Nanomaterials Nanomaterials Characterization for Characterization for

Studying Environmental Fate Studying Environmental Fate and Transportand Transport

Joel A. PedersenJoel A. Pedersen

Environmental Chemistry and Technology Environmental Chemistry and Technology ProgramProgram

University of Wisconsin – MadisonUniversity of Wisconsin – Madison

Meade (ed.) USGS Circular 1133, 1995

http://www.lbl.gov/ERSP/generalinfo/geochem_biogeo.html

Subsurface Transport and Subsurface Transport and FateFate

Fin

lays

on

-Pitt

s a

nd

Pitt

s, 1

98

6

Chemical CompositionChemical Composition Bulk chemical compositionBulk chemical composition

Elemental analysis, ICP-MS, energy-dispersive X-ray Elemental analysis, ICP-MS, energy-dispersive X-ray analysis (EDX), electron energy loss spectroscopy (EELS), analysis (EDX), electron energy loss spectroscopy (EELS), dynamic secondary ion mass spectrometry (SIMS), atom-dynamic secondary ion mass spectrometry (SIMS), atom-probe tomographyprobe tomography

Surface chemical composition Surface chemical composition X-ray photoelectron (XPS), Auger, FTIR, Raman and surface X-ray photoelectron (XPS), Auger, FTIR, Raman and surface

enhanced Raman spectroscopies; static SIMS; EELS, EDX enhanced Raman spectroscopies; static SIMS; EELS, EDX (with TEM)(with TEM)

Core-shell materials (e.g., quantum dots)Core-shell materials (e.g., quantum dots) Chemical composition of shell, defects, thicknessChemical composition of shell, defects, thickness

Bulk and/or surface contaminantsBulk and/or surface contaminants

Medin

tz e

t al. (

20

05

)

Nature and length of attached moleculeNature and length of attached molecule Functionalization densityFunctionalization density

Thermogravimetic analysis (TGA) + BET Thermogravimetic analysis (TGA) + BET [Marcinko and Fadeev, 2004][Marcinko and Fadeev, 2004]; XPS; XPS

Type of attachmentType of attachment Anchoring group (covalently grafted) Anchoring group (covalently grafted) Mechanism (e.g., adsorption, covalent)Mechanism (e.g., adsorption, covalent)

FTIR, XPSFTIR, XPS

Nanoparticle SizeNanoparticle Size Primary particle size distributionPrimary particle size distribution

SEM, TEMSEM, TEM Hydrodynamic size distributionHydrodynamic size distribution

Hard sphere that diffuses with the same speed Hard sphere that diffuses with the same speed as the particle under examinationas the particle under examination

DLSDLS

Aerodynamic size distributionAerodynamic size distribution Sphere of unit density with same settling velocitySphere of unit density with same settling velocity Moody impactor, differential mobility analyzer, Moody impactor, differential mobility analyzer,

etc.etc. Resuspension methodResuspension method

nebulization (solution composition), dry dispersionnebulization (solution composition), dry dispersion

Nanoparticle Morphology and Nanoparticle Morphology and StructureStructure

Physical formPhysical form Crystal phase: Powder X-ray diffraction (XRD), Crystal phase: Powder X-ray diffraction (XRD),

Raman spectroscopy, HR-TEMRaman spectroscopy, HR-TEM SWCNTSWCNT

Form (individual strand, rope, bundle, aggregate): Form (individual strand, rope, bundle, aggregate): Raman, TEM, SEMRaman, TEM, SEM

Eventually chiralityEventually chirality Number of graphene sheets (MWCNTs): TEMNumber of graphene sheets (MWCNTs): TEM

Shape (aspect ratio)Shape (aspect ratio) SEM, TEM, AFMSEM, TEM, AFM

Specific surface areaSpecific surface area BET methods – gas adsorption BET methods – gas adsorption

Particle-Particle and Particle-Particle-Particle and Particle-Surface Interactions in Aqueous Surface Interactions in Aqueous

MediaMedia Control suspension stability, particle Control suspension stability, particle

deposition and adhesion deposition and adhesion DLVO theory of colloid stabilityDLVO theory of colloid stability

