1

Nanotech Northern Europe

Copenhagen 23-25 September 2008

D.G. Rickerby and A.L. Carbone

david.rickerby@jrc.it

Nanosystems for Water Quality Monitoring

and Purification

2

Worldwide Freshwater Availability

Environment Canada

http://www.ec.gc.ca/WATER/en/info/facts/e_quantity.htm

3

EU Water Initiative

Launched at the 2002 World Summit for Sustainable Development

in Johannesburg

The EU is committed to contribute to achieving the following

international goals:

• To halve by 2015 the proportion of people without safe drinking

water and who do not have access to adequate sanitation

• To establish national water resource management plans by

2005

http://euwi.net

4

Sources of groundwater contamination and their migration paths

Water Framework Directive Information Centre

http://www.euwfd.com

Origins of Groundwater Pollution

5

0

1

2

3

4

5

6

7

8

9

Nonylp

henols

NPE1C

NPE2C

NPE3C

NPE1O

NPE2O

OPE2O

Bis

phenol A

PC

P

Nitr

ophenol

2,4

-Din

itrophenol

Pro

panil

Atr

azin

e

Diu

ron

Sim

azin

e

Ala

chlo

r

Chlo

rvenfinphos

Chlo

rpyrifo

s

Isopro

turo

n

Deseth

yla

trazin

e

Lin

uro

n

Terb

uty

lazin

e

Carb

ary

l

MC

PA

2,4

-D

Mecopro

p

Benta

zone

Dic

hlo

rpro

p

2,4

,5-T

Benzafibra

te

Gem

fibro

zil

Dic

lofe

nac

Ibupro

fen

Carb

am

azepin

e

Unib

lue A

Sulforh

odam

ine B

Dis

pers

e B

lue 1

4

Acid

Red 1

Benzenesulfonate

4-C

hlo

robz.s

ulfonate

2-A

min

o-1

-na.s

ulf.

Anth

raquin

onesulf.

Co

ncen

trati

on

[u

g/L

]

EDCs

Phenols

Pesticides

Dyes

Sulfonates

Atrazine

Pharmaceuticals

Typical Pollutants in River Water

• Development of analytical methods and monitoring tools

• Multi-residue analysis of water pollutants

6

DDT and metabolites

(DDD, DDE)

Aldrin

Dieldrin

Endrin

Isodrin

Carbon tetrachloride

Perchloroethylene

Trichloroethylen

Alachlor

Atrazine

Benzene

Brominated

Diphenylethers

C10-13 Chloroalkanes

Chlorfenvinphos

Chlorpyrifos

Dichloromethane

Di(2-

ethylhexyl)phthalate

Diuron

Endosulfan

Isoproturon

Lead and its

compounds

Mercury and its

compounds

Nickel and its

compounds

Nonylphenols

Octylphenols

Pentachlorobenzene

Pentachlorophenol

Polyaromatic

Hydrocarbons

Simazine

Tributyltin compounds

Trifluralin

Cadmium and compouds

1,2-Dichloroethane

Hexachlorobenzene

Hexachlorobutadien

Hexachlorocyclohexane

Mercury and its

compounds

Pentachlorophenol

Trichlorobenzene

Trichloromethane

2000/60/EC

WFD Priority

Substances

76/464/EEC

Dangerous

Substances

Directive

Target Analytes

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THEMATIC WORKING GROUP 2 - WATER FOR PEOPLE

WATER SUPPLY AND SANITATION IN URBAN,

PERI-URBAN AND RURAL AREAS

STRATEGIC RESEARCH AGENDA

A major priority is developing sensors for monitoring water and

wastewater quality

New biological and electronic techniques and new long life low

power systems need to be developed

This will allow improved monitoring and measurement technology

including in-pipe sensors

Eventually this could lead to completely decentralised control

Water Supply and Sanitation

Technology Platform

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Sensors at raw water sites to monitor spatial and temporal

changes in concentrations of pollutants

Data on water quality from the sites integrated in contaminant

migration models

Sensor Networks for Water Monitoring

Three main aspects of the

drinking water distribution

system to be considered:

