Dr.Thrivikramji.K.P.

thrivikramji@gmail.com

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Scale in Nanoscience

Light bulb

After: Hochella Jr. (2008)

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 Weathering of Charnockite
Laterite profile, Thenmala
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 Progressive weathering Microcline dissolution

Dissolution of ilmenite,Offshore Dissolution of ilmenite,Offshore

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 Etch pits:
a. Hypersthene,
B Hornblende
C Augite
D Augite

AJSci,282, Oct.1982

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 A S-s Hy
B e-e, Dio
C s-s Aug
D e-e Aug
All etch pits

B
AJSci,282, Oct.1982

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 Diopside
Augite

Hornblende Hornblende

AJSci,282, Oct.1982

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Augite
Hornblende

Clay in Hyp Clay in Hb

Courtesy:
AJSci,282,
Oct.1982

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Carbonate cement

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Opy to Talc
A,B&C Opy to Talc
D&E Opy to
Smectite

AJSci,282, Oct.1982

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OPy to Smectite and Talc AJSci,282, Oct.1982

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 AJSci,282, Oct.1982

Weathering of Opy to amorphous material 13

Random Aggregation of pyrite, Veli Kayal, Tvm (1992) 14
Pyrite framboid, Cretaceous Austin Chalk, Texas, coll. B Woods
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(Folk, 2005)
The
Lycurgus
Cup- The
Roman
nano-
technology.
Tiny amounts
of colloidal
gold and silver
in the glass
gives a
dichroic
property- green
in day light &
red under
candlelight.

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vary

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 NANOSCIENCE
plays out in
the critical zone of the Earth. Jordan (2001)
defines in a NRC book entitled Basic
Research Opportunities in Earth Science , as
the place where the land meets the fluid
envelopes of the Earth, i.e., the hydrosphere &
atmosphere. Fresh water, agriculture & many
vital natural resources such as most mineral
deposits & timber are here. Geo & bio aspects
make it most heterogeneous.
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Based on Physical, geochemical, and
biologic processes, four principal &
overarching categories identified.
1) biologic
2) weathering,
3) fluid transport, &
4) near-surface tectonics.
Boundary of Nanogeoscience & life
science fuzzy.
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 1) Biologic Activity:
Due to organism s nutritional
requirements, drives a significant amount
of chemical cycling within & between
water, soil, rocks &atmosphere;
2) Weathering:
Constantly at work in the critical zone,
generating soil, destroying & producing
minerals in the process & redistributing
elements among water, rocks, & organic
materials
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 3) Fluid transport:
the critical component in water
resources supply & management, as
well as everything from flooding to
landform development
4) Near-surface tectonics:
shapes the land surface through
faulting, subsidence, uplift & mass
movement
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 Transport of metals & organics in near
surface environment;
Global geochemical & climate cycles
(+carbon);
Ore genesis & exploitation;
soil science; microbial geochemical action;
origin of life; space weathering & planetary
surfaces; aerosol transport & ice
nucleation; even deep earth processes.
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 Nanoscale phenomena involving
nano-sized geomaterials-
Processes of elemental distribution;
Biologic abiotic Earth interaction;
Heterogeneous catalysis; Reaction
pathways & mineral growth; Mineral
Transformation & weathering.
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 Where are Nanominerals & mineral
nanoparticles?
Noticed widely & commonly in
atmosphere, oceans, ground &
surface waters & soils.
Also in/on most living organisms &
even within proteins like ferritin- iron
storing protein in body tissue.

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 Why Nanogeoscience?
Nutrients limit Oceanic Productivity;
Iron a chief nutrient, reaches ocean as
dissolved inorganic and organic
complexes..
Nanoparticles of 2 to 20 nm range
has good amount of iron.
Oceanic Iron flux via Fe-containing
nanoparticles far exceeds riverine
input. Phytoplankton does 50%
photosynthesis 39
Importance of Nanogeoscience
1. Iron in mineral nanoparticles is bioavailable to
various species of marine phytoplankton making
them more important source of Oceanic iron.

2. Also in toxic-metal transport in Earth s near-

surface terrestrial environment - Radionuclide
transport by groundwater over several
kilometers in short periods of time defies
thermodynamics based predictions
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Importance of Nanogeoscience

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 Why Nanogeoscience?
Contamination of an area of 1600 km2 by
Cu, Zn, As, Pb, and Cd due to 11/2 century
of mining - the largest Superfund site - in
western Montana,USA.
Metals moved many hundreds of km down
the hydrologic gradient & across
floodplains in the Clark Fork River basin.
Carried chiefly by nanominerals and
mineral nanoparticles of manganese and
iron oxyhydroxides (Hochella et al. 2005).
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 Nanogeoscience, Why?
Currently mechanical properties much less
studied; so impact on working of Earth less
known; so an area of exciting future research in
mineralogy.
Natural production of mineral nanoparticles by
mechanical grinding associated with earthquake-
generating faults in shallow crust & Earth s
surface is known.
Large volumes of mineral fragments of 10 20 nm
in size noticed in pulverized rock in fault zones of
up to 100 m width. Suggesting importance of
mineral nanoparticles in fault mechanics 43
Why Nanogeoscience ?
Nanoparticles of high-pressure silicates (e.g.,
ringwoodite and wadsleyite) may have key role in
deep-focus earthquakes (300 700 km depth) in
Earth s mantle.

