 2
400 W/m
1.E+03 1.E+05
1.E+02
1.E+04
1.E+01
1.E+03
1.E+00
8h 24h 48h 1.E+02
0 20 40 60 80 100
Time (min) 1.E+01 2
1000 W/m

Fig. 7. Photocatalytic disinfection of water coming from the 1.E+00

0 40 80 120 160 200 240 280 320 360 1500 3500
Leman lake, contaminated with E. coli (q). Conditions: 0.5 g/l
Total time (min)
TiO2, solar simulator adjusted at 1000 W/m2 of light intensity.
Control in the dark (p). Illumination time of 2 h. Monitoring of Fig. 8. Continuous irradiation of E. coli during 30 min in solar
the durability of solar disinfection in the dark (8, 24 and 48 h). simulator, at 400 and 1000 W/m2 of light intensity. Durability
The bars show the standard deviation of three experiments. of disinfection in the dark (24 and 60 h). Conditions:
Black dotted line signies commencement of dark incubation. VTOT = 40 ml, TiO2 = 0.5 g/l, suntest lamp, deionized water.
Black dotted line signies commencement of dark incubation.
The error data was between 28%, on three experiments.
these longer wavelengths are mediated by sensitizers
rather than by direct absorption of the energy by the
lightsensitive cellular components. Authors reported a light components of sunlight during the E. coli exposure
synergistic interaction of the UV-B, UV-A and visible to simulated solar radiation (Muela et al., 2000). Other
642 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648

Table 1 are applied (2.5 h of treatment). Note that in the absence

Some physicochemical characteristics of water coming from the of TiO2, total inactivation of bacteria is not reached
Leman Lake even if the same quantity of energy is accumulated (com-
Parameter Unit Value pare the point at 12.5 kJ/l in Fig. 2a and b). This shows
Turbidity FTU 0.18 that the action of photocatalytic process was more eec-
Conductivity at 20C lS/cm 252 tive that the action of only sunlight.
Absorbance 254 nm 1.079 There is a synergistic eect of sunlight and supple-
pH 7.83 mentary oxidative species generated by the photoactiva-
Chloride mg Cl
/l 8.0 tion of TiO2. The action of the radicals and other
Nitrate mg NO
3 /l 2.7 oxidative species on the bacterial cell membrane leads
Sulfate mg SO
24 /l 48 to the perturbation of dierent cellular processes and -
Hydrogencarbonates mg HCO
3 /l 107 nally to bacterial inactivation and death (Huang et al.,
Total organic carbon (TOC) mg C/l 0.8
2000). In the last period of photocatalytic treatment
Orthophosphates mg PO
34 /l 0.010
Aluminium mg Al+3/l 14
(Fig. 2b), inactivation of bacteria becomes slow because
Nitrites mg NO
of the reactivation mechanisms discussed above as well
2 /l 0.002
Ammonium mg NH4/l 0.001 as to the fact that a few active bacteria remaining in
the irradiated water are in competition for oxidative spe-
Water is ltrated on sand before distribution without signicant
cies with both the inactivated bacteria and the metabo-
modication of its chemical characteristics. The values corre-
spond to the average of three samples taken on February and lites leaked out during bacterial lysis (Rincon and
October, 2002 at Haute-Pierre depart. Pulgarin, 2003).
However, the eectiveness of solar photocatalytic dis-
infection is also inuenced by the UV light intensity and
the relative composition of visible wavelength arriving
authors suggest that the photoinactivation of bacteria is to the ground at dierent seasons and dierent moments
mainly induced by endogenous photosensitizers such as of the day. Photocatalytic disinfection was carried out in
porphyrin derivatives (Merchat et al., 1995) or some summer and winter; but disinfection below 1 CFU/ml
carotenoids which generate oxidative species after visible was only ever attained in summer. In winter, a quantity
light absorption. Similarly, a variety of chromophores of remaining active bacteria between 10 and 103 CFU/ml
exist inside the cell which absorb in the UV-A and are was observed after 4 h of photocatalytic treatment (solar
able to sensitize cells to light (Herbert and Codd, energy between 7 and 12 kJ/l) probably due to the low
1986). The experiments illustrated in Figs. 2a and 3a UV intensity that composes the solar spectra of winter
and b, were prolonged up the late afternoon when the days.
