Harjyoti Kalita

Michael Quamme

Department of Civil Engineering North Dakota State University, Fargo, ND

Environmental Nanotechnology Research at

NDSU

Nanoenvirology Research Group

1

Student (2006-1012) Project MS PhD

Jay Thompson √ √

Sita Krajangpan √ √

Harjyoti Kalita √ √

Rabiya Shabanam √ √

Dhritikshama Roy √ ----

Christopher Capecchi √ ----

Sharanya Shanbhogue √ ----

Michael Quamme √ √

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Source: NSF

US $ in Billion

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70

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Tools

Health Care

Sustainability

Aerospace

Chemicals

Phamaceutical

Electronics

Materials

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Late 1990s: rash of

research in NZVI

Laboratory results were

outstanding

Field studies have shown

moderate success

Image Credit: Zhang, W-X., 2003. J. Nanopart. Res. 5, 323-332.

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1. Will nanoparticles work for our contaminants?

2. Can we make them work better?

3. Will our new products be biocompatible?

4. Are nanoparticles harmful to microorganisms?

5. What other innovations possible with nanoparticles?

Funding: NDWRRI and Civil Eng

Herbicide for the control of grasses/weeds in corn and soybeans

Maximum Contaminant Level (MCL) = 2 ppb

Jay Thompson

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5

10

15

20

25

30

35

40

0 6 12 18 24 30 36 42 48 54 60 66 72

C, m

g/L

Time, hr

Sita Krajangpan

Chad Mayfield

Mike Quamme

Funding: NDWRRI and Civil Eng

Juan Elorza

Objective: To modify nanoscale

zero-valent iron (NZVI) particle

surface using APGC for effective

groundwater remediation

Hypothesis: APGC provide the

colloidal stability and improve

capabilities to NZVI for

groundwater contaminant removal

Bezbaruah et al., J. Hazard. Mater.,2009, 166,

1339-1343.

Oxidation rate↑, Dispersibility ↓,

and Reactive surface area ↓

Krajangpan et al., ASCE, 2009, pp 191-212.

Krajangpan et al., Polymer Preprint, 2008, 49, 921-922.

Coated Feo Nanoparticle

Dispersed in the Aqueous Phase

Coated Feo Nanoparticle

at the Aqueous/Organic Interface

Aqueous

Phase

Organic

Phase

Coated Feo Nanoparticle

Dispersed in the Aqueous Phase

Coated Feo Nanoparticle

at the Aqueous/Organic Interface

Aqueous

Phase

Organic

Phase

Coated Feo Nanoparticle

Dispersed in the Aqueous Phase

Coated Feo Nanoparticle

at the Aqueous/Organic Interface

Aqueous

Phase

Organic

Phase

Coated Feo Nanoparticle

Dispersed in the Aqueous Phase

Coated Feo Nanoparticle

at the Aqueous/Organic Interface

Aqueous

Phase

Organic

Phase

APGC synthesis

A schematic representation of APGC

coated NZVI (CNZVI)

SiO

SiO

SiO

Si

H

x y

+

O

O +O

On

SiO

SiO

SiO

SiO

a b

Si

c

O

O

nO

O

SiO

SiO

SiO

SiO

a b

Si

c

HO

O

nO

O

Pt

Hydrolysis

0.0

0.2

0.4

0.6

0.8

1.0

20 40 60N

orm

ali

zed

In

ten

sity

Time (min)

Bare nZVI CnZVIBare NZVI CNZVI

CNZVI has significantly higher colloidal

stability than bare NZVI

U.S

. P

ate

nt

11

Initial concentration of TCE and

As(V): 1, 15, and 30 mg/L

TCE batch study: 1.5 g/L of NZVI

and CNZVI

As(V) batch study: 1 g/L of NZVI

and CNZVI

Controls and blanks were ran

simultaneously

Aliquots withdrawn at definite

time intervals

TCE and As(V) were analyzed

using GC-MS and ICP-AES

0

0.2

0.4

0.6

0.8

1

0 2 4 6 8 10 12

TC

E N

orm

ali

ze

d

Co

nc

en

tra

tio

n

Time (h)

