Celebrating 50 years

Affordable clean water using nanotechnology

Department of Chemistry and Sophisticated Analytical Instrument Facility Indian Institute of Technology Madras Chennai 600 036, INDIA

T. Pradeep

http://www.dstuns.iitm.ac.in/pradeep_research_group.php

It is the poor who drive our society.

Potential Environmental Benefits of Nanotechnology: Fostering safe innovation-led growth OECD July 15-17, 2009

Chapter by T. Pradeep and Anshup

2 nm

O H
104.45O

99.84 pm

Gas hydrates to ozone chemistry

Water - prosperity, health, serenity, beauty, artistry, purity ..

Claude Monet, Waterlilies, 1906 Oil on Canvas, The Art Institute of Chicago

Water - the vehicle of nature" ("vetturale di natura) Leonardo Da Vinci

Subject: Leonardo, Old Man with Water Studies, c. 1513

Leonardo Old Man with Water Studies, c. 1513

Leonardo Machine for raising water

Water and civilizations

Mohenjodaro - well

http://dspace.rice.edu/bitstream/1911/9176/773/LanMa1890_135_a.jpg

Aqueducts - The Assyrians - the first structure to carry water from one place to another - 7th century BC

Archimedes screw - 287 and 212 BC - in the Netherlands Zoetermeer

Mohenjodaro the great bath

Nitrates Fluoride Asbestos

Microbes Heavy metals Chemicals, pesticides

Water filtration: various media

hof.povray.org/River.html

Important milestones in the history of water purification (1800-2007)

Year 1804 1810 1852 1879 1902 1906 1908 1914 1916 1935 1948 1959 1962 1965 1974 1975 1994 1997 1998 2000 2003 2004 2007 Milestone Setup of world's first city-wide municipal water treatment plant (Scotland, sand-filter technology) Discovery of chlorine as a disinfectant (Humphrey Davy) Formulation of Metropolis Water Act (England) Formulation of Germ Theory (Louis Pasteur) Use of Chlorine as disinfectant in drinking water supply (calcium hypo chlorite, Belgium) Use of ozone as disinfectant (France) Use of Chlorine as disinfectant in municipal supply, New Jersey Federal regulation of drinking water quality (USPHS) Last globally big invention Use of UV treatment in municipal supplies Discovery of synthetic ion exchange resin (Adams, Holmes) water purification Nobel Prize to Paul Hermann Mller (insecticidal properties of DDT) Discovery of synthetic reverse osmosis membrane (Yuster, Loeb, Sourirajan) Publishing of Silent Spring, first report on harmful effects of DDT (Rachel Carson) World's first commercial RO plant launched Reports on carcinogenic by-products of disinfection with chlorine Formulation of Safe Drinking Water Act (USEPA) Development of carbon block for drinking water purification Report on use Zerovalent Iron for degradation of halogenated organics (Gillham, Hannesin) Report on use Zerovalent Iron nanoparticles for degradation of halogenated organics (Wang, Zhang) Drinking Water Directive applied in EU Adoption of Millennium Declaration during the UN Millennium Summit (UN Millennium Development Goals) Report on use Noble metal nanoparticles for degradation of pesticides (Nair, Tom, Pradeep) Stockholm Convention, banning the use of persistent organic pollutants Launch of world's first nanotechnology based domestic water purifier (Pradeep, Eureka Forbes Limited)

in

Credits to several governments, organizations and individuals, we have moved ahead. Now, the journey of pure water for all calls for next big innovation. Source: Multiple sources from internet

The cost of RO solutions has seen a dramatic fall since the discovery, but the costs have flattened recently.