spectra of sunlight arriving to the earth surface is signif- The inuence of solar spectra was conrmed when a
icantly modied. It is well known that, the atmospheric similar experiment to that shown in Fig. 2b was carried
gases disperse shorter wavelengths (violet and blue) out the same day but starting in the late afternoon (Fig.
more than the long wavelengths (red and orange). This 4).
explains the blue color of the sky, which is known as In this latter case, because of the low initial concen-
Rayleigh Scattering, and the colors red and orange of trations of bacteria, E. coli arrive quickly to undetecta-
the early morning and late afternoon, known as Tyndall ble level but the E. coli increase again during the more
scattering. Probably not only the relative low UV inten- advanced state of treatment. The inuence of initial con-
sity but also the spectral characteristics of visible part of centration of bacteria on photocatalytic bacterial inacti-
sunlight in the late afternoon could favor the E. coli vation has been systematically reported elsewhere (Wei
photoreactivation. et al., 1994; Rincon and Pulgarin, 2004b).
(c) There is possibly a replication of the remaining
culturable cells. 3.2. Inuence of the volume of treated water during E. coli
The nal result of factors a, b and c is that, there is an inactivation in the absence of TiO2
equilibrium between bacterial inactivation, reactivation
and growth, that leads in Figs. 2a and 3a and b to a qua- Fig. 5 shows that the experiment carried out using a
si-stationary state where undetectable level of bacteria volume of 57 l shows an E. coli inactivation rate higher
(<1 CFU/ml) was not reached. than those where 70 and 90 l were used. That is also illus-
trated in the insert of Fig. 5 (i.e. at 30 min). The resi-
3.1.2. Discussion about the eect of sunlight on E. coli in dence time of water in a solar reactor is of primary
the presence of TiO2 importance to any water treatment process. In CPC
In the presence of TiO2 (Fig. 2b), active E. coli de- photoreactors, this parameter is mathematically dened
creases as the accumulated energy increases and arrives as the quotient of the photoreactor volume and the ow
to a non-detectable levels (<1 CFU/ml) when 12.5 kJ/l rate. Flow rate was obtained in our experiments, as the
 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648 643

Table 2
E. coli inactivation by sunlight as a function of the treated volume of water
Total volume (l) 57 70 90
Illuminated volume (l) 24 24 24
Temperature range (C) 3132.5 24.632.5 3133
Initial bacterial load (CFU/ml) 2240000 220000 506666
Time of treatment (h) 1.5 1.5 1.5
Flow (l/h) 38.00 46.67 60.00
Recirculation rate (l/min) 20.5 20.5 20.5
Residence time in illuminated part (h) 0.632 0.514 0.400
Bacterial elimination after 1.5 h (%) 99.9990 99.9320 99.6980
UV average (W/m2) 28 31.0 32.0

quotient of treated volume and the treatment time. Re-
sults obtained in Fig. 5, and summarized in Table 2
show that the residence time in the illuminated part of
the system decreases when the total volume increases
while residence time of bacteria in the non-illuminated
part of the system increases favoring the cell repair proc-
ess in the dark. Dark repair is a mode of reactivation
constituted by processes of excision-resynthesis and
post-replication repair. As in the case of photoreactiva-
tion, dark process involves dierent enzymes which
reverse the detrimental UV photodimerization of pyrim-
idines by reforming the monomeric pyrimidine (Harm,
1980; Oguma et al., 2001).
Furthermore, it is known that bacteria can attach to
the surfaces forming biolms (Markku et al., 2002;
Tenorio et al., 2003). Biolm formation will be more
favorable in the non-illuminated part of the reactor;
and a part of these bacteria will be continuously released
in the bulk of treated water. Biolm formation as the
dark repair depend on the residence time in the dark.
This subject would need more attention if the goal is
to disinfect water for drinking water purposes.
Temperature gradients are thought to be dependent
on residence time in the illuminated part of reactor.
However, a variation from 24.6 up 32 C observed in
the experiments (Table 2) does not aect signicantly
the eectiveness of treatment (Rincon and Pulgarin,
2003).