CNZVIBare NZVIBlankControl

TCE kinetic study

As

(V)

No

rma

lize

d

Co

nc

en

tra

tio

n

CNZVI(Aerobic)

Bare NZVI

Blank

Control

CNZVI (Anarobic)

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0.0

0.2

0.4

0.6

0.8

1.0

0 20 40 60 80 100 120

Norm

ali

zed

In

ten

sity

Time (min)

CNZVI sedimentation studies:12 month-

period

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5

10

15

20

25

30

0 2 4 6 8 10 12

TC

E C

on

cen

tra

tio

n

(mg

/L)

Time (h)

CNZVI-TCE kinetic studies: 6 month-

period

Sedimentation studies:

Batch studies: 3 g/L of NZVI and 15

g/L of APGC

30 min sonication and 72 hr of 28

rpm rotation

UV-VIS spectrophotometer

TCE kinetic studies:

1.5 g/L of NZVI and CNZVI

30 mg/L of TCE initial concentration

TCE was analyzed using GC-MS

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Funding: NDWRRI & ND Soybean Council

Objectives:

1. Development of novel ion imprinted polymer

for arsenic removal

2. Synthesis of biodegradable amphiphilic

copolymer from soybean oil

Harjyoti Kalita

SHAs(III), As(V)5 AsS

S

S SS

AsS

S

S

+

AsS

S

S

Polymerization

60 oC, 24 hr

+

AsS

S

SLeaching1:1 HCl

Monomer Crosslinker

Thiol -arsenic complex

Thiol -arsenic complex

February 11, 2013 14

Sample

Theoretical value(ppm)

Experimental value (ppm)

Thiol- arsenic complex

143.98 138.61

Elution of arsenic and preparation of IIP

10 ml HCL 150.85 147.67

20 ml HCL 150.85 145.38

30 ml HCL 150.85 149.74

Binding & Elution of As: IIP-As Synthesis

February 11, 2013

Weight of IIP-As (g)

Extraction (%)

Preconcentration time

(hr)

Extraction (%) Elution time ( hr)

Extraction (%)

0.05 > 87 1 >97 0.5 >98

0.1 >96 2 >99 1 >99

0.15 >98 3 >99 1.5 >99

0.2 >96 4 >99

0.25 >97 5 >99

0.3 >97

Influence of Various Parameters on As

Extraction

February 11, 2013

O

O

OR2

OR2

O

O

OO

O

O

O

HKOH, 70°C, 3H, N2

OH

OH

OH

+

U.S. Patent to be applied

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O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

O

n

C6H17Al2Cl3

Toluene, N2, 8hr

O

O

O

O

O

O

O

O

O

O

n

ab

c

d

f

g

h

i

j

e

k

l

m

n

o

p

q

r

s

t

u

v

O

x

w

y

z

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O

O

O

O

O

O

O

n

ab

c

d

f

g

h

i

j

e

k

l

m

n

o

p

q

r

s

t

u

v

O

x

w

y

z

HS OH

O

Benzophenone

UV , 3hr

O

O

O

O

O

O

O

n

ab

c

d

f

g

h

i

j

e

k

lm

n

o

p

q

r

s

t

u

v

O

x

w

y

z

S

HOOC

S

COOH

V-15/T-85:C20

where V-15 represent VOES 15wt%; T-15 represent TGEVE 85wt%

C represent – carboxilic acid & 20 represent 20 g/L polymer solution

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0.2

0.4

0.6

0.8

1

1.2

0 20 40 60 80 100 120

Ab

sorp

tio

n (

I/I

0)

Time minute)

V-15/T-85: C20

V-15/T-85: C15

V-15/T-85: C10

V-15/T-85: C5

Bare NZVI

Time - 0 m

Time - 1h

Time - 15m

Time - 2 h

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Oxy

gen

Up

tak

e (m

g/L

)

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Funding : NDWRRI & ECS Program