Costs analysis of Reverse Osmosis Plants

(converted to 1995 base year level)

Economic and technical assessment of desalination technologies, Fawzi Banat, From Red Sea to Dead Sea Water and Energy, Geneva, June 6-8, 2007 www.desline.com/Geneva/Banat.pdf

Review of major contaminants in drinking water

Major pollutant
Pesticides

Sources of origin
- Farming, effluents, home use Chlorination, effluents, home insecticide - Geological origin, mineral weathering, coal mining - Geological origin

Permissible limits
DDT: 1 ppb Carbofuran: 40ppb Simazine: 4 ppb CCl4: 5 ppb TCE: 5 ppb TTHMs: 80 ppb

Affected countries
US, Kenya, Egypt, India, European Union, Africa, China, Australia Japan, Central Asia, Arabian Peninsula, Sweden, Poland, Germany, USA, Egypt, China Asia, Mexico, Australia, Argentina, Africa, New Zealand

Population at risk (estimates)

Poisoning: 28 million agricultural workers in developing countries. ~18,000 deaths ~180 million people in US consume chloraminated water

Health effects
Cancer, cardiovascular/ reproductive/ neurological disorders, Liver/kidney problems -CCl4: High toxicity to liver and kidney, carcinogenic. TCE: Lung/liver tumor - Dental and skeletal fluorosis, Muscle fibre regeneration, nervous system malfunction High blood pressure, glucosuria, hyperpigmentation, keratoses, cancer Neurotoxicant, tremors, respiratory failure, gastrointestinal failures, and kidney damage

Remarks
Pesticide contamination in soft drinks, Union Carbide Bhopal tragedy (India) - 25 million pounds TCE were released in the U.S. environment by manufacturing plants in 1995 A union of 1,200 scientists, doctors and lawyers announced opposition to water fluoridation (1999) - Death rate: 1 in 100 people (Conc: 50 ppb) and 10 in 100 people (Conc: 500 ppb) - ~30% of the mercury in US comes from abroad e.g. China Unilever plant, Kodaikanal. Minamata, Niigata, River Nura. - Incidence of Gout due to leaded wine and rum- Use of lead in paints and discharge in environment

Halogenated organics

Fluoride

2 ppm

62 million (India)

Arsenic

10 ppb

Bangladesh, India, China, Pakistan, Nepal, Myanmar, Vietnam Indonesia, China, Africa, Philippines, Japan, Kazakhstan, USA, Brazil, Australia, Taiwan, EU Egypt, EU, USA, Thailand, China, Cambodia

65 million (Asia)

Mercury

- Industrial pollution, dental filling, Food (fish)

2 ppb

~630,000 infants are born with high Hg content in the blood every year (EPA)

Lead

- Old piping lines, mineral weathering, paint

15 ppb

>300,000 US children and 65% of Shanghai children have high lead concentration

Delays in physical or mental development, Kidney problems, high blood pressure

Review of major drinking water contaminants, their health impacts and a few associated eventsmultiple sources from internet

Quantum of Fluoride Contamination

Fluoride contamination: Indian Scenario

25 million people are suffering from fluorosis and 62 million are at the risk of fluorosis
Despite being a global contaminant, fluoride is still a unresolved mystery.
A.K. Susheela, Fluorosis management programme in India, Current Science 77 (10) (1999) 12501256

How much of our environment is polluted by cadmium?

Ground water (1995-96) (Source: PCB) Fresh water (Source: PCB)
Location Bellandur Lake, Bangalore Matla River, West Bengal Saptamukhi River, West Bengal Hugli River, West Bengal Subernarekha River, West Bengal Conc (mg/l) 0.70 0.68 0.85 0.59 0.47 Location
Korba Singrauli Gobindpur Parwanoo Kala Amb Pali Jodhpur Nazafgarh

State
Madhya Pradesh Utter Pradesh Punjab Himachal Pradesh Himachal Pradesh Rajasthan Rajasthan Delhi

Cd (mg/l) Min
NT NT NT NT NT 0.005 <0.005 NT

Max
0.01 0.01 0.08 0.062 0.150 0.224 0.042 0.013

Coastal water (Source: PCB)

Location Off Bombay Point Calimere Cuddalore Madras Coast River Coovum Parangipettai Coast East Coast Conc. (g/l) 80.00 (1980) 0.1-0.6 (1991) 2-27 (1994) 1.4 (1987) 0.98 (1991) 2-25 (1994) NT-2.9 (1999)

