Course on Innovative Processes and Practices for

Wastewater Treatment and Re-use

Solar disinfection of drinking water

Dr. Pilar Fernández Ibáñez

pilar.fernandez@psa.es
CIEMAT – Plataforma Solar de Almería

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Ankara University
8-11 October 2007

Contents

1. Introduction
2. Standard disinfection processes
3. Solar disinfection
4. Water disinfection with TiO2/UV
5. Fundamental parameters
6. Disinfection mechanisms
7. Solar reactors
8. Experiences on disinfection at PSA

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Ankara University
8-11 October 2007

1
Water availability

70% of the surface of the Earth has water

• 2,5 % freshwater
• 1 % human consumption

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Ankara University
8-11 October 2007

Water disinfection needs

Microbial contamination of potable water due to the lack of an

appropriate treatment of waste water is now a days a very
important problem, especially in regions of developing countries.

Water is the main vehicle of distribution of many waterborne

diseases. Water was responsible for big epidemics in the world
like tiphus and cholera.

WHO recognised the disinfection as one of the most important

barriers for protection of public health.

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8-11 October 2007

2
Access to water in the World in 2025

Everybody might have access to safe water to satisfying main

needs of drinking water consume, clean, food production and
energy at a reasonable cost. The water suply for these needs
has to be done in a sustainable way.

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Ankara University
8-11 October 2007

Water disinfection issue

Causes of the problem:
problem
• Lack of adecuated systems for
water treatment and
purification.
• Scarcity of rainwater.
• Restricted access to water
resources due to
contamination of hydric
resources.
• Lack of adequated intallations
Percentage of disinfected water
for water storage. in rural areas of Latinamerica.
• Lack of effective and adequate
water distribution systems.
• Etc.
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8-11 October 2007

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Contents

1. Introduction
2. Standard disinfection processes
3. Solar disinfection
4. Water disinfection with TiO2/UV
5. Fundamental parameters
6. Disinfection mechanisms
7. Solar reactors
8. Experiences on disinfection at PSA

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Ankara University
8-11 October 2007

Disinfection of water

Desinfection: killing or inactivation of pathogenic

microorganisms.

• Indicators: bacteria total coliforms and faecal coliforms.

• Standard methods:
Chlorine
Chloramine
Ozone
UV(C) light

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Ankara University
8-11 October 2007

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Water Disinfection
Disinfection techniques
Physiscal removal Microorganism
of microorganisms inactivation (death)

9Coagulation and sedimentation 9Chlorination

99Ozonation
High efficiency for virus and bacteria
9Filtering 99UV(C)
Widely disinfection
used: 100 years
Highly oxidative
ƒFast filtering 8 9Technologies
9 THM and other
Expensive
Germicidal undernm.research
carcinogenics
effect: 254
ƒSand filtering 9 ƒPhotocatalysis
8 Bromate
Flavour togeneration
No generateswater (toxic)
toxic by-products
ƒActive carbon 8 Non-oxidative
ƒElectrophotocatalysis
In-situ generation
ƒMembrane filtering 8 Not feasible with natural light
ƒPhotosensitation
8 Expensive
ƒSolar water disinfection
9 Widely used
8 Expensive
8 Do not really destroy microorganisms
EPA (Environmental Protection Agency) Clasification , 1999 -9-
Ankara University
8-11 October 2007

Chlorination

Gas chloride, sodium and calcium hypochlorite

Advantages
• Highly germicidal
• Residual effect
• Bacterial re-growth control

Disadvantages
• Generation of toxic by-products
• Bad odour and taste to water
• Dangerous reactivity with NOM

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Ozonation
Ozone (from Air or Oxygen)

Advantages
• Require low doses and contact times
(300-3000 faster than chlorine)
• Non-generation of THM, except for the
presence of Bromide.