• water source (surface and

groundwater)

• water network (from the

intake to the household)

• water from tap (at point of

delivery)

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Local refinement of the array of discrete points in a simulation

study of localised groundwater flow processes

http://www.bgs.ac.uk/science/3Dmodelling/zoom.html

Importance of High Spatial Resolution

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Assessment of the status of water bodies

S.cerevisiae

Cytotoxicity assay

Identification of specific

biomarkers

DNA microrray and

proteomics

F.rubripes

Cell line

Development and implementation of sensitive assessment

tools of integrated water quality

Molecular Based Methods

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40h incubation

Cell culture grown on interdigitated electrodes

Toxin Detection by Live Cells

1.00E+02

1.00E+03

1.00E+04

1.00E+02 1.00E+03 1.00E+04 1.00E+05 1.00E+06

Fr (Hz)

/Z/ (o

hm

)

cells after 16h incubation

medium

Balb 3T3 cells after 16 h

incubation/Z/ spectra with and without

cells on the electrodes

24h 5μM As treatment 24h 10μM As treatment

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Bioassays and Immunoassays

Toxin/

chemical Receptor Receptor binding Fluorescent Signal

Receptor

binding

Biomarker

gene

activation

Biomarker

detection

Receptor

Antibody

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Molecularly Imprinted Polymers

Creation of an artificial receptor in a synthetic polymer

Functional monomers, a cross-linker, and a template molecule

are mixed

Copolymerization forms an insoluble, cross-linked polymeric

around the template

Removal of the template leaves a complementary selective

binding site for this molecule

K. Haupt, Analytical Chemistry 75 (2003) 376A-385A

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Derivatives:

Estrone

Bisphenol A

Atrazine

Sulphonamides

Isoproturon

Propanil

Integrated optical chip with simultaneous illumination

of 32 immunoassay windows in miniaturised format

18 minutes per cycle and up to 500 analyses without regeneration

http://barolo.ipc.uni-tuebingen.de/awacss

Water Monitoring Biosensor

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Multi-analyte Measurements

G. Proll et al. Anal. Bioanal. Chem. 381 (2005) 61-63

J. Tschmelak et al. Biosens. Bioelectron. 20 (2005) 1499-1519

• No pre-treatment nor pre-concentration are needed

• LOD are in ppq range for many compounds of interest

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Modelling Microfluidic Systems

Microfluidic device for detection of radioactive isotopes in water

Finite element analysis - laminar flow conditions

Min (blue) = 0 mm/s

Max (red) = 10 mm/s

G. Janssens-Maenhout, Nanotechnology Perceptions 3 (2007) 183-192

17http://www.multisensor.co.uk

• Sensor array using commercial gas sensors sensitive to ppm

concentrations of Volatile Organic Compounds

• Remote transmission of data in real time

• Display of odour intensity profiles in real time

Real-time Monitoring of VOCs

K. Persaud, University of Manchester

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Wastewater Plant Monitoring

• Real-time odour concentrations at a sewage plant

• Early indication of organic load to the plant, unexpected

loads, unexpected pollutants or industrial waste

• Minimisation of chemical treatment of waste water

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Photocatalytic Water Treatment

Valence band

Cond uc tion bandhv

Oxidation

Reduction

Ox

Ox-

Red

Red+

+

-

• Incident photons of energy > Eg

(Band gap energy)

• Excitation of electrons from the valence band to the conduction

band

• Formation of electron-hole pair on the surface

• Chemical reaction with electron acceptor and donor molecules

• Formation of highly reactive species (Ο2

-and ΟΗ

-) that can

oxidize inorganic and organic compounds

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Particle Shape and Phase Stability

A.S. Barnard et al. J. Chem. Theory Comp. 1 (2005) 107-116

D.G. Rickerby, J. Nanosci. Nanotechnol. 7 (2007) 1-8

• Highly dispersed titanium dioxide nanoparticles have a large

reactive surface area

• Modelling of nanoparticle shape and anatase to rutile transition

point using a thermodynamic model

• Morphology is dependent on particle size due to the increasing

surface contribution to the free energy with decreasing size

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Groundwater Remediation

Groundwater

flow

UV lamp or

solar radiation?