3.3. Dose in solar disinfection
As with chemical disinfection, the performance of
UV irradiation systems (especially with 254 nm lamps)
is determined by the disinfectant UV dose. A typical
method of comparing the inactivation response of dier-
ent microorganisms to the UV intensity is to report the
values of UV intensity and exposure (or residence) time
together as UV dose. In our case, dose can then be cal-
culated from the average solar UV intensity and the res-
idence time in the irradiated part of the reactor, Eq. (2).
Note that only the UV part of the solar spectra is taken
in account.
dose I  tr 2
2
where dose is the solar UV dose, Wh/m , I is the average
intensity, W/m2, and tr is the residence time, h.
In this part of the paper we investigate the pertinence
of using the dose concept when a solar illumination is
applied. In order to compare the eect of solar illumina-
tion applied at dierent seasons of the year and at dier-
ent moment of the day (Table 3), we calculated for
each period the solar UV dose necessary to reach

Table 3
Solar UV dose necessary to inactivate approximately 99.9900% of E. coli using a CPC reactor in Lausanne Switzerland
Experiment date TiO2 (g/l) VTOT (l) Bacterial load UV average % bacterial UVa dose Period of
(CFU/ml) (W/m2) inactivation (Wh/m2) treatment (h:min)
1 January 17, 2003b 0.1 70 1200000 7.20 99.99167 9.87 12:0016:00
2 January 20, 2003b 0.1 70 807000 4.92 99.99876 6.75 12:3016:30
3 August 19, 2003b 0.1 70 295000 18.98 99.8986 19.52 15:3018:30
4 September 4, 2003 0.1 70 514000 33.83 99.9961 23.20 13:0515:05
5 August 21, 2003 0.1 70 414000 37.28 99.9976 17.04 12:2013:40
6 August 15, 2002b 70 220000 36.24 99.9909 37.28 11:3014:30
7 May 16, 2002b 70 400000 36.77 99.9405 37.82 12:2015:20
8 September 20, 2003b 70 365000 23.92 99.4247 43.74 10:5016:10
a
Dose was calculated as; d tUV G;n VV TOT
ILL
; where VILL: illuminated volume; VTOT: total volume; UVG;n average UV light; t:
treatment time.
b
Undetectable value (<1 CFU/ml) was not reached during irradiation.
644 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648
approximately 99.9900% of E. coli inactivation. In the
absence of TiO2 a high variability of the required dose
can be observed. Thus, on August 15 (experiment 6) a
dose of 37.28 Wh/m2 inactivated 99.9909% of bacteria
while in September 20 (experiment 8), 43.74 Wh/m2 inac-
tivated only 99.4247%. Note that these experiments were
carried out in dierent seasons of year and consequently
under a solar irradiation which had a dierent spectral
composition.
As expected, the dose necessary to inactivate a simi-
lar quantity of bacteria is higher in the absence (experi-
ments 6, 7 and 8) than in the presence of TiO2
(experiments 4 and 5). Notice that in winter (experi-
ments 1 and 2) it was possible to attain similar level of
solar photocatalytic inactivation with a much lower dose
than in summer (experiment 3) and autumn (experi-
ments 4 and 5) with a much lower dose. It is possible
that the water temperature (between 6 and 10 C) in win-
ter increased the susceptibility of bacteria to photocata-
lytic treatment. Authors have reported that E. coli
subjected to low-temperature storage results in an in-
crease in susceptibility to the subsequent environmental
stresses (Ingraham, 1999).
In addition, it is known that equilibrated level of dis-
solved oxygen is inversely proportional to water temper-
ature. Bactericidal action of sunlight on water is
dependent on dissolved oxygen levels and on the other
hand, oxygen is an electron acceptor which accelerates
the photocatalytic process.