Electrostatic double layer (EDL) interactionElectrostatic double layer (EDL) interaction Particle size (Particle size (rrpp)) Surface charge/potentialSurface charge/potential

Potentiometric titration; electrophoretic mobility (Potentiometric titration; electrophoretic mobility (--potential)potential)

Lifshitz-van der Waals (LW) interactionsLifshitz-van der Waals (LW) interactions Particle size (Particle size (rrpp) ) Hamaker constant (AHamaker constant (Aiiii))

Calculated from permittivities (Calculated from permittivities (((ii)) and refractive index )) and refractive index ((nnii))

Estimated from apolar surface tension component (Estimated from apolar surface tension component (AAiiii iiLWLW))

-300

-200

-100

0

100

200

300

0 5 10 15 20Separation Distance (nm)

Inte

ract

ion

en

erg

y (k

T)

DLVOXDLVO

-300

-200

-100

0

100

200

300

0 5 10 15 20

Separation Distance (nm)

Inte

ract

ion

En

erg

y (k

T)

EDLLWABBorn

Bell et al. (in prep.)

Interaction Energy Profile between PrPTSE and a Quartz Surface

Particle-Particle and Particle-Particle-Particle and Particle-Surface Interactions in Aqueous Surface Interactions in Aqueous

MediaMedia Non-DLVO interactionsNon-DLVO interactions

Polar or Lewis acid-base (AB) interactionsPolar or Lewis acid-base (AB) interactions LWLW, , ABAB , , , , [van Oss, 2006] [van Oss, 2006]

Steric interactionsSteric interactions Functionalization density, radius of gyration [Butt et al., Functionalization density, radius of gyration [Butt et al.,

2007]2007] Surface roughness Surface roughness [Bhattacharjee et al., 1998][Bhattacharjee et al., 1998]

Asperity size, asperity densityAsperity size, asperity density Aggregation/agglomeration stateAggregation/agglomeration state

Aggregation kineticsAggregation kinetics Critical coagulation concentration depends on Critical coagulation concentration depends on

electrolyte concentration and valenceelectrolyte concentration and valence [Chen and [Chen and Elimelech, 2006; Brant et al., 2007]Elimelech, 2006; Brant et al., 2007]

Change in Surface Chemistry: Change in Surface Chemistry: Acquisition of CoatingsAcquisition of Coatings

Amorphous mineral coatings Amorphous mineral coatings Humic substancesHumic substances [Hyung et al., 2007] [Hyung et al., 2007]

Organic compounds condensing on Organic compounds condensing on airborne nanoparticlesairborne nanoparticles

Hyung et al., 2007

MWCNTs: H2O 1% SDS SR-NOM SR H2O

Decomposition/Decomposition/TransformationTransformation

Dissolution Dissolution Nanoparticle Nanoparticle

dissolution kinetics as dissolution kinetics as function of pH, function of pH, EEHH, , other constituentsother constituents

Effects of roughness, Effects of roughness, porosity, lattice porosity, lattice defects defects [Yerba et al., 2006][Yerba et al., 2006]

Ruby et al. (1999)

Size-dependent Size-dependent EEHH00 (ZnO) (ZnO)

Hoyer and Weller (1994)

• Semiconductors – in quantum confinement regime Semiconductors – in quantum confinement regime [Brus, 1983; Rossetti et al., 1983; Hoyer and Weller, 1994][Brus, 1983; Rossetti et al., 1983; Hoyer and Weller, 1994]• Metals – Metals – EEHH

00 increases with nuclearity up to metal- increases with nuclearity up to metal-like phase (e.g., for Ag, like phase (e.g., for Ag, ddpp < 1.2 nm ( < 1.2 nm (nn = 80-100)) = 80-100)) [Belloni, 1996][Belloni, 1996]

Decomposition/Decomposition/TransformationTransformation

Surface chemical modificationsSurface chemical modifications Hydroxylation of nCHydroxylation of nC6060 fullerenes fullerenes [Brant et al., [Brant et al.,