Objective: To understand microorganism-NZVI

interactions

Hypothesis: Microorganisms can establish a

“symbiotic relationship” with NZVI

Rabiya Shabnam

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Bactericidal effects: NZVI

concentration dependent

Physical condition of the cell membrane

Growth phase of the bacteria

E. coli 8739, Jm109 and Pseudomonas putida F1 show similar effects with NZVI

Inactivation of E. coli 8739 in buffer

0.0E+00

2.0E-01

4.0E-01

6.0E-01

8.0E-01

1.0E+00

1.2E+00

1.4E+00

0 10 20 30 40 50 60 70

Ce

lls/m

L

Time, min

90 mg/L 200 mg/L500 mg/L 800 mg/L1000 mg/L

25 25

Findings:

Bacteria in a lag or early

exponential phase are

affected by NZVI

Actively growing bacteria are

not effected by NZVI

Non-replicating bacteria are

more susceptible to NZVI

toxicity

1.0E+05

1.0E+06

1.0E+07

1.0E+08

1.0E+09

0 2 4 6 8 10

Ce

lls/m

L

Time, h

10 mg NZVI 10 mg NZVI 10 mg NZVI

1.0E+05

1.0E+06

1.0E+07

1.0E+08

1.0E+09

0 2 4 6 8 10

Ce

lls/m

L

Time, h

10 mg NZVI

Funding: NDWRRI and NSF

Objective: Entrapment of NZVI in alginate beads for effective

treatment of selenium from contaminated waters

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Michael Quamme and Bryant Feist

Selenium Removal Mechanism

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Fe0

FeOOH

Fe0

Adsorption

Reduction

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0

0.1

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0.3

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0.5

0.6

0.7

0.8

0.9

1

1.1

0 2 4 6 8 10 12 14 16 18 20 22 24

Norm

ali

zed

Se

Con

cen

trati

on

Time, h

0.5 mg/L

5 mg/L

10 mg/L

0.5 mg L-1

5 mg L-1

10 mg L-1

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

1.1

0 1 2 3 4 5 6

Norm

ali

zed

Se

Con

cen

trati

on

Time, h

0.5 mg/L

5 mg/L

10 mg/L

0.5 mg L-1

5 mg L-1

10 mg L-1

Entrapped NZVI Bare NZVI

Bare and entrapped equally effective

Slower reaction rate for entrapped NZVI

Possible use in surface, ground and tap water

Ongoing and Future Work

Growth of microbes on PDMS need further study

Growth study on copolymer added mineral media is underway

Need to analyze PEG and AA degradation study along with PDMS

Isolation of fungi from the composting is in progress

Isolation of microorganisms from batch reactors is in progress

Iron polymer for metals removal

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Funding: Civil Engineering

Objective: Entrapment of NZVI in alginate beads for effective

treatment of arsenic contaminated groundwater

Chris Capecchi Bezbaruah et al., J. Haz. Mat., 2009

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Porous interior layer

Dense exterior layer

Bezbaruah et al., J. Haz. Mat., 2009

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Arsenic (IV) Batch Studies:

After 45-60 minutes entrapped

NZVI out performs bare NZVI

Blank and control show

negligible concentration

change

Entrapped beads can be used

in PRB’s

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Funding: Civil Engineering

Objectives: NZVI and

microorganism Co-entrapment in

alginate beads for groundwater

TCE degradation

Shanaya Shanbhogue

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Encapsulation of NZVI

Encapsulated NZVI

TCE degradation using Encapsulated NZVI

0

5

10

15

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0 20 40 60 80 100 120

Co

nce

ntr

atio

n (

mg/

L)

Time, min

30 mg/L

BLANK

Control

Avg TCE Conc

Bare NZVI

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1. Chisholm, B.J.; Kalita, H.; Bezbaruah, A. (2012), “ Vegetable Oil-Based Polymers for

Nanoparticle Surface Modification”, Provisional patent. (Patent)

2. Chisholm, B.J.; Kalita, H. (2013), RFT-438, “Plant Oil based Diluent”, Provisional

patent. (Patent)

3. Almeelbi T, Quamme M, Bezbaruah AN (2012), RFT-419A, “Aqueous Phosphate

Removal using Iron Cross-lined Alginate”, Patent Filed. Patent)

4. Almeelbi T, Quamme M, Khan E, Bezbaruah AN (2012), RFT-419B, “Selenium

Removal from Surface Waters: Exploratory Research with Iron Nanoparticles”, Patent

Filed. Patent)

5. Krajangpan, S., Chishlom, B., Bezbaruah, A. (2010), RFT-247 & RFT-247A, Novel

Polymer Modified Iron Nanoparticles for Environmental Remediation, US Patent.