Borehole

Catalyst

coating

Light

scattering

device

Light pipe

Groundwater

flow

UV lamp or

solar radiation?

Borehole

Catalyst

coating

Light

scattering

device

Light pipe

A. Orlov et al. Catalysis Commun. 8 (2007) 821-824

A. Orlov et al. Environ. Technol. 27 (2006) 747-752

Gold doped titania to increase

photocatalytic activity

0 1 2 3 4 5

0.002

0.004

0.006

0.008

Pseudo f

irst

ord

er

kin

etic r

ate

consta

nt

(min

-1)

Loading of Au (at.%)

MTBE decomposition

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A.G. Rincón and C. Pulgarin, Appl. Catalysis B 49 (2004) 99-112

C. Sichel et al. J. Photochem. Photobiol. A 189 (2007) 239-246

Compound Parabolic Collector

E. coli inactivation by sunlight is

more efficient in the presence of

the TiO2

catalyst

Enhanced Solar Disinfection

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Direct Injection of Nano Fe in Aquifer

G. Houben, Federal Institute for Geosciences and Natural Resources

1-10 μm

0.29 m2g-1

40-90 nm

20-32 m2g-1

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Nano Iron in Reactive Barriers

X.-Q. Li et al. Critical Rev. Solid State Mater. Sci. 31 (2006) 111-122

J. Anthony et al. J. Nanosci. Nanotechnol. 6 (2006) 568-572

Fe(0) core with oxide shell:

Trichloroethylene reduction

Nano Fe clusters

R.M. Powell, EPA 600/R-98/125 (1998) p.94

http://gnet.myweb.hinet.net

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Nanofiltration Membranes

K. Yoon et al. Polymer 47 (2006) 2434–2441

Comparison of 3-layer membrane

with a commercial membrane for

filtering oily water

Electrospun polymer scaffold with

hydrophilic chitosan coating layer

→ reduction of fouling

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Biomimetic Water Filters

• Aquaporins - natural proteins that transport water

through cell walls - embedded in organic membranes

• High permeation rate: 0.7-700 litres per second per gram

depending on the hydrostatic and/or osmotic pressure

• Potential applications: freshwater purification; desalination;

industrial wastewater recyling - 100% selectivity

H. Khandelia, University of Southern Denmark

http://www.membaq.eu

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Nanotechnology and the Environment

European research activities:

Air/water quality monitoring

Environmental remediation

Prevention of pollution

Energy production & storage

Environment & health issues

http://www.nanoforum.org/events/nanoenvironment

Projects funded during the

6th Framework Programme

D.G. Rickerby and M. Morrison, Sci. Technol. Adv. Mater. 8 (2007) 19–24

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Nanotechnologies for Water Treatment

Projects resulting from the joint call 2008:

Theme 6 - Environment (Including Climate Change)

Theme 4 - Nanosciences, Nanotechnologies, Materials and

new Production technologies

MONOCAT: Monolithic reactors structured at the nano and micro

levels for catalytic water purification

WATERMIM: Water Treatment by Molecularly Imprinted Materials

Nametech: Development of intensified water treatment concepts

by integrating nano- and membrane technologies

NEW ED: Advanced bipolar membrane processes for remediation

of highly saline waste water streams

Clean Water: Water Detoxification Using Innovative Nanocatalysts

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Nanosystems for improving water quality:

1. Cell based and molecular techniques for toxicology testing

2. Biosensors for water quality monitoring with detection limits

comparable to conventional analysis methods

3. Artificial receptors for more robust and reliable biosensors

4. Gas sensor arrays for odour detection to increase efficiency

in wastewater treatment

5. Nanoparticle photocatalysts for drinking water purification

and groundwater treatment

6. Fe nanoparticles for adsorption and reductive degradation of

contaminants in groundwater

7. Nanoporous membranes for removal of organic and inorganic

water pollutants

8. Highly selective water filters based on biomimetic structures

Summary and Conclusion

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Thank you for your attention!

http://expozaragoza2008.europa.eu