Disadvantages
• Non-residual effect
• Potentially toxic by-products
• In situ generation
• Immediately used
• Expensive O&M
• Technically complex
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Ankara University
8-11 October 2007

UV-C disinfection
UV-C lamps

Advantages
• Easy O&M
• Non-generation of toxic by-products

Disadvantages
• Non-residual effect
• Uneffective against protozoan
• Limited disinfectant effect by colour, turbidity and suspended matter
• Bacterial re-growth if genetic material is not destroyed

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UV-C disinfection

Disinfection mechanism with UV-C radiation

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8-11 October 2007

UV-C disinfection

More resistant

Less resistant

Required UV-C dose to reach a 90% of inactivation with

different microorganisms (adapted from Bitton, 2005).
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8-11 October 2007

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 Contents

1. Introduction
2. Standard disinfection processes
3. Solar disinfection
4. Water disinfection with TiO2/UV
5. Fundamental parameters
6. Disinfection mechanisms
7. Solar reactors
8. Experiences on disinfection at PSA

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Ankara University
8-11 October 2007

Solar disinfection: SODIS

Solar radiation itself has not germicidal effect. Nevertheless,

the synergistic effect of solar (UV-A) radiation and thermal
heating of water under solar exposure has an important
disinfectant capacity so-called SODIS or “Solar Disinfection”.
5
10 Temperature 60

4
From 195810 it is known that solar 50photons with wavelenghts
TC [CFU/100mL]

3 40
between10300 y 500 nm may inhibit the reproduction capacity
T(ºC)
30
2
10
of a variety of microorganisms. 20
1
10 total coliforms
10
0
10 0
Photo-repair0 mechanisms
20 40 60 80are also
100 well Caslake
known in bacteria (no
et al., Appl. Environ.
2
Dose UV-A [J/m ] Microbiol. 2004, 70, 1145–1150
virus) in the same spectral range (1967).
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Solar disinfection
When inactivation is done under constant irradiation conditions:
Disinfection kinetics (also for disinfecting agents like chlorine, UV, etc.)
obeys to a first order kinetics, Chick Law:

Nt: concentration of viable microorganisms at time t.

K: constant of disinfection rate.

This relationship under solar radiation changes to:

Gill & McLoughlin, Journal of Solar Energy Engineering, ASME, 2007.

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Ankara University
8-11 October 2007

Solar disinfection
Experimental time is used to compare results when lamps are used.
When solar radiation drives the process, we can use the following
evaluation parameters:
a) QUV: cumulative UV energy during exposure time per unit of
volume of treated water (J l-1).

b) UV Dose: UV energy received per unit surface during exposure

time (J m-2).
DoseUV = UVG,n· ∆tn

c) UV Energy: total UV energy received during exposure time (J).

EnergyUV = UVG,n·A· ∆tn

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Water Disinfection

WATERBORNE PATHOGENS
VIRUS BACTERIA PROTOZOA HELMINTHS
• Poliovirus • Salmonella • Giardia lamblia • Taenia saginata
• Hepatitis A • Shigella • Entamoeba • Ascaris
• Parvovirus • Campylobacter histolytica lumbricoides
• Adenovirus • Vibrio • Crystosporidium • Schistosoma
• Rotavirus • Escherichia coli

Inactivation
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Ankara University
8-11 October 2007

Solar disinfection: SODIS

www.sodis.ch (EAWAG, Switzerland) -20-

Ankara University
8-11 October 2007

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Solar disinfection of E. coli

Viability under
Natural solar
radiation at PSA
3.5 kJ
<UVA>=48 W m-2
20ºC

McGuigan et al., J. Applied

Microbiology 2006, 101, 453-463. -21-
Ankara University
8-11 October 2007

Solar disinfection of pathogenic bacteria

E. coli
Kehoe et al., Letters in Applied
Microbiology 2004, 38, 410–414. -22-
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8-11 October 2007

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Solar disinfection of C. Parvum oocysts

Mice Infectivity McGuigan et al., J. Applied

Solar simulator: 830 W m-2, 40ºC Microbiology 2006, 101, 453-463. -23-
Ankara University
8-11 October 2007

Solar disinfection of Fusarium spores

1000
Concentration (CFU/mL)

100

F. equiseti
10
F. antophilum
F. verticillioides
F. solani
1 F. oxysporum

0 2 4 6 8 10 12 14

QUV (kJ/L)

Under natural solar radiation C. Sichel, et al. Appl. Cat. B:

Wild fungal spores Environ. 74 (2007) 152-160. -24-
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8-11 October 2007

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Resistance relative to the solar radiation of
several microorganisms versus E. coli

Gill & McLoughlin,

Journal of Solar Energy
Engineering,
ASME, 2007. -25-
Ankara University
8-11 October 2007

Contents

1. Introduction
2. Standard disinfection processes
3. Solar disinfection
4. Water disinfection with TiO2/UV
5. Fundamental parameters
6. Disinfection mechanisms
7. Solar reactors
8. Experiences on disinfection at PSA

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AOPs

Ò AOPs are based on generation of a highly oxidative species.