The Palakkad controversy showed that excessive withdrawal of ground water can also expose us to high metal contamination The above figures are just a tip of the iceberg (itai-itai) India produces 1.46L tons of e-waste annually In India, 2M of computers become obsolete every year 67,000 tons of computer waste contributed 1.1 tons Hg, 4.5 tons Cd and 3012 tons Pb into landfills (Canada, 05) The average Cd generation per computer is 2.8 g

Affordable Drinking Water Purifier Market needs Unsolved technology problems

Mercury contamination, Minamata, Japan, 1956

Microbial contamination, Zimbabwe, 2009

Pesticide contamination, Kerala, 2001

Fluoride contamination, India, 2003

Images collected from arsenic, fluoride and pesticide affected areas in India

For 8-month old Sainaba to 18-year old Ramaswamy, science still has to deliver its benefits

Pictures from the web

Affordable Drinking Water Purifier Market needs Commercial unviability Pricing issues
Brand Model Number Retail Price Replacem ent Cost & Capacity Cost per gallon Chlorine Lead Cysts THMs VOCs Lindane Aquasana AQ-4000 $124.99 $48.00 / 500 Gal. Amway E-5199 $420.00 $120.00 / 1250 Gal. Culligan SY-2300 $159.99 $50.39 / 500 Gal. Kenmore Deluxe 38465 $149.99 $49.00 / 500 Gal. GE Smart Water GXSV10C $139.99 $60.00 / 540 Gal. Ever Pure H-54 $149.99 $79.95 / 750 Gal. Aqua-Pure DWS1000 $349.95 $79.99 / 625 Gal. PUR Plus FM3000 $49.95 $20.00 / 100 Gal. Brita Faucet Filter $34.95 $20.00 / 100 Gal. Brita Pitcher Filter $24.95 $7.70 / 30 Gal.

9.6 Per Gal. >99% >99% >99.99% >99% >99% >99%

9.6 Per Gal. 97.9% 98% 99.5% >99% >99% 72.7%

10 Per Gal. 97% 95% 99% 95% 95% 99%

9.8 Per Gal. 99% 92% NO 99% 95% 99%

11 Per Gal. 97% 98% >99% 95% 99% 99%

10.6 Per Gal. 96% 97% >99% NO NO NO

13 Per Gal. 97% 95% >99% 92% 92% >99%

20 Per Gal. 98% 96% 99.99% NO NO 97%

20 Per Gal. 99% 99% 99.99% NO NO 99%

25 Per Gal. >75% 93% NO NO NO NO

Alachlor
Atrazine Benzene TCE MTBE Cost per 1000 gals.

>98%
>97% >99% >99% >97% $172.99

95%
>97% >97% >98% NO $420.00

98%
97% 99% 99% 90% $210.38

95%
97% 83% 98% NO $198.99

98%
97% 99% 99% NO $199.99

NO
NO NO NO NO $229.90

98%
97% >99% >99% NO $349.95

NO
96% NO NO NO $229.95

99%
92% 96% 99% NO $214.95

NO
NO NO NO NO $273.91

Our goals of a socially relevant science has largely failed due to our inability to serve people at bottom-of-the-pyramid
Product Average cost Functions Price per liter (10 yrs) INR 7590 Turbidity, Chlorine, Bacteria, Virus, Aquaguard Classic Rs 0.61 ($ 168) Odor Aquaguard Nova and I- INR 7690 Turbidity, Chlorine, Bacteria, Virus, Rs 0.70 Nova ($ 171) Odor Aquaguard Gold INR 9,590 Turbidity, Chlorine, Bacteria, Rs 0.94 Nova ($ 213) Virus, Odor, Pesticides INR 15,500 TDS, Taste, Heavy metals, Aquaguard RO Rs 1.86 ($ 345) pesticides, F /NO3 INR 2,000 Aquasure 4-in-1 Turbidity, Chlorine, Bacteria, Virus Rs 0.33 ($ 45) INR 650 Aquasure on Tap Turbidity, Chlorine, Bacteria, Virus Rs 0.12 ($ 15) Boiling Rs 0.18 Bacteria, Virus INR 250 Bottled Water Rs 2.0 ($ 6) Reference: Eureka Forbes Ltd, Bangalore (2008) Products from Eureka Forbes Ltd