2007]2007]

Photocorrosion (semiconductors)Photocorrosion (semiconductors) Alterations in coatingsAlterations in coatings

Bacterial decomposition, redox reactions, Bacterial decomposition, redox reactions, ligand exchangeligand exchange

Biomodification of Surface Biomodification of Surface CoatingsCoatings

Daphnia magna Daphnia magna ingest ingest lysophophatidylcholine-coated SWCNTslysophophatidylcholine-coated SWCNTs

Coating removed and metabolizedCoating removed and metabolized Naked, insoluble CNTs excreted (confirmed Naked, insoluble CNTs excreted (confirmed

by Raman)by Raman)Roberts et al., 2007

Measurement Challenges Measurement Challenges

Detection of NPs in environmental Detection of NPs in environmental matricesmatrices Model, more easily tracked compoundsModel, more easily tracked compounds Radiolabeled materials Radiolabeled materials [Petersen et al., 2006][Petersen et al., 2006]

Stable isotope-labeled materialsStable isotope-labeled materials

Secondary EffectsSecondary Effects

Sorption of common organic (e.g., PAHs) Sorption of common organic (e.g., PAHs) and inorganic contaminants (e.g., metals) and inorganic contaminants (e.g., metals) [Yang and Xing, 2006][Yang and Xing, 2006]

Reactions with environmental Reactions with environmental contaminants and organic mattercontaminants and organic matter Materials that are active in the UV – mediate Materials that are active in the UV – mediate

reactions on surface of airborne NPs? reactions on surface of airborne NPs? Surface defects – influence adsorption, Surface defects – influence adsorption,

nucleation, surface reactions nucleation, surface reactions [Belon and Epron, 2005; [Belon and Epron, 2005; Butt et al., 2006]Butt et al., 2006]

Reactive surface area, porosity, ROS productionReactive surface area, porosity, ROS production

SummarySummary

Chemical compositionChemical composition Particle size and morphologyParticle size and morphology Specific surface areaSpecific surface area Surface charge/potential as Surface charge/potential as ff(pH)(pH) Surface energiesSurface energies Agglomeration stateAgglomeration state Reactive surface area, ROS production, Reactive surface area, ROS production,

etc.etc.

ReferencesReferences Aitken, R.J.; Hankin, S.M.; Tran, C.L.; Donaldson, K.; Stone, V.; Aitken, R.J.; Hankin, S.M.; Tran, C.L.; Donaldson, K.; Stone, V.;

Cumpson, P.; Johnstone, J.; Chaudhry, Q.; Cash, S. Cumpson, P.; Johnstone, J.; Chaudhry, Q.; Cash, S. RENANO: RENANO: Reference materialsfor engineered nanoparticle toxicology and Reference materialsfor engineered nanoparticle toxicology and metrologymetrology. Final report of Project CB01099. IOM, 2007. Final report of Project CB01099. IOM, 2007

Belin, T.; Epron, F. Characterization methods of carbon nanotubes: a Belin, T.; Epron, F. Characterization methods of carbon nanotubes: a review. review. Mat. Sci. Eng. B Mat. Sci. Eng. B 20052005, , 119119, 105-118., 105-118.

Belloni, J. Metal nanocolloids. Belloni, J. Metal nanocolloids. Curr. Op. Colloid Interface Sci. Curr. Op. Colloid Interface Sci. 19961996, , 11, 184-196., 184-196.

Bhattacharjee, S.; Ko, C. H.; Elimelech, M. DLVO interaction between Bhattacharjee, S.; Ko, C. H.; Elimelech, M. DLVO interaction between rough surfaces. rough surfaces. LangmuirLangmuir 19981998, , 1414, 3365-3375., 3365-3375.

Brus, L.E. A simple model for the ionization potential, electron Brus, L.E. A simple model for the ionization potential, electron affinity, and aqueous redox potentials of small semiconductor affinity, and aqueous redox potentials of small semiconductor crystallites. crystallites. J. Chem. Phys. J. Chem. Phys. 19831983, , 7979, 5566-5571., 5566-5571.