Oxidation
Species potential
ref. HgCl(2•(V)
Ò The AOPs that produce hydroxyl radicals OH) are the most
efficient. Fluorine 2.23
Hydroxyl radical 2.06
Oxygen 1.78
Hydrogen peroxide 1.31
Peroxide radical 1.25
Permanganate 1.24
Hypobromite acid 1.17
Chloride dioxide 1.15
Hypochlorite acid 1.10
Chlorine 1.00
Bromine 0.80
Iodine 0.54
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Ankara University
8-11 October 2007

AOPs - ●OH

HH2OO2/O33/UV
2 2/O /UV

HH2OO2/O γ-rays
γ-rays
2 2/O33
●OH

OO3/UV Supercritical
3/UV Supercritical
Water
WaterOxydation
Oxydation
UV/TiO
UV/TiO22/H
/H22OO22
Photocatalytical
Photocatalytical
processes
processes
UV/Fe
UV/Fe+3/H
+3
/H22OO22

Solar photocatalysis
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Ankara University
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AOPs - ●OH

Terrestrial and extraterrestrial solar spectrum (48.2º zenit angle)

2200

Direct Normal Irradiance (W/m µm)

2000 Estraterrestrial
IrradianciaSolar
Estraterrestrial solar irradiance
Irradiance
2
1800

1600

1400

1200

1000 O3
Direct solar irradiance
800 H2 O IrradianciaSolar Directa estándar
over the Earth surface
sobre la superficieterrestre(ASTM
O/CO2
600 O3 O2
H2 O (Air Mass:
E891-87, 1.5) Aire = 1,5)
para Masade

400
H2 O/CO2
200 O2
H2 O
0
0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8

Wavelength (µm)
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Ankara University
8-11 October 2007

AOPs - ●OH

Several semiconductors may act as photocatalisyts

9 High UV absorptivity
ZnS (3.7 eV)
9 High adsorption rate of many contaminants
ZnO (3.2 eV) 9 Redox potential (EBV-EBC) adequate for
TiO2 (3.05-
(3.05-3.25 eV) organics oxidation
Fe2O3 (2.2 eV) 9 High photocatalytic activity
CdO (2.1 eV), etc. 9 Resistant to photo-corrosion
9 Recyclable (re-usable)
9 Inocuos
9 Easy to handle
9 Low cost and high production
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Ankara University
8-11 October 2007

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AOPs - ●OH

Heterogeneous photocatalysis using semiconductor oxides

The photoexcitation of semiconductor particles promotes an electron
from the valence band to the conduction band thus leaving an electron
hole in the valence band; in this way, electron/hole pairs are generated.
EBG (TiO2) = 3.05-3.25 eV
Photon: E = h·ν
h·ν > EBG
λ < 300-390 nm
(5-7% Solar spectrum)
hν
TiO2 ⎯⎯→ TiO2 ( e − + h + )
e–/h+ recombination ⇔ e–/h+ separation h + + H O →• OH + H +
2

e − + O2 → O2•− -31-
Ankara University
8-11 October 2007

AOPs - ●OH
h·ν ≥ 3.2 eV
h·υ
TiO2 Recombination

e-/h+
eBC- hBV+ Red1 Oxid2
O2
e - Oxid1 Red2
O2-• h +

•
H2O OH + H+
Recombination
AQUEOUS PHASE Photo-oxidation

h + + Re d 2 ,ads → Ox2 ,ads e − + Ox1,ads → Re d1,ads

Before catalyst phoytoexcitation, Red2 and Ox1 species have to be previously
adsorbed on the catalyst surface to avoid recombinations of e-/h+ pais.
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8-11 October 2007