(Patent)

6. Kalita, H, Chishlom, B., Bezbaruah, A. (2010), Soybean-based Copolymer, to be filled

(Patent)

7. Alam, S.; Kalita, H.; Jayasooriya, A.; Chisholm, B.J. (2012), “Coatings Derived from

Novel Plant Oil-Based Polymers”, Submitted to ACS, 2012

8. Kalita, H.; Kudina, O.; Popadyuk, A.; Chishola, B.; Voronov, A. (2013), “Soy-Based

Surface Active Copolymers as Safer Replacement for Low Molecular Weight

Surfactants.” ACS Sustainable Chemistry & Engineering, 1, 19-22

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9. Krajangpan, S.; Kalita, H.; Chisholm, B.J.; Bezbaruah, A.N. (2012), “Iron Nanoparticles

Coated with Amphiphilic Polysiloxane Graft Copolymers Coated Iron

Nanoparticles: Dispersibility and Contaminant Treatability.” Environmental Science and

Technology, 2012, 46, 10130–10136

10. Thompson, J.M., Chisholm, B.J., Bezbaruah, A.N. (2010). Reductive Dechlorination of

Chloroacetanilide Herbicide (Alachlor) Using Zero-valent Iron Nanoparticles,

Environmental Engineering Science, 27, 227-232.

11. Bezbaruah, A.N., Shanbhogue, S.S., Simsek and S., Khan, E. (2011), Encapsulation of

iron nanoparticles in alginate biopolymer for trichloroethylene remediation, Journal of

Nanoparticle Research, 13, 6673–6681.

12. Bezbaruah, A.N. and Kalita, H. (2010) Sensors and Biosensors for Endocrine

Disrupting Chemicals State-of-the-art and Future Trends in Treatment of

Micropollutants in Water and Wastewater (Eds: Virkutyte, J., Varma, R.S.,

Jegatheesan, V.), International Water Association, London,, U.K., ISBN:

9781843393160, pp.92-128. (Book Chapter)

13. Krajangpan, S., Chisholm, B.J., Kalita, H., Bezbaruah, A.N. (2009). Challenges in

Groundwater Remediation with Iron Nanoparticles: Enhancement Colloidal Stability

(Chapter 8) in Nanotechnologies for Water Environment Applications (Eds: Zhang,

T.C., Surampalli, R.Y., Lai, K.C.K., Hu, Z., Tyagi, R.D., Lo, I.M.C.), American Society for

Civil Engineers, pp 191-212. (Book Chapter)

14. Kalita, H., Chisholm, B., Bezbaruah, A. (2009) Effects of different graft copolymer

constituent groups on sedimentation characteristics of coated iron nanoparticles,

PSME Preprints, 100:683-685.

15. Bezbaruah, A.N., Thompson, J.M., Chisholm, B.J. (2009) Remediation of alachlor

and atrazine contaminated water with zero-valent iron nanoparticles, Journal of

Environmental Science and Health Part B Pesticides, Food Contaminants, and

Agricultural Wastes, 44:518-524.

16. Thompson, J.M., Bezbaruah, A.N. Selected Pesticide Remediation with Iron

Nanoparticles: Modeling and Barrier Applications. Technical Report No. ND08-04.

North Dakota Water Resources Research Institute, Fargo, ND, 2008. Krajangpan, S.,

Jarabek, L., Jepperson, J., Chisholm, B., Bezbaruah, A. (2008). Polymer Modified

Iron Nanoparticles for Environmental Remediation, Polymer Preprint, 49, 921-922.

17. Bezbaruah, A.N., Krajangpan, S., Chisholm, B.J., Khan, E., Bermudez, J.J.E., (2009).

Entrapment of Iron Nanoparticles in Calcium Alginate Beads for Groundwater

Remediation Applications, Journal of Hazardous Materials, 166, 1339-1343.

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Thank You