Methods for in situ detection and characterization of metal-based

nanoparticles

Jason M.Unrine Department of Plant and Soil Sciences

University of Kentucky

Lexington, Kentucky, USA

TĪNĒ

Outline • Methods that work well at concentrations

relevant to toxicity

– Biota

– Environmental Samples

• Status of ultra-trace level detection

• Research, technology, training and facility needs

von der Kammer, F.; Ferguson, P. L.; Holden, P. A.; Masion, A.; Rogers, K. R.; Klaine, S. J.; Koelmans, A.

A.; Horne, N.; Unrine, J. M., Analysis of engineered nanomaterials in complex matrices (environment and

biota): General considerations and conceptual case studies. Environmental Toxicology and Chemistry

2012, 31, (1), 32-49.

Fate, transport, and, effects of manufactured nanoparticles in the environment

Emissions

Biogeochemical

Transformations

Plant

Uptake

Rhizosphere

Erosion/Runoff

Trophic Transfer

Land Application of Biosolids

Transport of Particles with GW Flow

Landfill

Vertical Transport

through Soil Profile

Resuspension incineration

X Distance (um)

500 1000 1500 2000

500

1000

1500

2000

2500

2000 4000 6000 8000 10000

20 nm 55 nm

Ti

Au

HAuCl4

500 1000 1500 2000

500

1000

1500

2000

2500

100100010000100000

500 1000 1500 2000

Y d

ista

nce

(um

)

500

1000

1500

2000

10 100 1000 10000

X distance (um)

500 1000 1500 2000

Y d

ista

nce

(um

)

500

1000

1500

2000

5.0e+4 1.0e+5 1.5e+5 2.0e+5 2.5e+5 3.0e+5 3.5e+5

500 1000 1500 2000 2500

500

1000

1500

2000

2500

10 100 1000 10000

X distance (um)

500 1000 1500 2000 2500

500

1000

1500

2000

2500

20000

40000

60000

80000

Using Au NPs as a probe for particle uptake –LA-ICPMS

Animals exposed to

25 mg kg-1 HAuCl4

or 50 mg kg-1 Au

NPs in OECD soil

media for 28 d.

Bulk tissue

concentrations are

< 1 mg kg-1

Unrine et al., 2010, Environmental Science & Technology 2010, 44, (21), 8308-8313.

Unrine et al., 2010, Environmental Science & Technology 2010, 44, (21), 8308-8313.

Cu SO4 - soil 20-40 nm Cu soil <100 nm Cu soil

Cu SO4 - tissue 20-40 nm Cu tissue <100 nm tissue

Fe

1 2

3

4 5

6

Cu – 0.475

CuO – 0.317

Cu2O – 0.208

6

Data

Fit

2 Cu – 0.10

CuO – 0.0

Cu2O – 0.90

Cu – 0.324

CuO – 0.548

Cu2O – 0.127

Unrine et al. Journal of Environmental Quality 2010, 39, 1942-1953.

Unrine et al. Journal of Environmental Quality 2010, 39, 1942-1953.

Ag NP cit Ag+ Ag NP PVP

Biosolids

Soil-200 mg Ag kg-1

Pore water

EXAFS analysis

pH

Major

cations/anions

DOC Total Ag then

Ultracentrifugation,

Ultrafiltration

Followed by Ag

analysis.

AF4-

MALLS/DLS

-ICP-MS

HR-TEM with EDS

0, 1 or 3%

sludge

Aging for 1

week, 2

months or

6 months

Solid state speciation

Dissolved Ag

in pore water

Physical and chemical

state in colloidal phase

Chemical environment in

pore water

Whitley et al., in prep

AgNO3 0%

AgNO3 3%

PVP 0%

PVP 3%

Citrate 0%

Citrate 3%

Ag (O) 0.13 0.13 1.05 0.36 0.97 0.27

Ag2S 0.34 0.57 0.85 0.94

AgCl 0.31 Ag-acetate 0.26

Ag-GSH 0.39

Whitley et al., in prep

AF4 with multi-detection (asymmetrical flow field flow fractionation)

AF4 separation

UV-Vis/ Fluorescence detector

LS detector

ICP-MS

Ag NP cit Ag+ Ag NP PVP

Biosolids

Soil

Pore water

Whitley et al., in prep

Whitley et al., in prep

Citrate –

No

Sludge

PVP –

3%

Sludge

Citrate –

3%

Sludge

Whitley et al., in prep

Needs for ultra-trace level detection

Environmental Toxicology and Chemistry 2012, 31, (1), 32-49.

Environmental Toxicology and Chemistry 2012, 31, (1), 32-49.

Needs • Training

• Multi-method approaches tailored to hypothesis or objective

• Better sample prep- preservation, pre-concentration

• Advances in particle mass spectrometry –faster, more sensitive, simultaneous detection (ICP-TOF?)

• More synchrotron micro/nanoprobe and EM facilities dedicated to environmental applications with faster more sensitive detectors

833335 834574 834857

TĪNĒ

This material is based upon work supported by the National Science

Foundation (NSF) and the Environmental Protection Agency (EPA)

under NSF Cooperative Agreement EF-0830093, Center for the

Environmental Implications of NanoTechnology (CEINT). Any opinions,

findings, conclusions or recommendations expressed in this material

are those of the author(s) and do not necessarily reflect the views of

the NSF or the EPA. This work has not been subjected to EPA review

and no official endorsement should be inferred.

Annie Whitley, Frank von der Kammer, Olga

Tsyusko, Greg Lowry, Clement Levard, Paul

Bertsch, W. Aaron Shoults-Wilson

• Portions of this work were performed at Beamline X26A,

National Synchrotron Light Source (NSLS), Brookhaven

National Laboratory. X26A is supported by the Department

of Energy (DOE) - Geosciences (DE-FG02-92ER14244 to The

University of Chicago - CARS) and DOE - Office of Biological

and Environmental Research, Environmental Remediation

Sciences Div. (DE-FC09-96-SR18546 to the University of

Kentucky). Use of the NSLS was supported by DOE under

Contract No. DE-AC02-98CH10886.