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TiO2-UV disinfection
The first contribution on water disinfection using TiO2 assisted
photocatalysis was done by Matsunaga in 1985.
Up to now:
- Electrophotocatalyisis and photocatalysis with TiO2
- supported and slurry TiO2 20 Scientific publications on
TiO photocatalytic 2
- Lamps and solar radiation

Indexed journals publications

water disinfection
15

1.0

Fotocatalysis-P25
Without catalyst
10
0.8
Ratio Viable Cell

0.6
5
C0=1000 CFU/mL

0.4 1mg/mL TiO2

Lamp: 320-420 nm

0.2
0
1980 1985 1990 1995 2000 2005
0.0 Year
0 10 20 30 40 50 60 70
Irradiation time, min
M. Bekbölet, Water Science &
Technology 35 (1997) 95-100. -33-
Ankara University
8-11 October 2007

TiO2-UV disinfection
BACTERIA: Enterococcus faecalis (Gram+) Escherichia coli (Gram-)

1 µm 1 µm

VIRUS AND BACTERIOPHAGE: Poliovirus 1, Phage MS2 (RNA-

bacteriophage)

CANCER CELLS: HeLa cells (cervical carcinoma), T24 (bladder cancer), U937
(leukemia).
FUNGI AND YEATS:

Saccharomyces Conidia
Cerevisiae Neurospora crassa

“Advanced Oxidation Processes for Water and Wastewater Treatment” IWA Publishing, 2004.
D.M. Blake et al., Separation and Purification Methods, 28 (1999) 1-50. -34-
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8-11 October 2007

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 Contents

1. Introduction
2. Standard disinfection processes
3. Solar disinfection
4. Water disinfection with TiO2/UV
5. Fundamental parameters
6. Disinfection mechanisms
7. Solar reactors
8. Experiences on disinfection at PSA

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Ankara University
8-11 October 2007

Fundamental parameters
Irradiation
Continuously irradiation has a higher efficiency than intermitent
exposure (TiO2 P25 1g/l).
1.E+08
Bacterial survival (CFU/ml)

30 minutes of interrumped
1.E+07
illumination
1.E+06

1.E+05

1.E+04

1.E+03

1.E+02
30 minutes of
1.E+01 continuous irradiation

1.E+00
0 10 20 30 40 50 60 70 80 90 100
Time (min)
Rincón, A.G and Pulgarin C. Appl. Catal. B: Environ. 44 (2003), 263 -36-
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Fundamental parameters
Concentration of catalyst
Initial inactivation rate increases with the catalyst concentration
until it reaches a certain value, due to the light screening efect.
1.E+08
400W/m2 0.25 g/l
1.E+07
Bacterial survival CFU/ml

0.5 g/l
1.E+06
0.75 g/l
1.E+05 1g/l
1.E+04 1.5 g/l The light screening
1.E+03 effect depends on
1.E+02 the intensity of
1.E+01
radiation and on
1.E+00
0 20 40 60 80 100
the initial bacteria
Time (min) concentration.

Rincón, A.G and Pulgarin C. Appl. Catal. B: Environ. 44 (2003), 263 -37-
Ankara University
8-11 October 2007

Fundamental parameters
Post-irradiation events
30 min. exposure to solar simulator radiation: certain inactivaton
and a later bacterial regrowth in the dark was observed. The
post-irradiation effect depends on light intensity.
1.E+09
dark

1.E+08
Bacterial survival CFU/ml

1.E+07 2
400 W/m

1.E+06

1.E+05
2
1000 W/m

1.E+04
0 60 120 180 240 300 360 420 480 540 1600 660
600 720 3600
780
Total time (min)

Rincón & Pulgarín, Applied Catalysis B: Environmental 49 (2004) 99–112 -38-

Ankara University
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Fundamental parameters
Post-irradiation events
The post-radiation effect after photocatalytic treatment provokes a
bacterial abatement in the dark.This effect is directly influenced
by the radiation intensity.
1.E+09
dark
1.E+08

1.E+07
400 Wm2
Bacterial survival CFU/ml

1.E+06

1.E+05

1.E+04

1.E+03

1.E+02
2
1.E+01 1000 W/m
1.E+00
0 40 80 120 160 200 240 280 320 360 4001600
440 480 520 560 3600
600
Total time (min)

