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OECD Conference on

Potential Environmental Benefits of Nanotechnology:

Fostering Safe Innovation-Led Growth

15-17 July 2009

OECD Conference Centre

Paris, France- 1 -

Plataforma Solar de Almería

OECD Conference on



15-17 July 2009


Paris, France- 2 -

The highest test facility for testing and development of applications of solar concentrating technologies.

Plataforma Solar de Almería

2. Parabolic-trough collector technology

1

1

2

9

7

6

4-5

3 81. Central receiver technology

5. Solar furnace (materials testing)

3. DSG Direct steam generation4. Parabolic dish + Stirling system

7. Solar desalination

6. Solar photocatalysis

9. Building materials testing

8. Solar hydrogen & fuel production

OECD Conference on



15-17 July 2009


Paris, France- 3 -

Solar photocatalytic processes

for water disinfection

Pilar Fernández Ibáñez*, Inmaculada Polo López,

Irene Fernández García

[email protected]

mailto:[email protected]

OECD Conference on



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Paris, France- 4 -

Overview

Water disinfection needs

Water treatment and solar photocatalytis

Disinfection of water for agriculture applications

- Irrigation water disinfection

Conclusions

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Water disinfection needsDRINKING WATER

• In communities with little or not access to safe drinking water, waterborne

diseases is the major cause of sickness and death.

• Approx. 1.8 million deaths occur per year due to a combination of

inadequate sanitation and poor water quality (WHO, 2008)

IRRIGATION WATER

• According to FAO, agriculture consumes 70% of fresh water used

worldwide (95% in developing countries).

• The daily drinking-water requirement per person is at least 2 - 4 liters, but it

is often forgotten that it still takes 2000 to 5000 liters of water to produce a

person‟s daily food requirement (FAO, 2008).

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15-17 July 2009


Paris, France- 6 -

Water disinfection needs

INTENSIVE AGRICULTURE

• The intensive agriculture activity is a very important economical sector in

Almería. There are more than 350 km2 of greenhouses.

• Initiatives to improve water management in agricultural lands are

increasingly required. Hydroponics can be adapted to arid and semi-arid

areas where the availability of water for irrigation is restricted (FAO, 2008).

OECD Conference on



15-17 July 2009


Paris, France- 7 -

Hydroponic cultures

Hydroponics literally means “waterworks,” and includes all methods and

systems to grow plants without soil. The most common hydroponic systems are:

a) Cultivation in liquid media: plants have their roots

immersed in the nutrient solution and the type of

support depends on the crop.

b) Open-cultivation on solid: plants anchor to the solid,

inert and porous substrate and acquires the nutrient

solution by percolation.

c) Closed-cultivation on solid: the nutrient solution is

provided and drained through the same inlet. The

system is “closed” and recycles the nutrient solution.

OECD Conference on



15-17 July 2009


Paris, France- 8 -

Hydroponic cultures• Advantages (compared to traditional agriculture):

- promotes efficient water and nutrient use.

- allows the use of poor quality water, either

moderately saline or alkaline.

- provides some protection against limiting climatic

factors such as drought and light frosts.

- modular: efficient utilization of limited volumes of

water.

- size of the hydroponic system can be adjusted.

• Disadvantages:

- high energy input.

- initial investment.

- basic water-quality analysis and training are

needed to prepare and maintain the nutrient

solutions (FAO, 2008).

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Paris, France- 9 -

The main problem found in hydroponic

cultivation is the accumulation of

phytopathogens in the nutrient solution.

Hydroponic cultures

Fungi Viruses Bacteria

•Fusarium spp.

•Olpidium sp.

•Phytophthora sp.

•Pythium sp.

•Rhizoctomia sp.

•Verticillium spp.

•Watermelon

mosaic virus

•Tomato

mosaic virus

•Cucumber

green mottle

mosaic virus

•Pseudomonas

syringae

•Clavidobacter

michiganensis

•Erwinia amylovora

•Xanthomonas

Closed hydroponic culture

water-

recycling

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15-17 July 2009


Paris, France- 10 -

Water disnfection & solar photocatalysis

Escherichia coli

• Matsunaga et al., 1985. Lamp / TiO2-Pt slurry / 120 min

• Zhang et al., 1994. Solar radiation / TiO2 slurry / 23 min

• Rincón et al., 2001-2004. Simulated sunlight / TiO2 slurry / 20 min

• Rincón and Pulgarin 2005, Fernández et al. 2005-2009. Solar radiation /

TiO2 slurry and immobilized in solar reactors.