Affordability of Technology

Income Annual Household Segment Income ($) Community <$ 2,000 $2,000-$4,500 Low-Budget $4,500-$11,000 $11,000-$22,000 $22,000-$44,000 High-Budget $44,000-$111,000 $111,000-$222,000 $222,000 Source: www.ncaer.org - Year 2005

# of Households (in '000) 132,249 53,276 13,183 3,212 1,122 454 103 52

What does this cost-of-ownership for access to pure water and income-based societal structure mean to us? Need for a revolutionary theme for guaranteeing access to pure water to everybody - under INR 1,000 water purifier (<$20) Universal purifier: Remove suspended particles, pesticides, microbes, metals and anions Zero electricity Minimum maintenance and low-cost of annual replacement (< INR 450/-) (<$10) Indeed, early signs of success of nanotechnology gives a ray of hope

An object for the nanotechnology - nanomaterials

5 nm

20 nm

2 nm

20

Height (nm)

15 10 5 0 0 100

C
200 300 400

Distance (nm)

0.6

Absorbance

0.4 0.2 0.0

I II

III
D 100 nm 400

600 800 1000 Wavelength (nm)

200 nm

Range of nanostructured materials

Y. Xia et. al., Adv. Mater 2002, 14,11,833

http://www.nanolab.com/imagegallery.html

http://www.physics.upenn.edu/~dr ndic/group/graphene.html

PJF Harris et. al., J. Phys.: Condens. Matter 20 (2008) 362201

Nanocatalysis

STM image of MoS2 nanoflakes. From, Nanotechnology 14, pp. 385-389 (2003)

USEPA has played a key role in determining the regulations for many toxic species found in drinking water

Regulatory coverage of USEPA for safe drinking water has increased over 4 times since its inception, with revisions in regulations of many old contaminants

Future of water purification: An enigma with some pointers

25 25 20 20 15 15 13 13 9 9 4 4 1 1 m m 5 5 6 6 5 5 6 6 6 6 9 9 5 5 1 1 j j i i h h g g f f e e d d c c 2 2 b b a a 10 10 15 15 10 10 5 5 0 0

Candidate contaminant list Contaminants regulated by EPA

7 7

1 1 r r

3 3 1 1 q q

4 4 1 1 p p 1 11 1 11 o o n n

2 1 21 1 1 k k

44 44

(a): Halogenated organic (b): Metal (c): Organochlorine pesticide (d): Inorganic salt (e): Biological contaminant (f): Nuclear (g): Benzo derivative (h): Carbamate pesticide (i): Pesticides (others) (j): Unclassified (k): Triazine derivative pesticide (l): Organophosphorus pesticide (m): Organobromine pesticide (n): Non-metal (o): Nitrophenol derivative, (p): Dioxin, (q): Benzo and halogenated organic (r): Organometallics

Label for contaminants Label for contaminants

l l

Category-wise distribution of contaminants regulated by USEPA and future contaminants

Continued focus of USEPA regulatory activities on various other halogenated organics found in drinking water. The allowed concentration limits for a number of species may shift to subppb range. Source: www.epa.org and www.who.int

Number of contaminants Number of contaminants

21 21

Future of water purification: Shrinking limits for allowed concentration of contaminants in water
200
200 Lead Arsenic

Concentration (in ppb)

150 100 50 0
100 100 50 50

50 10

1950

1960

1970

1980

1990

Year

Changes in maximum allowable concentration for lead and arsenic in drinking water, based on WHO advisory

2000

Nanotechnology holds the future for effectively removing many drinking water contaminants

- Number of contaminants present in extremely low concentration range (< 1015 molecules per glass of water) are quite significant - Many of those contaminants contain C-Cl bond or are metallic in nature