Rincón & Pulgarín, Applied Catalysis B: Environmental 49 (2004) 99–112 -39-

Ankara University
8-11 October 2007

Contents

1. Introduction
2. Standard disinfection processes
3. Solar disinfection
4. Water disinfection with TiO2/UV
5. Fundamental parameters
6. Disinfection mechanisms
7. Solar reactors
8. Experiences on disinfection at PSA

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8-11 October 2007

20
Disinfection mechanisms
Effects of biocidal agents on cells

External
e
cid cell wall
Bio

Inactivation
(cidal effect)

Inhibition
DNA
Cytoplasmatic
membrane
Structural
Enzymes proteins

“Wastewater microbiology”. Gabriel Bitton,

John Wiley & Sons, New Jersey, 3rd Ed., 2005.
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8-11 October 2007

Disinfection mechanisms
Bacterial inactivation under solar radiation

Indirect action

UV Photocatalytic effect
Direct action
of TiO2 attacks the
cell membrane.
UV absorption by
DNA molecules of TiO2
H2OÆ Æ •OH
Decrease of
microorganisms Coenzyme-A levels
by photo-oxidation,
which induces celular
death.

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21
Disinfection mechanisms
Photocatalytic inactivation O2-•

Adsorbed
OH•
TiO2

Solar UV

M
IS
OH•

N
A
G
h+

R
O
O
R
e-/h+

IC
M
Very small
e- particles
TiO2 of TiO2
O2-• suspended
TiO2
40 nm 300 nm >1µm
TiO2 TiO2-aggregates cells
Malato, Fernandez-Ibáñez y Blanco, J. Solar Energy Engineering 129 (2006) 1-12. -43-
Ankara University
8-11 October 2007

Disinfection mechanisms
AFM image of E. coli cells on a TiO2 film
Light intensity: 1.0 mW/cm2
Without radiation 6 days of exposure

Cylindrical shape Complete cell

Size ∼ 1–2.5 µ m decomposition

K. Sunada et al. J. Photochemistry and Photobiology A: Chemistry 6221 (2003) 1–7

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Disinfection mechanisms
Scheme of photo-destruction (TiO2) process

1) Partial destruction of 2) Reactive species 3) Reactive species

external cell wall: partial reach the cytoplasmatic attack the lipidic
viability lost. membrane. membrane: cell death.

K. Sunada et al. J. Photochemistry and Photobiology A: Chemistry 6221 (2003) 1–7

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8-11 October 2007

Adsorption of TiO2 on E. coli cells

TiO2-aggregate in contact with E. coli

• D. Gumy et al. Appl. Cat. B:

Environ., 63 (2006) 76-84.
• J. Kiwi and V. Nadtochenko,
Composition of cell membrane Langmuir 2005, 21, 4631-4641.

favours contact with the catalyst. -46-

Ankara University
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23
Adsorption of TiO2 on Fusarium spores
TiO2-aggregates in contact with F. equiseti

TiO2
Macroconidia of F. Equiseti before and
C. Sichel, et al. Appl. Cat. B:
after the photocatalytic treatment (5h) Environ., 74 (2007) 152-160.
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Ankara University
8-11 October 2007

Adsorption of TiO2 on Fusarium spores

TiO2-aggregates in contact with F. solani

TiO2
Chlamydospores de F. solani before and
after 6h of photocatalytic treatment. C. Sichel, Phytopathology,
submitted, 2007.
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24
Contents

1. Introduction
2. Standard disinfection processes
3. Solar disinfection
4. Water disinfection with TiO2/UV
5. Fundamental parameters
6. Disinfection mechanisms
7. Solar reactors
8. Experiences on disinfection at PSA

-49-
Ankara University
8-11 October 2007

Lab Photo-reactor

- Lamp (UV/VIS)
- IR filter
- Photo-reactor
- Refrigeration
- Matraz
- Sensors
- Pump
pH
T

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25
Requirements for solar photocatalytic reactors

ÒChemical resistance to water, pH, without reagents changing.