Butt, H.-J.; Graf, K.; Kappl, M. Butt, H.-J.; Graf, K.; Kappl, M. Physics and Chemistry of InterfacesPhysics and Chemistry of Interfaces, , 22ndnd ed. Wiley-VCH: Weinheim, 2006. ed. Wiley-VCH: Weinheim, 2006.

Giese, R.F.; van Oss, C.J. Giese, R.F.; van Oss, C.J. Colloid and Surface Properties of Clays and Colloid and Surface Properties of Clays and Related Minerals.Related Minerals. Surfactant Science Series Vol. 105, Marcel Dekker: Surfactant Science Series Vol. 105, Marcel Dekker: New York, 2002. New York, 2002.

Goodwin, J. Goodwin, J. Colloids and Interfaces with Surfactants and Polymers: Colloids and Interfaces with Surfactants and Polymers: An IntroductionAn Introduction. Wiley: New York, 2004.. Wiley: New York, 2004.

ReferencesReferences Gu, B.; Schmitt, J.; Chen, Z.; Liang, L.; McCarthy, J.F. Adsorption Gu, B.; Schmitt, J.; Chen, Z.; Liang, L.; McCarthy, J.F. Adsorption

and desorption of natural organic matter on iron oxide and desorption of natural organic matter on iron oxide Mechanisms and models. Mechanisms and models. Environ. Sci. Technol.Environ. Sci. Technol. 19941994, , 2828, 38-46., 38-46.

Gu, B.; Schmitt, J.; Chen, Z.; Liang, L.; McCarthy, J.F. Adsorption Gu, B.; Schmitt, J.; Chen, Z.; Liang, L.; McCarthy, J.F. Adsorption and desorption of different organic matter fractions on iron oxide. and desorption of different organic matter fractions on iron oxide. Geochim. Cosmochim. Acta Geochim. Cosmochim. Acta 19951995, , 5959, 219-229., 219-229.

Gu, B.; Mehlhorn, T.L.; Liang, L.; McCarthy, J.F. Competitive Gu, B.; Mehlhorn, T.L.; Liang, L.; McCarthy, J.F. Competitive adsorption, displacement, and transport of organic matter on iron adsorption, displacement, and transport of organic matter on iron oxide. I. Competitive adsorption. oxide. I. Competitive adsorption. Geochim. Cosmochim. Acta Geochim. Cosmochim. Acta 19961996, , 6060, 1943-1950., 1943-1950.

Gu, B.; Mehlhorn, T.L.; Liang, L.; McCarthy, J.F. Competitive Gu, B.; Mehlhorn, T.L.; Liang, L.; McCarthy, J.F. Competitive adsorption, displacement, and transport of organic matter on iron adsorption, displacement, and transport of organic matter on iron oxide. I. Displacement and transport. oxide. I. Displacement and transport. Geochim. Cosmochim. Acta Geochim. Cosmochim. Acta 19961996, , 6060, 2977-2992., 2977-2992.

Hiemenz, P.C.; Rajagopalan, R. Hiemenz, P.C.; Rajagopalan, R. Principles of Colloid and Surface Principles of Colloid and Surface ChemistryChemistry, 3, 3rdrd ed.; Marcel Dekker: New York, 1997. ed.; Marcel Dekker: New York, 1997.

Hoyer, P.; Weller, H. Size-dependent redox potentials of quantized Hoyer, P.; Weller, H. Size-dependent redox potentials of quantized zinc oxide measured with an optically transparent thin layer zinc oxide measured with an optically transparent thin layer electrode. electrode. Chem. Phys. Lett.Chem. Phys. Lett. 19941994, , 221221, 379-384., 379-384.

Hyung, H.; Fortner, J. D.; Hughes, J. B.; Kim, J. H. Natural organic Hyung, H.; Fortner, J. D.; Hughes, J. B.; Kim, J. H. Natural organic matter stabilizes carbon nanotubes in the aqueous phase. matter stabilizes carbon nanotubes in the aqueous phase. Environ. Sci. Technol.Environ. Sci. Technol. 20072007, , 4141, 179-184., 179-184.