Permissible contamination

1012 molecules

Time

Permissible contamination reaches limits of detection

Organics
Pesticides
Tansel and Nagarajan, Advances in Environmental Research 8, 2004, 411415

Traditional methods (activated carbon, membranes) Nanomaterials Metals, oxides, clays, dendrimers

Plakas, Karabelas, Wintgens and Melin, Journal of Membrane Science 284, 2006, 291300

Illustration of metal adsorption on nanoparticle surface (ZVI surface)

TEM image of Fe nanoparticle and Cartoon representation of chemistry at Fe nanoparticle, Iron Nanoparticles: the Core-Shell Structure and Unique XPS wide-scan survey of iron nanoparticles after exposure to a metal Properties for Ni(II) Sequestration, Xiao-qin Li and Wei-xian Zhang, Langmuir salt containing solution, Sequestration of Metal Cations with Zerovalent 2006, 4638-4642 Iron Nanoparticless A Study with High Resolution X-ray Photoelectron Spectroscopy (HR-XPS), Xiao-qin Li and Wei-xian Zhang, J. Phys. Chem. C 2007, 6939-6946

Cartoon representation of chemistry at Fe nanoparticle surface (left) and metal ion removal efficiency for different adsorbents, Iron Nanoparticles: the Core-Shell Structure and Unique Properties for Ni(II) Sequestration, Xiao-qin Li and Wei-xian Zhang, Langmuir 2006, 4638-4642

(b)
Counts (X 104)

Metal adsorption on nanoparticle surface (ZVI surface)

Ni2+ 24 hrs 3 hrs 1 hr Ni0

(c)

2.4 1.8 1.2

Ni(II)

Sorption

Ni(II)

Reduction

Ni(0) Fe(0)
856 853 Binding energy (eV) 850

0.6 15 min 0 859

FeOOH
Ni2+ + 2e- Ni E = -0.25 V Fe Fe3+ + 3 e- E = 0.44 V

(L) HR-XPS survey on the Ni 2p3/2 of iron nanoparticles (R) a conceptual model for nickel deposition on iron nanoparticles

Hg(II) Hg 4f7/2

After 24 hrs Ag@citrate-Hg(OAc)2 Hg 4f5/2

101.4

Counts

Hg(0)
100.2 104.2 105.4

100 ppm 50 ppm 10 ppm 7 ppm 108 111

96

99

102

105

Binding Energy (eV)

Bootharaju et al. Unpublished

Metal oxide and MWNT assembly based membrane filtration

X.B. Ke, H.Y. Zhu, X.P. Gao, J.W. Liu, Z.F. Zheng, Adv. Mater. 19 (2007) 785
X.B. Ke, Z.F. Zheng, H.W. Liu, H.Y. Zhu, X.P. Gao, L.X. Zhang, N.P. Xu, H. Wang, H.J. Zhao, J. Shi, K.R. Ratinac, J. Phys. Chem. B 112 (2008) 5000.

1 m

(a)

(b)

1 m

(a) Schematic illustration of ceramic membranes and TEM images of the boehmite (top) and titanate (bottom) nanofibers, (b) SEM image of feed water containing 60 nm latex spheres and permeate water (inset). Filtration efficiency=96.8%

G. Hummer, J.C. Rasaih, J.P. Noworyta, Nature 414 (2001) 188.

(a)

0 sec

15 sec

Pt wire 30 sec

(b)

Z.Wang, L. Ci, L. Chen, S. Nayak, P.M. Ajayan, N. Koratkar, Nano Lett. 7 (2007) 697

45 sec

60 sec

80 sec

Images of water droplet shape change with a +2.6 V potential applied with a multiwalled nanotube film as anode and Pt wire as cathode. The droplet sinks into the nanotube membrane in about 90 s. (b) SEM image of a cylindrical macrostructure assembly showing the wall of the bulk tube consisting of aligned MWNTs with lengths equal to the wall thickness (scale 100 m)

Noble metal nanomaterials: Novel chemistry for water purification

Halogenated organics & pesticides
Absorbance
0.4
A

0.2
B

0.0 400

With Gold Endosulfan nanoparticles

C

Wavelength(nm)

600

800

1000

Bacteria & virus

Absorbance
B

The novel chemistry of noble metal nanomaterials help them target broad range of toxic contaminants. We will see a glimpse of it in the later slides.