ÒFlow guaranteed at minimal pressure and maximal
homogeneisation.
ÒEfficient distribution of UV radiation from the solar collector to
the fluid media.
ÒResistance to temperatures lightly high: 40-50ºC.
ÒRobust and resistant to environmental condictions.
ÒEasy handling, low cost operation and maintenance (modular
systems).
ÒCheap and accesible. -51-
Ankara University
8-11 October 2007

Development of solar collectors

Compound Parabolic Collectors (CPC)
After middle 90s the “Compound Parabolic Collector” or CPC was
technologically developed.

CPC concentrates all the incoming radiation within an acceptance

angle (2θa) over the recector (fluid), which leads to a Concentration
Factor of 1 when θa = 90º.

The CPC recovers all the UV radiation (direct and diffusse) received in
the aperture area of the solar collector.

Partial view of
Solar Chemistry facilities
at PSA, Almería (CIEMAT)

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8-11 October 2007

26
 Experiences at pilot plant

Prototype of solar reactor

- Solar radiation
- Photo-reactor (solar collector)
- Tank s
- Air
- Sensor
- Pump
- Additives
- Catalyst

Isometric scheme
SOLARDETOX project, Brite Euram,
European Commission (1997-2000) -53-
Ankara University
8-11 October 2007

Experiences at pilot plant

SOLWATER project, INCO Programme,

European Commission (2002-2005)

17
c m 5 ,5
ic
ct r
E le x
Bo
Tank ,5
90
cm
F
50 cm
P
100 cm
P: pump
F: Flowmeter
T: Termocouple

30 cm

Compact module of solar photo-reactor

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27
Optical development of CPC for disinfection

Application of Compound Parabolic Collectors (CPC) using new

geometries for several configuration of the catalyst (AO SOL, Portugal).

50 mm
50 mm

Cylindrical Support in a CPC Flat support with a special geometry

reactor (Ahlstrom paper) (patent pending) solar collector

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Ankara University
8-11 October 2007

Contents

1. Introduction
2. Standard disinfection processes
3. Solar disinfection
4. Water disinfection with TiO2/UV
5. Fundamental parameters
6. Disinfection mechanisms
7. Solar reactors
8. Experiences on disinfection at PSA

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28
Protocol for solar experiments

1. Catalyst preparation.
2. Solar collector covering.
3. Inoculation of culture &
recirculation.
4. TiO2 adding dispersed in
small volume.
5. Remove the cover.
6. Experiment starting.
7. Average solar UV energy
per unit of time and surface
(WUV·m-2) incoming the
photo-reactor.

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Ankara University
8-11 October 2007

Irradiated collector surface

Solar Disinfection of E. coli in a CPC reactor

4
10
Q UV(60min) = 0 kJ/L
Concentration (CFU/mL)

Q UV(60min) = 0.8 kJ/L

3
10 Q UV(60min) = 2.2 kJ/L
Q UV(60min) = 3.3 kJ/L
2
2 0.125 m Q UV(60min) = 6.5 kJ/L
10
2
0.25 m
2
10
1 0.50 m

2
0.75 m
0
10

0 20 40 60 80 100 120 140

Time, min
Fernández-Ibáñez et al. Catalysis Today, 101 (2005) 345-352. -58-
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29
Catalyst disposal
Disinfection with TiO2 of E. coli in a solar CPC reactor
100000

No catalyst
10000
C, CFU/mL

2
Fixed TiO 2 (19,3 g/m )
1000

Fixed TiO 2 reused

100
Slurry TiO 2 (50 mg/L)

10
0 1 2 3 4 5
Q UV, kJ/L

Fernández-Ibáñez et al. Catalysis Today, 101 (2005) 345-352. -59-

Ankara University
8-11 October 2007

Reactor flow rate

Disinfection of E. coli with immobilised TiO2 in a CPC reactor
8
GinaFit model
2Lmin
5Lmin
6 10Lmin
Log (concentration)

2 Experimental data
2L/min
5L/min
10L/min
0
0 1 2 3 4
Q UV (kJ/L)
C. Sichel, et al. J. Photochem. Photobiol. A, 189 (2007) 239-246. -60-
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30
Matrix of the water
Solar disinfection of E. coli in a CPC reactor
6
10
Real (well) water

E.coli survival (CFU/mL)