Candida albicans

• Seven et al., 2004. Lamp / TiO2, ZnO and Sahara sand / 120 min

• Lonnen et al., 2005. Solar simulator / TiO2 supported / 04 h

Fusarium spp.

• Lonnen et al., 2005. Solar simulator / TiO2 supported / 4 h.

• Sichel et al., 2007-2009. Solar radiation/TiO2 slurry/ solar reactor / 4-6 h.

BACKGROUND

OECD Conference on



15-17 July 2009


Paris, France- 11 -

Damages of UV radiation on microbial cellscosmic

raysg-rays X-rays UV visible infrared

radiowaves

Far UV: 10-200 nm

10nm 100nm 200nm 300nm 400nm

UV-C200-280 nm

UV-A320-400 nm

Damages

cells DNALethal &

mutagenic Cell death

Chromophores absorb UV-B &UV-A

ROS (HO2•, H2O2,

•OH) generation

•Oxidation of proteins

•Damage of membrane

•Single strand breaks (SSB´s)

•Nucleic base modifications

McGuigan, JAM 2006, 101, 453-463.

OECD Conference on



15-17 July 2009


Paris, France- 12 -

TiO2/ Solar UVA disinfection

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

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

IrradianciaSolarDirecta estándar sobrela superficieterrestre(ASTM E891-87,para MasadeAire= 1,5)

IrradianciaSolar

(W/m

2µ

m)

O3

O2

O2

O3

H2O/CO2

H2O

H2O

O/CO2

H2O

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

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

IrradianciaSolarDirecta estándar sobrela superficieterrestre(ASTM E891-87,para MasadeAire= 1,5)

Estraterrestrial Irradiance

Dir

ect N

orm

al Ir

radia

nce

(W/m

2µ

m)

Wavelength (mm)

O3

O2

O2

O3

H2O/CO2

H2O

H2O

O/CO2

H2O

Estraterrestrial solar irradiance

Direct solar irradiance

over the Earth surface

(Air Mass: 1.5)

Terrestrial and extraterrestrial solar spectrum

(48.2º zenit angle)

Solar radiation

Direct „cydal‟ action related with UV absorption

and increased by temperature.

+ TiO2 Indirect „cydal‟ action due to photocatalytic

effect of TiO2 generating hydroxil radical whcih attack

the cell membrane. Also, a decrease of Coenzyme-

A levels by photo-oxidation, which induces celular

death.

OECD Conference on



15-17 July 2009


Paris, France- 13 -

TiO2/ Solar UVA disinfection Blanco, Fernandez-Ibáñez,

Malato,J. Solar Energy

Engineering 129 (2007) 1-12.

40 nm 300 nm >1mm

TiO2 TiO2-aggregates cells

TiO2

h+

OH•

e-

O2-•

Solar UV

e-/h+

Very small particlesof TiO2

suspendedTiO2

OH•

O2-•

Adsorbed TiO2

OECD Conference on



15-17 July 2009


Paris, France- 14 -

Macroconidia of Fusarium equiseti before (left) and after (right) 5 hours of

photocatalytic treatment.

TiO2

C. Sichel, et al. Appl. Cat. B:

Environ., 74 (2007) 152-160.

TiO2 nanoparticles adsorption on

Fusarium macroconidia

OECD Conference on



15-17 July 2009


Paris, France- 15 -


Fusarium chlamydospores

Fusarium solani chlamydopores after

6h of solar exposure without TiO2.

TiO2

Fusarium solani chlamydopores after

6h of solar exposure with TiO2.

OECD Conference on



15-17 July 2009


Paris, France- 16 -


Phytophthora spores

Phytophtora after 5 h of solar

exposure without TiO2.

Phytophtera after 5 h of solar

exposure with TiO2.