+
+

+ + +

Heavy metals

0.6 0.4
A

0.2

0 300 500 700 900 Wavelength (nm)

With mercury Gold C nanoparticles

Reactions with pesticides

Color of gold nanoparticles with endosulfan

Example

200

100

Endosulfan

Endosulfan concentration in ppm Color changes with pesticide concentration

Pesticide removal Good response at lower concentrations Indian Patent granted Down to 0.1 ppm International patent filed Adsorbed pesticides can be removed from solution Technology commercialized J. Environ. Monitoring. 2003

Some of the pesticides contain halocarbons whereas others have P or S, which can bind metal nanoparticles which is used for pesticide detection and extraction.
Endosulfan Chlorpyrifos Malathion

0.5

0.4

a
0.4

b cd e
0.3 t

Absorbance

0.3

Absorbance

0.2

0.2

0.1

Endosulfan
400 500 600 700 800 900 1000

Chlorpyrifos 0.1
1100

c b

Malathion

0.0

0.0 400 500 600 700 800 900 1000 1100

Wavelength(nm)
UV-visible spectra of gold nanoparticles showing the detection of endosulfan at different concentrations (b.2, c.10, d.100 and e. 250 ppm). Inset (A-D): Color changes of the solutions corresponding to traces a, b, c and d, respectively.

Wavelength (nm)
Time dependent adsorption of endosulfan on gold nanoparticles and the corresponding spectral changes (a-t). The shifts in the plasmon band are due to the binding of the pesticide on the nanoparticle surface.

Supported nanoparticles for pesticide removal

Activated alumina globules (A) and gold (B) and silver (C) nanoparticles coated on the same. Silver nanoparticles coated on activated alumina (neutral) powder These can be made in ton quantities. 4 cm

Nanoparticle loaded alumina can remove pesticides

0.15

a b
Absorbance

0.16 0.12 0.08 0.04 0.00

0.15

0.10

Absorbance

Absorbance

0.10

Absorbance

a b

0.12

0.08

0.04

0.05

0.05

100

200

300

400

500

600

Time (minutes)
s
0.00 300 400 500 600 700 800

p q
0.00

0.00

100

200

300

400

500

600

Time (minutes)

Wavelength (nm)

300

400

500

600

700

800

Wavelength (nm)

Absorption spectra showing the time dependent removal of 1 ppm chlorpyrifos (left) and malathion (right) by supported nanoparticles. The reduction in the absorbance feature with time is due to the adsorption of the pesticides on the nanosurface. Inset shows reduction in absorbance with time. Time interval between spectra was 20 minutes.

Other scientific tests conducted confirm the complete removal of commonly occurring pesticides from water
A

0.10 a

% Transmittance (Arb.Units)

100

80

60

Absorbance

40

0.05

20
70 B

3000

2500
b

2000

1500

1000

500

% Transmittance (Arb.Units)

60 a

0.00

b-e

50

40

30

400

600

800

1000

Wavelength (nm)
Absorption spectra showing the complete removal of pesticides when contaminated water was passed through a column of the nanomaterial. Trace a is the spectrum of the parent pesticide solution, b-e after passing through the nanoparticle-loaded column, in repeated experiments.

3000

2500

-1 Wavenumber (cm )

2000

1500

1000

500

Infrared spectra of the free pesticides (a) and that adsorbed on the nanoparticle surfaces (b) chlorpyrifos (A) and malathion (B).