5
10 + solar radiation (CPC)
reactor1
4 reactor2
10

3
10

2
10

1
10
Distilled water
+ solar radiation (CPC)
0
10 2L/min 10 L/min

0 2 4 6 8 10 12 14
QUV (kJ/L)
Solar disinfection for real water is slower and less efficient than for distilled
water. This graph shows the “tailing effect” attributed to resistant colonies of
bacteria. -61-
Ankara University
8-11 October 2007

Weather conditions
Solar disinfection of F. antophilum with slurry TiO2
nd
Sunny day (March 22 2006)
solar-only Hourly average UV irradiance
4
10 sunlight+TiO2 Cumulative UV dose 1000 50
SUNNY DAY
F. antophilum (CFU mL )

800 40
-1

3
10
Max. UV Irradiance:
UV Irradiance (W m-2)
UV Dose (kJ m-2)

42 Wm-2
600 30
2
10
Max. UV Dose:
400 20 750 kJm-2
1
10

200 10
0
10
0 0
10:00 11:00 12:00 13:00 14:00 15:00
Local Time C. Sichel, et al. Catalysis
Today 2007, in press. -62-
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Weather conditions
Solar disinfection of F. antophilum with slurry TiO2
st
Cloudy day (March 21 2006)
solar-only Hourly average UV irradiance
4 sunlight+TiO2 Cumulative UV dose
10 1000 50

CLOUDY DAY
F. antophilum (CFU mL )
-1

800 40

UV Irradiance (W m-2)
3
10
Max. UV Irradiance:

UV Dose (kJ m-2)

2
600 30 25 Wm-2
10

400 20 Max. UV Dose:

1
10 380 kJm-2
200 10
0
10
0 0
10:00 11:00 12:00 13:00 14:00 15:00
Local Time
Similar photocatalytic kinetics for both cases. C. Sichel, et al. Catalysis
Solar disinfection yields very different results. Today 2007, in press. -63-
Ankara University
8-11 October 2007

Weather conditions
Disinfection of E. coli with immobilised TiO2
Spring & Summer seasons
Initial concentration SPRING AND SUMMER
50 -2
Solar UV irradiance (W m )

Max.~ 45 W m
Final concentration (UVmax:38-45wm-2).
-2

6
10 40

5 30
10
E. coli (CFU mL )

Spring and summer

-1

20 th
May 8 2004
nd
4 July 2 2004
10 10 th
April 20 2005
th
September 30 2005
0
3 10:00 12:00 14:00 16:00 18:00 20:00
10 Local time

2
10
Detection
1 limit
10

4.63 5.72 9.85 10.79 13.12

-1 C. Sichel, et al. Catalysis
QUV (kJ L ) Today 2007, in press. -64-
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32
Weather conditions
Disinfection of E. coli with immobilised TiO2
Autumn &Winter seasons
Initial concentration AUTUM AND WINTER
6
10 Final concentration 50 (UVmax: 28-38Wm-2).

Solar UV irradiance (W m )
-2
-2
40 Max.~ 38 W m
5
10
E. coli (CFU mL )
-1

30

4 20
10 Autumn and winter
th
October 27 2004
th
10 January 30 2004
th
February 11 2005
3
10 0 November 28 2005
th

10:00 12:00 14:00 16:00 18:00 20:00

Local time
2
10

1
10 Detection limit

3.33 3.47 3.83 3.95 4.04

-1 C. Sichel, et al. Catalysis
QUV(kJ L )
Today 2007, in press. -65-
Ankara University
8-11 October 2007

Role of solar radiation

Comparison of experiments in different seasons, early and later in

the day, and under cloudy and sunny conditions, leads us to
conclude that solar photocatalytic disinfection does not depend
proportionally on solar UV irradiance (solar UV intensity) as long
as enough photons have been received for disinfection.

The minimum UV energy necessary to reach a certain disinfection

depends on the microorganism and the reactor configuration.