OECD Conference on



15-17 July 2009


Paris, France- 17 -

0 2 4 6 8 10 12 14

1

10

100

1000

Co

nce

ntr

atio

n (

CF

U/m

L)

QUV

(kJ/L)

F. equiseti

F. antophilum

F. verticillioides

F. solani

F. oxysporum250 mL

Bottlereactor

200 mL fungal

suspension

Glass cover

irradiating light

irradiating lightirradiating light

250 mL

Bottlereactor

200 mL fungal

suspension

Glass cover

irradiating light

irradiating lightirradiating light

Glass cover

200mL suspension

of fungal spores

Magnetic stirrer

Solar ligth

Inactivation of Fusarium spores

C. Sichel, et al. Appl. Cat. B:

Environ., 74 (2007) 152-160.

OECD Conference on



15-17 July 2009


Paris, France- 18 -

Pilot plant design with CPC modules, catalyst

sedimentation tank filters for post- treatment.

Design of a solar prototype

OECD Conference on



15-17 July 2009


Paris, France- 19 -

Solar CPC reactor for water disinfection

20 Borosilicate glass tubes

Irrradiated collector surface of 4.5 m2

CPC moduleRecirculation tank

pH, Temperature, Dissolved Oxigensensors

Settling tank

Glass tube (L:1500mm, di:50mm thickness: 2.5mm)

CPC mirror (aluminium annodized quality MIRO SUN)

OECD Conference on



15-17 July 2009


Paris, France- 20 -

Radiometer

4. Solar collector covering.

2. Inoculation of culture & catalyst.

3. Dark recirculation.

1. Catalyst preparation.

5. Remove the cover.

6. Experiment starting.

7. Spread in malta agar.

Incubated: 2 days, 28 ºC

8. F. solani colonies counting

Methodology

OECD Conference on



15-17 July 2009


Paris, France- 21 -

Inactivation of Fusarium solani microconidia

WELL WATER

TiO2 concentrations: 0, 50, 100, 250 mg/L

30 L/min

V = 60 L

11:00 12:00 13:00 14:00 15:00 16:00

100

101

102

103

0 mg/L TiO2

100 mg/L TiO2

DL

Controls

F. s

ola

ni

Co

nc

en

tra

tio

n (

CF

U/m

L)

Local Time (HH:MM)

50 mg/L TiO2

41,2

kJ/L

QUV

needed to Detection Limit

41,5

kJ/L

DISTILLED WATER

11:00 12:00 13:00 14:00 15:00 16:00

100

101

102

103

DL

Controls

F.

so

lan

i C

on

ce

ntr

ati

on

(C

FU

/mL

)

Local Time (HH:MM)

QUV


0 mg/L TiO2

250 mg/L TiO2

50 mg/L TiO2

100 mg/L TiO2

30 k

J/L

41 k

J/L

52 k

J/L

OECD Conference on



15-17 July 2009


Paris, France- 22 -

Inactivation of Fusarium equiseti spores

30 L/min

100 mg/L of TiO2

11:00 12:00 13:00 14:00 15:00 16:0010

0

101

102

DL

Controls

F.

so

lan

i C

on

ce

ntr

ati

on

(C

FU

/mL

)

Local Time (HH:MM)

39,4

kJ/L

30,4

kJ/L

Solar disinfection

Well water

QUV


Distilled water

28

,5 k

J/L

MACROCONIDIA

11:00 12:00 13:00 14:00 15:00 16:0010

0

101

102

DL

Controls

F.

eq

uis

eti

Co

nc

en

tra

tio

n (

CF

U/m

L)

Local Time (HH:MM)

45,3

kJ/L

37,2

kJ/L

Well water

Distilled water

QUV


Solar Disinfection

36,4

kJ/L

CHLAMYDOSPORE

OECD Conference on



15-17 July 2009


Paris, France- 23 -

Conclusions

This study showed that Fusarium spores in distilled and

well water can be inactivated with TiO2 slurry in a CPC 60-

L photo-reactor.

The reactor was also evaluated to find out the best

operating parameters, which were found to be a flow

regime of 30 L/min and optimal TiO2 concentration of

100 mg/L.

We demonstrated that it is possible to scale up the

photocatalytic treatment for further use and reuse of water

for hydroponic culture when the catalyst recover is done by

different methods like sedimentation, filtration, etc.

OECD Conference on



15-17 July 2009


Paris, France- 24 -

Acknowledgements

FITOSOL project, AGL2006-12791-C02.

Spanish Ministry of Education and Science

Thanks for your attention

[email protected]

mailto:[email protected]

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