It has been reported in the context of UV disinfection
in the absence of TiO2, a greater eectiveness of apply-
ing a high UV intensity for a short time than applying
a lower intensity for a longer period of time (Sommer
et al., 1998). Authors suggest that this eect may be
due to the action of repair enzymes in the cell which
are more negatively inuenced by high UV intensities
(Sommer et al., 1998). Because of the similarity of the
process it is possible that this phenomenon occurs also
in our experiments. For example, note that in the exper-
iment 3 (August 19) a dose of 19.52 Wh/m2 achieved less
bacterial inactivation (active E. coli  1 CFU/ml) than
in the experiment 5 with a dose of only 17.04 Wh/m2.
In experiment 3, the photocatalytic water disinfection
curve showed a similar tendency (not shown here) to
that observed for the phototreatment in the absence of
TiO2 (experiments 68), where E. coli concentration
reincreases at the end of phototreatment. That could
be due to two reasons: the rst is that the experiment
3 began in the late afternoon when visible light has spec-
tral characteristics less favorable for E. coli inactivation
as discussed in Section 2. The second reason is that the
average of solar UV intensity on August 19, 2003 (exper-
iments 3) was lower (18.98 W/m2) than that of the exper-
iment 5 of August 21, 2003 (37.28 W/m2). Therefore, a
dose of 19.52 Wh/m2 reached in experiment 3, was not
enough to attain total inactivation of E. coli, as was
the case with 17.04 Wh/m2 in experiment 5. Some papers
have reported the positive inuence of the increase of
UV light intensity on photocatalytic bacterial inactiva-
tion (Lee et al., 1997). However, a non-linear correlation
between light intensity and deactivation of bacteria was
found; that could be due to the fact that excessive OH
radical generation at high intensity leads to their self-
recombination, which lead to a decrease in the attack
to target organism (Rincon and Pulgarin, 2003). More-
over, when a high photonic ux is applied, high concen-
tration of electrons and holes is generated in the
semiconductor which results in a high recombination
rate.
Consequently, the solar UV dose is not a good
parameter to accurately predict and standardize the im-
pact of the solar photocatalytic process on bacteria. In-
deed, the relative UV and visible wavelengths intensities,
characteristics of each season and day period signi-
cantly aect the solar photoinactivation, and photoreac-
tivation as well as the bacterial behavior in the
subsequent dark period.
3.4. Durability of solar disinfection: post-irradiation
events
Sensitivity of bacteria to solar disinfection in the ab-
sence and presence of TiO2 can vary for each species of
microorganism according to strain, stage of the culture,
growth medium, initial bacterial load and type of plating
medium used for bacterial cultivation and counting
(Acra et al., 1990; Rincon and Pulgarin, 2004a,b).
Physicochemical parameters and reactor design amongst
others also inuence the process. However, to comply
with requirements in the disinfection systems, it is
important to determine for each condition the length
of the irradiation period or eective disinfection time
(EDT) that ensures death of the bacteria and conse-
quently the end of the treatment. In this section, the
behavior of an E. coli suspension during the subsequent
dark period is discussed in order to estimate the poten-
tial of using the solar (photo)catalytic treatment process
in real water disinfection situations.
Each sample taken during the experiment carried out
on August 8 and 13, (showed in Fig. 2a and b) were
incubated in dark conditions at 37 C for 24 h. As shown
in Fig. 6a, the concentration of active E. coli photo-
treated in the absence of TiO2, decreases during illumi-
nation but increases again during the subsequent dark
period. As expected, bacterial growth was observed for
all illuminated samples, possibly because the photoinac-
tivation was not complete, and hence some still active
(cultivable) E. coli continue to be active and replicate
in the dark. Conditions are favorable for E. coli replica-
tion since even the non-illuminated sample 1 undergoes
a growth (Fig. 6a) although the low concentration of
dissolved organic carbon (0.8 mg/l) of water limits the
 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648
bacterial growth. Furthermore, as mentioned above the
DNA damage caused to some bacteria can be repaired
in the dark. This process could also contribute to the in-
crease of the active E. coli during 24 h in the dark (after
illumination).
Similar experiments made with samples illuminated
in the presence of TiO2 are presented in Fig. 6b. It shows
a bacterial growth after 24 h in the dark for all samples
with the exception of samples 10, 11 and 12. In sample
10 the low bacterial concentration attained during pho-
tocatalytic treatment continues to decrease in the dark
and reach undetectable level (<1 CFU/ml) after 24 h.
