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Christine Hendren, Duke University Increasing Production of Engineered Nanomaterials

Egyptian Eye Makeup and Hair Dye (~ 2000 BC): Fabrication of quantum dots in your hair!! Nano Lett., 2006, 6 (10), pp 2215–2219 The composition and supramolecular organization of keratins can control PbS nanocrystal growth inside a hair

Maya Blue Paint (2000 BC – AD 250): An hybrid organic-inorganic composite nanomaterial Resistance to acid and biocorrosion, color retention after centuries in the extreme conditions of the rain forest Science 273, 223 (1996)

The Lycurgus Cup (~ 4 AD): Most sophisticated glass objects before the modern era NPs are silver-gold alloy, with a ratio of silver to gold of about 7:3, containing in addition about 10% copper.

Nanotubes and nanowires in ancient Damascus blades (~900 AD) Multiwalled tubes, bent like a rope, with the characteristic layer distance d 0.34 nm Young’s modulus and tensile strength of CNT is about 10 and 20 times higher than that of steel Nature 444, 286 (2006)

Nanoparticles are Ubiquitous in Water and Wastewater Source: Hochella et al., 2007 The Clark Fork River in Western Montana Mine Drainage Hydrothermal Vent Sediment Porewater

Nanoparticles are Ubiquitous in Water and Wastewater Benn & Westerhoff, 2008 Environ. Sci. Technol., 2008, 42 (11), 4133–4139 Municipal Wastewater Kim et al., 2010 Environ. Sci. Technol. 44,19, Sewage Sludge Hochella et al., 2007 J. Environ. Monit. 9, Drinking Water Distribution System

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10 Source Receptor Stability Mobility Bioavailability Toxicity Formation What do environmental researchers have to do with nano?

Source: Aggarwal et al., Advanced Drug Delivery Reviews, 61, , (2009)

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Levard et al., ES&T, 2012, 46 (13), pp 6900–6914

17 Kaegi et al. Environ. Sci. Technol. 2011, 45, 3902–3908.

Floc particle 18 Capped AgNPs “Pristine” NanoComposix, Inc. Capped-Sulfidized AgNPs “Transformed” Levard et al., 2011

19 pH 7 5mM NaNO 3

20 pH 7 5mM NaNO 3

Nanoparticles as an unintended by-product Source: Suzuki et al., 2002, Nature Bioreduction of hexavalent uranium, U(VI), to tetravalent uranium, U(IV), which precipitates as uraninite. Assumption: the formation of highly insoluble uraninite (UO 2 ) will inhibit the mobilization of uranium. Source: oceanworld.tamu.edu/.../Images/schematic.gif Zero-valent iron (ZVI) Permeable Reactive Barrier (PRB) Δ in chemical & biological gradient

Contact Information Meters Electrons Bacterial Cells Red Sea Distant Galaxies Mineral Cluster Human being Sun

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Source: Andrew Maynard, Woodrow Wilson Center, Project on Emerging Nanotechnologies

Are these two particles the same? Core composition, size, and shape Hydrodynamic diameter Ligand composition Ligand packing density Would you expect them to have the same fate and transport behaviors in the environment?

Verma et al., Nature Materials 7, (2008) Big impact due to small difference on NP surface! Only the structured NPs penetrated the plasma membrane without bilayer disruption Core particle size (4.3 to 4.9 nm) and shape Ratio of hydrophilic to hydrophobic ligands (2:1) Ligand-shell packing density (11 to 15%)

Wen et al. 2005, J. Phys. Chem. B, 109, Zhong et al., 2006 Adv. Mater., 18, 2426 Hochella et al., 2007 J. Environ. Monit. 9, Park et al., 2004 Nat. Mater. 3,

Madden and Hochella, Geochim. Cosmochim. Acta, 69, Madden et al., Geochim. Cosmochim. Acta, 70, Size-Dependent Reactivity of Hematite Nanoparticles Hematite’s catalytic efficiency (surface area normalized rates) in Mn- oxidation reactions increases by 1 to 2 orders of magnitude when going from 37nm to 7nm in size Good contaminant scavenger with a significant increased sorption affinity for aqueous Cu 2+

32 pH 6 10mM NaNO 3

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