ReferencesReferences Lifshitz, E.M. Lifshitz, E.M. Zh. Eksp. Teor. Fiz. Zh. Eksp. Teor. Fiz. 19551955, , 2929, 94., 94. Marcinko, S.; Fadeev, A.Y. Hydrolytic stability of organic monolayers Marcinko, S.; Fadeev, A.Y. Hydrolytic stability of organic monolayers

supported on TiO2 and ZrO2. supported on TiO2 and ZrO2. Langmuir Langmuir 20042004, , 2020, 2270-2273., 2270-2273. Medintz, I; Uyeda, H.T.; Goldman, E.R.; Mattoussi, H. Quantum dot Medintz, I; Uyeda, H.T.; Goldman, E.R.; Mattoussi, H. Quantum dot

bioconjugates for imaging,labelling and sensing. bioconjugates for imaging,labelling and sensing. Nature Mat.Nature Mat. 20052005, , 44, , 435-446.435-446.

Plumlee, G.S.; Morman, S.A.; Ziegler, T.L. The toxicological Plumlee, G.S.; Morman, S.A.; Ziegler, T.L. The toxicological geochemsitry of earth materials: An overview of processes and the geochemsitry of earth materials: An overview of processes and the interdisciplinary methods used to understand them. interdisciplinary methods used to understand them. Rev. Mineral. Rev. Mineral. Geochem. Geochem. 20062006, , 6464, 5-51., 5-51.

Roberts, A. P.; Mount, A. S.; Seda, B.; Souther, J.; Qiao, R.; Lin, S. J.; Ke, Roberts, A. P.; Mount, A. S.; Seda, B.; Souther, J.; Qiao, R.; Lin, S. J.; Ke, P. C.; Rao, A. M.; Klaine, S. J. In vivo biomodification of lipid-coated P. C.; Rao, A. M.; Klaine, S. J. In vivo biomodification of lipid-coated carbon nanotubes by carbon nanotubes by Daphnia magnaDaphnia magna. . Environ. Sci. Technol.Environ. Sci. Technol. 20072007, , 4141, , 3025-3029.3025-3029.

Rossetti, R.; Nakahara, S.; Brus, L.E. Quantum size effects in the redox Rossetti, R.; Nakahara, S.; Brus, L.E. Quantum size effects in the redox potentials, resonance Raman spectra, and electronic spectra of CdS potentials, resonance Raman spectra, and electronic spectra of CdS crystallites in aqueous solution. crystallites in aqueous solution. J. Chem. Phys.J. Chem. Phys. 19831983, , 7979, 1086-1088., 1086-1088.

van Oss, C.J. van Oss, C.J. Interfacial Forces in Aqueous MediaInterfacial Forces in Aqueous Media, 2, 2ndnd ed. Taylor and ed. Taylor and Francis: Boca Raton, FL, 2006.Francis: Boca Raton, FL, 2006.

Yerba, D.M.; Kiil, S.; Weinell, C.E.; Dam-Johansen, K. Dissolution rate Yerba, D.M.; Kiil, S.; Weinell, C.E.; Dam-Johansen, K. Dissolution rate measurements of sea water soluble pigments for antifouling paints: measurements of sea water soluble pigments for antifouling paints: ZnO. ZnO. Prog. Org. Coatings. Prog. Org. Coatings. 20062006, , 5656, 327-337., 327-337.

Energy Balance DiagramEnergy Balance Diagram

van Oss (2006)

Variability in Variability in KKococ and and KKd,solidd,solid

Adapted from Tolls (2001), Thiele (200) and Loke et al. (2002)

log log KKdomdom vs. Hydrophobicity vs. Hydrophobicity

log Kow

-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

log

Kd

om

0

1

2

3

4

5pH 3pH 4pH 4.5pH 5pH 6pH 7pH 8pH 9.2model

(2000) Burkart

11.0log85.0log owdom KK

Tolls. Environ. Sci. Technol. 2001

tetracyclines and fluoroquinolones

Plumlee et al. (2006)