Samples 11 and 12 presented already undetectable value
at the moment of sampling; this level was maintained
during the subsequent 24 h in the dark. Other authors
have also observed a negligible E. coli regrowth during
72 h in the dark after solar photocatalytic treatment
(Vidal and Daz, 2000). In this latter study tap water
was used and only the last sample was maintained in
the dark.
Thus, the behavior in the dark of sample 10 suggest
that during photocatalytic disinfection radicals and
other oxidative species produced by illuminated TiO2 in-
duce damage that can in certain cases get worse in the
dark, generating a residual eect of the photocatalytic
treatment. For this reason in sample 10 bacterial popu-
lations continue to decrease in the dark. In this case,
sample 10, as well as in samples 11 and 12, the DNA re-
pair mechanism becomes less active rendering the E. coli
inactivation irreversible. In other words, the bacterial in-
jury generated by photocatalytic treatment continuous
to enhance in the dark. For this delayed process we ap-
ply the term of residual eect but it is not necessarily
induced by the residual presence of any active oxidative
compound. In a previous article we reported that that
this residual eect in the dark is dependent on the
light intensity previously applied (Rincon and Pulgarin,
2003).
The post-irradiation events for the experiments
shown in Table 2 were also followed during 24 and
48 h in the dark only for samples taken at the end of
phototreatment. It was found (not shown here) that in
samples illuminated in the absence of TiO2, the concen-
tration of active E. coli increases again in the dark to
reach a concentration of only 1 log lower than that ob-
tained at the beginning of treatment. Samples photo-
treated in the presence of TiO2 did not show growth
after 24 and 48 h of incubation in the dark; that was also
the case, even for experiments where undetectable value
(<1 CFU/ml) was not reached. It has been reported that
exposure of some enzymes which play an important role
in the bacterial defense against oxidative stress (such as
catalase) to a photosensitiser in the presence of light re-
sulted in loss of enzymatic or functional activity due to
direct photooxidative damage (Straight and Spikes,
1985). A further decline in activity after the cessation
645
of illumination was also observed by other authors sug-
gesting that subsequent dark reactions can also contrib-
ute to the loss of enzyme activity (Davies, 2003). Our,
observations concerning the post-irradiation events in
the dark after photocatalytic treatment could then be
related with these ndings.
In order to study the post-irradiation process without
the inuence of the chemical composition of natural
water and the wavelengths variation of the solar spectra
in Lausanne; some experiments were carried out using a
solar lamp in well controlled conditions of the labora-
tory. After 100 min of treatment, it can be observed in
Fig. 7. a complete photocatalytic bacterial inactivation
of the E. coli suspended in the water coming from the
Leman Lake. No bacterial regrowth was observed after
8, 24 and 48 h of dark incubation at 37 C.
Photocatalytic experiments performed using deion-
ized water contaminated with E. coli are shown in Fig.
8. Water was irradiated for 30 min thereafter the bacte-
rial suspensions were examined under permanent agita-
tion during a subsequent dark period of 60 h. As
expected, photocatalytic inactivation was accelerated
by the increase in light intensity from 400 to 1000 W/
m2. After irradiation at 400 W/m2 (trace D), culturable
bacteria gradually reach 1 CFU/ml after 60 h in the dark.
When the process was conducted at 1000 W/m2 (trace p),
the inactivation of bacteria continuous also in the dark
as it was observed in the former experiments carried
out at 400 W/m2 and in sample 10 of Fig. 6b. But at
1000 W/m2 the post-irradiation events are drastically
accelerated. For instance, E. coli treated at 1000 W/m2
for 10 min (dose: 167 Wh/m2) reach a value of < 1 C-
FU/ml after around 3 h in the dark. In contrast to that,
if a light intensity of 400 W/m2 is applied for 30 min
(dose: 200 Wh/m2), the total disinfection is attained only
after 60 h in the dark. This fact suggests that, in our
experimental conditions, the residual disinfecting ef-
fect of the photocatalytic process observed during the
subsequent dark period is dependent on the irradiation
intensity, but not on the dose. To assure no bacterial
re-growth before water consumption, the eective disin-
fection time (EDT) required for total killing of bacteria
have to be determined during the evaluation of the solar
disinfection process (Rincon and Pulgarin, 2004a,b). In
the illuminated system without catalyst (Fig. 6a), the
EDT was not reached. Thus, if all bacteria are not killed,
the recovery of the damaged bacteria and/or the cellular
reproduction of the not aected cells could occur in the
dark. By contrast, in the photocatalytic system (Fig. 6b),
the EDT was reached after about 1.5 h (samples 10, 11
and 12) of irradiation. EDT was also reached in Fig.