Solar-only disinfection requires higher minimum solar UV

irradiance and higher minimum UV dose for disinfection than solar
photocatalytic disinfection.
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Inactivation of C. parvum
Sodis and solar photocatalysis with fixed TiO2
100

Global Irradiance (Wm-2)

1000
SODIS Real Sunlight
80 SPCDIS Real Sunlight
750
Control
Viability (%)

500
60
250

40
DAY 1 DAY 2 DAY 3
0
0 4 8 12 16 20 24

20 Cumulative Exposure Time (h)

C. parvum oocysts
0
0 10 20 30 40 50 60
-2
Cumulative Global Exposure (MJ m )

F. Mendez-Hermida, et al. J. Photochem. Photobiol. A, 88 (2007) 105-111. -67-

Ankara University
8-11 October 2007

Photocatalytic inactivation Fusarium

F. equiseti
1000
F. antophilum
F. verticillioides
Concentration (CFU/mL)

F. solani
F. oxysporum
100

10

0 2 4 6 8 10 12 14
QUV (kJ/L) C. Sichel, et al. Appl. Cat. B:
Environ., 74 (2007) 152-160.
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34
Applications

The AQUACAT and SOLWATER projects were financed by EU

under the INCO-DEV program during (2003-2006)

MAIN OBJECTIVE: development of a completely autonomous

solar system chemical-
chemical-free for drinking water disinfection and,
additionally, elimination of potential organic pollutants at trace level.

SOLWATER
prototype
at PSA
Fixed catalyst Ahlstrom
patent, 1999 France

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8-11 October 2007

Applications

Design of the final system for disinfection of drinking water

1
5 1. PV panel
2. & 3. Solar
3 4 Photo-reactor
4. Pump
5. Electric box
6. Connections
2
6

S. Malato et al., Review, Catalysis Today 122 (2007) 137-149. -70-

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35
Applications
Final reactor systems in South-America and North-Africa

ESTF. Fez, MOROCCO Photo Energy Center. Cairo, EGYPT

IMTA. Morelos, MEXICO. CNEA. Tucumán, ARGENTINA -71-

Ankara University
8-11 October 2007

Applications
SODISWATER project
Solar Disinfection of Drinking Water for Use in
Developing Countries or in Emergency Situations
Partners: Objetive:
1. RCSI (IRELAND) The objective of this project is the development
2. UU (UK) of an implementation strategy for the
3. CSIR (SOUTH AFRICA) adoption of solar disinfection of drinking
4. EAWAG (SWITZERLAND) water as an appropriate, effective and
5. IWSD (ZIMBABWE) acceptable intervention against waterborne
6. CIEMAT (SPAIN) disease for vulnerable communities in
7. UL (UK) developing countries without reliable access to
8. ICROSS (KENYA) safe water, or in the immediate aftermath of
9. USC (SPAIN) natural or man-made disasters.

The main activity of PSA within this project is the development of a solar
reactor to enhance the disinfection results of “batch” SODIS processes.
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36
Applications

FITOSOL project
Elimination of phytopathogens in water through photocatalytic
processes: application for the water disinfection and reuse in
recirculation hydroponic cultures

Main objetives:

• Study at laboratory scale of solar photocatalytic elimination of model

phytopathogenic microorganisms in recirculation liquid nutrient solutions
in soil-less cultures.

• Design and construction of a pilot solar reactor for disinfection of water

containing the mentioned phytopathogenic organisms to reuse in
recirculation hydroponic cultures.

• Demonstration of the photocatalytic process ability to disinfect water from

nutrient solutions of hydroponic cultures. -73-
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8-11 October 2007

Future

1. Low-cost solutions for drinking water suply at house-hold level.

2. Use of AOPs (different to TiO2) for water disinfection.

3. Improve the knowledge on the disinfection mechanisms at

microbiological level.

4. Investigate the effects of the disinfection treatment using

infectifivity tests for pathogenic microorganisms.

5. Field trials of solar disinfection to better Health Impact

Assessment of the technology.
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37
Acknowledgements
This work has been financed by:

European Commission under the SOLWATER

project ICA4-CT-2002-10001.

European Commission under the AQUACAT

INCO project, ICA3-CT2002-10016.

European Commission under the SODISWATER

project, contract FP6-2004-INCO-DEV-3-301650.

Spanish Ministerio de Educación y Ciencia under the

FITOSOL project, AGL2006-12791-C02.
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8-11 October 2007

THANKS

Dr. Pilar Fernández Ibáñez

pilar.fernandez@psa.es

Plataforma Solar de Almería –CIEMAT

Ministerio de Educación y Ciencia
www.psa.es

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38