Mineral nanoparticles fill anticracks (planes of

weakness that need not dilate to make empty
space), in contrast to a normal crack.

As nanoparticles easily move past each other

without mechanical shearing of individual grains
(like talc) high pressure does not restrict the
movement. 44
 NATURAL AMORPHOUS
NANOMATERIALS
Far less known due to:
Limited diffraction information
Hard to interpret Spectroscopic
measurements
Highly variable chemistry and form
But growing recognition of natural
abundance and importance.

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1.Zhu et al. (2006) reported thick amorphous silica-
rich (leached from feldspar or from ground water)
layers of nanofilms (10 50 nm) on feldspar
surfaces in the Jurassic Navajo Sandstone, Black
Mesa, Arizona, USA.

Weathering rate of K-feldspars is 10E5 times

slower under natural conditions than under
similar conditions in weathering experiments
Nanofilm study explains difference the rate
weathering in the lab and under nature. 46
TL, K feldspar grain-amorphous over layer , 10-50
nm thick; TR, Weathered basalt with clay
precursors; BL- Zn sulfide nanoaggregates, Clark
fork River bed sediment, Montana
(After:Hochella,2008)

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 Several year-long leaching
experiments:
Amorphous nanofilms on uranium-
containing pyrochlore (a calcium
titanate considered for immobilizing
fissile elements), slows release of U
(Stubbs et al. 2008).
May play a crucial role in dictating
uranium s mobility through the vadose
zone
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The Clark Fork riverbed and Floodplains, Mo
Reducing zones of river bed with amorphous,
aggregated Zn-sulfide nanoparticles.
Their environmental role almost completely
unknown a research opportunity.

Amorphous, metal-bearing, naturally occurring

nanomaterials still undocumented or completely
unknown.

Recent studies showed secondary amorphous

silica with toxic heavy metals are relatively
common. 49
NANO-MATERIALS OUTSIDE EARTH:
(

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Chondritic meteorites & Interplanetary
Dust Particles.
Diamond nanoparticles of average 2 to
3 nm dia and grains as small as 1 nm
(<150 carbon atoms) in minute
quantities.
Nanodiamonds separated by multistep
acid digestion process or burning
down the haystack to find the needle .
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Nanopores and Mesopores?

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 A vast array of structures & mechanisms
symbolize Inorganic nanosystems (+ living
things).
Nanoscale physics & chemistry basis of
Nanobiomachines (molecular motors). For
better knowledge of inorganic systems and
to better appreciate nanogeo and nanobio
interactions.
Better perception of
characteristics and behavior of natural
nanoscale biological properties.
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 Highly confined pores & tubes greatly
modify mineral fluid interface reaction
pathways & kinetics compared to
reactions at unconfined mineral fluid
interfaces. Such changes affect
sorption, desorption and diffusion,
greatly affecting precipitation,
weathering & transport phenomena.
(e.g. Hochella and Banfield 1995; Wang
et al. 2003). 55
 Surface charge, cluster growth
characteristics, stability & fluid dynamics
principles dictate aggregation/dis-
aggregation behavior of natural
nanoparticles in air & water (e.g. Gilbert
et al. 2007).
A combination of experiments &
modeling will help researchers to infer
the characteristics & behavior of the
nano-aggregates.
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 The mineral kingdom is more
complex than previously thought.
Nanogeoscience is at a relatively
early stage of development, and
large gaps exist in our knowledge.
The next few years and decades will
be an exciting time of new
realizations, discovery, and change .
(Hochella JR, 2007)
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TL- High-resolution TEM images of 2 3 nm nanodiamonds recovered from the
Murchison meteorite; TR - interplanetary dust particles (After: Hochella Jr, 2008)

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 Potential applications of
nanoscience
include: ultra-small sensors &
devices, including transducers for
force, pressure & chemical
compounds; molecular gears,
motors & actuators.
Now is the time to plan
for applications & shape the future
with
groundbreaking innovations 60
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Pyrite Framboids of cube-octahedron crystals
Pyrite Framboids of octahedron crystals 63
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Folk (2003)
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Folk (2003)

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Folk ( 2003)

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Folk (2003)

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