8. To assess the eld experiments under direct solar irra-
diation, it is necessary to determine the EDT which
avoids bacterial growth after stopping of the photocata-
lytic treatment. This EDT is dependent not only on the
classical parameters as chemical characteristics of water,
646 A.-G. Rincon, C. Pulgarin / Solar Energy 77 (2004) 635648
type and concentration of bacteria, reactor geometry,
etc., but also on the UV and visible composition of sun-
light spectra in dierent geographic locations, seasons
and period of day.
4. Conclusions
A CPC photoreactor was used to disinfect water be-
cause it represents an approximation to the real eld
application of solar technology for water decontamina-
tion. Natural water from the Leman Lake was used to
suspend E. coli in the presence and absence of TiO2.
TiO2 concentrations ranging between 0.02 and 0.1 g/l
were enough to enhance the solar disinfection of 70 l of
E. coli contaminated water. Photocatalytic disinfection
was obtained in winter and summer periods of year
and no bacterial regrowth was observed after stopping
of treatment, while regrowth was observed if stopped
in middle of exposure. Similar post-irradiation events
especially a residual disinfection eect were observed
in pilot and laboratory scale experiments after solar
photocatalytic treatment.
In the absence of TiO2 total disinfection was not
reached during illumination and bacterial recovery was
observed even before the illumination was stopped as
well as in the post-irradiation period.
Eective disinfection time, EDT was dened as the
treatment time necessary to avoid some bacterial re-
growth after 24 (or 48 h) in the dark, after stopping
the phototreatment. During E. coli inactivation in the
absence of TiO2 the EDT was not reached. Residence
time of water in the illuminated part of the system, light
intensity and the moment of the day selected for the
treatment (morning and afternoon) strongly inuence
the EDT.
The UV solar dose necessary to reach a target disin-
fection level is not a good indicator to predict the impact
of the solar photocatalytic process on bacteria. Indeed,
the relative UV and visible wavelengths intensities, char-
acteristics of each season and day period signicantly af-
fect the solar photoinactivation, and photoreactivation
as well as the bacterial behavior in the subsequent dark
period. According to our results and for practical appli-
cations; we propose to determine the EDT for each spe-
cic condition. Thereafter the obtained EDT value can
be raised of a certain percentage in order to introduce
a range of security.
Laboratory experiments using E. coli suspended in
deionized water and exposed to a solar simulator con-
rmed that E. coli survival during both irradiation and
post-irradiation periods are aected dierently under
similar doses which are composed of dierent light
intensities.
In order to guarantee a residual disinfecting eect
during water storage before consumption, the use of a
chemical disinfectant as chlorine could be considered
after the solar photocatalytic treatment. In this case
the formation of disinfection by-products (DBPs) such
as trihalomethanes is limited as the precedant photocat-
alytic treatment degrades an important part of the disin-
fection by products precursosrs (DBPPs), (Rincon et al.,
2001).
Acknowledgments
We are pleased to thank the Swiss Academy of
Engineering Sciences (SATW) for the doctoral grant
of the rst author. We especially thank to Emmanuel
Poget, Florian Golay and Christian Marin for their
collaboration in the experiments with the CPC reactor.
We thank Dr. Maricel Marin for their help in the man-
uscript corrections of our recent publications. The
authors thank to OFES No 02.0030 within the SOL-
WATER research project No ICA4-CT-2002-10001 of
the European community as well as AQUACAT Con-
tract No ICA3-CT-2002-10016 OFES No 02.0316. We
acknowledge the cooperation project environment
EPFL-Colombia and the VPF-cooperation for encour-
aging this research.
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