Nanoparticles in Soils

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1 Diversity of Natural Nanoparticles in Soils Joe B. Dixon Emeritus Professor of Soil Clay Mineralogy Soil and Crop Sciences Dept. Texas A&M University

2 Ferrihydrite Structure update: Michel, et al., Science 316,1726 (2007).

3 Properties of ferrihydrite Granular at the nanometer scale XRD peaks are very broad; 2 to 6 depending di on crystallinity it High phosphate adsorption Closely associated with lepidocrocite in some soils

4 Rice field in the spring in southeast Texas when soils are drying & iron oxides are forming

5 Lepidocrocite on the surfice of a Vertisol: moist (L) & dry (R)

6 Lepidocrocite laths with ferrihydrite granules

7 L e p i d o c r o c i t e Lattice fringes of lepidocrocite

8 Properties of lepidocrocite- ferrihydrite i mixtures Form and dissolve seasonally in soils of rice paddy culture Visible color change in a few weeks Prominent coatings on ped surfaces, tillage surfaces, and in pores Bright colors of iron oxides orange to dark red in common terms Influence the phosphate fixation and dissolution in Vertisols cropped to rice in southeast Texas

9 This goethite is a twin or aggregate of four crystals The spot pattern indicates multiple crystals Dixon, 1999

10 This enlargement shows numerous lattice fringes & crystal faces at the edges This nm scale particle of goethite particle is well crystallized Dixon, 1999

11 Vertisol from Oklahoma: lattice fringes of goethite

12 Goethite occurs in soils as very complex crystalline aggregates that influence soil structure This example is from a Vertisol Dixon, 1999

13 Todorokite: a Mn oxide Forms in nodules of a Vertisol of central America Forms on siderite boulders exposed in lignite mines of east Texas Has fibrous morphology, tunnel structure, t & twins Has 1 nm lattice fringes that help identify it in soil clays with TEM

14 a. Birnessite (cultured), b. todorokite (siderite coating), c. todorokite (soil), and d. lithiophorite (Oxisol, macro particle) G ld ett al., Golden l 1992 S k i ett al., Senkayi l 1986 G ld ett al., Golden l 1993

15 Section of soil nodule containing Fe and Mn oxides: small crystals in aggregate: thus oxides with high surface area Concentric banding of oxides White & Dixon, 1996

16 Todorokite twinning Slickenside surface in Vertisol: Central America

17 Palygorskite fibers on calcite crystals in Israel Palygorskite fibers deposited on a quartz grain in Australian soil

18 Petrified log composed of silica minerals, College Station, TX

19 Cross section of petrified log with nanoparticle zone a the top: fine white powder

20 a. Nanoparticles of opal-ct formed on the outside of the a petrified log b. Quartz particles with nanoparticles of opal-ct in the background Senkayi et al., 1985

21 Properties of colloidal opal-ct Bright white color Readily dispersed: seldom seen on exposed petrified wood. Identifiable by XRD in many soils of Texas

22 Allophane spheres or circles and imogolite fibers: 50 nm scale Wada, 1989

23 Allophane and imogolite properties They often occur together in volcanic soils e.g. Andisols They produce very broad XRD peaks They form a jell that commonly has a distinctive color brownish or reddish yellow They yield water when massaged between the fingers Cottage cheese-like soils

24 a. Smectite with folds indicated by lattice fringes b. Also, folds on the edges below. Folds indicate flexibility of some smectite particles Dixon, 2002

25 Langmuir adsorption isotherms of aflatoxin B1 for three bentonite clays AfB 1 ad dsorbed [m mol/kg] R 2 = R 2 = = isotherm of 8TX = isotherm of 3MS = isotherm of 16MX 0.10 R 2 = E E E E E E-05 AfB 1 in equilibrium concentration [mol/l] Kannewischer et al, 2006

26 Smectite clay has the familiar 2:1 structure & the aflatoxin molecule is almost planar with localized charge Aflatoxin B1 a) Smectite structure b) Aflatoxin molecule

27 Aflatoxin molecules between smectite layers: exchange cations and water molecules are not shown

28 Colloidal gold with protective layer of thiol Why do colloidal crystals stay small? This study answers the question with a protective monolayer. Au in gold; S in blue; C in white; red electron density. P.D. Jadzinsky et al. Science 318:430, 07.

29 Common properties of nanoparticles in soils and soil systems High surface area Rapid chemical reactions Dispersible Often exhibit colloidal behavior Adsorb abundant water and organics Resemble small organic particles: starch, casein

30 Acknowledgements Texas Corn Producers Board, Lubbock, TX Special Nutrients Inc., Miami, FL Electron Microscopy Facility, NSF supported, Arizona State t University, it Tempe Microscopy & Imaging Center, TAMU, College Station, TX

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