Product of this reaction is amorphous carbon

Noble metal nanoparticles: removal of pesticides from water

A.S. Nair, T. Pradeep, Curr. Sci. 84 (2003) 1560

1.5

Absorbance

2.14 2.5 2.933 CP 3.307

[V] 0.5 0.0

[mV] 400 200 0 -200 -400 -600

1.0 0.5 0.0

o p 400

Wavelength (nm)

600

800

1000

-0.5

Variation of the UV-visible absorption spectrum of silver nanoparticles upon the addition of CCl4

4 2 0 4 2 Time (min) Time (min) Gas chromatogram of chlorpyrifos solution (L) and after treatment with silver nanoparticles (R)

(a) 0

A.S. Nair, R.T. Tom, V.R. Rajeev Kumar, C. Subramaniam, T. Pradeep, Cosmos 3, (2007) 103

June 2007
(b)

(L) Silver nanoparticles coated on activated alumina (R) Photograph (c) pesticide filter device using supported of a nanoparticles (WQA certified)

Product is marketed now Cartridges are recovered after use

A pesticide test kit has been developed > 25 ppb

Noble metal nanoparticles: removal of heavy metals from water

A a

b B

(220)

Absorbance

K.P. Lisha, Anshup, T. Pradeep, Gold Bull. 42 (2009) 144

20 nm
(B)

Intensity

(100) (002)

100nm

0 300

(102)

(110)

++ *

(111)

20nm

700 500 Wavelength (nm)

900

30

40

50 60 70 2 (degrees)

(Left) Large area TEM image of gold nanoparticles (A) before Hg(0) treatment (B) after Hg(0) treatment (Center) UV-vis absorption spectra of gold nanoparticles before and after mercury treatment (Inset: photographs) (Right) XRD patterns of gold nanoparticles (D) before and (E) after mercury treatment (symbols: + Au3Hg, * Au)

(103) (112) (201) (004) (222)

0.2

(101)

(311) (222)

0.4

(200)

(111)

(A)

(C) 0.6

(D)

+++

80

Noble metal nanoparticles: removal of heavy metals from water 2+

Hg (50ppm, 50ml) with Ag NP (5ml)
(i)

(a) 0.10

Absorbance

(b) (b)

0.05

(ii)

T. Pradeep et al (unpublished)

0.00 200

(viii) (ix)

Wavelength (nm)

400

600

5 m

(a) UV-vis absorption spectra of silver nanoparticles (i) before Hg2+ treatment (ii-ix) after Hg2+ treatment. (b) Large area SEM image of the Ag-Hg bimetallic nanoparticles

(a)

(b)

(c)

2 m

Ag|Si

Hg|Si

(a) SEM image of an Ag-Hg alloy nanoparticle, (b) elemental image of Ag and (c) elemental image of Hg overlaid on Si (Si is from ITO substrate).

Noble metal nanoparticles: removal of bacteria (E. coli) from water

J.R. Morones, J.L. Elechiguerra, A. Camacho, K. Holt, J.B. Kouri, J.T. Ramirez, M.J. Yacaman, Nanotechnology 16 (2005) 2346

(A) a c a c

b d b d

AgNO3

a c a c

b d b d

Rod

(B)8
6 4 2
log(1+X)

AgNO3 8 R2 = 0.98 6
4 2 0 0 40 80 8 4 2 0 0 0

Rod R2 = 0.9689

0 8 6 4 2 0

40

80

Sphere R2 = 0.9878 6

Triangle R2 = 1

Sphere

Triangle

0 40 80 40 Concentration of silver (g)

80

(A) Petri dishes initially supplemented with 107 CFU/ml of E. coli and incubated with different forms of silver nanoparticles at (a) 1, (b) 12.5, (c) 50, and (d) 100 g. (B) Number of E. coli colonies, expressed as log(1+number of colonies grown on plates under the conditions used for panel A) as a function of the amount of silver nanoparticles in agar plates.

Noble metal nanomaterials: detection of toxic species

(a)
SERS Intensity
K.P. Lisha, Anshup, T. Pradeep, J. Environ. Sci. Health M. Mulvihill, A. Tao, K. Benjauthrit, J. Arnold, P. Yang, Angew. Chem. Int. Ed. B. (in press) 47 (2008) 6456

(b)
SERS Intensity

(c)
SERS Intensity
PVP BT HDT MDA

AsIII + AsV AsV

300 500 700 900 Raman Shift (cm-1)

300 500 700 900 Raman Shift (cm-1)

500

600 700 800 900 1000 Raman Shift (cm-1)

SERS spectra of arsenate ion (1X10-6 M) on (a) LB films of silver nanocrystals (b) LB arrays of silver octahedra coated with various organic species. BT: benzenethiol, HDT: hexadecanethiol, MDA: mercaptodecanoic acid. (c) SERS-based speciation of arsenate and arsenite ions (18 ppb) A
A

(A)

a a

b b

c c

e e

f f

0.3 0.3

f e

Au

(B)

B a

C b

Absorbance Absorbance

a+Na2SO4 b+50 ppb b+100 ppb b+500 ppb b+1 ppm CP CP CP CP

0.2
0.2

d
d c c

0.1
0.1

b b a a 0.0 0 600 800 (c) 400 500 600 700 800 (C) 400 50 nm 50 nm 50 nm Wavelength (nm) Wavelength (nm) Colorimetric detection of chlorpyrifos using the gold nanoparticle-Na2SO4 system C

900

Pollutants

Harmless products

TiO2

CO2

HCs

Polluted water

Purified water

As adsorption

Magnetic Fe3O4 nanopartilcles

Purification by circulation

Low-Field Magnetic Separation of Monodisperse Fe3O4 nanocrystals, C. T. Yavuz, J. T. Mayo, WW Yu, A Prakash, JC Falkner, S Yean, L Cong, HJ Shipley, A Kan, M Tomson, D Natelson, VL Colvin, Science 2006, 314, 964

Magnetic batch separation of 16-nm water-soluble Fe3O4 nanocrystals (A) Fe3O4 solution (B) After application of magnetic field (C) TEM images of the nanocrystals

Magnetic clays for oil cleanup Antibody tagging Magnetic hyperthermia

Commercial interests in drinking water purification

iw Product Name Aquaguard Gold Nova, Eureka Forbes Limited Adsorbia Nanomaterial utilized Silver nanoparticles supported on alumina Titania nanoparticles Contaminants removal Pesticides and halogenated organics Adsorption capacity Product life Product price 12-15 gm As(V) and 34 gm As(III) per kg of adsorbent 38 mg of Arsenic per gm of adsorbent 6000 liters $50 -

Arsenic and disinfection AD33, Adedge Technologies, Inc. Nanoceram, Argonide Iron oxide nanoparticles Heavy metals including arsenic, lead, chromium, zinc, copper Electropositive alumina nanofibers Disinfection, natural organic matter, on a glass filter substrate turbidity, salt, radioactivity, heavy metals Hydrous iron oxide nanoparticles on Arsenic, vanadium, chromium, uranium polymer substrate

3,800-11,400 liters $50 $3-10 per sq m , $75 per filter $0.07-0.20 per 1,000 liters (amortized due to reusability) 2

ArsenX, SolmeteX, Inc.

Nanopore, Nanovation AG

Membrane filters based on ceramic Disinfection nanopowder supported on alumina

Examples of a few nanotechnology-based products in drinking water purification market (compiled from multiple sources on the World Wide Web)

Current developments
Purifiers for specific areas local issues seasonal problems All inclusive solutions Local manufacture Community involvement NGOs

What OECD can do?

A white paper on available technologies Act as a link between those who need the technology and those who have the solutions Conduct discussions in places where technologies are needed

E. F. Schumacher

Pure water can be affordable..

IIT Madras

Nano Mission, Department of Science and Technology World Gold Council Well-meaning individuals Thank you all

Confocal Raman Microscope MALDI TOF MS

Transmission Scanning Electron Microscope Electron Microscope

QTrap MS Ultramicrotome

XPS

Nanoscience and Nanotechnology Initiative of the DST